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Chief specialist Chief specialist High category engineer High category engineer First category engineer

V. Nam . Khusainov G. Shadrova . Erimbetova G. Nam

TABLE OF CONTENTS INTRODUCTION 1. 2. NOTIONS AND TERMINOLOGY TECHNICAL ASSESMENT TO DETERMINE DIFFERENT OPEN-STORED BULKED SULFUR IGNITING MECHANISMS AND GENERAL RE-IGNITION RISK 8 9

14 14 15 17 25 25 25 27

2.1 2.2 2.3 2.4 2.5

Physical & chemical properties of sulfur Sulfur combustion hazard Sulfur ignition mechanisms General risk of re-ignition Reference information on sulfur combustion prevention and open storage of bulked sulfur. 2.5.1 Methods of sulfur recovery reducing combustion risk 2.5.2 Methods of sulfur blocks handling 3. ASSESMENT OF EXISTING TCO CAPABILITIES TO DETECT AND LIQUIDATE BULKED SULFUR COMBUSTION AT TENGIZ Requirements of regulatory documents of Republic of Kazakhstan with regard to fire safety at the enterprise under consideration Requirements of GOST (National Standard) 12.1.004-91 Fire safety: General requirements. Requirements of ONTP-I-86 (industrial sector norms for process design) National norms for technological process designing of oil & gas treatment plants Requirements of GOST (National Standard) 127.1-93 Technical sulfur. Technical conditions Requirements of Safety and Industrial sanitary requirements and norms for construction and operating apatite, nephelite, phosphorite, barium containing flotation concentrate, ground rock phosphate, sulfur (bulked and ground), white arsenic production facilities Goskhimizdat (State publishing house for chemical industry), Moscow, 1961 Requirements of PB (Safety requirements) 08-389-00 Industrial safety requirements to gas treatment plants and operations Requirements of PB (Safety requirements) 09-310-99 Industrial safety requirements to oil producing plants and oil operations Requirements of PPB RoK (Industrial safety requirements of

29 29 29 32 32

3.1 3.1.1 3.1.2 3.1.3 3.1.4

32 34 35
3

3.1.5 3.1.6 3.1.7

Republic of Kazakhstan) 08 2006 Fire safety requirements in Republic of Kazakhstan 3.2 Project design and technical approaches 3.2.1 Main project design approaches of Unit 600 3.2.2 Project design in part of normal operations conditions and technical safety provision 3.2.3 Fire safety project design philosophy 3.3 Present technical condition of Unit 600 3.3.1 Condition of sulfur pads 3.3.2 Necessary actions to detect bulked sulfur combustion 3.3.3 Technical condition of firefighting means and deluge system 3.3.4 Firefighting plan. Unit 600 (including bulked sulfur pads), developed by TCO 4. GENERAL ASSESMENT OF BULKED SULFUR IGNITION RISK AT TENGIZ INCLUDING SMALL AREA COMBUSTION AND LARGE SCOPE COMBUSTION INCIDENTS TAKING INTO ACCOUNT CHARACTERISTICS AND VELOCITY OF FIRE PROPAGATION AS WELL AS TCO EMERGENCY PREPAREDNESS TO ELIMINATE SULFUR PADS IGNITION 4.1 4.1.1 4.1.2. 4.1.3 4.1.4 Calculation of manpower and materials required for fire extinguishing Calculation of manpower and materials required for fire extinguishing at sulfur pad during handling and loading of bulked sulfur (Variant 1) Calculation of manpower and materials required for fire extinguishing at sulfur pad during pouring of liquid sulfur (Variant 2) Calculation of manpower and materials required for fire extinguishing at sulfur pad during storage of solidified sulfur (Variant 3) Results of manpower and materials calculation required for fire extinguishing as per 3 variants

36 37 37 40 42 47 47 49 49 51

55 55 56 65 76 85

5. EXPERIMENTAL DETERMINATION OF DATA DEPENDING ON SULFUR IGNITION MECHANISM: DETERMINATION OF LINEAR VELOCITY OF FIRE PROPAGATION AT A STAGE OF SULFUR COMBUSTION. DETERMINATION OF SULFUR SPONTANEOUS COMBUSTION CONDITIONS 5.1 Determination of sulfur combustion velocity using experimental method in accordance with UNO (United Nations Organization) methodology, section 33 Classification procedures, methods and

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criteria relating to class 4 (ST/SG/AC.10/11/Rev.3. Recommendations on the TRANSPORT OF DANGEROUS GOODS/ Manual of Tests and Criteria. Section 33/ Classification procedures, methods and criteria relating to class 4). 5.1.1 Description of UNO methodology 5.1.2 Testing performance Determination of fire propagation velocity index using experimental approach in accordance with GOST (National Standard) 12.1044-89 Combustion hazard of matters and materials, indices nomenclature and methods of determination 5.2.1. Determination of linear fire propagation velocity in the time of sulfur combustion 5.2.1.1 Brief description of methodology used to determine linear fire propagation velocity VL. 5.2.1.2 Drawing of experimental unit used to determine fire propagation index which is a basis for determination of linear fire propagation velocity 5.2.2 Preparation for testing 5.2.3 Testing performance Experimental method of determination solid matters and materials thermal spontaneous combustion conditions 5.3.1 Methodology as per GOST (National Standard) 12.1.044-89 Combustion and explosion hazards of matters and materials. 5.3.2 Experimental part 5.3.2.1 Spontaneous combustion testing of sulfur samples from TCO (without moisture in samples) under ambient temperature conditions adequate to the hottest period of time in the area of sulfur storage (as per reference sources) (Variant 1) 5.3.2.2 Spontaneous combustion testing of sulfur samples (containing moisture) from TCO under ambient temperature conditions adequate to the hottest period of time in the area of sulfur storage (as per reference sources) (Variant 2) 5.3.2.3 Spontaneous combustion testing of sulfur samples (covered with sulfuric dust) from TCO under ambient temperature conditions adequate to the hottest period of time in the area of sulfur storage (as per reference sources) (Variant 3) Spontaneous combustion temperature testing of sulfur samples from TCO to determine the temperature of spontaneous combustion (Variant 4) 5.3 5.2

90 90 91

92 93 93 94 95 95 98 99 102

103

104

5.3.2.4

105 106 110


5

5.4

Conclusions on experimental part

6. CONCLUSIONS ENCLOSURES: ENCLOSURE A. ENCLOSURE B. ENCLOSURE C. Historical information on fire incidents at sulfur pads Unit 600 Historical information on fire incidents at sulfur pads Unit 600 (July 16, 2005) Causes of suspicion of sulfur combustion incidents at TCO within the period since October 10, 2002 through April 18, 2005 (diagram). Brief information report concerning field works performed by SSI RSRCSCI specialists (Shymkent city), State Subsidiary Institution Republican scientific research centre on safety in chemical industry Protocol summarizing results on sulfur combustion velocity determined in accordance with UNO methodology (sulfur samples taken from sulfur pad 4) Protocol summarizing results on sulfur combustion velocity determined in accordance with UNO methodology (sulfur samples taken from sulfur pad 7) Protocol summarizing results on sulfur combustion velocity determined in accordance with UNO methodology (sulfur samples taken from sulfur pad 9) Protocol summarizing results on sulfur linear velocity of fire propagation. GOST 12.1.044-89 (sulfur samples taken from sulfur pad 4) Protocol summarizing results on sulfur linear velocity of fire propagation. GOST 12.1.044-89 (sulfur samples taken from sulfur pad 7) Protocol summarizing results on sulfur linear velocity of fire propagation. GOST 12.1.044-89 (sulfur samples taken from sulfur pad 9) Fire propagation velocity for different materials (diagram) Fire propagation velocity for different materials (table) Protocol summarizing results on thermal

111 115 116 119

120

ENCLOSURE D.

121

ENCLOSURE E.

122

ENCLOSURE F.

123

ENCLOSURE G.

124 125 126 127 128 129


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ENCLOSURE H. ENCLOSURE I. ENCLOSURE J. ENCLOSURE K. ENCLOSURE L. ENCLOSURE M.

ENCLOSURE N.

ENCLOSURE O.

ENCLOSURE P.

spontaneous combustion conditions for sulfur samples (without moisture) from TCO determined in accordance with GOST methodology 12.1.044-89 (sulfur samples taken from sulfur pad 4, 7, 9) Protocol summarizing results on thermal spontaneous combustion conditions for sulfur samples (containing moisture) from TCO determined in accordance with GOST methodology 12.1.044-89 (sulfur samples taken from sulfur pad 4, 7, 9) Protocol summarizing results on thermal spontaneous combustion conditions for sulfur samples (containing moisture) from TCO determined in accordance with GOST methodology 12.1.044-89 (sulfur samples taken from sulfur pad 4,7,9) Protocol summarizing results on thermal spontaneous combustion conditions for sulfur samples from TCO in accordance with GOST 12.1.044-89 (sulfur samples taken from sulfur pad 4,7,9)

130

132

134

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INTRODUCTION The upgrading of treatment technology of high-sulfur containing gas significantly increases volumes of recovered sulfur. Producing sulfur as a byproduct is a frequent practice for oil & gas operations. Volume of sulfur produced normally exceeds the demand and requires storing. The excess of sulfur can be accumulated at large plants recovering significant volume of sulfur due to interruptions in regular dispatch because of transportation shortage. That is why; the enterprises generating significant quantity of by-product sulfur have large buffer storages. The worldwide practice in the aspect is to pour sulfur and form sulfur pads which is the most cost-effective way of long-term storage of large sulfur quantities. Sulfur storage in blocks as well as handling may cause ecological problems. Besides, handling the blocks with the help of bucket-wheel or bucket excavators with following crushing of sulfur and loading bulked sulfur generates lots of dust what may cause sulfur ignition at the block itself. During the operations at Tengiz oil field about 8.5 million ton of sulfur was accumulated in open storage area in the form of blocks for the period since 1993 through 2004. The given report encompasses the technical assessment of different ignition mechanisms of bulked sulfur stored in open area as well as the report gives description of general re-ignition risk. It covers physical & chemical properties of sulfur, fire-hazardous properties of sulfur as well as sulfur ignition mechanisms. The document provides the assessment of existing detection and liquidation capabilities of TCO in case of bulked sulfur combustion at Tengiz. The general assessment of possible combustion of Tengiz bulked sulfur was performed including small area combustion and large scope combustion incidents taking into account characteristics and velocity of fire propagation as well as TCO emergency preparedness to eliminate such incidents.

1. NOTIONS AND TERMINOLOGY Terms Combustibility of a matter Incombustible matters Fire retardant matters Definitions Property of a matter or material to propagate flaming combustion or smoldering combustion. Matters which dont burn in air. Matters which get inflamed in air from the igniting source and stop burning after source is eliminated. Matters which can get combusted spontaneously and burn from igniting source even after the source is eliminated The lowest temperature of inflammable matter under which in special testing conditions fumes and gases having property to flare up from igniting source emit, but generation rate is not sufficient for stable combustion. The lowest temperature of inflammable matter under which in special testing conditions fumes and gases emit with the generation rate sufficient for stable flaming combustion after flaring up. combustion The lowest temperature of inflammable matter under which, in special testing conditions, exothermal (heat-generating) reaction velocity significantly increases leading to flaming combustion.

Inflammable matters

Flashing point

Flaring point

Spontaneous temperature

Low and high concentration Minimum and maximum concentrations on inflammable matter in the mixture inflammable levels of fire propagation matter oxidizing medium, which conduce fire propagation along the mixture for any distance from ignition source (the terms: explosion level and inflammability level are also used). Temperature levels of fire Temperature of a matter under which its saturated fumes form, in a certain oxidizing medium, propagation concentrations equal to low (low temperature level) and high (high temperature level)
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concentration levels of fire propagation. Temperature of self-heating The lowest temperature of a matter under which self-heating takes place which leads to smoldering combustion or flaming combustion

Smoldering temperature heating

combustion Temperature of a matter under which oxidation under self- exothermal reaction velocity significantly increases leading to smoldering combustion. Non-flaming combustion of a solid matter (material) under comparatively low temperature (400-6000) frequently generating smoke.

Smoldering combustion

Temperature thermal combustion

conditions of Dependence educed using experimental approach spontaneous of ambient temperature, mass of a matter and time till spontaneous combustion takes place. The lowest electrical charge energy which may ignite the most easy-inflammable mixture of dust and air.

Minimum igniting energy

Normal fire propagation The velocity of flame front movement along the velocity (normal combustion unburnt mixture in perpendicular direction of its surface velocity) Regression rate Fire propagation rate Quantity of inflammable material burning per time unit at the given area unit. Conventional rate reflecting the property of a matter for fire propagation along the surface and associated heat generation. Fire propagation rate is used for classification of materials depending on propagation property. Materials are divided into: Materials which dont propagate fire along the surface fire propagation rate is equal to 0; Materials which slowly propagate fire along the surface fire propagation rate is above 0 up to 20; Materials which rapidly propagate fire along the surface fire propagation rate is higher than 20. The method of fire propagation rate determination assesses the property of a material to ignite,
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generate heat and propagate fire along the surface being influenced with external heat flow. Fire Uncontrolled combustion outside the special laboratory sole which brings material damage. Fire life, time of heat influence on environment as well as severity of material damage depend on fire load. m relation of mass of inflammable and fire retardant materials including construction components and the area the materials occupy in open space (kg/m2). The space of fire development is divided into three zones: combustion, heat influencing and smoke screening. ST denotes a part of fire area where fire extinguishing activities using special means take place. (Efficiency of extinguishing using water depends on effective extinguishing depth h). fire denotes length of external limit of fire area in the given moment which is taken into account during supplying water and extinguishing fire area besides the neighbor sections which length is equal to effective depth of fire extinguishing h. If fire area has a round shape perimeter of fire extinguishing decreases due to circuit decreases from external limit to the center. of fire Practice shows that the one third of water jet is effective for fire extinguishing that is why for the calculations the effective depth of fire extinguishing equal to 5 meters (manual nosepiece) and 10 meters (wheeled nosepiece) are taken.

Fire load rate. m

Fire extinguishing area ST

Perimeter of extinguishing

Effective depth extinguishing h.

Water consumption during Amount of fire extinguishing material by weight or volume supplied per time unit onto fire fire extinguishing parameter unit for fire extinguishing or for protection of area which is in danger of fire propagating on it.
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Actual water consumption Actual amount of fire extinguishing material by weight or volume supplied per time unit onto fire during fire extinguishing parameter unit for fire extinguishing or for protection of area which is in danger of fire propagating on it. Total water consumption Amount of fire extinguishing material by weight or volume required for complete fire liquidation during fire extinguishing and protection of not burning objects including reserve. Total water consumption is used to determine the required amount of fire extinguishing materials to liquidate fire, to check the provision of water at the site given fire water storage is available and to develop necessary action plans for fire extinguishing. Intensity of supply extinguishing material of Amount of extinguishing material supplied per time unit on appropriate unit of geometric parameter of fire (area, volume, perimeter or front). It is determined by experimental method and practices of fire extinguishing. Change of fire parameters in time and space starting from igniting through complete liquidation of fire. There are three phases (periods) in fire development: free development , localization and liquidation of fire.

Fire development

Free fire development phase Fire develops without any obstacles starting from , igniting through the moment of taking up initial fire extinguishing measures (applying the first fire nosepiece and other means of combustion liquidation). This phase is characterized with expansion of fire area, burning-out of fire load, heating of construction components, their crushing, explosion hazards and other dangerous factors. Fire localization phase Fire develops till the moment of taking up focused measures and applying special means to restrict fire propagation along the area and eliminate emergency situation. This phase is characterized with further expanding of fire area, decreasing fire propagation velocity due to
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applying extinguishing means, burning-out of fire load at the free flaming and smoldering areas as well as other phenomena and dangerous factors. Fire liquidation phase During this phase fire area decreases, but fire develops until complete elimination of burning along all surfaces covered by fire load and prevention of re-ignition hazard at the area. Occurs when fire emerges inside the area with large fire load and propagates in all directions with approximately equal linear velocity under comparatively windless weather. Occurs when fire emerges at the limit of the area with large fire load and propagates within the angle under any weather conditions. Fire takes the shape at the same areas as round shape fire.

Fire area of round shape

Fire area of angle shape

Fire area shape

of

rectangular Occurs when fire emerges at the limit or inside the gaunt area with fire load and propagates in one or several directions: downwind with higher, upwind with lower, under comparatively windless weather with approximately equal linear velocity.

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2. TECHNICAL ASSESMENT TO DETERMINE DIFFERENT OPENSTORED BULKED SULFUR IGNITING MECHANISMS AND GENERAL RE-IGNITION RISK 2. 1 Physical & chemical properties of sulfur Sulfur is a yellow powder or fragile crystallized mass without smell and flavor which cannot be dissolved with water. Sulfur has several allotropic modifications. The most widespread are: crystallized sulfur rhomb shaped (native sulfur, a-S) and monoclinic (prism shaped, b-S); amorphous sulfur colloidal and plastic sulfur; intermediate amorphous-crystallized sublimated (sublimed sulfur). Nuclear charge number Atomic mass Nuclide stable unstable Melting point, Boiling point, Density, g/cm3 Flintiness (as per Moos) Content in earth crust, % (mass) Rate of oxidation 32, 33, 34, 36 31, 35, 37 112,8 (a, rhomb shaped), 119,0 (b, monoclinic) 444,6 2,06 (rhomb (monoclinic) 1,52,5 0,052 2, +2, +4, +6 (rarely 1, 0, +1, +3, +5) shaped), 1,957 16 32,066

Crystallized sulfur. Crystallized sulfur has two modifications; one of them the rhomb shaped is received as a result of sulfur dissolving in carbon sulfide (CS2) by evaporating the solution at the ambient temperature. The rhomb shaped hyaline crystals are formed possessing light yellow color which can easily be dissolved in CS2. This modification is stable up to 96 ; the monoclinic form is stable under higher temperature. As a result of self-cooling of melted sulfur large deformed crystals of rhomb modification (octahedron which has partially cut angles or planes) are formed in cylindrical crucible. Such material has an industrial name bulked sulfur. Amorphous sulfur. Block sulfur also exists in two non-crystalline, amorphous forms. Besides the crystallized and amorphous forms there is an
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intermediate form known as sublimed or sublimated sulfur which is received by sulfur fumes condensation passing by the liquid stage. It consists of microparticles which have crystallized centre and amorphous cover. This form slowly and not completely dissolves in CS2. After treating with amine and recovery of such admixtures like arsenic the product is received known in the medicine as washed sulfur which is applied similarly to colloidal sulfur. Sulfur is a typical non-metal. Its external electron shell comprises six electrons and it easier adsorbs electrons of other elements than allows other elements to adsorb its. It reacts with many metals generating heat (for example, reacts with copper, iron, zinc). It aggregates with almost all non-metals but not so vigorously. 2.2 Sulfur combustion hazard From chemical point of view fire is a process of uncontrolled burning. At burning inflammable matter get oxidized. Oxygen is the most frequent oxidizing agent. Inflammable materials have different aggregative and oxidizing properties. Most of inflammable materials oxidize slowly under normal temperature conditions. Oxidizing reaction velocity before burning increases when heating inflammable matters. Heat generated as a result of reaction creates conditions for independent development of burning process. Therefore, in order to ignite inflammable material so that it continues to burn as a rule the following is required: certain amount of air oxygen and thermal impulse capable to heat the inflammable matter up to its combustion temperature. Only simultaneous combination of the three factors inflammable material, oxygen and ignition source may cause fire. Self-flaring is a phenomenon when a matter gets ignited without open ignition source after getting heated up to the certain temperature self-flaring temperature. At heating inflammable material under certain temperature oxidation reaction takes place. The term self-flaring can also be used to denote ignition in the result of material self-heating up to the level when heat generation velocity during oxidation reaction exceeds the velocity of heat dissipation. Spontaneous combustion is a phenomenon when matters get ignited without open ignition source due to heat generation inside a matter in the result of matter oxidation-with-oxygen reaction or biological process life activity of microorganisms and chemical reaction. Sulfur combustion hazard is determined by its physical & chemical and combustion hazardous properties.

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Sulfur is characterized with low melting heat (1.72 kJ/mol) and low evaporating heat (9.2 kJ/mol). Therefore, to ignite sulfur ignition source may have comparatively low energy. Sulfur possessing high specific resistance (1.91013 Ohmcm), has electrostatic charging property. Electrostatic charge emerges during crushing, handling and grinding of sulfur and also friction of particles may cause electrostatic charging with the possible following discharge and sulfur combustion. Combustion hazardous properties of sulfur are characterized with fire hazard indices (GOST 12.1.044 91). Basic indices are given below: Flashing point (207 C); Flaring point (232 C). Sulfur with dispersion less than 74 mkm has a flaring point at 220 C (aerogel form); Concentration levels of fire propagation. The sulfuric dust has low concentration level of fire propagation 35 g/m3. Maximum pressure during explosion of sulfuric dust and air mixture is 500 kilopascal; Fine-grained sulfur is inclined to self-combustion in the presence of moisture. Sulfur forms explosives with strong oxidizers such as bleach powder, nitrates, chlorates and perchlorates; Minimum ignition energy is 15 mJ; combustion heat 9205 kJ/kg.

Sulfur possesses good dielectric properties. Dangerous (positive) electrostatic charges emerge as result of either turbulent motion of sulfur or jet impacting side of vessel or fluid surface. Charges may emerge in sulfuric dust jets as well. Elementary sulfur of any size (dispersion) is a very hazardous if gets ignited as in the result of ambient temperature increase intensive melting of sulfur takes place then sulfur evaporating and boiling. Melted burning sulfur when flowing makes other inflammable materials burn and sulfur fumes when getting burnt may cause quick fire propagation to areas remote from fire seat and may cause explosion. Burning sulfur aggravates fire extinguishing due to generation of sulfuric gas which requires application of special protection means and deteriorates (in presence of water vapor) metallic structures including fire extinguishing equipment. Ferric sulfide and pyrophoric iron may deposit on the surfaces of equipment and pipelines under the influence of melted sulfur.

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2.3 Sulfur ignition mechanisms Causes Self-flaring of sulfur Ignition mechanism Self-flaring of sulfur can take place in the following cases: - high moisture content in sulfur; - contacting oxidizers; - contacting coal; - contacting fats; - contacting oils; - contacting bleach; - impact (mixture with oxidizer); - friction (mixture with oxidizer). Sulfuric dust when deposited is easily combustible from low energy ignition sources. The emerged flame quickly propagates along the dust layer. Fine-grained sulfur is inclined to self-combustion. Process gets more intensive in the presence of moisture and when reacting with oxidizers, in mixtures with coal, lamp black, with fats and oils. Flaring temperature of sulfur it easily ignites under ambient temperature from low energy ignition sources. Self-flaring temperature is 478 . Sponginess of material plays a significant role in the development of self-flaring. Air filling spaces among particles of material and air adsorbed in voids takes part in self heating. In the result of diffusion it comes to reacting surface. That is why the materials possessing high porous structure which allows oxygen reaching the point of reaction are inclined to thermal self-flaring. Fine-grained sulfur is inclined to chemical self combustion in the presence of moisture and when reacting with oxidizers, in mixtures with coal, with fats and oils. It gets self ignited when contacting bleach. Fine-grained sulfur stored in large piles is inclined to thermal self combustion. When contacting oxidizers sulfur is inclined to chemical self combustion. Influence of technological equipment hot surfaces Sulfur can ignite in the following cases: - local overheat of equipment and pipelines; - absence of thermal insulation of equipment and pipelines. Example:
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Fire emerged at stores in Sovetsk city, Kaliningradsk region (Russian Federation) was caused in the result of sulfuric dust contact with stem pipeline which surface had high temperature. Influence of weather conditions Self-ignition of sulfur may take place in the following cases: - lightning strike; - direct sunlight. Example of technical bulked sulfur ignition: during transportation of bulked sulfur in open rail cars the fire took lace at Syzran railway station, Samara region (Russian Federation) in the result of direct sunlight impact.

