Solving Stability Problems from PKN Orlens Residue Hydrocracker

Ireneusz Bedyk, Polski Koncern Naftowy Orlen SA, Poland; James Colyar, IFP North America, INC., USA; Iwona Skret, Institute of Petroleum Processing, Poland; Lawrance Wisdom, IFP North America, INC., USA

Abstract
A method selection of residual product processing, especially that of vacuum residuum, becomes more and more important recently but creates a serious technical and economic challenge for every refinery. One of possible approaches to this issue is an hydrocracking and hydrodesulfurization process of vacuum residue, H-Oil, offered by IFP (Axens) Company. This paper shows some aspects concerning stability of products received from the process when processing vacuum residue derived from Ural crude oil. Taking proper corrective measures in the process itself and respective product preparation we succeeded to improve product stability caused by specific chemical composition of vacuum residue received from Ural crude oil.

1 Introduction
The radical constrains referred to environment protection regulations and the resulting limits for harmful substances emissions have brought the violent increase of quality requirements for fuels produced in petroleum refineries, during the last 10 years. It concerns the motor fuels and fuel oils. The necessity of substantial emissions decrease from power stations has forced the direct impact on fuels structure change. Heavy fuel oils are gradually replaced with light oils and fuel gas. The growth of demand for middle distillates is observed in result of these changes (motor fuel oils and light fuel oils). In parallel the low sulphur fuels are required. The very rigorous requirements for low sulphur residue fuel oils are difficult to fulfil and strongly influence the whole crude oil processing scheme and residue oils disposal The one problem solution may be the residue oil hydrocracking and hydrodesulphurisation.In this process the desulphurised residue oil and motor fuel distillates are obtained. The product properties depend on process conditions and conversion. In commercial scale two residue hydrocracking processes are used: LC-Fining (ABB Lummus Global) and H-Oil (IFP). The seventh H-Oil Plant was started up in PKN Orlen SA refinery, in Plock, Poland, in 1999. The Unit is processing vacuum residue from Russian Ural crude oil.

2 H-Oil process characteristic

Process H-Oil with ebullated-bed reactor was invented by HRI in the mid-1960s to overcome problems experienced by fixed-bed processes when processing heavy or dirty feedstocks. To fully develop and commercialise the process, HRI teamed-up with Cities Service R&D (CSRD). This effort resulted in the construction and successful operation of a 2,500 BPSD demonstration plant at Cities Lake Charles refinery in 1963 and the licensing of the first commercial plant to the Kuwait National Petroleum Corp. In 1981, HRI teamed up with Texaco to continue the development and marketing of the process. Then in 1995 HRI became part of the IFP family. Today HRI/IFP is the sole licensor for both the H-Oil and T-Star Processes. Ebullated-bed reactors have the unique characteristics of CSTR type operation and a fluidised bed of catalyst. This results in the ability to handle reaction exotherms, solids containing feedstocks and for providing a flexible operation for changing feedstocks and operating objectives.

The typical operating conditions for the H-Oil Process are shown in Table 1. It is a high pressure, high temperature process. The lowest operating temperatures utilised are approximately those used at the fixed-bed EOR conditions. The operating pressure is relatively high to insure a sufficient reactor outlet hydrogen partial pressure, resulting in stable operation. The catalyst replacement rate in the H-Oil Process is typically 1.0 kg of catalyst per ton of feed which is equivalent to one to three percent of the inventory in the H-Oil Reactors. Commercial H-Oil Plants have been designed with a feedstock throughput of up to 34,00 BPSD in a single train. With the use of even larger H-Oil reactors, throughputs of over 40,000 BPSD are possible and are being evaluated. Table 1. H-Oil Process Operating Conditions Temperature, Pressure, Catalyst Space Velocity, Catalyst Replacement Rate, Single Train Throughput, C bar h-1 kg/t feed BPSD 415 - 440 170 - 210 0.4 - 1.3 0.3 - 2.0 Up to 34,000

Typical process performance and yields for the H-Oil Process are shown in Table 2. The ranges shown are for a two-stage operation at a typical space velocity and catalyst replacement rate. Most commercial H-Oil Process applications are in the 50-70 %(V/V) residue conversion range with a desulphurisation level of approximately 70 - 85 (m/m). H-Oil performance for both the standard or first generation catalyst and for the newer, second generation catalyst are shown in Table 2. The chemical hydrogen consumption for the H-Oil Process is typically 200 Nm3/m3 of feed or 1,200 SCF/Bbl. Relative to fixed-bed processes, this value appears high, however most of the additional hydrogen is a result of the higher hydroconversion severity of the vacuum residue feedstock with H-Oil. The hydrogen efficiency of the H-Oil Process is nearly as high as the fixed bed processes. Table 2. H-Oil Process Performance Performance: Residue Conversion, %V/V Hydrodesulphurisation, %m/m CCR Conversion, %m/m Nitrogen Removal, %m/m Metals Removal, %m/m Chem H2 Consumption, m3/Nm3 2nd Generation 1st Generation Catalyst Catalyst 45 90 45 - 85 55 - 80 75 - 92 45 - 65 65 - 75 25 - 35 30 - 50 65 -90 130 - 300

Typical gas and liquid yields, based on a Russian vacuum residue and for two-stage in series operation at 68 %V/V (538C+ basis) conversion are shown in Table 3. The H-Oil Process has good selectivity to middle distillates and vacuum gas oil. Other yields would include H2S, NH3 and H2O formed from heteroatom removal reactions. The yield pattern is a strong function of the level of residue conversion. At higher conversions, the selectivity towards lighter products, including light gases, increases. The unconverted residue from the H-Oil Process is upgraded relative to the vacuum residue in the feedstock and thus has a greater utility and value. This unconverted residue can be utilised for the production of a stable, heavy fuel oil product, for cocker feedstock (one-stage conversion type operation), for feed to a residue FCC Unit or can be blended into an asphalt product.