Sulfur combustion can take place in the following cases: Sulfur combustion - mechanical equipment sparks (friction of metal from spark surfaces); - repair and maintenance works (sparks from electrical welding, gas welding); - sparks from equipment working nearby or auto transport passing by; - sparks from passing by locomotives; - sparks from closely located open fire sources (furnaces, boilers). The research of VNIIZhT (Union-wide Science and Research institution in the field of Rail transport), sparks from locomotives are quite powerful sources of ignition. Igniting properties (ignition tile) of spark were tested on different inflammable solid materials. Results of testing are given below Name of material Time till first signs of smoldering combustion, sec 2...4 10...15 25...35 30...40 13...18 20...25

Cotton Cotton flocks Wood dust Compacted wood Straw Paper (Newspaper)

As per the data given in the above table, sparks ignite


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paper, ignition energy is 20 mJ, at the same time sulfur ignition energy is 15 mJ. Therefore, sulfur ignites from sparks easier than paper. It requires mentioning that smoldering sparks have temperature (500...600 C) which exceeds self combustion temperature of sulfur. Thus, sparks, having high temperature and significant duration of flaming combustion and smoldering combustion (more than one minute), are possible ignition sources of sulfur. Impact of size of sulfur particles Combustion property of sulfur to get ignited from low powerful ignition source within short period of time depends on size of sulfur particles. There is a relation of surface of particle to its volume. Diagram 1 depicts the relation of particle surface to its volume depending on diameter.

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Surface/volume

Diameter of spherical particles, mm

Diagram 1. Relation curve of spherical particles surface to volume depending on diameter Taking into account the relation of spherical particle surface and volume area of heat sensitivity of sulfur finegrained volumetric unit is much higher than that of particles of bigger size having the same volume. That is why finer sulfur can easily ignite from low energy ignition sources. It is necessary to point out that sulfur particles which are not spherical and have same volume are of higher combustion hazard and can ignite from low energy ignition source. Combustibility testing was performed on grinded sulfur (diameter of particles less than 1 mm), granulated sulfur produced at Astrakhan gas processing plant (GPZ), received using wet method, and is represented with the mixture of spherical granules of different size (3...7 mm, bulk density 1029 kg/m3), as well as granulated sulfur of Orenburg gas processing plant (GPZ), received using dry method. Bulk density of sulfur is 1169,4 kg/m3.
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Results of combustibility test of granulated and grinded sulfur from low energy ignition source within short period of time are given in the below table 2. Table2 Name of Number Numbe Ambient Atmosph of ignition of r of temperature eric test source ignitions combu C pressure, stions Mmhg Sulfur of Orenburg gas processing plant GPZ 1 10 5 +2 746 2 10 6 +4 746 3 10 5 +4 746 4 10 4 +5 750 5 Flame of 10 4 +5 750 match 6 10 4 +20 748 7 10 6 +20 748 8 10 4 +20 750 9 10 6 +15 735 10 10 4 +15 735 Summary 100 48 Sulfur of Astrakhan gas processing GPZ, size of granules more than 3mm,but less than 5mm 1 10 7 +20 750 2 10 7 +15 735 3 10 8 +13 736 4 10 5 +13 736 5 Flame of 10 5 +13 736 match 6 10 9 +12 743 7 10 5 +12 743 8 10 8 +12 743 9 10 8 +12 743 10 10 7 +13 740 Summary 100 69 Grinded sulfur 1 10 10 +13 735 Flame of 2 10 10 +14 730 match 3 10 9 +14 730 4 10 10 +14 730
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5 6 7 8 9 10 Summary

10 10 10 10 10 10 100

9 10 10 9 10 9 96

+14 +14 +14 +14 +16 +15

730 735 735 735 740 750

Data received during testing show that grinded sulfur ignites in 96 cases out from 100, granulated sulfur of Astrakhan gas processing plant GPZ ignites in 69 cases out from 100 when applying flame of match, and granulated sulfur of Orenburg gas processing plant GPZ ignites in 48 cases out from 100 trials. The reason for the different combustibility level from low energy ignition sources is in the method of granulated sulfur recovery. Granules received using wet method (Astrakhan GPZ), are represented as spherical formations which have many voids, hollows (Diagram 2). Sometimes there are exit openings in granules. It significantly increases thermal sensibility area from ignition source and leads to more frequent combustions comparing to granulated sulfur of Orenburg GPZ. Particles of granulated sulfur of Orenburg gas processing plant GPZ are denser (monolith), and they have a few number of small inside voids. That is why thermal sensitivity area is less comparing to granulated sulfur of Astrakhan gas processing plant

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Fig. 2. Granules of sulfur: 1 craters; 2 pulled surfaces; 3 exit openings As per GOST 127.1 93, liquid sulfur disengage hydrogen sulfide [2]. Mass fraction and concentration of hydrogen sulfide in 1 ton of liquid sulfur at different ppm (number of H2S molecules per 1 million of S atoms) are given in the table 3. Table3 Volume of hydrogen sulfide per 1 ton of liquid sulfur, liter 7,4 29,6 74,8 183,5

Hydrogen sulfide Mass concentration in fraction of liquid sulfur, ppm hydrogen sulfide, % 10 0,00105 40 0,0042 100 0,0106 250 0,026

Diagram 3 shows that at the concentration 10 ppm 1 ton of liquid sulfur can disengage 7,4 liters of hydrogen sulfide (at the temperature 20 C and pressure 760 Mmhg).
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When liquid sulfur gets cooled hydrogen sulfide may be captured in micro voids (capsules) of solidified sulfur. Thus granulated sulfur may contain hydrogen sulfide. Content of hydrogen sulfide in the solidified sulfur increases its combustion hazard as when disengaging hydrogen sulfur creates micro voids. Self-combustion of pyrophoric depositing (ferric sulfide) ferric is one of the reasons of fires and explosions. Pyrophoric depositing possessing self-combustion properties are formed in reservoirs or other metallic vessels storing oil and hydrocarbons with high content of sulfur. The depositing comprises sulfuric iron and is formed as a result of impact on iron and its hydrogen sulfide contained in hydrocarbons, elementary sulfur and dissolved hydrogen sulfide contained in hydrocarbons. Statistical data analysis shows that every year there is an increase of the number of explosions and fires in the oil and gas industry due to self combustion of pyrophoric ferric sulfide. Ferric sulfide is formed in technological equipment, reservoirs, oil wells in the result of reaction of corrosion products with hydrogen sulfide contained in high sulfur oil. Pyrophoric depositing on the surfaces of equipment is represented with foliate or porous solid formations. On the surface of depositing elementary sulfur gets crystallized being thermal insulation and increasing combustibility. Activity of pyrophoric depositing i.e. level of combustibility depends on chemical content. static In the presence of explosive hazardous concentration of sulfuric dust and oxygen explosion (and possible fire) can take place due to electro static discharge. Sulfur can ignite due to: - electric arc generation; - heating of voltage lines; - electric discharge taking place when opening live electrical circuit (with breaker or in emergency situation).

Impact sulfide

of

Impact of electricity

Impact of emergency operation modes of equipment

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Mechanical impact

Sulfur can ignite due to: - impacts, friction during handling of bulked sulfur blocks; - impacts, friction from transportation and repair means. - deliberate (terrorist acts, thug acts etc.); - non-deliberate (due to careless usage of fire, smoking in restricted areas etc.)

Arsons

2.4 General risk of re-ignition Sulfur fires are frequent and very cunning as they may be repeated even after initial combustion was eliminated. Besides, new fire seats emerge sometimes. This is so in our opinion due to combustible gas - most probably hydrogen sulfide - is contained in closed voids of sulfur granules. Hydrogen sulfide is a colorless toxic combustible and explosion hazardous gas with the distinguished smell of spoiled eggs; this gas is heavier than air. 2.5 Reference information on sulfur combustion prevention and open storage of bulked sulfur 2.5.1 Methods of sulfur recovery reducing combustion risk Transition to granulated sulfur production tendency 1. Sulfur property to get ignited from low energy source of ignition applied for a short period varies depending on particles granules size. There is a dependency of particle surface to its volume. It is necessary to point out that sulfur particles which are not spherical and have same volume are of higher combustion hazard and can ignite from low energy ignition source. Thus, shaping the particles into spherical type reduces heat sensitivity area related to its volume. Therefore, granulating sulfur (from the point of fire safety) shall be considered as feasible. 2. Fragility rate is the most critical factor when determining opportunities of granulated sulfur transportation. Elementary sulfur is fragile and gets crushed generating a lot of dust during loading & handling works. Dust is explosion hazardous and possesses noxious properties. Moreover large amount of small fractions affects moisture adsorption and accumulation, sulfur properties. The term
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moisture encompasses moisture content in the product, adsorbed during stage of formation, moisture adsorption during wetting and moisture losses in place. Granulated sulfur loading & handling operations efficiency depends on size of particles, their shape and uniformity, structure of surface, area of surface, density, hardness, deforming and engaging capabilities. To compare handling and storing properties of granulated sulfur received by different methods the four basic properties have been identified: bulk density, natural slope angle, compressibility and flowability. Bulk density and natural slope depend on size and shape of particles, compressibility and flowability are calculated values. Canadian specialists define compressibility as per the formula: 100(-) % of compressibility = , Where is bulk density when compacting, is bulk density when ventilating. Flowability value is required to design storing system and loading & handling operations. Flowability is determined as per seven categories varying from very good to very, very bad (maximum is 100%). Sulfur flowability may change depending on moisture and peculiarities of loading & handling operations. For example, Flowability of wet sulfur samples is lower for 510% than of dry. During the fragility test the typical load was applied which appears during handling works. In Canada granulated sulfur was tested using fragility test method which is similar to hardening of metal (quick cooling). The samples of sulfur granulated by different methods were tested using ultimate tensile strength test, ultimate compressive strength test and impact strength test. During the testing it was determined that mechanical properties of samples change in the course of time, it means that it is necessary to take into account aging of sulfur when performing any tests. As result of testing the following conclusions were made: The higher temperature before hardening the worse results of ultimate tensile strength test, ultimate compressive strength test and impact strength test of the sample which was hardened; Samples with size more than 6.5 mm are subject to shrinkage loss. It happens due to difference of temperatures outside and inside a granule as sulfur has low thermal conductivity. It is determined that relation of granule cover state and strength is too significant and it cant be neglected; Hydrogen sulfide contained in has low influence on strength and needs to be recovered only from the point of environment protection. Canadian specialists also studied the influence of different factors on sulfur granules destruction after impact. It is discovered that cracking is increasing with increase of motional energy and diameter of particles. In order to decrease cracking and through that dust generation height of sulfur unloading is to be decreased and unloading should be performed onto slope surfaces if possible. It was concluded that type and age of sulfur, motional energy of hitting metallic surface, diameter
26

of particle, and angle of slope influence the extent of granule destruction. Minimum height of destruction is a smooth ascending curve of particle diameter. Basic properties of typical granulated sulfur which are important to determine loading & handling philosophy as per the different researches are as follows: Size, mm, max. .5-6 Bulk density, kg/m3 1000-1400 Slope angle, degrees..28-35 In Japan solidified sulfur was tested for strength and dust generation. Taking into account that Japan produces sulfur on an industrial scale with size of granules equal to 1 mm, there is a hazard of sulfur dust generation and its explosion as minimum explosion hazardous concentration of sulfur dust in air is 35 g/m3 (explosion limits 35 1400 g/m3). Problems appearing during the loading & handling operations and transportation of sulfur have been resolving at different periods of time in all the countries large producers of sulfur. For example specialists from Poland believe that solid sulfur must have the following physical parameters: - to be spherical to reduce the abrasive surface to minimum; - the surface must be as even as possible; - size of particles must be more or less same; - in spite it is solid sulfur must behave as fluid during loading & handling operations; - bulk density must be consistent most of the time; - formation must not affect the quality characteristics of the product. 2.5.2 Methods of sulfur blocks handling Sulfur blocks handling Information sources say that sulfur is stored in blocks of different size in Canada, Poland, France, Mexico, Saudi Arabia and USA. Canada has accumulated the largest reserves of sulfur in blocks as of end of 1970s. Total amount reached 20.5 million ton, the biggest block contained up to 7 million ton of sulfur with the height 16 m. Mechanical method of sulfur blocks handling used in Canada till the end of 1980s was creating serious problems for environment due to generation of dust. Sulfur was crushed into small pieces before melting as a result a lot of dust was generated and cases of sulfur combustions at block itself were frequent. That is why melting of sulfur directly in block was preferred. Economical feasibility of in place melting could have been argued comparing with mechanical handling, however, advantages of zero dust generation
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give significant positive results which economical aspect sometimes cannot be estimated. Analysis of different methods and mechanisms of solid sulfur processing and melting gave the basis to single out three different variants with regard to sulfur stored in blocks: - mechanical handling of sulfur blocks and loading bulked sulfur; - mechanical handling of sulfur blocks with the consecutive melting of bulked sulfur; - melting of sulfur directly in place. Storing facilities and loading & handling mechanisms. Large scale of sales requires efficient high-performing facilities for storing and loading & handling operations. Herewith a lot of attention is paid to eliminate fire and explosion hazards. To control dust generation which cannot be avoided when operating at high speed the special foam received from foaming agent and compressed air is applied at the loading point. Foaming agent being an organic matter does not affect the quality of sulfur. Foam not only reduces dust generation for 60-80%, but also reduces moisture in the handled sulfur (foam contains only 0.1-0.3% of water) if compare with method where water is used. Foam method also provides minimum accumulation of static electricity.

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3. ASSESSMENT OF EXISTING TCO CAPABILITIES TO DETECT AND LIQUIDATE BULKED SULFUR COMBUSTION AT TENGIZ Assessment of existing TCO capabilities to detect and liquidate bulked sulfur combustion at Tengiz is performed on the basis of and after: - Project design documentation Unit 600 (Storage of bulked sulfur on the open sulfur pads); - TCO operations documentation Unit 600; - Physical familiarization with condition of sulfur pads; - Familiarization with production activities at each separate sulfur pad; - Familiarization with statistics, causes, scale and detection methoeds of combustion at sulfur pads; - Familiarization with the Action plan on fire fighting measures with regard to sulfur pads; - Application of results and conclusions made during 1-st stage works.

3.1 Requirements of regulatory documents of Republic of Kazakhstan with regard to fire safety at the enterprise under consideration Section 3.1 contains requirements of regulatory documentation effective in Republic of Kazakhstan with regard to fire safety at the site under consideration:

3.1.1 Requirements of GOST (National Standard) 12.1.004-91 Fire safety: General requirements. General provisions Clause 1.1. Fire safety is to be provided by fire prevention and fire fighting systems as well as organizational & technical measures are to be developed. Fire safety systems must provide fire safety of people and company property. Fire safety systems must be economically effective and cover all stages (research and development, designing, construction, operations) of plant activities providing fulfillment of one of the following requirements: Suspend fire development; Provide fire safety of people; Provide fire safety of company property; Provide fire safety of people and company property simultaneously. Clause 1.2. Facilities must be equipped with fire safety systems properly
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functioning to prevent at the required level the influence of hazardous fire factors on people as well as repeated emerging of the factors. Required level of fire safety provision with help of the stated systems must be not less than 0,999999 of hazardous fire factors prevention per year with a view to each individual. Acceptable level of fire hazard for people must not exceed 10-6 of influence of hazardous fire factors per year with a view to each individual. Clause 1.5. Hazardous fire factors affecting people and damaging company property are: Flame and sparks; Increased ambient temperature; Toxic products of burning and thermal decomposition; Smoke; Decreased oxygen concentration. Secondary hazardous fire factors affecting people and company property are: Sharp pieces, pieces of damaged equipment, devices, plants, structures; Electrical shock due to short circuiting on current conductive parts of structures, devices, equipment; Hazardous explosion factors in accordance to GOST 12.1.010 emerged in the result of fire; Fire extinguishing materials. Requirements to methods of fire safety provision by means of fire safety systems Clause 2.1. Prevention of fire should be achieved by prevention of formation inflammable medium and (or) elimination of ignition sources application. Clause 2.2. Prevention of inflammable medium formation must be provided through one of the following methods or through combination of several methods: To maximally apply non-flammable or fire retardant materials and matters; To maximally restrict, taking into account operation and construction needs, the quantity and (or) volume of inflammable matters and materials. To provide maximally safe location of the materials and matters; To maintain safe concentration medium in accordance with norms and rules stated in regulatory-technical, regulatory documents and fire safety rules; To maximally use automatic machines and systems for process control covering application of inflammable materials; To install fire unsafe equipment if possible inside the isolated premises or in open area; To apply protection systems for the process equipment associated with inflammable materials to prevent damage or emergency situations by provision the system of emergency shutdown, blocking and other devices.
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Clause 2.3. Prevention of ignition sources emerging in inflammable medium must be provided through one of the following methods or through combination of several methods: To use such machines, mechanisms, equipment and devices operated without generating ignition hazard; To use electrical equipment that meets the requirements of the appropriate fire hazardous and explosion hazardous zones, groups and categories in accordance with GOST 12.1.011 and Rules for electrical units (PUE); To operate technological process and use equipment in accordance with electrostatic and intrinsic safety in accordance with GOST 12.1.018; To provide lightning arresters for the buildings, installations and equipment; To eliminate possibility of sparking discharge to inflammable medium with energy that is equal or more the minimum energy of ignition; To use intrinsically safe equipment when working with inflammable fluids and combustible gases; To fulfill construction requirements, rules and standards. Requirements to methods of fire safety provision and fire fighting systems Clause 3.1. Fire protection must be provided by one or combination of the methods enumerated below: Application of fire extinguishing means and appropriate types of fire equipment; Application of automatic devices of fire signalization and extinguishing systems; Application of basic structures and constructiion materials including those used for coating with the fire hazard level meeting requirements; Installation of devices restricting fire propagation; Organization of timely announcement and people ecvacuation using technical means including autiomatic ones; Application of collective and individual protection means for people to prevent negative influence of dangerous fire hazards; Clause 3.4. Collective and individual protection means must provide safety of people continuously during effect of fire hazards. Collective protection is to be provided by means of fire safe zones and other special construction provisions. Individual protection means are to be used by fire fighters involved in fire extinguishing. Clause 3.6. Each commercial object must have arrangements to provide timely announcement of people and (or) fire signalization in its initial stage by technical or organizational means. Clause 3.8. It is also necessary to determine: High-perfomance and intensity of fire extinguishing means supply;
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Allowable fire extingushing means (in terms of environment suitability and compatibility with inflammable materials); Sources and means of fire extinguishing materials supply to eliminate foire; Calculated as per the norms reserve of special extinguishing materials (powder type, gas type, foam, combined type); Required speed of building-up the fire extinguishing materials supply with help of transportation means of fast reacting fire services; Requirements to resistance to negative impact of dangerous primary and secondary fire hazards; Safety requirements. 3.1.2 Requirements of ONTP-I-86 (industrial sector norms for process design) National norms for technological process designing of oil & gas treatment plants 35.7 . , , . ( ) . 3.1.3 Requirements of GOST (National Standard) 127.1-93 Technical sulfur. Technical conditions 5.3. . . 3.1.4 Requirements of Safety and Industrial sanitary requirements and norms for construction and operating apatite, nephelite, phosphorite, barium containing flotation concentrate, ground rock phosphate, sulfur (bulked and ground), white arsenic production facilities Goskhimizdat (State publishing house for chemical industry), Moscow, 1961 Access roads, driveways, raw materials, coal and finished product warehouses Clause 60. All roads and driveways on the territory of plant are to be illuminated during night. Illuminating intensity must be not less than 10 lux. Clause 69. Open sulfur storages are to be arranged at the industrial area downwind. Sulfur is piled or sulfur blocks are formed.
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Each sulfur pile must have fire resistant sides around the perimeter having height of 80 sm and 1 brick thickness. Gap between rail ceneterline and pile must be not less than 3 meters. Lightning arresting system and electrostatic protection Clause 144. Pipelines stretching inside the territory of the plant, systems and pipelines located inside and outside the workshops must be arranged as continuous uninterrupted electrical circuit. Each system and pipeline must be provided with double earthing inside the workshops. Extinguishing of burning sulfur is to be performed using oxygen breathing mask. Clause 145. To discharge static electricity accumulated on people it is necessary: ) at the entrance to premise of bulked sulfur grinding and at the storages of grinded sulfur it is necessary to arrange electrical conductive grounded plates (aluminum and other grounded plates on which devices can be installed); Mechanization of labour-intensive, hazardous and dangerous activities Clause 475. To prevent sulfuric dust explosion bucket elevators and scraper conveyors are not allowed to be used for transportation of sulfur or sulfuric ore. Equioment and devices for fire extinguishing Clause 150. Fire services at the plant are to be provided by professional fire team and volunteers at a discretion of administration. Clause 151. Instructions how to use fire extinguishers and fire tools are to be put in visible places. Clause 152. Before fire team comes it is necessary to cover the burning sulfur with sand, earth, fine sulfur. To prevent flowing of burning sulfur it is necessary to bank up fire seat or dig up collecting trench. Extinguishing of burning sulfur is to be performed using oxygen breathing mask.. Special technological requirements to production of bulked sulfur Clause 372. Application of any structures (channels, pipes, trays etc.) for pouring sulfur is prohibited. Access to sulfur draining valves must be provided by means of specially barricaded platforms installed at higher level above valves.
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Clause 373. When handling sulfur pile using excavator the working zone is to be barricaded and notices to be provided. Clause 374. At sulfur storage where pouring is performed (onto open area), it is necessary to strictly divide sections where sulfur pouring is made and which are ready for handling. It is strictly prohibited to walk on the first type of sections. It is prohibited as well to lay electrical cables, water hoses, arms and any other temporal lines at these sections.

Workshop networking and requirements to pipelines and valves Clause 512. Each sulfur pipeline section must have heat expansion installations between stationary supports. Clause 515. Under the flange connections of horizontal sulfur pipings it is necessary to install concave metallic net with slot size 2 mm. Clause 520. Pipelines for sulfur are to be installed so that full emptying by gravity can be provided. They must have slope not less than 1. Clause 523. It is prohibited to provide flange connections of sulfur pipelines above doors and main passages inside the workshop as well as above driveways and roads in case pipeline goes from one workshop to another. 3.1.5 Requirements of PB (Safety requirements) 08-389-00 Industrial safety requirements to gas treatment plants and operations Clause 4.3.29. Sulfur handling and loading is prohibited at wind speed more 15 m/sec, at thunderstorm and limited visibility (less than 50 m). Clause 4.3.31. Workers engaged in sulfur pouring, handling and loading must be provided with individual protection means as per the specially developed list. Clause 4.3.32. During perfoming the works the special uniform must be fully zipped, buttoned, pants are to be put above the boots and must be tied at boottop. Use of protection glasses and hard hats is obligatory. Clause 4.3.33. Liquid sulfur pouring, handling and loading of bulked and granulated sulfur must be logged in the register of higher danger works.
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Clause 4.3.34. When pouring liquid sulfur it is prohibited to perform works inside the banked up (cased) area (pad) till it fully solidifies as well as to approach pouring faucet (tower) closer than 30 meters. Clause 4.3.35. Workers can accesse inside the banked up (cased) area not earlier than in 12 hours after last pouring of sulfur. Clause 4.3.36. Prior to start handling sulfur in blocks ensure it solidified fully by check boring. Clause 4.3.37. Workers must approach the sulfur storage areas by means of ladders (gangways). Clause 4.3.38. Machinery must approach sulfur storage areas through ramps filled up from bulked sulfur with slope angle not more than 35 to the basis of area. Clause 4.3.39. Transportation machinery must be located near the edge of the area at a distance equal to one and half of length of excavator bucket operating radius. Clause 4.3.41. Trucks before transporting the sulfur must be washed and cleaned. 3.1.6 Requirements of PB (Safety requirements) 09-310-99 Industrial safety requirements to oil producing plants and oil operations Clause 3.15.15. When pouring sulfur it is prohibited: - to step on solidified sulfur; - to stand near the open lid of sulfur storage; - to make sulfur measurements in pit, storage without gas masks and use not explosion-proof portable torches. Clause 3.15.16. Sulfur pump can be initiated only as per the oral instructiojns of person in charge. Clause 3.15.17. Loading and unloading of sulfur must be fully mechnized. Clause 3.15.18. All sulfur loading and unloading activities are to be performed in presence person in charge. Clause 3.15.20. When loading sulfur to rail cars it is prohibited: - for people to stay inside the rail cars;
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- fill up excavator bucket with sulfur above the sides of bucket; - to run over the power supplying cable by excavator. Pyrophoric compounds controls Clause 3.17.1. Design must provide controls and means to deactivate pyrophoric compounds during production cycle and at preparation of equipment and pipelines for repair. Clause 3.17.2. Units and pipelines after taking out from system and draining the product must be purged with steam. Clause 3.17.4. When cleaning the units it is necessary to moisten depositing on sides of unit. When cleaning it is necessary to use tools which dont generate sparks. To perfrom the work permit is prepared in the order described in Common instructions for safe organization of gas hazardous works. Clause 3.17.5. Pyrophoric depositing removed from equipment must be kept wet till destruction. 3.1.7 Requirements of PPB RoK (Industrial safety requirements of Republic of Kazakhstan) 08 2006 Fire safety requirements in Republic of Kazakhstan Maintenance of fire water networking Clause 1). Fire water networks must be in working condition and provide the required water supply for the needs of fire extinguishing. Checks of the system functioning are to be performed at least twice a year (in spring and in autumn). Fire hydrants must be kept in working condition. During winter it is necessary to provide wheat insulation and protect from snow and ice. In case of switching of the sections of water pipeline and hydrants or reducing the pressure in the system to the lvel lower than the required one it is necessary to inform the division of state fire fighting service about it. Power system of the plant must provide uninterrupted power supply of fire pumps electrical motors. Clause 2). The special notices (three dimensional with the lamp or flat with use of light reflecting coating) are to be installed on hydrants and near watersources (waterbodies) as well as on the way to them. Notices must show the distance to watersources with clearly recognized numbers. In the night the notices of fire hydrants and fire water bodies are to be illuminated.

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Maintenance of fire signalization and fire fighting systems, antismoke systems, people announcement and people evacuation controlling systems. Clause 2) In the dispetcher control room (fire post) it is necessary to put in visible place the instructions describing the actions of fast reacting personnel in case of getting fire alarm or failure of fire detection automatic system. Dispetcher point (fire post) must be provided with telephone and working electric torches (minimum3 pieces). Clause 6) Fire station must be provided with Piping diagram and unit emeregency operations instruction. Near each control point it is necessary to provide notice stating the protected premises, type and number of sprinklers in the section of the unit. Valves and faucets must be numbered as per the piping diagram. Clause 9) Sound speakers must be installed without volume regulators and connected to the system without detachable connections. To provide a reliable transfer of messages for announcement and evacuation control it is admittable to use internal wire broadcasting networks and other type of communication networks available at site. Maintenance of fire transportation means Clause 1) Fire trucks must be parked in fire depot or special garages provided with heating, power supply, telephone communication, hard floors, heat insulated gates and other devices and equipment required to ensure normal and safe conditions for work of state fire fighting team. It is prohibited to dismantle fire extinguishing equipment from fire trucks and use them with different purpose. Clause 2) Fire trucks and other fire machinery must be equipped with fire extinguishing equipment, filled with fuel, fire extinguishing material and be in running condition. 3.2 Project design and technical approaches 3.2.1 Main project design approaches of Unit 600 Liquid sulfur supply to Unit 600 Hydrocarbons of Tengiz deposit have high hydrogen sulfide H2S content. Hydogen sulfide is recovered from produced gas at amine treatment unit 300 so that the segregated propane, butane and sales gas would meet the qulity specifications as well as to reduce the quantity of burning hydrogen sulfide. Hydrogen sulfide after segregation at amine treatment unit 300 goes along with
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gas to Sulfur Recovery units 400 and 500. These units provide maximum conversion of hydrogen sulfide into liquid sulfur with burning of hydrogen sulfide left. Liquid sulfur received at units 400 and 500 is directed to unit 600. Liquid sulfur is degassed at unit 400, at D-401 degassing contactors. Degassing contactors remove H2S up to 10 weight pro mille at the normal mode of operation. Samples of liquid sulfur are taken from each of fourteen degassing contactors on daily basis and send for analysis in order to control quality of degassed liquid sulfur. Technological process of sulfur pads Unit 600 produces four types of sulfur: - Liquid sulfur loaded to rail tank-cars. - Granulated sulfur received at granulation unit. - Flake sulfur received at the sulfur flaking unit. - Bulked sulfur. Sulfur is regenerated from the existing sulfur pads and being crushed. Sulfur which does not correspond to technical conditions and sulfur corresponding technical conditions but produced exceesing demand in both cases sulfur is sent to sulfur pads. Two sulfur pads must be ready to receive liquid sulfur. Presently these are sulfur pads 8 and 9. Sulfur pouring is performed by means of pouring arm and pouring tower. Towers are provided with pouring arms and mobile installations Devco to increase the radius of sulfur pouring. Pouring tower is a supporting column to which 1 pouring arm is attached at the height of 18900 mm. Arm is attached to swing boom with help of load bearing structure. The structure has rollers which guide the arm up and down. Lifting and dipping of structure with pouring arm is performed by winch equipped with electrical drive installed at the basis of pouring tower. Three platforms are provided to perform maintenance. Platforms are designed as per the document Safety at designing, Chevron, 1997. The towers are designed with one sulfur pouring arm. Sulfur piping is made as double pipe pipe inside pipe. Liquid melted sulfur is supplied through the internal pipe and into the gar between internal and external pipe heated water steam is supplied. Besides, the external pipe is equipped with heat insulation without heat tracing. Pouring arm is made of stainless steel and attached to the load bearing structure with flexible connectors. Bear loading structure is fixed to swing boom with help of rope and block system. The structure is lifted and dipped with help of electric winch. Load bearing
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structure with pouring arm must have two degrees of freedom when swing boom only one. Winch with electric drive is installed at the basis of tower and must be properly fastened. Emergency shutdown buttons are provided near each tower to stop supply of liquid sulfur in case of emergency. Buttons stop liquid sulfur supply pumps. Puoring of liquid sulfur is performed usin the mobile wheeled installation. The installation has an electric drive mounted on one wheel axle it allows bow moving and randomly distributing of liquid sulfur on the top of sulfur pad. The unit is controlled by operator using remote control device. To protect from aggressive medium of melted sulfur all equipment parts surfaces not made of stainless steel are covered with corrosion proof coating (manufacturers Ameron, Hempel or Jotun).

Pouring towers have the following technical characteristics: 1. Pouring arm radius 34 m from the center of tower, sulfur piping is connected to pouring arm by means of articulated joint at the height of 18.9 m from the basis of the tower. 2. Pouring arm winch with electrical drive is delivered along with tower. It is installed at the basis of tower to simplify maintenance and operation. 3. 2 steam supply pipeline. 4. 6 pouring arm. 5. 6-8 sulfur pipeline with steam casing. 6. Sulfur consumption 155m3/hour. 7. Operating inlet pressure of liquid sulfur 3 bar. 8. Operating temperature of liquid sulfur 155. 9. Steam pressure 4 bar. 10. Steam pressure 165. Electrical wiring of explosion proof type EExd. Swing installation (DEVCO) Liquid sulfur pouring is performed by means of mobile wheeled swing unit. Swing unit (Devco) has the following technical characteristics: 1. Mobile swing unit is framed structure mountedon two wheeled chassis. Mobile swing unit is connected to pouring arm by means of
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flexible armoured arm with steam casing. Electrical drive is installed on one of chassis. The drive provides bow moving of swing unit. The unit is controlled by operator with the remote control who stands at the edge of sulfur pad during liquid sulfur pouring activities. 2. 6 liquid sulfur supply pipeline. 3. 6 flexible armoured arm with steam casing. 4. Sulfur consumption 155 m3/hour. 5. Operating inlet pressure of liquid sulfur 3 bar. 6. Operating temperature of liquid sulfur 155. 7. Steam pressure 4 bar. 8. Steam temperature 165. Sulfur piping Sulfur piping is made as double pipe pipe inside pipe. Liquid melted sulfur is supplied through the internal pipe and into the gar between internal and external pipe superheated saturated water steam is supplied with temperature 152 . Besides, the external pipe is equipped with heat insulation without heat tracing. Steam heating Sulfur solidifies at the temperature 119C. Due to this fact steam heating is provided for sulfur pipeline, pouring tower and arms to prevent sulfur solidifying. For that purpose MP saturated steam pressure regulation within 20 to 4 bar is performed. Saturated temperature 152C at the steam pressure 4 bar is almost identical to liquid sulfur temperature supplied from liquid sulfur storages. Thus steam pressure reduces to minimum heat exchange of steam and sulfur, maximally decreasing steam consumption and excluding thermal sulfur loss to environment. Steam condensate is pumped from LP Condensate drums F-610 and F-613 of Unit 600 back to boiler for repeated utilization. Utilization of steam condensate allows decreasing technical water utilization, volume of waste water produced from the well and quantity of chemical agents used for treatment. 3.2.2 Project design in part of normal operations conditions and technical safety provision Project design provides: 1. Gas detection system. Hydrogen sulfide detectors are installed in places of potential leaks near the pouring towers. Beacons and sounders are installed around the perimeter of sulfur pads to provide required level of signalization for the personnel.
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2. Illumination of sulfur pads territory for round oclock operation. 3. Electric system of lightning arresting. 4. Emergency shutdown system for pumps. ESD buttons stopping sulfur pumps are installed near pouring towers. 5. Steam flowmeters installed. 6. Barricading of sulfur pads. 7. Drainage system and water collection system. 9. Intrinsically safe (I\S) signals. 10. Grounding of all metallic equipment. 11. Provision of special uniform and individual protection means. 12. Fire deluge system. 13. Arrangement of roads, ramps, control checking points etc. 14. Air analyzing for sulfuric dust, H2S, SO2, Nox content. System of storm water collection Design provides emptying by gravity system of wells-collectors for drainage of surface waters and storm water collectors at sulfur pads to remove storm water from barricaded sections of sulfur pads. This water is pumped from water collectors into gathering pond. Areas near sulfur pads are additionally equipped with perforated drainage lines and collectors with pumps which direct surface water to the nearest water collector and then to gathering pond. Water accumulated in gathering pond is pumped then into evaporation pond consisting of 3 sections. Electrical motors, starting equipment, instrumentation, grounding are installed as per PUE (Rules of electrical units management). Static electricity hazard is removed by system of special measures creating leak of electrostatic charges preventing accumulation of charge energy higher than 0,4 min or conditions are created excluding possibility of explosion hazardous concentration formation.
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To protect equipment and personnel from accumulation and discharge of static electricity the following leasures are taken: Charge divertion by grounding the casing of equipment and piping as well as provision of consistent electrical contact of the product pumped and humans body; Charge divertion by reducing specific volumetric and surface electric resistances; To divert static electricity from humans body electrical conductive boots are used All devices and equipment are maintained in working condition and periodically are checked as per the schedule stated in passports and manuals of plant-manufacturers. Lightning arresting system is arranged as per RD 34.21.122-87. Protection from static electricity of equipment and installations is arranged as per Rules of protection from static electricity in chemical. Petrochemical and oil & gas industries. All repair works of equipment are performed as per Fire safety rules during welding works at site, Common procedure for peformance of hot works at explosion hazardous and fire hazardous sites. Safety and labor protection approaches Personal protection equipment. Protection of eyes/ face: protection means are used to prevent contact of eyes and some material. Protection means include: glasses, chemical glasses, face shields or their combination depending on type of works. Protection of skin: Wearing of special uniform is not required normally. Respiratory organs protection: impact of dangerous dust levels in athmosphere. Protection respirators are used to perform works such as air filtering respirator for dust and mist or high effective air filter. In case air high effective respirator is unable to provide required level of protection air respirators with positive pressure are used. 3.2.3 Fire safety project design philosophy Fire signalization system and fire detection system Fire signalization system of plant is equipped with detectors of different type smoke, ultraviolet (detecting flame). Besides, manual call points with
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breaking glass are installed. Case of detectors is defined as per the classification of danger zones. Alarm is generated only in case two devices in raw (with daisy chain ctype of connection) detect flame /smoke/ high temperature. Alarms from call points come to graphics and in Central control room visual and sound signalization initiates. The number of unit where call point worked out is displayed at graphics. Control system provides determination of false signals or initiates fire deluge system. In case of fire plant-wide signal is initiated. Push-button break glass assemblies Push-button break glass assemblies are installed at all building exits, along emergency exits and equipment perimeter at 50m intervals. Single-line copper conductors 9/10 are used for their connection. Several push-button assemblies in one zone can be connected to one circuit. Push-button break glass assemblies are connected to fire automation board - mnemocircuit in Central Control Room. These detectors have signal function only. Actuating of manual detectors results in following effects: - intermittent audible alarm switches on in control room; - device call number becomes yellow; - alarm ring, belting device, flashes amber light on mnemocircuit. Fire alarm board Firefighter panel board (mnemocircuit), which gives audiovisual signals, is set in the control room. It indicates geographic position of installation or building, where fire is found out. It indicates installation number, if glass on push-button assembly is broken out, but does not indicate its place. Single phase current 220 Volt, 50 Hz is used for electric power supply to the panel board. In case of standard electric power supply dump, the panel board is powered by self-contained power plant. The signal light indicates standard power supply dump. Alerting system (horn) Public address system provides the audio fire warning throughout plant. The horn is installed on control room roof. Fire-alarm system works apart of gas alarm system, which is used for dangerous and explosive atmosphere detection. The panel boards of both systems are connected together. Fire fighting water network
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Fire fighting water pipelines are run underground on depth of 1.7 m, i.e. 0.5m below frost penetration level. Stop valves on underground pipework are equipped by outlet water flow indicator (as per Specifications for underground water or other liquid pipework, where there is a freezing hazard). Fire fighting water pipelines are used for the purpose of fire extinguishing only and any other connections to it are prohibited. All fire hydrants are antifreezing. Fire hydrants are designed for connection to fire trucks. Fire precaution measures, provided for project of Unit 600 Fire hazard, operational code for electrical installations and fire-resistance classification. Explosion and fire hazard data, fire hazard categories are shown in table 3. All electrical customers refer to III power supply category. Technological process plants, being the sources of negative impact on environment and human health, should have Sanitary Protection Zone, defined for total plant capacity. As per RNTP 01-94 the plant categories are divided as follows: - Restricted zone (where the filling tower is installed) - A - Restricted zone around liquid sulfur filling device - A - Solid sulfur storage area - As per Kazakhstan operational code for electrical installations the explosion hazard zones are classified as follows: Restricted zone (where the filling tower is installed) B 1 Restricted zone around liquid sulfur filling device 1 Zone between fence and sulfur block 1 Solid sulfur storage area III

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Fire and explosion hazard classification Table 4


Explosion and fire hazard class - III item7.4.6, Operational code for electrical installations - III item7.4.6, Operational code for electrical installations -1 item 7.3.43, Operational code for electrical installations -1 item 7.3.43, Operational code for electrical installations -1 item 7.3.41, Operational code for electrical installations -1 item 7.3.44() Operational code for electrical installations Fire hazard category Matter existing in zone

Solid sulfur storage areas

Sulfur, sulfurous dust

Solid sulfur storage areas

Sulfur, sulfurous dust

Filling tower and zone around the perimeter of sulfur spreading in horizontal and vertical direction 5m.

2S

Access around perimeter of sulfur pad and access zone in 5m diameter

2S

Drainage wells

2S

Zone over the drainage well around perimeter in horizontal and vertical direction 3m

2S

The fire and explosion safety category of sulfur pads is determined as (explosive) and -III (fire dangerous).

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Selection of fire fighting remedies and methods Selecting the fire fighting remedies and methods on the sulfur pads the following key factors are considered: Fire hazard classification for constructions. Fire hazard of technological processes. Fire hazard of matters, applying in technological processes. Fire hazardous matters storage method. Fire propagation capability. Building structures. Sources of water and power supply. Quoted by actual factors and requirements of normative technical documents the following fire fighting systems, remedies and methods are accepted: - water fire extinguishing; - primary fire-extinguishing means. Following facilities are subject to fire protection: - filling tower; - liquid sulfur filling device; - zone between fence and sulfur block; - solid sulfur storage area. Water fire extinguishing system Water fire extinguishing system comprises ring network with fire hydrants. On the territory there are 39 fire hydrants, installed into the water line in 200mm diameter. Interval between the hydrants is 60-80m. The east part of sulfur pad No. 2 is provided by 4 monitor compatible fire hydrants. The detailed arrangement of fire hydrants, sulfur pads, accesses and other facilities is pointed on general diagram of Unit 600. External fire extinguishing is carried out from system of ring fire main with mounted fire hydrants. The extinguishing on sulfur maps is carried out by force of TCO Emergency Response Service. The application of hand fire nozzles is foreseen. The fitting of stationary fire extinguishing systems is not required for sulfur pads.

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TCO Emergency Response Service (ERS) Main tasks of ERS: - Fire extinguishing and carrying rescue and first medical aid operations on TCO and contractors sites. - Cleaning of oil and other hazardous substance spill. - Gas leakage elimination on processing facilities. - Carrying out preventive measures on fire prevention and other emergency situations at secured facilities. Four fire stations are provides for main tasks performing at TCO facilities: - Fire station No. 1 security service of Tengiz Gas Processing Plant. - Fire station No. 2 - security service of purpose-designed machinery and equipment park. Fire station No. 3 - security service of TCO and Shanyrak villages.

- Fire station No. 5 - security service of SGI. The staff of Emergency Response Service is 245 employees. There is 4 shift twenty-four-hour alert of operating crew on the fire stations. Two shifts work simultaneously, one of which works from 7 a.m. till 19 p.m., and the second one from 19p.m. till 7 a.m. The both shifts are ready to response on emergency situation at any time. Two other shifts are on rotation vacation. 3.3 Present technical condition of Unit 600 3.3.1 Condition of sulfur pads Physical condition of sulfur pads Today the sulfur filling is carried to sulfur pads No. 7, 8, 9, which are fitted by filling towers. Liquid sulfur pipelines, heating by steam, which supplied to tube space, are connected with filling towers (annular tubes type). The project provides the steam heating of sulfur pipelines, filling towers and pouring arms to prevent the solidification of liquid sulfur.
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Sulfur from the pad No.5 is developed in full and dispatched to consumer. The sulfur pad No.5 is occupied by unconditioned, contaminated sulfur for temporary storage before further processing. Sulfur from pad No. 3 and 4 is developed in full and dispatched to consumer. Today the sulfur pads No.3 and 4 are sulfur free and clean. At the present time the works on block development and sulfur dispatch to rail transport are carried out on the pad No.4. Power shovel tractor loads the sulfur, previously processed by bucket excavator, into the special container, which is fixed on motor transport. Further this container on truck is directed to train set of high-sided wagons. Sulfur unloading from flat end container into high-sided wagons is performed by means of special crane. After careful sulfur surfacing in high-sided wagons, sulfur is covered by special artificial fabric, asbestos infiltrated.

Sulfur ignition causes 1. Sparks from locomotives fall to the sulfur pads, which are situated near rail ways. 2. Regularly static electricity accumulates on excavator bucket, processing the sulfur block, on shovel bucket of loader. Due to friction and contact with sulfur the static electricity charges take place that can lead to sulfur ignition. 3. Sometimes units of moulding board, used for sulfur filling, are not removed from the sulfur pads. Scrap, various metal wastes can fall on the sulfur blocks that leads to pyrophoric ferric sulphides formation able to spontaneous ignition. Information of sulfur ignition cases on sulfur maps 1. As per statistical data a number of ignition cases were registered on TCO sulfur pads (see TCO Data Report U 600 Ignition). 2. Generally fire hazards were eliminated by primary fire-extinguishing means, since moderate fire scope and timely detection. Fire events history of the sulfur pad No. -600 is indicated in the Attachment . Fire events history of the sulfur pad No.-600 (July 16, 2005) is indicated in Attachment .
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Data of probable sulfur ignition causes on TCO within the period from October 10, 2002 to April 18, 2005 are shown in Attachment . 3.3.2 Necessary actions to detect bulked sulfur combustion Visual inspection for possible sulfur combustions on the pad area: - Special fireman on duty point dedicated for inspection of fire safety situation during any job on sulfur pads, in particular, mining of sulfur slabs. The special fireman on duty point has to be on the area of sulfur slab demolition and loading in truck container and in the point of unloading of the mentioned container in railway open wagons. The fireman on duty is equipped both by personal alarms (if necessary) and primary firefighting mean (extinguisher). - Special movable team of fire inspectors for visual control of sulfur pads. Information about ignitions on sulfur pads is reported by operators of Unit 600 or Motor Patrols Group-4. To avoid ignitions during summer season it is provided for water spraying on the sulfur pad area.

3.3.3 Technical condition of firefighting means and deluge system TCO Emergency Response Service Main tasks of Emergency Response Service: Fire extinguishing and wrecking activities for human life rescue and providing First Medical Aid at emergency situations on objects belonging to TCO and its subcontractors. Elimination of oil and other dangerous substances outflows. Elimination of gas leakages in process equipment. Preventive activities for fire and other accidents prevention on the guarded objects. There are four Fire Stations for implementation of the main tasks on the guarded objects of TCO: Fire Station # 1 for Tengiz Gas Processing Plant. Fire Station # 2 for Special Equipment Park. Fire Station # 3 for TCO and Shanyrak villages. Fire Station # 5 for SGI.
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Fire Station # 4 is under construction to be ready before start-up of SGP. Specification of TCO firefighting and emergency equipment 1. Gas Rescue Car Chevrolet - 2 pcs, model year: 1994; fighting crew: 5 men; transports gas protection and rescue equipment. 2. Gas Rescue Dept Car 1 pc; year model 2005; fighting crew: 5 men; transports gas protection and rescue equipment. 3. Anti-Outflow Car ZIL-131 - 1 pc; year model: 1985 ; transports equipment and materials for elimination of hazardous liquids outflow. 4. Water Car (E-ONE) - 4 pcs; year model: 1994; water capacity: 1000 gallon (3780 l), pumping capacity: 1250 gpm (78.8 l/s). 5. Foam Car (CNF) - 3 pcs; year model: 1994; foaming capacity: 1500 gallon (5670 l); pumping capacity: 1500 gpm (95.4 l/s). 6. Foam Car (FL-80) - 1 pcs; year model: 2004; water capacity: 1000 gallon (3780 l); pumping capacity 1250 gpm (78.8 l/s). 7. Aviation Firefighting Car Chevrolet - 1 pc; year model 1994; powder tank: 204 kg; foam emulsion tank: 379 l. 8. Staff Car Chevrolet - 3 pc; year model: 1994; transports necessary staff equipment for emergency elimination. 9. Fast Response Car (foam) Chevrolet - 1 pc; year model: 1994; water capacity: 265 gallon (1000 l), pumping capacity: 211 gpm (13 l/s). 10. Fast Response Car (water) Chevrolet - 1 pc; year model: 1994; foaming capacity: 79.4 gallon (300 l); capacity of stationary gun HF-350: 340 gpm (21.42 l/s). 11. Hydraulic Ram BRONTO SKYLIFT (Finland) - 1 pc; year model: 1990: foaming capacity: 1190 gallon (4500 l); foam pump capacity: 158.7 gpm (10 l/s); dedicated for ground tanks firefighting. 12. Fire Hose Car ZIL-131 - 1 pc; year model: 1987; transports 2 km fire hose 127 mm. 13. Haulage Truck MAZ- 1 pc; year model: 2005; dedicated for transportation of fire pump station and other equipment.
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14. Cars of Emergency Medical Aid: - Ford; year model: 1991; capacity: 2 victims. - Ford - year model: 1993; capacity: 2 victims. - Ford - year model: 2004; capacity: 2 victims. - Mercedes - year model 2002; capacity: 2 victims. - Mercedes - year model 2003; capacity: 2 victims. - Chevrolet-Blazer; year model: 1994; re-equipped for EMA. - Toyota-Landcruiser; year model: 1994 re-equipped for EMA. 15. Fire Pump Station (US); year model: 1997; pumping capacity 3000 gpm (189 l/s). 16. Movable Fire Gun Units Terminator; 2 units; Capacity: 3000 gpm (189 l/s) and 2500 gpm (157 l/s). 17. Lighting Units 2 pc; year model: 1993; used for nigh-time emergencies. 18. Respiratory apparatus: - Magnum - 70 pcs - Viking - 7 pcs 19. Gas Analyzers: - Micromax - 11 pcs. - Miniwarn - 4 pcs. - Pac III 7 pcs. 3.3.4 Firefighting plan. Unit 600 (including bulked sulfur pads), developed by TCO Site characteristics There are 9 sulfur pads at Unit 600: Data on size of sulfur pads and quantity of bulked sulfur as on 01.05.2007: - sulfur pad 2 227m 105m; - sulfur pad 3 22m 85.2m; sulfur); - sulfur pad 4 237m 110m; and loaded ti consumers); 24000 tons; 0 tons (presently sulfur pad is free of 330939 tons (presently sulfur is handled

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- sulfur pad 4 99m 110m; sulfur);

0 tons (presently sulfur pad is free of

- sulfur pad 5 237m 110m; 65000 tons (presently sulfur pad is free of sulfur, non-conditioned sulfur is temporally stored there); - sulfur pad 6 351m 110m; - sulfur pad 7 425m 310m; - sulfur pad 8 425m 310m; - sulfur pad 9 504.5m 281m; 649828 tons; 2537583 tons; 2756127 tons; 2281284 tons;

Calculation of manpower and means Situation forecast for the moment of first fire team with fire nosepieces comes to extinguish fire at sulfur pad 9. - Determination of free fire development time (since fire emerged till first fire team comes); - Determination of distance propagated by fire; - Determination of fire area and fire extinguishing area; - Calculation of required water consumption to eliminate fire; - Calculation of required number of extinguishing material supply units (water nosepieces); - Determination of water supply from water pipeline; - Calculation of required number of fire trucks; - Calculation of manpower required for fire extinguishing; - Determination of required number of fire teams. Data on development and course of extinguishing possible fire at sulfur pad 9 and actions of ERT personnel Possible variant of fire development: Burning in central part of sulfur pad Recommendations to person in charge of emergency liquidation:
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Two fire trucks, one rescue vehicle as well as one ambulance vehicle come to the place of fire. All personnel of ERT must come to place of fire with breathing apparatus put on. At the place of fire it is necessary: 1. To estimate situation: - to define the correct place of fire (to inspect the top side of sulfur pad it is necessary to use pouring towers and scaffolding to get onto the pad the equipment must be available at the burning pad or at nearby pad (use binocular). 2. At the same time: - it is required to continuously perform air analyzing at the place fire; - to determine hot and warm zones limit: - To block access gates by the personnel not involved in fire extinguishing (to use Group 4 patrols at safe sections); - to give a command to start deployment (park trucks near hydrants, to lay main lines with connections near points of mounting onto sulfur pad (construction scaffolding), bringing of additional equipment to the connection points (deployment as per the scheme); - after estimation of situation to call additional forces with extinguishing means (there must be at least 14 fire fighters at fire place (including commanders), directly engaged in deployment and fire extinguishing (drivers are not taken into account). Possible situation at fire: Situation is fully known. Actions of ERT are liaised with the Supervisor of emergency liquidation in place. Arrival of additional forces and extinguishing means. Recommendations to Supervisor of emergency liquidation 1. What is required to be done at fire place: - give a command to lift working lines (one nosepiece from each truck) onto top side of sulfur pad. To handle the nosepiece under pressure use the special support; - Instructor ERT (coordinator) should account the personnel mounting onto sulfur pad (keep in mind that people will be mounting from two sides); - deploy forces and extinguishing means; - To distribute additional fire fighters arrived (2 teams) to help to working teams; - To put one more nosepiece and connect to line onto top side of sulfur pad; - Personnel deployed near the sulfur pad must prepare two nosepieces (95 gpm) from two sides to extinguish (cool down) flowing liquid sulfur if necessary; - Fire trucks not used for fire extinguishing is kept to provide reserve.
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2. At fire place it is necessary to foresee: - manpower reserve to make air analyzing from plume; - manpower reserve to replace people working at the fire place; - delivery of reserve air containers for SCBA.

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4. GENERAL ASSESMENT OF BULKED SULFUR IGNITION RISK AT TENGIZ INCLUDING SMALL AREA COMBUSTION AND LARGE SCOPE COMBUSTION INCIDENTS TAKING INTO ACCOUNT CHARACTERISTICS AND VELOCITY OF FIRE PROPAGATION AS WELL AS TCO EMERGENCY PREPAREDNESS TO ELIMINATE SULFUR PADS IGNITION 4.1 Calculation of manpower and materials required for fire extinguishing Calculation of manpower and materials required for extinguishing of possible fire was performed as per methodology described in the reference book Supervisor of fire extinguishing. In calculations the linear velocity of fire propagation and fire load are taken as per data spreadsheet given in the reference book Supervisor of fire extinguishing - V. = 0.8 (m/min). Calculations are given in 3 variants taking into account the most probable development of situation. To perform calculations the following factors were taken as basic: 1. Condition of sulfur pad: - sulfur pad at a stage of handling and loading of bulked sulfur (variant I); - sulfur pad at a stage of pouring of liquid sulfur (variant II); - sulfur pad at a stage of storing of solidified sulfur (variant III). 2. Nature of mechanism of possible bulked sulfur combustion:

- electrostatic discharge from metallic parts of running equipment; - sparks of passing by locomotives; - spontaneous combustion of pyrophoric sulfides of iron. 3. Condition of fire safety system of sulfur pads: - presence and capacity of ring firewater pipeline network with hydrants; - presence and organizational & technical equipment status of TCO Emergency Response Team (ERT); - presence of special fire watchmen in place; - presence of motorized mobile service of Group 4 - fire training of operating personnel. 4. Possible shapes of fire area (round shaped, angle shaped, rectangular shaped). 5. Possible variants of fire propagation in terms of time.

4.1.1 Calculation of manpower and materials required for fire extinguishing at sulfur pad during handling and loading bulked sulfur (Variant 1) BACKGROUND DATA 1. Fire takes place at sulfur pad from where sulfur is handled and then loaded to consumers. 2. Equipment involved (excavator, pay loader, trucks). 3. Possible reasons of combustion: - electrostatic discharge from metallic parts of equipment (bucket, hammer); - sparks of passing by locomotives (railway line is located nearby); - spontaneous combustion of pyrophoric sulfides of iron (forgotten metallic garbage, parts of casing, scrap). 4. Presence of special fire watchman with fire extinguisher. 5. Operating personnel trained how to act in case of fire emergency. 6. Mobile patrol of Group 4. CALCULATION OF MANPOWER AND MATERIALS I. Situation forecast at the sulfur pad 4 till the fire team with first fire extinguishing nosepieces comes (round shape of fire development) 1. Free fire development phase ., i.e. time since fire emerging till supply of first fire extinguishing means: . = . + . + . + ..1 = 20 + 1 + 3 + 6 = 30 min. . - period of time since fire emerging till communicating to fire station about emergency; . - time of mustering fire team on alert (as per the norm less than 1 min.); . - time taken by fire team to drive to the place of fire is calculated as per the formula: . = 60 L / V . = 60 2 / 45 = 2,66 = 3 min. L length of way from fire station to the place of fire (km.); V . average speed of fire trucks is taken at a rate of 45 km/hour along wide streets with paved road. ..1 - time of deployment by fire team before applying first fire extinguishing means (nosepieces etc.) is taken as per the fire fighting norms and real experience of fire extinguishing. 2. Calculation of the distance propagated by fire (R):
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R = 5 V. + V. .1 = 5 0,8 + 0,8 20 = 20m. V. - linear velocity of fire propagation along fire load (is calculated after estimate the fire situation or is taken as per the reference data). V. = 0.8 (m/min) is taken as per the reference data; .. free fire development phase (min); .1 free fire development phase without first minutes of burning, i.e. .1 = . 10 = 30 10 = 20 min. 3. Calculation of fire area (round shaped development) and extinguishing area: S.. = R2 = 3,14 202 = 1256 m2 S = h (2 R h) = 3,14 5 (2 20 5) = 550 m2 S. fire area at round fire development (m2); R distance propagated by fire (m); h effective depth of fire extinguishing the burning area. If in the given moment extinguishing is not performed at the whole fire area then it is necessary to focus forces and means around the perimeter or at fire front to extinguish fire stage-by-stage. Calculation is made in this case as per the area of extinguishing from external limits of fire area. Extinguishing area depends on effective depth of fire extinguishing h, that is why for the calculation purposes effective depth of fire extinguishing is taken at a rate of 5 meters for manual nosepieces. 4. Calculation of extinguishing matter (water) consumption required to eliminate fire: Q = S J + = 550 0,2 =110 liters/sec To calculate the required consumption for possible protection (extinguishing of bulked sulfur) we take 2 fire nosepieces with capacity 95 gpm (6 liters/sec), we get total 12 liters/sec. Total required water consumption will be: Q = Q + Q = 110 + 12 = 122 liters/sec Q - consumption (quantity) required for fire extinguishing (liters/sec);
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Q - consumption (quantity) of fire extinguishing matter required for protection (liters/sec); S - fire extinguishing area, m2; J intensity of fire extinguishing matter supply (liters/m2sec) 5. Calculation of the required number of units (water nosepieces with capacity 95 gpm (6 liters/sec) supplying fire extinguishing matter: N = Q / Q =110 / 8 = 14 nosepieces N = Q / Q = 12 / 6 = 2 nosepieces. N - number of units supplying fire extinguishing matter (pieces.); Q - consumption (quantity) of fire extinguishing required to eliminate fire, (liters/sec); Q consumption of the defined fire extinguishing matter supplied by special units (liters/sec) (6 liters/sec per nosepiece); 6. Calculation of water intake from water pipeline network: ) calculated as per the formula: Q = (V d)2 = (1,7 8)2 = 185 liters/sec V - velocity of water flow in the pipeline (meters/sec), is taken 1.7 for the piping of 200 mm diameter and pressure 7 bar; d diameter of piping (inch) 1 inch = 25 mm. 7. Calculation of the number of fire trucks required: N = Q/ Q = 110 / 78 = 2 trucks Q - capacity of water pump sufficient to provide supply for nosepieces as per the scheme of fire fighting equipment deployment, liters/sec; It is possible to provide water supply for: N = Q / Q = 184 /78 = 2,3 = 2 trucks 8. Calculation of the fire fighting manpower required for fire extinguishing: N / = N 2 = 14 2 = 28 people N / = N 2 = 2 2 = 4 people
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2 is number of people required to work with one nosepiece at the height; Besides, 2 people are required to control nosepiece lines. 9. Calculation of the number of fire teams required: N = N / / 4 = 32 / 4 = 8 teams 4 is number of fire fighters in one fire truck. II. Situation forecast at the sulfur pad 4 till the fire team with first fire extinguishing nosepieces comes (angle shape of fire development, degrees a) 90, b) 180, c) 270). 1. Free fire development phase ., i.e. time since fire emerging till supply of first fire extinguishing means: . = . + . + . + ..1 = 20 + 1 + 3 + 6 = 30 min. . - period of time since fire emerging till communicating to fire station about emergency; . - time of mustering fire team on alert (as per the norm less than 1 min.); . - time taken by fire team to drive to the place of fire is calculated as per the formula: . = 60 L / V . = 60 2 / 45 = 2,66 = 3 min L length of way from fire station to the place of fire (km.); V . - average speed of fire trucks is taken at a rate of 45 km/hour along wide streets with paved road. ..1 - time of deployment by fire team before applying first fire extinguishing means (nosepieces etc.) is taken as per the fire fighting norms and real experience of fire extinguishing. 2. Calculation of the distance propagated by fire (R): R = 5 V. + V. .1 = 5 0,8 + 0,8 20 = 20 m. V. - linear velocity of fire propagation along fire load (is calculated after estimate the fire situation or is taken as per the reference data). V. = 0.8 (m/min) is taken as per the reference data; .. free fire development phase (min); .1 free fire development phase without first minutes of burning, i.e. .1 = . 10 = 30 10 = 20 min
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3. Calculation of fire area (angle shaped development) and extinguishing area: S.. = 0,5 R2 = 0,5 2 202 = 400 m2 Extinguishing area: forces and extinguishing means are located along the localization front: a) fire development shape angle, value 90 degrees. S =0,25 h (2R - h) = 0,25 3,14 5 (2 20 5) =138 m2 b) fire development shape angle, value 180 degrees. S= 0,5 h (2R - h) = 0,5 3,14 5 (2 20 5) = 275 m2 c) fire development shape angle, value 270 degrees. S = 0,75 h (2R - h) = 0,75 3,14 5 (2 20 5) = 413 m2 Extinguishing area: forces and extinguishing means are located around the perimeter a) fire development shape angle, value 90 degrees. S = 3,57 h (R - h) = 3,57 5 (20 - 5) = 268 m2 b) fire development shape angle, value 180 degrees. S = 3,57 h (1,4R - h) = 3,57 5 (1,4 20 - 5) = 411 2 c) fire development shape angle, value 270 degrees S = 3,57 h (1,8R h) = 3,57 5 (1,8 20 - 5) = 554 m2 S. fire area at round fire development (m 2); as R>3h R distance propagated by fire (m); h effective depth of fire extinguishing the burning area angle limiting fire development, radian. (1 radian 57). If in the given moment extinguishing is not performed at the whole fire area then it is necessary to focus forces and means around the perimeter or at fire front to extinguish fire stage-by-stage. Calculation is made in this case as per the area of extinguishing from external limits of fire area.
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Extinguishing area depends on effective depth of fire extinguishing h, that is why for the calculation purposes effective depth of fire extinguishing is taken at a rate of 5 meters for manual nosepieces. 4. Calculation of extinguishing matter (water) consumption required to eliminate fire: Q = S J Quantity of extinguishing matter (water) required for fire elimination; forces and extinguishing means are located along the localization front: a) fire development shape angle, value 90 degrees. Q = S J = 138 0,2 = 28 liters/sec b) fire development shape angle, value 180 degrees. Q = S J = 275 0,2 = 55 liters/sec c) fire development shape angle, value 270 degrees. Q = S J = 413 0,2 = 83 liters/sec Quantity of extinguishing matter (water) required for fire elimination; forces and extinguishing means are located around the perimeter: a) fire development shape angle, value 90 degrees. Q = S J = 268 0,2 = 54 liters/sec b) fire development shape angle, value 180 degrees. Q = S J = 411 0,2 = 82 liters/sec c) fire development shape angle, value 270 degrees. Q = S J = 554 0,2 = 111 liters/sec To calculate the required consumption for possible protection (extinguishing of bulked sulfur) we take 2 fire nosepieces with capacity 95 gpm (6 liters/sec), we get total 12 liters/sec. Total required water consumption will be: Q = Q + Q - forces and extinguishing means are located along the localization front:

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a) fire development shape angle, value 90 degrees. Q = Q + Q = 28 + 12 = 40 liters/sec b) fire development shape angle, value 180 degrees. Q = Q + Q = 55+ 12 = 67 liters/sec c) fire development shape angle, value 270 degrees. Q = Q + Q = 83+ 12 = 95 liters/sec - forces and extinguishing means are located around the perimeter: a) fire development shape angle, value 90 degrees. Q = Q + Q = 54 + 12 = 66 liters/sec b) fire development shape angle, value 180 degrees. Q = Q + Q = 82+ 12 = 94 liters/sec c) fire development shape angle, value 270 degrees. Q = Q + Q = 111+ 12 = 123 liters/sec Q - consumption (quantity) required for fire extinguishing (liters/sec); Q - consumption (quantity) of fire extinguishing matter required for protection (liters/sec); S - fire extinguishing area, m2; I intensity of fire extinguishing matter supply (liters/m2sec), I = 0.2 (liters/m2sec) it is taken as per the reference data. 5. Calculation of the required number of units (water nosepieces with capacity 95 gpm (6 liters/sec) supplying fire extinguishing matter: N = Q / Q - forces and extinguishing means are located along the localization front: a) fire development shape angle, value 90 degrees. N = Q / Q = 40 / 8 = 5 nosepieces b) fire development shape angle, value 180 degrees. N = Q / Q =67 / 8 = 8 nosepieces c) fire development shape angle, value 270 degrees. N = Q / Q = 95 / 8 = 12 nosepieces
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- forces and extinguishing means are located around the perimeter: a) fire development shape angle, value 90 degrees: N = Q / Q =66 / 8 = 8 nosepieces b) fire development shape angle, value 180 degrees: N = Q / Q = 94 / 8 = 12 nosepieces c) fire development shape angle, value 270 degrees: N = Q / Q = 123/ 8 = 15 nosepieces N = Q / Q = 12 / 6 = 2 nosepieces. N - number of units supplying fire extinguishing matter (pieces.); Q - consumption (quantity) of fire extinguishing required to eliminate fire, (liters/sec); Q consumption of the defined fire extinguishing matter supplied by special units (liters/sec) (6 liters/sec per nosepiece); 6. Calculation of water intake from water pipeline network:: ) analytically calculated as per the formula: Q = (V d)2 = (1,7 8)2 = 185 liters/sec V - velocity of water flow in the pipeline (meters/sec), is taken 1.7 for the piping of 200 mm diameter and pressure 7 bar; d diameter of piping (inch) 1 inch = 25 mm. 7. Calculation of the number of fire trucks required: N = Q/ Q - forces and extinguishing means are located along the localization front: a) fire development shape angle, value 90 degrees: N = Q/ Q = 40 /78 = 0,51 = 1 truck b) fire development shape angle, value 180 degrees: N = Q/ Q = 67/78 = 0,86 = 1 truck c) fire development shape angle, value 270 degrees: N = Q/ Q = 95 /78 = 1,21 = 2 trucks - forces and extinguishing means are located around the perimeter:
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a) fire development shape angle, value 270 degrees: N = Q/ Q =66 /78 = 0,85 = 1 truck b) fire development shape angle, value 180 degrees: forces and extinguishing means are located around the perimeter. N = Q/ Q = 94 /78 = 1,21 = 2 trucks c) fire development shape angle, value 270 degrees: forces and extinguishing means are located around the perimeter. N = Q/ Q =123 /78 = 1,58 = 2 trucks Q - capacity of water pump sufficient to provide supply for nosepieces as per the scheme of fire fighting equipment deployment, liters/sec; It is possible to provide water supply for: N = Q / Q = 184 /78 = 2,3 = 2 trucks

8. Calculation of the fire fighting manpower required for fire extinguishing: N / = N 2 - forces and extinguishing means are located along the localization front: a) fire development shape angle, value 90 degrees. N / = N 2 = 8 2 = 16 people b) fire development shape angle, value 180 degrees. N / = N 2 = 8 2 = 16 people c) fire development shape angle, value 270 degrees: N / = N 2 = 12 2 = 24 people - forces and extinguishing means are located around the perimeter: a) fire development shape angle, value 90 degrees: N / = N 2 = 8 2 = 16 people b) fire development shape angle, value 180 degrees:: N / = N 2 = 12 2 = 24 people
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c) fire development shape angle, value 270 degrees: N / = N 2 = 15 2 = 30 people N / = N 2 = 2 2 = 4 people 2 is number of people required to work with one nosepiece at the height; Besides, 2 people are required to control nosepiece lines. 9. Calculation of the number of fire teams required: N = N / / 4 4 is number of fire fighters in one fire truck. - forces and extinguishing means are located along the localization front: a) fire development shape angle, value 90 degrees: N = N / / 4 = 16 / 4 = 4 teams b) fire development shape angle, value 180 degrees: N = N / / 4 = 16 / 4 = 4 teams c) fire development shape angle, value 270 degrees: N = N / / 4 = 24 / 4 = 6 teams - forces and extinguishing means are located around the perimeter: a) fire development shape angle, value 90 degrees: N = N / / 4 = 16 / 4 = 4 teams b) fire development shape angle, value 180 degrees: N = N / / 4 = 24 / 4 = 6 teams c) fire development shape angle, value 270 degrees: N = N / / 4 = 30 / 4 = 8 teams 4.1.2 Calculation of manpower and materials required for fire extinguishing at sulfur pad during pouring of liquid sulfur (Variant 2) BACKGROUND DATA 1. Fire takes lace at sulfur pad at a stage of liquid sulfur pouring.
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2. Special equipment for pouring sulfur (pouring tower, motorized swing mechanism, liquid sulfur piping). 3. Possible reasons of combustion: - sparks of passing by locomotives (railway line is located nearby); - spontaneous combustion of pyrophoric sulfides of iron (forgotten metallic garbage, scrap). 4. Operating personnel trained how to act in case of fire emergency. 5. Mobile patrol of Group 4. CALCULATION OF MANPOWER AND MATERIALS

I. Situation forecast at the sulfur pad 9 till the fire team with first fire extinguishing nosepieces comes to eliminate fire which took place at a stage of sulfur pouring. We calculate free fire development phase as per the formula: = .. + .. + .. + ..1 = 8 + 1 + 3 + 6 = 18 min. .. period of time since fire emerging till communicating to fire station about emergency (we take 812 min. as per the regulatory documentation); .. time of mustering fire team on alert (as per the norm less than 1 min.); .. time taken by fire team to drive to the place of fire is calculated as per the formula: .. =60L/V= 60 2/45 = 2,67 = 3 min. L length of way from fire station to the place of fire (km.); V. average speed of fire trucks is taken at a rate of 45 km/hour along wide streets with paved road and 25 km/hour at bad roads; ..1 time of deployment by fire team before applying first fire extinguishing means is taken equal to 6 minutes as per the fire fighting norms and real experience of fire extinguishing. Round shape fire development. Time of fire propagation - 1 10. 1. Calculation of the distance propagated by fire (R):
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R = 0,5V 1= 0,5 0,8 10 = 4 m. V. - linear velocity of fire propagation along fire load (is calculated after estimate the fire situation or is taken as per the reference data). V. = 0.8 (m/min) is taken as per the reference data; 1 time of fire propagation 10 min. 2. Calculation of fire area, fire perimeter and fire front: - fire area: S = (0,5V 1)2 (Table 5.1) S fire area at round shape development (m2); S = 3.14 (0.5 0.8 10)2 = 50.24 m2 - fire perimeter: P = 2R = 2 3,14 4 = 25,12 m - fire front: = 2R = 2 3,14 4 = 25,12 m 3. Calculation of fire extinguishing area with forces and extinguishing means location at round fire development: Along the front ST = h (2R - h) = 3.14 5 (2 4 - 5) = 47.1 m2 R distance propagated by fire 4 m; h effective depth of fire extinguishing the burning section (5 meters is taken for manual fire nosepieces and 10 meters for wheeled nosepieces). Around the perimeter ST = h (2R h) = 3.14 5 (2 4 - 5) = 47.1 m2 4. Calculation of water consumption for fire extinguishing: Q = S I = 47.1 0.2 = 9.42 liters/sec

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S fire extinguishing area, m2; I intensity of fire extinguishing matter supply (liters/m2sec), I = 0.2 liters/(m2sec) data from reference source. 5. Calculation of water consumption required for protection of the area: Q = I value of calculated protection parameters: area, m2; perimeter or part of protected section of extinguishing area; I surface (or accordingly linear) rate of water supply for the protection purposes depending on calculated parameter, liters/(msec), liters/(m2sec). As per TCO experience one fire nosepiece provides water supply at a rate of 6 liters/sec. For calculation we take one nosepiece from each side of sulfur pad, then Q = 2 6 = 12 liters/sec. 6. Calculation of total water consumption for fire extinguishing and area protection: Q = Q + Q = 9.42 + 12 = 21.42 liters/sec 7. Calculation of the number of nosepieces required for fire extinguishing (with water supply rate N T = Q / Q
N = Q / Q

- 6 liters/sec) as per the formula:

Q., Q. total quantity of fire extinguishing material required for fire elimination and area protection, liters/sec; N., N. number of extinguishing material supply units (water fire nosepieces) to provide fire extinguishing and area protection, pieces. N. = 9.42/6 = 1.57 = 2 pieces. N. = 12/6 = 2 pieces.
8. Calculation of actual water consumption for fire extinguishing and area protection:

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Q = N. Q. = 2 6 = 12 liters/sec Q = N. Q. = 2 6 = 12 liters/sec Q = 12 + 12 = 24 liters/sec


9. Water for extinguishing fire is supplied through the pipeline with 8 inches (200 mm) diameter, water consumption will be:

Q = (V d)2 = (1.7 8)2 = 184 liters/sec V velocity of water flow in the pipeline (meters/sec), is taken 1.7 for the piping of 200 mm diameter and pressure 7 bar; d diameter of piping (inch) 1 inch = 25 mm.
10. Calculation of the number of fire trucks required

N = Q/ Q = 24/78,8 = 0,3 = 1 truck Q capacity of water pump installed on fire truck is equal to Q = 78.8 liters/sec as per TCO data.
11. Calculation of number of fire trucks which can be connected to water pipeline:

N = Q/ Q = 184/78.8 = 2.3 = 2 trucks


12. Calculation of required manpower of fire team:

N . = NCT 3 + NCT 2 + N + N + N + NCB = 2 3 + 2 2 + 1 1 + 4= 15 people N 3 is a number of people engaged in work with fire nosepieces including nosepiece handlers; N 2 is a number of people engaged in work with nosepieces including nosepiece handlers; N is a number of people supervising functioning of pump & nosepiece system (as per number of trucks); N is a number of people who provide support with telescopic three-throw ladder (as per the number of ladders); N is a number of safety watchmen at the safety points (as per the number of safety points); N is a number communicating persons, N = 4 people.
13. Calculation of fire teams:
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N = N . / 4 = 15/4 = 3,75 = 4 teams. 4 is a number of people in one fire truck.


Time of fire propagation - 1 >10 , 2 = -10. 1. Calculation of distance propagated by fire (R) as per the formula:

R = 5V + V 2 = 5 0.8 + 0.8 8 = 10.4 m. 2 = -10 = 18 10 = 8 min. 2. Calculation of fire area, fire perimeter and fire front: - fire area: S = (5V + V 2)2 S - fire area at round shape fire development (m2); V. - linear velocity of fire propagation along fire load (is calculated after estimate the fire situation or is taken as per the reference data). V. = 0.8 (m/min) is taken as per the reference data; 2 time of fire propagation, 2 = 18 10 = 8 min. S = 3,14 (5 0,8 + 0,8 8)2 = 339,62 m2 - fire primeter: P = 2R = 2 3.14 10.4 = 65.3 m - fire front: = 2R = 2 3.14 10.4 = 65.3 m
3. Calculation of fire extinguishing area with forces and extinguishing means location at round fire development:

Along the front ST = h (2R - h) = 3.14 5 (2 10.4 - 5) = 248.06 m2

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R the distance propagated by fire 10.4 m; h effective depth of fire extinguishing the burning section (5 meters is taken for manual fire nosepieces and 10 meters for wheeled nosepieces). Around the perimeter ST = h (2R h) = 3.14 5 (2 10.4 - 5) = 248.06 m2

4. Calculation of water consumption for fire extinguishing:

Q = S I = 248.06 0.2 = 50 liters/sec S fire extinguishing area, m2; I intensity of fire extinguishing matter supply (liters/m2sec), I = 0.2 liters/(m2sec) data from reference source.
5. Calculation of water consumption for protection of the area:

Q = I value of calculated protection parameters: area, m2; perimeter or part of protected section of extinguishing area; I surface (or accordingly linear) rate of water supply for the protection purposes depending on calculated parameter, liters/(msec), liters/(m2sec). As per TCO experience one fire nosepiece provides water supply at a rate of 6 liters/sec. For calculation we take one nosepiece from each side of sulfur pad, then Q = 2 6 = liters/sec.
6. Calculation of total water consumption for fire extinguishing and area protection:

Q = Q + Q = 50 + 12 = 62 liters/sec
7. Calculation of the number of nosepieces required for fire extinguishing (with water supply rate - 6 liters/sec):

N T = Q / Q
N = Q / Q

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Q., Q. total quantity of fire extinguishing material required for fire elimination and area protection, liters/sec; N., N. number of extinguishing material supply units (water fire nosepieces) to provide fire extinguishing and area protection, pieces. N. = 50/6 = 8,3 = 9 pieces. N. = 12/6 = 2 pieces.
8. Calculation of actual water consumption for fire extinguishing and area protection:

Q = N. Q. = 9 6 = 54 liters/sec Q = N. Q. = 2 6 = 12 liters/sec Q = 54 + 12 = 66 liters/sec


9. Water for extinguishing fire is supplied through the pipeline with 8 inches (200 mm) diameter according to TCO data, water consumption will be:

Q = (V d)2 = (1.7 8)2 = 184 liters/sec V velocity of water flow in the pipeline (meters/sec), is taken 1.7 for the piping of 200 mm diameter and pressure 7 bar according to TCO data; d diameter of piping (inch) 1 inch = 25 mm.
10. Calculation of the number of fire trucks required

N = Q/ Q = 66/78,8 = 0,8 = 1 truck Q capacity of water pump installed on fire truck is equal to Q = 78.8 liters/sec as per TCO data.
11. Calculation of number of fire trucks which can be connected to water pipeline:

N = Q/ Q = 184/78.8 = 2.3 = 2 trucks


12. Calculation of required manpower of fire team:

N . = NCT 3 + NCT 2 + N + N + N + NCB = 9 3 + 2 2+ 1 1 +4 = 36 people

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N 3 is a number of people engaged in work with fire nosepieces including nosepiece handlers; N 2 is a number of people engaged in work with nosepieces including nosepiece handlers; N is a number of people supervising functioning of pump & nosepiece system (as per number of trucks); N is a number of people who provide support with telescopic three-throw ladder (as per the number of ladders); N is a number of safety watchmen at the safety points (as per the number of safety points); N is a number communicating persons, N= 4 people. 13. Calculation of fire teams: N = N . / 4 = 36/4 = 9 teams. , 4 is a number of people in one fire truck.
Fire development of rectangular shape. Time of fire propagation - 1 10.

For example fire took place from the short side of block ( = 70 m, b = 1 m), fire develops in one direction.
1. Calculation of fire area, fire perimeter and fire front:

- fire area: S = V 1 = 1 70 0,8 10= 560 m2 S - fire area at rectangular shape fire development (m 2); , b width and length of rectangular, m. V linear velocity of fire propagation along fire load (m/min), V=0.8 m/min; 1 time of fire propagation, 1=10 min. - fire perimeter: P = 2( + b) = 2 (70+ 1) = 142 m - fire front: = = 1 70 = 70 m

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number of fire development directions in horizontal plane, =1.


2. Calculation of fire extinguishing area as per the formula:

ST = h = 1 70 5 = 350 m2 h effective depth of extinguishing the burning section (5 meters is taken for manual fire nosepieces and 10 meters for wheeled nosepieces).
3. Calculation of water consumption for fire extinguishing:

Q = S I = 350 0,2 = 70 liters/sec S fire extinguishing area, m2; I intensity of fire extinguishing matter supply (liters/m2sec), I = 0.2 liters/(m2sec) data from reference source.
4. Calculation of water consumption required for protection of the area:

Q = I value of calculated protection parameters: area, m2; perimeter or part of protected section of extinguishing area; I surface (or accordingly linear) rate of water supply for the protection purposes depending on calculated parameter, liters/(msec), liters/(m2sec). As per TCO experience one fire nosepiece provides water supply at a rate of 6 liters/sec. For calculation we take one nosepiece from each side of sulfur pad, then Q = 2 6 = 12 liters/sec.
5. Calculation of total water consumption for fire extinguishing and area protection:

Q = Q + Q = 70 + 12 = 82 liters/sec
6. Calculation of the number of nosepieces (water supply rate - 6 liters/sec) required for fire extinguishing

N T = Q / Q
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N = Q / Q

Q., Q. total quantity of fire extinguishing material required for fire elimination and area protection, liters/sec; N., N. number of extinguishing material supply units (water fire nosepieces) to provide fire extinguishing and area protection, pieces. N. = 70/6 = 11.6 = 12 pieces. N. = 12/6 = 2 pieces.
7. Calculation of actual water consumption for fire extinguishing and area protection:

Q = N. Q. = 12 6 = 72 liters/sec Q = N. Q. = 2 6 = 12 liters/sec Q = 72 + 12 = 84 liters/sec


8. Water for extinguishing fire is supplied through the pipeline with 8 inches (200 mm) diameter according to TCO data, water consumption will be:

Q = (V d)2 = (1.7 8)2 = 184 liters/sec V velocity of water flow in the pipeline (meters/sec), is taken 1.7 for the piping of 200 mm diameter and pressure 7 bar; d diameter of piping (inch) 1 inch = 25 mm.
9. Calculation of the number of fire trucks required

N = Q/ Q = 84/78.8 = 1.06 = 2 trucks Q capacity of water pump installed on fire truck is equal to Q = 78.8 liters/sec as per TCO data.
10. Calculation of number of fire trucks which can be connected to water pipeline:

N = Q/ Q = 184/78.8 = 2.3 = 2 trucks


11. Calculation of required manpower of fire team:

N . = NCT 3 + NCT 2 + N + N + N + NCB = 12 3 + 2 2 + 2 1 + 4 = 46 people


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N 3 is a number of people engaged in work with fire nosepieces including nosepiece handlers; N 2 is a number of people engaged in work with nosepieces including nosepiece handlers; N - is a number of people supervising functioning of pump & nosepiece system (as per number of trucks); N is a number of people who provide support with telescopic three-throw ladder (as per the number of ladders); N - is a number of safety watchmen at the safety points (as per the number of safety points); N is a number communicating persons, N= 4 people.
12. Calculation of fire teams:

N = N . / 4 = 46/4 = 11.5 = 12 teams. 4 is a number of people in one fire truck.

4.1.3 Calculation of manpower and materials required for fire extinguishing at sulfur pad during storage of solidified sulfur (Variant 3) BACKGROUND DATA

1. Fire takes place at solidified sulfur storage 7 2. Absence of any running equipment. 3. Possible reasons of combustion: - sparks of passing by locomotives (railway line is located nearby); - spontaneous combustion of pyrophoric sulfides of iron (forgotten metallic garbage, parts of casing, scrap). - spontaneous combustion during summer due to absence of sprinkling. 4. Absence of special fire watchman with fire extinguisher. 5. Absence of operating personnel trained how to act in case of fire emergency 6. Mobile patrol of Group 4.
7. Unit 600 comprises 9 sulfur pads.

8. Size and quantity of bulked sulfur stored at sulfur pad 7 (project design data):
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Size of pad - 425 m 310 m, Quantity of sulfur - 2865888,3 tons.

9. Fire hazardous material in use. Fire hazard of sulfur is determined as per physical & chemical and combustible properties. Sulfur - S, inflammable solid matter, melting point - 112,8 -119,3C; boiling point - 444,6C; flaring point - 170C, cannot be dissolved in water. Sulfur is characterized with low melting heat (1.72 kJ/mol) and low evaporation temperature (9.2 kJ/mol). Therefore, sulfur can ignite from comparatively low energy ignition sources. 10. Fire hazardous properties of sulfur are reflected with fire hazard indices (GOST 12.1.044 91), basic are: Flaring point (207 C); Self-ignition temperature (232 C). Sulfur that has size less than 74 mkm possesses self-ignition temperature in the form of aerogel 220 C; Concentration limits of flame propagation. Low concentration limit for sulfur dust is 35 g/m3. Maximum pressure under explosion of sulfur and air mixture is 500 Kpa; Fine-grained sulfur tends to chemical combustion in the presence of moisture. Sulfur forms explosives with strong oxidizers such as bleach powder, nitrates, chlorates and perchlorates; Minimum ignition energy is 15 mJ; combustion heat 9205 kJ/kg.

Elementary sulfur of any size (dispersion) is a very hazardous if gets ignited as in the result of ambient temperature increase intensive melting of sulfur takes place then sulfur evaporating and boiling. Melted burning sulfur when flowing makes other inflammable materials burn and sulfur fumes when getting burnt may cause quick fire propagation to areas remote from fire seat and may cause explosion Burning sulfur aggravates fire extinguishing due to generation of sulfuric gas which requires application of special protection means and deteriorates (in presence of water vapor) metallic structures including fire extinguishing equipment.
Fire fighting water supply system

There 39 fire hydrants installed on the territory of sulfur pads which are connected to water pipeline with diameter 200 mm. The distance between hydrants
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is 60-80 meters. From eastern side of sulfur pad 2 there are 4 hydrants installed along with wheeled fire nosepieces.
Situation forecast at the sulfur pad 7 till the fire team with first fire extinguishing nosepieces comes CALCULATION OF MANPOWER AND MEANS I. Determination of main geometrical and physical fire parameters depending on fire area shape. Fire area shape: round

angle S = 0,5 R2 P = R(2+) = R (1) (2) (3) (4)

Fire area Fire perimeter Fire front Linear velocity of fire propagation Rate of fire area expansion Rate of fire perimeter increase

S = R2 S = 0,785 D2 P = 2R = 2R V = R/ VS = S / VS = V2 V = / V = 2V

VS = 0,5 V2

(5)

V = V (2+) V = V

(6) (7) (8)

Rate of fire front increase Burning area In the given formulas:

V = 2V S = S

R fire radius; it is determined by measurement or through formulas, m. V linear velocity of fire propagation, m/min (calculated after estimate the fire situation or is taken as per the reference data). time of fire propagation till fire localization. angle limiting fire development, radian. (1 radian 57). At: 90 = 90/57 1,6;
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180 = 180/57 3,16; 270 = 270/57 4,7; coefficient of fire load level (that is taken as per the characteristics of the object) is equal to 1 for the sulfur pad 7.
1. Radius of fire or distance propagated by fire (R) in meters are calculated through then formula (4):

R = V , m , If time of fire propagation is higher than 10 minutes, then R is calculated as follows: R = 5 V + V 1 (9) 1 burning. is time of free fire development phase without first 10 minutes of

V linear velocity of fire propagation taken as equal to 0.8 m/min. is a duration of fire since emerging till restriction of firing (localization) calculated as follows = + , min (10) - free fire development phase i.e. time since fire emerging till supply of first fire extinguishing means: = + + + 1 = 12+ 1 + 3 + 6 = 22 min 1 = 22 10 = 12 min - period of time from fire emerging till communicating to fire station (it depends on several factors) that is taken equal to 8...12 min; - time of mustering fire team on alert (as per the norm less than 1 min.); - time taken by fire team to drive to the place of fire is calculated as per the formula: = 60L/V = 60 2 / 45 = 3 min L - length of way from fire station to the place of fire (km.); V - average speed of fire trucks is taken at a rate of 45 km/hour along wide streets with paved road and 25 km/hour at bad roads; 1 - time of deployment by fire team before applying first fire extinguishing means is taken as per the fire fighting norms and real experience of fire extinguishing, min
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- time of fire localization from supplying first extinguishing means (nosepiece, nosepieces) till restriction of fire propagation, min. When forces and means of first fire teams are sufficient to extinguish fire is calculated as per the formula: = 1 = 1 1 time spent by fire team for applying (focusing) of the required extinguishing means (nosepiece, nosepieces etc.) to localize fire, min. We insert data in formula (10) and find : = 22 + 6 = 28 min We insert data in formula (9) and find R: R = 5 0,8 + 0,8 12 14 m

2. We insert the calculated R in formulas 18 and find geometrical and physical properties of fire depending on fire area.

Round: S = 3,14 142 616 m2

Angle (at three angle values): S = 90/57 142 310 m2 S = 180/57 142 619 m2 S = 270/57 142 930 m2

P = 2 3,14 14 88 m = P 88 m VS = 3,14 0,82 28 56 m2/min V = 2 3,14 0,8 4 m/min V = V = 4 m/min S = 1 616 = 616 m2

P = 14(2 + 3,16) 72 m = 3,16 14 44 m VS = 0,5 3,16 0,82 28 28 m2/min V = 0,8 (2+3,16) 4 m/min V = 3,14 0,8 2,5 m/min S = 1 310 = 310 m2 , 1 619 = 619 m2, 1 930 = 930 m2,
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II. Calculation of fire extinguishing area

Fire extinguishing area ST is a part of fire area where extinguishing means are applied at the moment of localization. Fire extinguishing area depends on effective depth of extinguishing burning section h. Practice shows that the one third of water jet is effective for fire extinguishing that is why for the calculations the effective depth of fire extinguishing equal to 5 meters (manual nosepiece) and 10 meters (wheeled nosepiece) are taken.
1. Round shape fire development: forces and means location along the front:

at R>h ST = h (2R - h) = 3,14 5 (2 14 5) 361 m2


2. Angle shape of fire development: forces and means location along the front at three different angles:

At R>h ) 90 ST =0,25 h (2R - h) = 0,25 3,14 5 (214 5) 91 m2 ) 180 ST=0,5 h (2R - h) = 0,5 3,14 5 (214 5) 181 m2 ) 270 ST=0,75 h (2R - h) = 0,75 3,14 5 (214 5) 271 m2

III. Fire extinguishing material consumption

There several types of fire extinguishing material consumption: required, actual and total.
Required consumption (quantity of extinguishing material supplied per time unit onto fire parameter unit for fire extinguishing or protection of area which is in danger) is calculated as per the formula:

Q = S I Q quantity of extinguishing material required for fire extinguishing, liters/sec; S fire extinguishing area, m2; I intensity of fire extinguishing material supply to eliminate fire. I = 0,2 liters/(m2sec) (determined by experimental method and fire extinguishing practice). Total required water consumption is calculated as per the formula: Q = Q + Q Q quantity of fire extinguishing material required for protection (liters/sec)

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As it is not possible to determine the original extinguishing area we take Q equal to capacity of one nosepiece 6 liters/sec.
1. For round shape fire area: Q = S I + Q = 361 0,2 + 6 78 liters/sec 2. For angle shape fire area: Q = 91 0,2 + 6 24 liters/sec Q = 181 0,2 + 6 42 liters/sec Q = 271 0,2 + 6 60 liters/sec IV. On the basis of required consumption we define the required number of extinguishing material supply units (water nosepieces).

N = Q /Q N number of extinguishing material supply units (water nosepieces) for fire fighting, pieces; Q required consumption of fire extinguishing material (water) to eliminate fire, liters/sec, Q - supply of fire extinguishing material by means of supply unit, liters/sec.
1. For round shape fire area: N = 78 : 6 = 13 nosepieces 2. For angle shape fire area: N = 24 : 6 = 4 nosepieces N = 42 : 6 = 7 nosepieces N = 60 : 6 = 10 nosepieces V. Calculation of water intake from water pipeline as per the formula:

Q = (V d)2 = (1,7 8)2 = 184 liters/sec Q water intake from ring water pipeline network, liters/sec; VB velocity of water flow in the pipeline (meters/sec) is taken 1.7 for the piping of 200 mm diameter and pressure 7 bar; d diameter of piping (inch) 1 inch = 25 mm. The plant is provided with water for fire fighting and protection if Q Q.
VI. Calculation of actual water consumption for fire extinguishing and protection.

Actual consumption actual amount of fire extinguishing material by weight or volume supplied per time unit onto fire parameter unit for fire extinguishing or for protection of area which is in danger of fire propagating
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on it. It has same measurement units as required consumption. Actual consumption is calculated as per the formula: Q = Q + Q Q, Q actual consumption of extinguishing material for fire fighting and protection, liters/sec, Actual consumption depends on number and technical characteristics of fire extinguishing material supply units (water nosepieces). Taking this into account actual consumption for fire fighting and protection is calculated as per the formulas: Q = N Q Q = N Q Actual consumption allows estimating the real velocity of extinguishing material concentration and conditions of localization comparing to the required consumption. It allows calculating required number of fire trucks with full utilization of pumps, checking sufficient quantity of water at site if fire water pipelines available and controlling other parameters. Actual consumption cannot be less than the required one; this important condition to provide all necessary for fire localization.
1. For round shape fire area: Q = 13 6 + 1 6 = 84 liters/sec 2. For angle shape fire area: Q = 4 6 + 1 6 = 30 liters/sec Q = 7 6 + 1 6 = 48 liters/sec Q = 10 6 + 1 6 = 66 liters/sec VII. Calculation of number of fire trucks with regard to pumps full utilization installed on fire trucks: N = Q / Q Q water intake pump. At the site water tank trucks (E-ONE) with pumps having capacity 78.8 liters per second are used. 1. For round shape fire area: N = 84/78,8 = 1,1 2 trucks 2. For angle shape fire area:

N = 30/78,8 = 0,4 1 truck N = 48/78,8 = 0,6 1 truck N = 66/78,8 = 0,9 1 truck


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It is possible to connect to water pipeline: N = Q/ Q = 184/78 = 2,3 2 trucks


VIII. Water consumption for fire extinguishing and protection. Total consumption Amount of fire extinguishing material by weight or volume required for complete fire liquidation and protection of not burning objects including reserve. Total water consumption is used to determine the required amount of fire extinguishing materials to liquidate fire. Total water consumption for fire liquidation and fire protection is calculated as per the formula:

Q = Q 60 + Q 3600 Q total consumption of extinguishing material (water in the given case), liters.; calculated time of fire extinguishing (we take 60 min); coefficient of fire extinguishing material reserve (determined by extinguishing practices and is equal to 5); 3 time during which reserve of extinguishing material would be sufficient (determined by extinguishing practices and is equal to 3).
1. For round shape fire area: Q = 78 60 60 5 + 6 3600 3 = 1404000 + 64800 = 1468800 1469 2. For angle shape fire area: Q = 24 60 60 5 + 6 3600 3 = 496800 497 m3 Q = 42 60 60 5 + 6 3600 3 = 820800 821 m3 Q = 60 60 60 5 + 6 3600 3 = 1144800 1145 m3 IX. The required manpower for fire extinguishing and protection is calculated as per the formula: N / = N 2 N / = N 2

m3

2 number of people to work with one water nosepiece


1. For round shape fire area: N / = 13 2 = 26 people
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N / = 1 2 = 2 people 2. For angle shape fire area: N / = 4 2 = 8 people N / = 1 2 = 2 people N / = 7 2 = 14 people N / = 1 2 = 2 people N / = 10 2 = 20 people N / = 1 2 = 2 people To get onto the sulfur pads scaffolding is to be used which should be installed around the perimeter of sulfur pad. If it is not possible to use scaffolding two-throw ladders are to be applied.
X. Required number of fire teams :

N = N / / 4 4 is a number of people in one fire truck


1. For round shape fire area: N = 28 / 4 = 7 teams 2. For angle shape fire area: N = 10 / 4 = 2,5 3 teams N = 16 / 4 = 4 teams N = 22 / 4 = 5,5 6 teams 4.1.4 Results of manpower and materials calculation required for fire extinguishing as per 3 variants. As per variant I

Table 5
Calculated data Existing facilities

Round shape of fire development

1. Required water consumption = 122 liters/sec

1. Fire water network supply = 184 liters/sec


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2. Required number of fire trucks = 2. 3. Required manpower = 32 people. 4. Required number of teams = 8 teams

2. Organizational & technical capabilities of TCO ERT (Emergency Response Team) provide required number of fire trucks and fire fighters

Angle shape of fire development

1. Required water consumption = 123 liters/sec 2. Required number of fire trucks = 2. 3 Required manpower = 30 people. 4. Required number of teams = 8 teams

1. Fire water network supply = 184 liters/sec 2. Organizational & technical capabilities of TCO ERT (Emergency Response Team) provide required number of fire trucks and fire fighters

As per variant II

Table 6
Calculated data Existing facilities

Round shape of fire development

1. Required water consumption =

1. Fire water network supply = 184


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66 liters/sec 2. Required number of fire trucks = 2. 3 Required manpower = 36 people.. 4. Required number of teams = 9 teams

liters/sec 2. Organizational & technical capabilities of TCO ERT (Emergency Response Team) provide required number of fire trucks and fire fighters

Rectangular shape of fire development

1. Required water consumption = 84 liters/sec 2. Required number of fire trucks = 2. 3 Required manpower = 46 people. 4. Required number of teams = 12 teams

1. Fire water network supply = 184 liters/sec 2. Organizational & technical capabilities of TCO ERT (Emergency Response Team) provide required number of fire trucks and fire fighters

As per variant III

Table 7
Calculated data Existing facilities

Round shape of fire development

1. Required water consumption = 84 liters/sec

1. Fire water network supply = 184 liters/sec

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2. Organizational & technical 2. capabilities of TCO ERT (Emergency 3. Required manpower = 26 people.. Response Team) provide required number 4. Required number of teams = 7 of fire trucks and fire fighters teams

2. Required number of fire trucks =

2. Required number of fire trucks = 2. 3. Required manpower = 20 people. 4. Required number of teams = 6 teams

2. Organizational & technical capabilities of TCO ERT (Emergency Response Team) provide required number of fire trucks and fire fighters

1. All the variants are provided with necessary facilities to extinguish fire with water. Water supply of fire water ring pipeline network exceeds the required water consumption (Q > Q). 2. For all the variants the number of hydrants at the pad under consideration are sufficient for the required number of fire trucks (N. >N). 3. Organizational & technical capabilities of TCO ERT (Emergency Response Team) provide required number of fire trucks and manpower.

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5. EXPERIMENTAL DETERMINATION OF DATA DEPENDING ON SULFUR IGNITION MECHANISM: DETERMINATION OF LINEAR VELOCITY OF FIRE PROPAGATION AT A STAGE OF SULFUR COMBUSTION. DETERMINATION OF SULFUR SPONTANEOUS COMBUSTION CONDITIONS

To determine capacities of TCO to detect and liquidate combustion of sulfur at Tengiz we have prepared calculations of manpower and means required for fire extinguishing in accordance with Fire Extinguishing Manager. Calculations provide three variants taking into account the forecasted situations (see Section 4). One of the main indexes in the calculations is linear velocity of fire propagation. Earlier in our calculations we were taking linear velocity of fire propagation from reference book Supervisor of fire extinguishing equal to V. = 0,8 (m/min). As per the stated methodology linear velocity is a basic index and other fire indices depend on it: - geometric parameters of fire for the definite period of time; - fire area; - water consumption; - required quantity of extinguishing means, fire hydrants, fire equipment and trucks; - manpower required for fire extinguishing. That is why the results on linear velocity analysis received by experimental method using sulfur samples from TCO will allow us to determine more precisely the capacities of TCO to detect and extinguish combustion of bulked sulfur stored in open area. The section gives the data on linear velocity received using experimental method. Besides, experiments were made on conditions of bulked sulfur combustion. Sulfur samples were taken from different sulfur pads of TCO with different mode of operations: - pad 4, sulfur is stored for the longest period of time here, handling and loading of bulked sulfur are performed at the pad; - pad 7, till recent time it was in storage mode (presently its handling has been started); - pad 9 which is in the stage of liquid sulfur pouring. Short report on field activities of SSI RSRCSCI specialists conducted with the purpose of taking sulfur samples, the report is given in the Enclosure D.
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Experiments on linear velocity and combustion conditions for bulked sulfur have been conducted along with Experimental fire laboratory South-Kazakhstan regional affiliated company of fire fighting and emergency rescue service of Ministry on Emergency situations of RoK.
5.1 Determination of sulfur combustion velocity using experimental method in accordance with UNO (United Nations Organization) methodology, section 33 Classification procedures, methods and criteria relating to class 4 (ST/SG/AC.10/11/Rev.3. Recommendations on the TRANSPORT OF DANGEROUS GOODS/ Manual of Tests and Criteria. Section 33/ Classification procedures, methods and criteria relating to class 4).

Linear velocity is tested by igniting the matter and defining time of burning. To conduct testing the following equipment and materials were used: - Aluminum container with length 250 mm with triangle shaped inside section, with height 10 mm and width 20 mm; Asbestos plate with low conductivity.
5.1.1 Description of UNO methodology Determination of linear velocity

Container is filled with powder or granulated material. Then container is dropped onto solid surface from the height of 20 mm. Remove side limits and install on top side of container hermetical, non-flammable plate with low conductivity. Then container is turned and put on its top side, and container is removed. The plate with material is put into exhaust cupboard. The speed of air should be sufficient to prevent smoke coming inside laboratory and should be changed during the course of testing. To ignite the sample any ignition source is used from one side. Ignition source can be small flame or hating wire with temperature 1000 . When burning of sample reaches 80 mm, it is necessary to change burning velocity at the following 100 mm. Testing is to be performed six times using the clean cooled plate every time.
Experimental part Equipment applied:

- Timer -1-2 as per GOST 5072-79.


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- Metallic measuring tape as per GOST 7502-80. - Aluminum container with length 250 mm with triangle shaped inside section, with height 10 mm and width 20 mm; - Weight scales 500, category 4.
5.1.2 Testing performance

As per the methodology the samples of bulked sulfur from sulfur pads of TCO 4, 7 and 9 were taken by SSI RSRCSCI specialists on 12 May 2007. Samples were prepared as per the methodology of UNO using the aluminum container with length 250 mm with triangle shaped inside section, with height 10 mm and width 20 mm. When preparing samples the difficulties were faced due to fragility of sulfur. It was revealed the older sulfur the more fragile it is. Before testing the sulfur stripe was weighed. Sulfur stripe was put onto clean asbestos plate and was ignited by gas burner from one side. When flame reached till the mark of 80 mm on the sample the counting of time of the following 10 mm was performed. After reaching 180 mm flame was extinguished and records logged. Unburnt part of sulfur sample was cooled and weighed. Testing protocols are given in Enclosures E, F, G.
Experimental data processing:

Table 8. Experimental data on testing performed as per UNO methodology determining sulfur burning velocity.

olf exp eri me nt 1 1 2 3 4 5 6

Date of Weight of sample, g experime of Before After tn pa testing testing d 2 26.05.07 26.05.07 26.05.07 26.05.07 26.05.07 26.05.07 3 4 4 4 4 4 4 4 44 57,11 49,67 48,35 50,28 49,86 5 13,85 17,76 18,27 18,15 18,48 18,14

Time of burning

Weig Burning ht of velocity, sulfur m/min. burnt, g 7 30,15 39,35 31,40 30,20 31,80 31,72 8 0,00306 0,00433 0,00455 0,00481 0,00451 0,00445
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6 32 min 35 s 23 min 05 s 21 min. 58 s 20 min 45 s 22 min 10 s 22 min 28s

1 7 8 9 10 11 12 13 14 15 16 17 18

Arithmetic mean velocity, m/min 2 3 4 5 6 28.05.07 7 53,00 17,00 24 min 51 s 28.05.07 7 50,10 16,30 23 min 42 s 28.05.07 7 49,70 13,98 24 min 06 s 28.05.07 7 48,33 13,85 23 min 35 s 28.05.07 7 51,26 16,24 23 min 52 s 28.05.07 7 50,48 16,38 24 min 53 s Arithmetic mean velocity of burning, m/min 29.05.07 9 55,87 22,89 26 min 25 s 29.05.07 9 47,81 13,32 22 min 30 s 29.05.07 9 53,51 16,55 24 min 20 s 29.05.07 9 50,95 16,22 21 min 54s 29.05.07 9 49,85 17,02 23 min 28s 29.05.07 9 49,25 16,71 22 min 53s Arithmetic mean velocity of burning, m/min Total arithmetic mean velocity of burning, m/min

7 36,00 33,80 35,72 34,48 35,02 34,10 32,98 34,49 36,96 34,73 32,83 32,54

0,00428 8 0,00402 0,00422 0,00415 0,00424 0,00419 0,00403 0,00414 0,00378 0,00444 0,00411 0,00456 0,00426 0,00437 0,00425 0,00422

Experimental data received show that burning velocity of TCO sulfur is very low and equals to in average 0.00422 m/min The low velocity can be justified by the fact that part of heat is consumed for melting of sulfur as before burning sulfur melts and then only fumes get ignited.

5.2 Determination of fire propagation velocity index using experimental approach in accordance with GOST (National Standard) 12.1044-89 Combustion hazard of matters and materials, indices nomenclature and methods of determination

Experiments were performed as per the methodology given in GOST 12.1.044-89 Fire and explosion hazard of substances and materials. Nomenclature of indices and methods of their determination. The standard is applied for simple matters, chemical compounds and their mixtures in different state and combinations including polymers and composite materials (further matters and materials), used in different spheres of economy. Standard does not cover explosives and radioactive materials. Standard defines the Nomenclature of indices and methods of their determination.

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5.2.1 Determination of linear fire propagation velocity in the time of sulfur combustion linear velocity of fire propagation To determine , 4.19 12.1.044-89, I . - , , . , .

5.2.1.1 Brief description of the method using for determination of linear flame propagation velocity, V. 1. Apparatus: 1 - stand; 2 - electric radiation heater; 3 frame of sample holder; 4 exhaust hood; 5 - ignition burner (see diagram of experimental unit for determination of flame propagation index). 2. Preparation of test device: 2.1. Preparation of sulfur samples (fitting the sample sizes by 32014020mm; conditioning within 48 hours). 2.2. Gas flow adjustment through ignition burner, followed by switch-off and adjustment of the burner to control mode. 3. Test performance: 3.1 Material sample fixation into the holder, sample surface marking at interval of 30 mm. 3.2 Ignition burner firing. At that the following values are determined: ) time from the test beginning to the moment of flame front passing zero , s ) time of the flame front passing i section of sample surface - , s ) distance of flame front propagation - , mm;
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The test lasts until the flame stops its propagation along the sample surface.
4. Result analysis: Calculation of linear fire propagation velocity - V, m/min as per the values determined during the test: - distance of flame front propagation - , m - time of flame front passing a distance , min, Arithmetic mean value of linear velocities for 5 tested samples from three sulfur pads is accepted as linear fire propagation velocity for sulfur under test. 5.2.1.2 Drawing of experimental unit used to determine fire propagation index which is a basis for determination of linear fire propagation velocity

Fig. 3. 1 - stand; 2 - electric radiation heater; 3 frame of sample holder; 4 exhaust hood; 5 - ignition burner. Electrical radiation board consists of ceramic heater, in channels of which 2080- wire coil is set. Total power consumption electrical radiation board is 4 kW. Ceramic heater is fixed into heat electric insulated case, perforated for device binding to the stand
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and electrical power supply leading-in socket. Refractory steel mesh is set in front of ceramic heater for infrared light expansion and air flow minimization. The sample holder consists of stand and frame. The frame is fixed on the stand so that the sample surface is inclined on 30 vertically towards the radiation board. The sample holder is set so that the distance from the sample edge, limited by the frame, to the mesh of radiation board is 70 mm. The frame side has the control graduation in every (301) mm, numbered from zero to ninth. Exhaust hood (360 360 700) mm, fixed over the sample holder, collects and removes the combustion products. The ignition burner is fixed so that the distance from the burner pipe, across the center of zero section, to the surface of the sample under test is (81) mm, and the axles of five holes are positioned along the normal to sample surface. In order to stabilize the burner flame, the burner has single-layered cover of mesh wire. The burner is set out of the frame edge in control mode. The stopwatch shall be to a precision at most 1 s.
5.2.2 Test preparation

1. Sample preparation. Five samples (3202) mm long, (1402) mm width and ~20 mm thick of the material under test from each sulfur pad are prepared. The samples are conditioned in laboratory within 48 hours. 2. Adjustment of gas ignition burner. The gas flow through the ignition burner is adjusted that the flamelet height is (112) mm. After that the ignition burner is switched off and set in control mode.
5.2.3 Test performance

Tests are performed by three ways:


Way 1. Prepared sulfur sample is set as per GOST 12.1.044-89, item 4.19.1.2: - holder frame is fixed on the stand so that the sulfur sample surface is inclined at 30 vertically towards the radiation board; - sample holder is set so that the distance from the sample edge, limited by the frame, to the mesh of radiation board is 70 mm.
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Test course: 1. Fix the sulfur sample to the holder and mark the surface by graduation at intervals of (301) mm. 2. Fire the ignition burner and set to the operation mode. 3. Fire the sulfur. Test shall last until the fire stops propagation along the sample surface. In course of test the following need to be determined: - time of flame from passing i section of the sample surface (i = l, 2, ...9) i , s; - average time of flame front passing along the whole surface of the sample, , s; - distance of flame front propagation, , mm.
Way 2. The slice of melted sulfur ( 2 mm) is applied on the surface of asbestos-cement board. Note the size of asbestos-cement board meets the size of the sample under test, indicated in GOST 12.1.044-89, item 4.19.2.1. The sample adjustment and test course is the same as in way I. Way 3. Prepared sulfur sample is set into holder aflat.

Test course: 1. Set the sample into the holder and mark the surface by gradations at interval of (301) mm. 2. Fire the ignition burner and set in operation mode. 3. Fire the sulfur. 4. Use the first sample interval 30mm long for the fire and flame stabilization. Switch on the stopwatch and measure the burning time of i section of sulfur sample (i =1, 2,9). 5. Determine the average burning time of sulfur sample 270mm long according to i values, , s. 6. Make a table for test results.
Results analysis by test ways: I. Following is noted in the first way: Sulfur under action of burner fire melted, inflamed and by flamy drop rolled down the sample surface. At that the flame went out. II. The second way is the same as described in the first way. III. Following is noted in the third way:

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Sulfur under action of burner fire melted and inflamed. This process (melting and firing) gradually pervaded the sulfur testing length. When the flame run to i section of sulfur sample (i =9), the flame was extinguished. Test results are indicated in the table 9: Table 9
Test No.

Test date

Sulfur pad No.

, s

, mm

1 2 3 4 1 30.05.07 4 78 min 26s 2 30.05.07 4 76min 24s 3 30.05.07 4 75min 00s 4 30.05.07 4 76min 06s 5 30.05.07 4 77min 36s Arithmetical average of linear velocity, V, 1 2 3 4 7 31.05.07 7 76min 49s 8 31.05.07 7 84min 12s 9 31.05.07 7 79min 35s 10 31.05.07 7 80min 36s 11 31.05.07 7 79min 12s Arithmetical average of linear velocity, V, 12 01.07.07 9 80min 36s 13 01.07.07 9 83min 08s 14 01.07.07 9 85min 31s 15 01.07.07 9 82min 22s 16 01.07.07 9 85min 44s Arithmetical average of linear velocity, V, Total arithmetical average of linear velocity, V,
Conclusions:

5 270 270 270 270 270 0,00353 5 270 270 270 270 270 0,00339 270 270 270 270 270 0,00325 0,00339

Linear flame propagation velocity, V, m/min 6 0,00345 0,00356 0,00360 0,00355 0,00349 6 0,00353 0,00321 0,00342 0,00336 0,00343 0,00336 0,00325 0,00318 0,00330 0,00316

I. In three ways of test there is no flame propagation along the surface of block sulfur sample.

II. The value of linear flame propagation velocity set as a result of three test ways (0,00339 m/min) is much less than the value of linear flame propagation velocity accepted according to the tabular equivalents in reference book For Fire Extinguishing Manager and than the value used in calculations made before as per above indicated method.
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In calculations made before and for the fire extinguishing medium on TCO sulfur pads the value of linear velocity was adopted as 0,8 m/min. The calculations were made by three ways for possible fire situations on the sulfur pads. According to the results of calculations, indicated in section 4, the conclusion is as follows: 1. As per all ways the complete water provision to the plant, being subject to extinguishing, is performed. Fire main water capacity exceeds the water flow requirement (Q > Q). 2. As per all ways the number of fire plugs, situated on concerned pads, corresponds to required number of fire trucks (N. >N). 3. Engineering capabilities of TCO Emergency Response Service (ERS) are in position to provide the required quantity of fire-extinguishing equipment and staff.
Conclusion: Whereas the value of linear fire propagation velocity, get by experimental way is much less than value, accepted according to the calculations, the conclusion, made according to the calculation results and indicated in section 4, is in force.

Test reports are indicated in Attachments , , . In order to imagine the sulfur flame propagation graphically in comparison with specified index for different materials (flax-fibre, rubber resin, rubber items, flexible foam, peat, paper) in Attachments M and H there are table and diagram, shown the values of flame propagation for indicated materials.
5.3 Method of experimental determination of conditions for heat spontaneous ignition of solid matters and materials

The firing can arise in two different forms: - as an ignition (inflammation) by thermal pulse effecting; - as a spontaneous ignition - ignition source free combustion. Test data on sulfur spontaneous ignition are not found out in the references. The testing was carried out as per GOST 12.1.044-89 method of experimental determination of conditions for heat spontaneous ignition of solid matters and materials.

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5.3.1 Method as per GOST 12.1.044-89 Fire Explosion Hazard of Matters and Materials 1. Apparatus

Apparatus for determination of conditions for heat spontaneous ignition includes the following components: 1.1. Thermostat with process chamber capacity at least 40 dm3 including heat control unit enabling to maintain the temperature from 60 to 250 to a precision of 3 . 1.2. Cubical- or cylinder-shaped baskets of noncorrosive metal 35, 50, 70, 100, 140 and 200 mm high (in 10 pieces for each size) with covers. Diameter of cylinder-shaped basket should be equal to its height. The basket wall thickness (1,00,1) mm. 1.3. Thermoelectric converters (not less than 3) with max. diameter of hot junction not more than 0.8 mm.
2. Test preparation

2.1. Calibration test is carried for the purpose of correction factor (DtT) determination for indications of the thermoelectric converters 2 and 3. To this effect the basket with incombustible matter (for example, calcined sand) is placed to thermostat, heated to preset temperature. The thermoelectric converters (Fig. 2) are set so that the hot junction of the first thermoelectric converter contacts with the sample and being situated in its center, the second hot junction is in contact with exterior side of the basket, the third hot junction outlies in (301) mm from the wall basket. The hot junctions of three thermoelectric converters should be situated on one surface level, corresponding to the center line of thermostat.

Fig. 4.
1, 2, 3 - hot junctions of thermoelectric converters
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The basket with incombustible matter is placed to thermostat until the steady conditions set, at which indications of all thermoelectric converters stay put within 10 min or fluctuate with permanent amplitude near average temperatures t1, t2, t3. Correction DtT is calculated by formula: 2.2. Test sample should mark the average properties of investigated material. Testing the sheet material it is required to collect it in cup, fit to internal dimensions of the basket. It is required to drill the hole in diameter of (7,00,5) mm in the samples of solid material.
3. Test course

3.1. Fill testing sample into the basket. Set the thermoelectric converters in accordance with 2.1. Cap the basket and place it to the center of thermostat, heated to test preset temperature (e.g., 200 ). The average indication of thermoelectric converters 2 and 3 minus correction DtT is accepted as a test temperature. 3.2. Hold the sample in thermostat until spontaneous ignition occurs or (in case of spontaneous ignition failure) within time indicated in table 10. Table 10 Basket height, mm 35 50 70 100 140 200 Testing time for spontaneous ignition, h 6 12 24 48 96 192

Sample increase of temperature is accepted as a spontaneous ignition (as per indications of thermoelectric converter 1) up to (45050) . 3.3. If there is no spontaneous ignition in the first test within the time indicated in table 1, the next test with new sample shall be carried at temperature more. 3.4. If there is a spontaneous ignition in the first test, the next test with new sample shall be carried at temperature less (e.g., 20 less).
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3.5. The tests shall be repeated at different temperatures with the samples until they reach min. Temperature, at which spontaneous ignition occurs. The average value of these temperatures is accepted as a temperature of the sample spontaneous ignition for certain size. The same tests shall be carried for the tested material samples in the baskets of other sizes.
4. Result analysis

4.1. Quoted per test findings it is required to construct the graphs of spontaneous ignition temperature log against specific surface log and time prior to spontaneous ignition log (Fig. 2), which are generated by equation of line: ; ,

Fig. 5 where tc - temperature of spontaneous ignition, ; Ap, np, An, nn - rates, definable per test data; t - test length from the moment of sample and thermostat temperature equalization to the moment of spontaneous ignition, h; S - sample specific surface, m-1 , calculated by formula

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where F - total sample external surface, m2; V sample volume, m3.


5. Safety requirements

Due to exhalation of thermal decomposition toxic products the thermostat should be set in the separate room with forced-air-exhaust ventilation, providing the number of air exchanges at least eight. The operator station should meet the sanitary requirements as per GOST 12.1.005.
5.3.2 Experimental part

The tasks of experimental work of RRCCI SSE on this section are the following: I. To conduct internally-induced flammability test of TCO sulfur (at lack of moisture in the samples) at the environmental temperature corresponding to the hottest season of year within the area of sulfur storage (reference data). II. Test of moistened samples of TCO sulfur at the environmental temperature corresponding to the hottest season of year within the area of sulfur storage (reference data). III. Test if TCO sulfur samples contained sulfur dust on their surfaces at the environmental temperature corresponding to the hottest season of year within the area of sulfur storage (reference data). IV. Test of TCO sulfur samples in order to define its self-ignition temperature. On all variants we used the following equipment: - -type heater 3,5.3,5.3,5/3; - -4 type potentiometer: upper-range value 10 MB, chart strip velocity 20 mm/h; - -type thermocouples as per GOST 6616-74; - cubic stainless steel baskets; - ceramic beakers; - slide gauge; - -1-2 stopwatch as per GOST 5072-79. Pre-test activities:

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We cut out cubic samples of block sulfur with different size of their edges. The samples were accurately measured. We drilled a hole in each sample in order to install thermocouple there. The sulfur samples were placed to stainless steel baskets. While conducting the pilot tests we revealed that molten sulfur flows out from the baskets, although we selected the smallest. Therefore, in order to conduct the main tests, the baskets contained with sulfur samples were put into the ceramic beakers. Thermoelectric thermocouples were installed so, on thermocouple could measure the temperature in the center of sample, the second thermocouple could measure the temperature of beaker side and the third one could measure the air temperature around. If the temperature of environment spontaneously increased above the temperature of inside part of the oven, then its considered that the test sulfur inclines to self-ignition.

5.3.2.1 Internally-induced flammability test of TCO non-moistened sulfur samples if the environment temperature corresponds to the temperature of the boiler season of year within the sulfur storage area (reference data) (Variant 1) Test course

Sulfur samples were sustained at room temperature around 48 hours. In order to conduct the internally-induced flammability test the oven was heated up to 430 as this temperature is the maximum air temperature in Atyrau as per SNiP of RK 2.04-01-2001 Construction climatology , Astana, 2002. Then, ceramic beaker contained with the test sample was placed to the oven, thermocouple was connected to potentiometer and then the oven closed. The sample was stood in the oven until its self-ignition or if no self-ignition then the sample was stood in the oven within the time specified by the procedure for this dimension-type of sample. After we fixed evident features of ignition or after completion of the sustain process the oven was switch off. All data was registered with Test report (Appendix P).

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Table 11 Test experimental data


# of test sample Sample dimensions (as per basket size), mm Sample specific surface area, m-1 Thermoelectric converter readings, 0 Test tempe rature , Tine prior to selfigniti on, h 8 8 Test period, h

1 1 2 3 4 5 6 1 7 8 9

2 34 35 36 52 50 51 71 73 70 36 37 36 50 53 54 72 74 71 2 35 37 36 54 52 51 70 72 73

1 2 3 4 5 Sulfur from sulfur pad 4 171,5 43 43 117,7 43 43 84,1 44 44 Sulfur from sulfur pad 7 165,2 43 44 114,8 43 43 83,0 43 44 3 4 5 Sulfur from sulfur pad 9 166,8 43 44 114,7 43 43 83,7 43 44

3 6 44 43 45 44 44 44 6 44 44 44

7 43 43 44 44 43 44 7 44 43 44

9 6 12 24 6 12 24 9 6 12 24

Conclusion: On the basis of the tests conducted we can note that nonmoistened block sulfur does not incline to self-ignition at the temperature of 430.

5.3.2.2 Internally-induced flammability test of TCO moistened sulfur samples if the environment temperature corresponds to the temperature of the boiler season of year within the sulfur storage area (reference data) (Variant 2) Test course

Sulfur samples were soaked in water around 48 hours. In order to conduct the internally-induced flammability test the oven was heated up to 430 as this temperature is the maximum air temperature in Atyrau as per SNiP of RK 2.04-01-2001 Construction climatology , Astana, 2002. Then, ceramic beaker contained with the test sample was placed to the oven, thermocouple was connected to potentiometer and then the oven closed.
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The sample was stood in the oven until its self-ignition or if no self-ignition then the sample was stood in the oven within the time specified by the procedure for this dimension-type of sample. After we fixed evident features of ignition or after completion of the sustain process the oven was switch off. All data was registered with Test report (Appendix P). Table 12 Test experimental data
# of test sample Sample dimensions (as per basket size), mm Sample specific surface area, m-1 Thermoelectric converter readings, 0 Test tempe rature , Tine prior to selfigniti on, h 8 Test period, h

1 1 2 3 4 5 6 7 8 9

2 35 36 36 53 52 51 72 71 70 34 38 36 53 53 55 70 74 72 36 37 37 53 54 52 71 73 74

1 2 3 4 5 Sulfur from sulfur pad 4 168,3 42 43 115,4 43 43 84,5 42 43 Sulfur from sulfur pad 7 167 43 43 111,8 43 43 83,4 42 43 Sulfur from sulfur pad 9 163,7 44 44 113,2 43 43 82,6 43 43

3 6 43 44 44 44 44 43 44 44 44

7 43 43 43 43 43 43 44 43 43

9 6 12 24 6 12 24 6 12 24

Conclusion: On the basis of the tests we can note that moistened sulfur does not incline to self-ignition at the temperature of 430. 5.3.2.3 Test of TCO sulfur samples when there is sulfur dust in the surface with the risk of spontaneous ignition or its absence at the same temperature of environment as at storage area temperature within the boiler season of year (reference data) (Variant 3) Test operation

According to this variant, sulfur samples were sustained at room temperature around 48 hours; 2 mm thick layer of sulfur dust was placed to upper edge of the sample.
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In order to conduct the internally-induced flammability test the oven was heated up to 430 as this temperature is the maximum air temperature in Atyrau as per SNiP of RK 2.04-01-2001 Construction climatology , Astana, 2002. Then, ceramic beaker contained with the test sample was placed to the oven, thermocouple was connected to potentiometer and then the oven closed. The sample was stood in the oven until its self-ignition or if no self-ignition then the sample was stood in the oven within the time specified by the procedure for this dimension-type of sample. After we fixed evident features of ignition or after completion of the sustain process the oven was switch off. All data was registered with Test report (Appendix ).

Table 13 Test experimental data


Test sample No. Sample size (as per basket size), mm Sample specific surface area, m-1 Thermoelectric converter readings, 0 Test tempe rature , Time prior to selfigniti on, h 8 Test period, h

1 1 2 3 4 5 6 7 8 9

2 35 36 36 53 52 51 72 71 70 34 38 36 53 53 55 70 74 72 36 37 37 53 54 52 71 73 74

1 2 3 4 5 Sulfur from sulfur pad 4 168,3 43 43 115,4 43 43 84,5 43 44 Sulfur from sulfur pad 7 167 43 43 111,8 43 43 83,4 42 43 Sulfur from sulfur pad 9 163,7 44 44 113,2 43 43 82,6 43 43

3 6 44 44 44 44 44 43 44 44 44

7 43 43 44 43 43 43 44 43 43

9 6 12 24 6 12 24 6 12 24

5.3.2.4

Test of TCO sulfur samples in order to define its self-ignition temperature (Variant 4)

Test operation

In order to hold the internally-induced flammability test, the oven was heated up the required temperature. Then, ceramic beaker contained with the test
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sample was placed to the oven, thermocouple was connected to potentiometer and then the oven closed. The sample was stood in the oven until its self-ignition or if no self-ignition then the sample was stood in the oven within the time specified by the procedure for this dimension-type of sample. If the test sulfur spontaneously increased above air temperature within the oven, then it was considered that the test sulfur inclines to self-ignition. After we fixed evident features of ignition or after completion of the sustain process the oven was switch off. TCO sulfur from sulfur pad 7 was used for the test conduction. The first internally-induced flammability test was held using the smallest sample (edge length - 35 mm). The repeated tests using the same samples were conducted at temperature of 10-20 0 below of the first test temperature. These tests were repeated unless we defined two types of environment temperature distinguishing for 50, one temperature is conductive for sulfur self-ignition, and another one rejects such ignition. All data was registered with Test report (Appendix ). On the basis of the tests we defined the empirical dependence of self-ignition temperature of TCO sulfur on the ratio of the sample surface against its volume and on the ratio of the time to self-ignition. Table 14
Item No. Sample size (as per basket size), mm x 35 35 35 35 40 40 53 50 75 76 100 101 y 35 35 36 35 38 40 51 48 76 76 100 101 z 35 34 36 35 38 39 51 49 76 77 102 101 Sample specific surface area, m-1 s 171,4 173,1 169,8 171,4 155,3 151,3 116,2 122,5 79,3 78,6 59,6 59,4 Thermometer indications, 0 t1 239 230 210 219 211 206 205 200 195 191 192 184 t2 240 228 209 219 210 206 207 198 195 191 191 184 t3 239 230 209 220 210 205 205 200 196 190 191 185 Time prior Test period, to self- h ignition, h 0,17 0,42 0,67 1,08 1,63 2,75 4,25 0,17 0,42 6 0,67 1,08 6 1,63 12 2,75 24 4,25 48

1 2 3 4 5 6 7 8 9 10 11 12

Experimental data treatment. In order to graph the dependence of self-ignition temperature logarithm on the specific surface logarithm S and time logarithm before self-ignition , we can calculate lgS, lgtc and lg
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Table 15 S 170,6 153,3 119,3 79 59,5


tc 214 208 203 193 188

lgS 2,2320 2,1855 2,0766 1,8976 1,7745

lgtc 2,3304 2,3181 2,3075 2,2856 2,2742 Table 15

tc

0,17 0,42 0,67 1,08 1,63 2,75 4,25

239 229 219 210 206 195 191

lg 0,7696 0,3768 0,1739 0,0334 0,2122 0,4393 0,6284

lgtc 2,3784 2,3598 2,3404 2,3222 2,3139 2,2900 2,2810

On the basis of the calculations we can make the diagram.

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lgt c
2,35 2,34 2,33 2,32 2,31 2,30 2,29 2,28 2,27 2,26 2,25 lgS 1,50 1,60 1,70 1,80 1,90 2,00 2,10 2,20 2,30 2,40

Drawing 6. Diagram of dependence of TCO sulfur self-ignition temperature tc on the sample specific surface S.

lgt c
2,44 2,42 2,40 2,38 2,36 2,34 2,32 2,30 2,28 2,26 2,24 2,22

-1,20 -0,95 -0,70 -0,45 -0,20 0,05 0,30 0,55 0,80 1,05

lg

Drawing 7. Diagram of dependence of environment temperature tc, when self-ignition of TCO sulfur sample occurs, on the time before self-ignition .

where tc self-ignition temperature, ; - test period from leveling of the sample temperature and the oven temperature before solf-ignition, h; S sample specific surface, m-1.
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Using the diagrams we can calculate the parameters Ap, np, An, nn for the following equations: lgtc = + np lgS lgtc = + nn lg Parameter np equals to tangent of inclination of line lgtc = f( lgS) against the axis of abscisses, and parameter Ap equals to the segment intercepted by this line on the axis of ordinates. The parameters An and nn are defined by the same way, but for their calculation we use lgtc = f(lg ) graph. So, we got the following equations for TCO sulfur from sulfur pad 7: lgtc = 2,0622 + 0,1185lgS lgtc = 2,3265 + 0,0732 lg Using the data of above-mentioned dependences we can forecast the incline to heat self-ignition for any volumes of TCO block sulfur being in contact with environment in the test conditions. At the same time, the initial structure and physical state of the samples and the forecasting factors should be identical.

5.4 Conclusions on the experimental part I. Determination of linear velocity of sulfur combustion

1. The value of linear velocity of flame propagation of sulfur combustion calculated within the tests: - as per UNO methodic - 0,00422 m/min, - as per GOSTs methodic 12.1.044-89 - 0,00339 m/min In the scope of TCO contract 200369 Survey of impact of sulfur ground storage to environment, RSRCSCI SSI made the calculations (in 3 variants of possible fire situation on sulfur pads) for the forces and means for fire extinguishing on TCO sulfur pads. These calculations indicate the value of linear velocity of fire propagation as per the table analogues, specified in the reference book Guidelines for fire extinguishing, equaled to 0,8 m/min As per the calculation results we made the conclusion: . On all variants we defined adequate provision of the object liable to extinguishing with. Water yield of the fire line exceeds the required water flow (Q > Q).
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b. On all variants the number of fire hydrants located within the pad meets the required number of fire-engines (N. >N). c. Organizational-engineering opportunities of TCO Fire-Emergency Service (FES) are capable to provide the required number of fire-fighting means and personnel. Taking into consideration that the value of linear velocity of fire propagation, calculated by experimental way, is less than the value of such velocity, accepted in the calculations; so, the conclusion remains in force.
II. Determination of the conditions of heat self-ignition of TCO sulfur.

1. The numerous tests, where the state conditions of sulfur samples were changed (dry, wet, sulfur dust content on the sample surface), indicated that no sulfur self-ignition observed at the temperature of environment of 430. 2. With help of the mentioned dependences we can forecast the incline to heat self-ignition of any volumes of TCO block sulfur being in contact with the environment in the conditions approximate to the test conditions. At the same time, the initial structure and physical state of samples and forecasting objects should be identical. On the basis of above-mentioned RRCCI SSE considers the following: In the condition of full observance and if all necessary measures, stipulated by TCO Fire Safety System, are met then the risk of fire propagation on sulfur pads from small ignition up to major incident is practically excluded.

6. Resume and conclusion

1. Technical estimation of self-ignition of the block sulfur being stored on the ground as well as the estimation of common risk of repeated ignition indicates that the ignitions often occur by the following reasons: - different origin sparkles (sparkles of mechanical equipment, sparkles occurred at repair works - electric welding, autogenous welding, sparkles produced by motor transport or diesel locomotive passing by, etc.) - static electricity discharge, accumulation of static electricity on metal surfaces of equipment. - pyrophorus iron sulphides having occurred in sulfur pad, pyrophorus deposits, which arisen if sulfur-bearing crude oil and oil products are stored in metal reservoirs or other metal vessels.
111

2. The estimation of possible TCO opportunities on detection and liquidation of Tengiz block sulfur ignitions, which was made on the basis of Project and Operational documentation on Unit 600, and on the basis of the inspection of physical state of the sulfur pads and operational activity within each pad, in accordance with the methods of detection of sulfur pad ignitions and the set of fire preventive activities, allows us to make the following conclusions: a) The primary reasons of block sulfur ignition on TCO sulfir pads are: - sparkles occurred in sulfur pads from locomotives passing though neighboring rail way lines. - static electricity discharge, accumulated on metal surfaces of equipments (excavator bucket, shovel bucket) being used at sulfur processing with the purpose of its shipment. - pyrophorus iron sulphides occurred in sulfur pads. Pyrophorus deposits, which incline to self-ignition, are formed in the results of metal items occurred in the sulfur pads by different reasons: falsework components, metal debris, scrap, etc. b) TCO opportunities on detection and liquidation of Tengiz block sulfur ignition are identified in the set of fire-preventive measures on the sulfur pads, which stipulates for the following: - Visual control over any potential ignitions on the sulfur pads: * Special point-duty fireman, who monitors the fire situations at any operations within the sulfur pads, particularly when sulfur blocks processing. The point-duty fireman is equipped with either reporting facilities or with the primary fire-fighting equipment fire extinguisher. * Special mobile detachment consisting of fire-inspectors for visual control over sulfur pad conditions. Any information of ignition on the sulfur pads is reported by Unit 600 operators or by Group-4 employees. Awareness and ability of the personnel operating on the sulfur pads to execute all measures stipulated by appropriate TCO documents (Local Emergency Liquidation Plan on Unit 600 - LELP, job descriptions, etc.). - Equipping with the primary fire-fighting means (fire extinguishers) for special point-duty fireman.

112

- Ring fire-fighting water pipeline equipped with fire hydrants on the sulfur pad perimeter. Availability of TCO Fire-Emergency Service (FES), which as per its engineering and organizational features is efficiently capable to resolve all issues on prevention of fire development and its full liquidation. c) The reasons of sulfur ignition in most cases are the organizational defects committed by personnel and are subject to nullification (elimination the cases when false work elements occur on the sulfur pads, control over scrap and debris to be occurred, etc.). d) Necessity to develop the number of measures on maximum reduction or elimination of the cases when sparkles from locomotives passing nearby occur on the pads, control over static electricity to accumulate on the operating equipment. e) Lack of capacity of sulfur to instantaneous fire propagation, and the possibility of operative detection and liquidation of seat of fire in its initial stage. f) TCO existing possibilities whole complex of organizational and engineering fire-preventive measures on the sulfur pads allows resolving the issues on prevention of fire development and its full liquidation. 3. Total risk estimate of Tengiz sulfur ignition from small ignition to major incident and TCO emergency preparedness to liquidate such incidents, made using the Methods of estimation of forces and means for extinguishing possible fire (the estimations were made on three variants, considering the most possible forecasting situations) indicates the following: ) On all variants (variant 1 pad in the stage of its processing and shipment of block sulfur; variant 2 pad in the stage of pouring of liquid sulfur; variant 3 pad in the stage of storage of sulfur) we defined full provision of the object with all necessary means. While estimating we took into account the following factors: character of possible ignition of block sulfur, state of the Fire-Fighting System on the sulfur pads, possible variants of fire area forms (circle, angular, rectangular) and the possible variants of time of fire propagation. ) On all variants we determined that the water yield of fire water line exceeds the required water flow for fire-fighting (Q > Q). The number of fire hydrants, installed on the sulfur pads, meets the required number of fire-brigade trucks (N. >N), and the organizational-engineering abilities of TCO FireEmergency Service (FES) are capable to provide the required number of firefighting engines and personnel.

113

4. The determination of data on mechanisms of sulfur ignition by experimental way, conducted with the purposes to confirm the estimates made previousG for the fire-fighting forces and means (section 4), summarizes the y following:
) on linear velocity if fire propagation at sulfur combustion: The value of linear velocity of fire propagation is the main indication, on which the values of following indication depend: - geometry of fire for the certain period of time; - fire area; - required water flow; - required number of fire-fighting means (fire hydrants, fire equipments); - required number of personnel for fire extinguishing.

As the result of the tests for TCO sulfur samples (the samples from sulfur pads ## 4, 7, 9) we defined the value of linear velocity of fire propagation at sulfur ignition: on UNE methodology - 0,00422 m/min, on GOSTs methodology 12.1.044-89 - 0,00339 m/min The values of linear velocity of fire propagation at sulfur ignition, defined by the experimental way, are significantly below than the value accepted on Table data in the reference book Guidelines for fire extinguishing - V.l = 0,8 (m/min), and which was used in the above estimates.
In this connection, all tests allow to confirm all previously conducted estimates of TCO fire-preventive forces and means intended to detect and liquidate fire, as well as all conclusions made on the basis of these estimates. ) on conditions of sulfur self-ignition: The tests on definition of sulfur self-ignition on TCO sulfur samples (sulfur samples from the pads ## 4, 7, 9), where we changed the sample state conditions (wet, dry, sulfur dust contented), indicated that at the environment temperature of 430 (absolute maximum air temperature in Atyrau, as per the data of SNiP of RK 2.04-01-2001 Construction climatology, Astana, 2002) sulfur self-ignition does not occur. SUMMARY: On the basis of the above stated, RRCCI SSE considers that if the operating practices are observed and if all measures, stipulated by TCO Fire Safety System, are executed, then the risk of fire propagation at sulfur ground storage from small ignition up to major incident is practically excluded. The set of organizational and engineering fire-fighting measures, which is available on TCO sulfur pads, allows resolving all issues on prevention of fire development and its full liquidation.
114

ENCLOSURES

115

Enclosure A Historical information on fire incidents at sulfur pads Unit 600 Date of incident
10 November 2002 Fire at sulfur pad 4 16 August 2002 Fire at sulfur pad 2

Core reason of the previous investigation


Core reason not defined. Possible reason is a friction of loader bucket on surface of pad.

Recommendations
See 16 July 2005, point 1 To develop procedure for loading and transportation of small volume of crushed sulfur to be used in future at the plant.

Surface of pad was not moisturized before handling thus creating sulfur dust. Ensure all personnel of Unit 600 is familiar with procedure and understands risk involved when working with crushed No special procedure for this type of works. sulfur. 22 September 2003 Fire at sulfur pad 7 See 16 July 2005 point 3 new recommendations. Combustion was caused by strong wind due to spark To provide training and review of SI-129 and SI-104 for the generation after metal piece fell on the pad. Place of works personnel of contractual organization at Unit 600. was not prepared prior to start. To remove temporal roads (made of sulfur blocks) to berms of all sulfur pads or roads constructed using appropriate safe materials. Probably due to pyroforic compounds. See 16 July 2005 point 1-6 new recommendations. Recommendations were not recorded.

14 July 2003 Fire at sulfur pad 2 23 October 2003 Fire at sulfur pad 5

See 16 July 2005 point 1-6 new recommendations. Electrostatic charge was caused in the result of HITACHI To develop instructions for work of the personnel. excavator friction on sulfur surface. No special procedure for this type of works. To provide additional training on work with sulfur for Ariadna. Ariadna workers and U-600 operators should be made aware of the results of investigation. See 16 July 2005 point 1-6 new recommendations. Core reason high ambient temperature which caused Improve sulfur fire protection conditions. combustion of sulfur dust. 116

31 May 2004 Fire at sulfur pad 5

To start periodical monitoring and moisturizing of sulfur when working at sulfur pad 5. To provide one more toolbox talk with Ariadna employees and Operations personnel. To review results of investigation with Operations personnel and contractual agency. 03 January 2005 Fire at sulfur pad 8 Pouring arm Core reason pyroforic compounds. See 16 July 2005 point 1-6 new recommendations. Continuous monitoring during loading. After loading is complete to check the area for possible combustions. To follow fire extinguishing rules. 25 March 2005 Fire at sulfur pad 2 Core reason not defined. See 16 July 2005 point 1-6 new recommendations To provide special instructions for operators of loader. To start monitoring of the area by operators. To remove combustion. 09 April 2005 Fire at sulfur pad 2 construction garbage which may cause

See 16 July 2005 point 1-6 new recommendations. Pyroforic compounds got formed in the contact of fiber of To prohibit dump from Unit 400, 500. fibered-glass, metallic particles with sulfur. To provide fire arm for sulfur pad 2. Special instructions for operators. To review investigation results. See 16 July 2005 point 1-6 new recommendations.

117

18 April 2005 Fire at sulfur pad 9

Working area was cleaned timely. Fire safety rules were violated.

To remove construction garbage from sulfur pad 9. To develop procedure restricting works at the pad which leads to generation of construction garbage.

The work on sulfur treating was performed on the surface of pads. To provide the fire arm at all sections of sulfur pad. To perform Toolbox talk with operators regarding daily responsibilities with regard to monitoring and inspection of sulfur pads. To review investigation results with operating personnel. See 16 July 2005 point 1-6 new recommendations.

118

16 July 2005

ENCLOSURE B Historical information on fire incidents at sulfur pads Unit 600 (July 16, 2005) Determined core reasons Recommendations to be fulfilled at sulfur pad 2
No security and control provided for the access to sulfur pad 2. Not adequate training and understanding of environment protection procedures. Report on industrial wastes doesnt include information on different forms of sulfur and corresponding utilization sections. Sulfur pad the most unstable sulfur form. There is a potential generation of static electricity existing which may cause combustion. To stop storing contaminated sulfur of any kind at the sulfur pads and to provide security gates to prevent unathorized access to pad 2. To provide training for opersations personnel regarding requirements of Environmental protection and procedures on transportation of contaminated sulfur to the agreed area. To make corrections in the report on industrial wastes including different types of solid sulfur and the appropriate section of underground disposal. To make measurements and control sulfur moisturizing to reduce to minimum generation of dust when crushing and transporting sulfur. To organize periodical inspections to be ensure utilization and maintain control for sulfur dust To analyse the equipment failure at drums of sulfur granulation unit and conveyors. To fulfill recommendations to improve reliability of equipment.

Point 1 Point 2

Point 3

Point 4

Point 5

Frequent leaks in the system of drums and conveyors at sulfur granulation unit leads to leakage of large quantity of sulfur. Process and problems of maintenance of granulation unit are not quite clear. Operators dont fully understand the process of operations To make changes in procedures to be sure that equipment is parameters restriction. Operations mode is changed from hitch operated at its design capacity and number of leaks is reduced to hitch, operations management lacks consistency. to minimum.

Point 6

Operations personnel and contractor are not fully familiar with To provide training for Operations personnel and contractual sulfur physical properties and its most unstable state agency regarding sulfur units with stating the most unstable condition.

119

CAUSES OF SUSPICION OF SULFUR COMBUSTION FOR THE PERIOD 10 OCTOBER 2002 - 18 APRIL 2005

pyroforms 45%

air temperature 11%

electrostatic 22%

not determined 22%

120

ENCLOSURE D Short informative report on field activities of SSI RSRCSCI specialists, Shymket city State Subsidiary Institution Republican Scientific and Research Center on Safety in Chemical Industry

Group was working on the territory of TCO partnership within the period 11-13 May 2007 as per subject: Estimate of influence on population health and environment impact of open air sulfyur storage. Purpose of work: taking sulfur samples for Experimental testing and determination of spontaneous combustion conditions and sulfur fire propagation index. The samples of bulked suflur were taken from sulfur pads 4, 7 and 9. Pads were selected on the basis of term of sulfur storage and condition of pad: 4 is under handling, 7 is under storing, 9 is in pocess of sulfur pouring (blocks forming). Sulfur samples were packed in polymer bags. Total weight of samples was approximately 35 kg. SSI RSRCSCI specialists: Shadrova G, Nam G were working in field. From TCO U-600 consultant Zhakibaev B. Coordinatio and control provided by Nurgaliev M. and Titarenko L. from Environment protection department

SSI RSRCSCI specialists TCO HSE department Coordinator

. .

13.05.07

ENCLOSURE E APPROVED: SSI RSRCSCI Director

_____________. Sharafiev 31 May 2007 .

PROTOCOL determination of sulfur burning velocity as per UNO methodology Date - 26 May 2007 . Material - TCO sulfur, pad 4 Conditions in the premise: Temperature, 0 - 25 Athmospheric pressure, kpa - 0,0961 Relative humidity, % - 65 Length of sample to burn - 100 mm. Table Experimental data of testing.

of exp eri me nt 1 1 2 3 4 5 6

Date of Weight of sample, g experime of Before After nt pa testing testing d

Time of burning

Mass Burning of velocity sulfur m/min burnt. g 8 0,00306 0,00433 0,00455 0,00481 0,00451 0,00445

2 3 4 5 6 7 26.05.07 4 44 13,85 32 35 sec 30,15 26.05.07 4 57,11 17,76 23 05 sec 39,35 26.05.07 4 49,67 18,27 21 min 58 sec 31,40 26.05.07 4 48,35 18,15 20 min 45 sec 30,20 26.05.07 4 50,28 18,48 22 min 10 sec 31,80 26.05.07 4 49,86 18,14 22 min 28sec 31,72 Mean arithmetic burning velocity, m/min 0,00428

Deputy director SSI RSRCSCI Chief TFL Deputy chief TFL Chief specialist Engineer of high category Engineer of first category

G. Bashaev K. Sabdenov Sh. Azimov A. Khusainov G. Shadrova G. Nam


122

ENCLOSURE F APPROVED: SSI RSRCSCI Director

_____________. Sharafiev 31 May 2007 .

PROTOCOL determination of sulfur burning velocity as per UNO methodology Date - 28 May 2007 . Material - TCO sulfur, pad 7 Conditions in the premise: Temperature, 0 - 22 Athmospheric pressure, kpa - 0,096 Relative humidity, % - 65 Length of sample to burn - 100 mm. Experimental data of testing.

of exp eri me nt 1 1 2 3 4 5 6

Date of Weight of sample, g experime of Before After nt pa testing testing d

Time of burning

Mass Burning of velocity sulfur m/min burnt. g 8 0,00402 0,00422 0,00415 0,00424 0,00419 0,00403

2 3 4 5 6 7 28.05.07 7 53,00 17,00 24 min 51 sec 36,00 28.05.07 7 50,10 16,30 23 min 42 sec 33,80 28.05.07 7 49,70 13,98 24 min 06 sec 35,72 28.05.07 7 48,33 13,85 23 min 35 sec 34,48 28.05.07 7 51,26 16,24 23 min 52 sec 35,02 28.05.07 7 50,48 16,38 24 min 53 sec 34,10 Mean arithmetic burning velocity, m/min 0,00414

Deputy director SSI RSRCSCI Chief TFL Deputy chief TFL Chief specialist Engineer of high category Engineer of first category

G. Bashaev K. Sabdenov Sh. Azimov A. Khusainov G. Shadrova G. Nam


123

ENCLOSURE G APPROVED: SSI RSRCSCI Director

_____________. Sharafiev 31 May 2007 .

PROTOCOL determination of sulfur burning velocity as per UNO methodology Date - 29 May 2007 . Material - TCO sulfur, pad 9 Conditions in the premise: Temperature, 0 - 22 Athmospheric pressure, kpa - 0,096 Relative humidity, % - 65 Length of sample to burn - 100 mm. Experimental data of testing.

Date of Weight of sample, g of experime of Before After exp nt pa testing testing eri d me nt 1 2 3 4 5 1 29.05.07 9 55,87 22,89 2 29.05.07 9 47,81 13,32 3 29.05.07 9 53,51 16,55 4 29.05.07 9 50,95 16,22 5 29.05.07 9 49,85 17,02 6 29.05.07 9 49,25 16,71 Mean arithmetic burning velocity, m/min Deputy director SSI RSRCSCI Chief TFL Deputy chief TFL Chief specialist Engineer of high category Engineer of first category

Time of burning

Mass Burning of velocity sulfur m/min burnt. g 7 32,98 34,49 36,96 34,73 32,83 32,54 0,00425 8 0,00378 0,00444 0,00411 0,00456 0,00426 0,00437

6 26 min 25 sec 22 min 30 sec 24 min 20 sec 21 min 54sec 23 min 28sec 22 min 53sec

G. Bashaev K. Sabdenov Sh. Azimov A. Khusainov G. Shadrova G. Nam


124

ENCLOSURE H APPROVED: SSI RSRCSCI Director

_____________. Sharafiev 7 June 2007

PROTOCOL determination of sulfur fire propagation velocity as per GOST 12.1.044-89. Date - 30 May 2007 Conditions in the premise: Temperature, 0 - 26 Athmospheric pressure, kpa - 0,0962 Relative humidity, % - 65 Name of material

TCO sulfur, pad 4

Number of sample tested

Sample size, mm

Mean arithmetic time of burning, ,

1 32014020 78min 26sec 2 319,514119 76min 24sec 3 31913819,5 75min 00sec 4 320,513918 76min 06sec 5 318,414020 77min 36sec Mean arithmetic burning velocity, V,

Length of burnt section of sample, mm 270 270 270 270 270

Linear velocity of fire propagation, V, m/min 0,00345 0,00356 0,00360 0,00355 0,00349 0,00353

Deputy director SSI RSRCSCI Chief TFL Deputy chief TFL Chief specialist Engineer of high category Engineer of first category

G. Bashaev K. Sabdenov Sh. Azimov A. Khusainov G. Shadrova G. Nam

125

ENCLOSURE I APPROVED: SSI RSRCSCI Director

_____________. Sharafiev 7 June 2007

PROTOCOL determination of sulfur fire propagation velocity as per GOST 12.1.044-89. Date - 31 May 2007 Conditions in the premise: Temperature, 0 - 26 Athmospheric pressure, kpa - 0,0962 Relative humidity, % - 65 Name of material

TCO sulfur, pad 7

Number of sample tested

Sample size, mm

Mean arithmetic time of burning, ,

1 32213815 76min 49sec 2 32014119 84min 12sec 3 31913820 79min 35sec 4 31813918 80min 36sec 5 32114020 79min 12sec Mean arithmetic burning velocity, V, Deputy director SSI RSRCSCI Chief TFL Deputy chief TFL Chief specialist Engineer of high category Engineer of first category

Length of burnt section of sample, mm 270 270 270 270 270

Linear velocity of fire propagation, V, m/min 0,00353 0,00321 0,00342 0,00336 0,00343 0,00339

G. Bashaev K. Sabdenov Sh. Azimov A. Khusainov G. Shadrova G. Nam


126

ENCLOSURE J APPROVED: SSI RSRCSCI Director

_____________. Sharafiev 7 June 2007

PROTOCOL determination of sulfur fire propagation velocity as per GOST 12.1.044-89. Date - 31 May 2007 Conditions in the premise: Temperature, 0 - 26 Athmospheric pressure, kpa - 0,0962 Relative humidity, % - 65 Name of material

TCO sulfur, pad 9

Number of sample tested

Sample size, mm

Mean arithmetic time of burning, ,

1 317,514115 80min 36sec 2 32013919 83min 08sec 3 32214220 85min 31sec 4 321139,518 82min 22sec 5 31814020 85min 44sec Mean arithmetic burning velocity, V,

Linear velocity of Length of burnt section fire propagation, of sample, V, m/min mm 270 0,00336 270 0,00325 270 0,00318 270 0,00330 270 0,00316 0,00325

Deputy director SSI RSRCSCI Chief TFL Deputy chief TFL Chief specialist Engineer of high category Engineer of first category

G. Bashaev K. Sabdenov Sh. Azimov A. Khusainov G. Shadrova G. Nam

127

FIRE PROPAGATION VELOCITY FOR DIFFERENT MATERIALS

re t

ha ne R ub be rr es br e Fo am ed R ub be r Li gn um -fi fo ss ile po ly u in

Fl ax

Pa p

Su l

fu r

er

1 0.5 0 -0.5 -1 -1.5 -2 -2.5 -3

lgv

ENCLOSURE L Fire propagation velocity for different vaterials


Material Average fire propagation velocity, m/min (V) 4,30 1,25 1,10 0,80 0,65 0,25 0,0038

Flax-fibre* Rubber resin* Rubber* Foamed polyurethane* Lignum fossile* Paper* Sulfur** * - Reference data. ** - Experimental data.

lgV 0,633 0,097 0,041 -0,097 -0,187 -0,602 -2,420

ENCLOSURE M APPROVED: SSI RSRCSCI Director

_____________. Sharafiev 12 June 2007

PROTOCOL determination of TCO sulfur thermal spontaneous combustion conditions for samples without moisture as per methodology of GOST 12.1.044-89. Date - 1 - 9 June 2007. Name of tested matter TCO sulfur, pads 4, 7 and 9. Conditions in the premise: Temperature, 0 - 22 25 Athmospheric pressure, kpa 0,096 0,0961 Relative humidity, % - 65 66 Equipment used: - heat chamber SNOL 3,5.3,5.3,5/3; - potentiometer KSP-4 with top limit of measurements 10 MW, speed of diagram tape 20 mm/hour; - thermocouples THA as per GOST 6616-74; - containers made of stainless netwire of square shape; - ceramic laboratory cups; - caliper rule.

Dry sulfur samples were kept under indoor temperature during 48 hours before testing. Sulfur in heat chamber was heated up to 430. This is a maximum absolute air temperature in Atyrau as per SNIP (Sanitary Norms and Rules) of RoK 2.04-01-2001, Construction clymatology, Astana , 2002.
If temperature of tested sulfur was spontaneously increasing inside the heat chamber, then it was considered that tested sulfur intents to spontaneous combustion. 130

Table Experimental testing data.


Number of tested sample Size of sample (as per the size of container), mm Specific surface of sample, m-1 Readings of thermoelectric converter, 0 Testin g tempe rature , Time Test till duration, spont hour aneou s comb ustion , hour 8 9 6 12 24 6 12 24 6 12 24

1 1 2 3 4 5 6 7 8 9

2 34 35 36 52 50 51 71 73 70 36 37 36 50 53 54 72 74 71 35 37 36 54 52 51 70 72 73

1 2 3 4 5 Sulfur from pad 4 171,5 43 43 117,7 43 43 84,1 44 44 Sulfur from pad 7 165,2 43 44 114,8 43 43 83,0 43 44 Sulfur from pad 9 166,8 43 44 114,7 43 43 83,7 43 44

3 6 44 43 45 44 44 44 44 44 44

7 43 43 44 44 43 44 44 43 44

Conclusion: Spontaneous increase of sulfur temperature under ambient temperatute 430 was not observed, spontaneous combustion did not take place.

Deputy director SSI RSRCSCI Chief TFL Deputy chief TFL Chief specialist Engineer of high category Engineer of first category

G. Bashaev K. Sabdenov Sh. Azimov A. Khusainov G. Shadrova G. Nam

131

ENCLOSURE N APPROVED: SSI RSRCSCI Director

_____________. Sharafiev 12 June 2007

PROTOCOL determination of TCO sulfur thermal spontaneous combustion conditions for samples containing moisture as per methodology of GOST 12.1.044-89. Date - 1 - 9 June 2007. Name of tested matter TCO sulfur, pads 4, 7 and 9. Conditions in the premise: Temperature, 0 - 22 25 Athmospheric pressure, kpa 0,096 0,0961 Relative humidity, % - 65 66 : - heat chamber SNOL 3,5.3,5.3,5/3; - potentiometer KSP-4 with top limit of measurements 10 MW, speed of diagram tape 20 mm/hour; - thermocouples THA as per GOST 6616-74; - containers made of stainless netwire of square shape; - ceramic laboratory cups; - caliper rule.

Samples of sulfur were kept in water during 48 hours before testing. Sulfur in heat chamber was heated up to 430.

132

This is a maximum absolute air temperature in Atyrau as per SNIP (Sanitary Norms and Rules) of RoK 2.04-01-2001, Construction clymatology, Astana , 2002.
If temperature of tested sulfur was spontaneously increasing inside the heat chamber, then it was considered that tested sulfur intents to spontaneous combustion.

Table Experimental testing data.


Number of tested sample Size of sample (as per the size of container), mm Specific surface of sample, m-1 Readings of thermoelectric converter, 0 Testin g tempe rature , Time Test till duration, spont hour aneou s comb ustion , hour 8 9 6 12 24 6 12 24 6 12 24

1 1 2 3 4 5 6 7 8 9

2 35 36 36 53 52 51 72 71 70 34 38 36 53 53 55 70 74 72 36 37 37 53 54 52 71 73 74

1 2 3 4 5 Sulfur from pad 4 168,3 42 43 115,4 43 43 84,5 42 43 Sulfur from pad 7 167 43 43 111,8 43 43 83,4 42 43 Sulfur from pad 9 163,7 44 44 113,2 43 43 82,6 43 43

3 6 43 44 44 44 44 43 44 44 44

7 43 43 43 43 43 43 44 43 43

Conclusion: Spontaneous increase of sulfur temperature under ambient temperatute 430 was not observed, spontaneous combustion did not take place.

Deputy director SSI RSRCSCI Chief TFL Deputy chief TFL Chief specialist Engineer of high category Engineer of first category

G. Bashaev K. Sabdenov Sh. Azimov A. Khusainov G. Shadrova G. Nam

133

ENCLOSURE O APPROVED: SSI RSRCSCI Director

_____________. Sharafiev 12 June 2007

PROTOCOL determination of TCO sulfur thermal spontaneous combustion conditions for samples having sulfur dust as per methodology of GOST 12.1.044-89. Date - 1 - 9 June 2007. Name of tested matter TCO sulfur, pads 4, 7 and 9. Conditions in the premise: Temperature, 0 - 22 25 Athmospheric pressure, kpa 0,096 0,0961 Relative humidity, % - 65 66 Equipment used: - heat chamber SNOL 3,5.3,5.3,5/3; - potentiometer KSP-4 with top limit of measurements 10 MW, speed of diagram tape 20 mm/hour; - thermocouples THA as per GOST 6616-74; - containers made of stainless netwire of square shape; - ceramic laboratory cups; - caliper rule.

Before testing sulfur samples were covered with 2 mm layer of sulfuric dust. Sulfur in heat chamber was heated up to 430. This is a maximum absolute air temperature in Atyrau as per SNIP (Sanitary Norms and Rules) of RoK 2.04-01-2001, Construction clymatology, Astana , 2002.
134

If temperature of tested sulfur was spontaneously increasing inside the heat chamber, then it was considered that tested sulfur intents to spontaneous combustion.

Table Experimental testing data.


Number of tested sample Size of sample (as per the size of container), mm Specific surface of sample, m-1 Readings of thermoelectric converter, 0 Testin g tempe rature , Time Test till duration, spont hour aneou s comb ustion , hour 8 9 6 12 24 6 12 24 6 12 24

1 1 2 3 4 5 6 7 8 9

2 35 36 36 53 52 51 72 71 70 34 38 36 53 53 55 70 74 72 36 37 37 53 54 52 71 73 74

1 2 3 4 5 Sulfur from pad 4 168,3 43 43 115,4 43 43 84,5 43 44 Sulfur from pad 7 167 43 43 111,8 43 43 83,4 42 43 Sulfur from pad 9 163,7 44 44 113,2 43 43 82,6 43 43

3 6 44 44 44 44 44 43 44 44 44

7 43 43 44 43 43 43 44 43 43

Conclusion: Spontaneous increase of sulfur temperature under ambient temperatute 430 was not observed, spontaneous combustion did not take place.

Deputy director SSI RSRCSCI Chief TFL Deputy chief TFL Chief specialist Engineer of high category Engineer of first category

G. Bashaev K. Sabdenov Sh. Azimov A. Khusainov G. Shadrova G. Nam

135

ENCLOSURE P APPROVED: SSI RSRCSCI Director

_____________. Sharafiev 26 June 2007

PROTOCOL determination of TCO sulfur thermal spontaneous combustion as per methodology of GOST 12.1.044-89. Date - 10 - 22 June 2007. Name of tested matter TCO sulfur, pads 4, 7 and 9. Conditions in the premise: Temperature, 0 - 23 26 Athmospheric pressure, kpa 0,096 0,0961 Relative humidity, % - 65 66 Equipment used: - heat chamber SNOL 3,5.3,5.3,5/3; - potentiometer KSP-4 with top limit of measurements 10 MW, speed of diagram tape 20 mm/hour; - thermocouples THA as per GOST 6616-74; - containers made of stainless netwire of square shape; - ceramic laboratory cups; - caliper rule.

Table Experimental testing data.


Sl Size of sample, no mm x 35 35 35 y 35 35 36 z 35 34 36 Specific surface of sample, m-1 s 171,4 173,1 169,8 Readings of thermometer, Time till Test 0 spontaneous duration, combustion, hour hour t1 t2 t3 239 240 239 0,17 0,17 230 228 230 0,42 0,42 210 209 209 6 136

1 2 3

4 5 6 7 8 9 10 11 12

35 40 40 53 50 75 76 100 101

35 38 40 51 48 76 76 100 101

35 38 39 51 49 76 77 102 101

171,4 155,3 151,3 116,2 122,5 79,3 78,6 59,6 59,4

219 211 206 205 200 195 191 192 184

219 210 206 207 198 195 191 191 184

220 210 205 205 200 196 190 191 185

0,67 1,08 1,63 2,75 4,25 -

0,67 1,08 6 1,63 12 2,75 24 4,25 48

Deputy director SSI RSRCSCI Chief TFL Deputy chief TFL Chief specialist Engineer of high category Engineer of first category

G. Bashaev K. Sabdenov Sh. Azimov A. Khusainov G. Shadrova G. Nam

137

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