Table 3. Typical H-Oil Process Yields %(m/m) Product: C1 C4, C5 180C, 180 370C, 370 538C, + 538C , C4+, 3.5 6.3 25.5 33.9 28.8 94.5 %(V/V) 8.7 29.8 36.3 28.9 102.7 density kg/m3 726 864 942 100.6 0.914 Sulphur cont. %(m/m) <0.01 0.05 0.21 0.91 0.36

PKN Orlen H-Oil Plant was started up in 1999. It is two stages process, with capacity 225 tons of vacuum residue /hour. The unit process scheme is shown on Figure1.

Tail Gas

Treated Gas Treated Gas Treated Gas

PSA
Amine Amine Amine Amine Amine

LPG LPG LPG LPG LPG

Feed H2FEED Hydrogen

Make up

DEA

SPOGAS
H2S

NPSSTK NPSSLP
Naphtha Reactors Fuel Gas

VRREC
Atm. Fractionator Diesel LVG HVG HVG Sour water rec. Catalyst VGO VGO

Feed Vacuum Residue

Vacuum Tower Vacuum Residue

Recycle

Figure 1. PKN Orlen H-Oil Plant process scheme. The main operating conditions and product yields are shown in table 4.

Table 4. PKN Orlen H-Oil Reactor 1 Operating conditions: - Temperature, - Pressure, - Catalyst Space Velocity, - catalyst Replacement Rate, - Hydrogen Consumption, - Process Conversion, Product yields, % (m/m) - H2S - Dry gas - LPG - Gasoline - Gas Oil - Vacuum Oil - Vacuum Residue C MPa h-1 kg/t of feed 3 3 Nm /m of feed % (V/V) 415 18.1 0.84 1.4 186 53 2 1 1 5 12 27 52 Reactor 2 417 17.7

3 PKN ORLEN H-Oil Plant feed and products characteristics

Properties of the vacuum residuum from Ural crude oil fed to the distillation process are shown in the table 5 and basic product specifications in the table 6. Table 5. Properties of the feedstock for H-Oil process in PKN Orlen Results Properties: Density at 15C, Viscosity at 180C, %(V/V) recovered at 538C, 5%(V/V) recovered at:, Sulphur content, Nitrogen content, Ni content, Fe content, V content, Mo content, Na content, Ca content, Carbon residue CCR, n-C7 insoluble content, Toluene insoluble content, C content, H content Total existent sediment Ash content kg/m3 mm2/s %(V/V) C %(m/m) %(m/m) mg/kg mg/kg mg/kg mg/kg mg/kg mg/kg %(m/m) %(m/m) %(m/m) %(m/m) %(m/m) %(m/m) %(m/m) 1.008 26.4 10.38 517 2.79 0.5551 58 32 176 <2 18.8 2.3 19.02 5.69 0.036 86.71 9.81 <0.01 0.023 Test method EN ISO 12185 ASTM 4052 ISO 3104 ASTM D 2983 ASTM D 1160 ASTM D 1160 ISO 8754 ASTM D 4294 ASTM D 4629 HRI 105 HRI 105 HRI 105 HRI 105 HRI 105 HRI 105 EN ISO 10370 ASTM D 4530 UOP 614 UOP 614 ASTM D 5291 ASTM D 5291 ASTM D 4870 ISO10307-1 EN-ISO 6245 ASTM D 482

Table 6. Specification of basic products from H-Oil process in PKN Orlen Product: Properties: Density at 15C, Boiling range, Sulphur content, Nitrogen content, Research octane number, Vapour pressure, kg/m3 C %(m/m) %(m/m) RON kPa Gasoline 725 40-185 0.017 0.0088 57.0 39.0 7.0 93.0 Gas oil 846 185-370 0.0865 0.1334 45.0 2.50 29.2 4.0 1.5 34.7 6.0 0.052 Vacuum oil 930 0.41 0.340 7.32 41.6 +18 Vacuum residue 987.3 1.01 0.505 176.0 40.9 +15 50.5 15.67 Test method EN-ISO 12185 ASTM 4052 EN-ISO 3405 ASTM D 86 ISO 8754 ASTM D 4294 ASTM D 4629 EN 25164 ASTM D 2699 pr EN 13016-1 ASTM D 5191 ISO 3837 ASTM D1319 EN ISO 4264 ASTM D 4737 ASTM D 445 EN ISO 3104 IP 391/95

Hydrocarbons type content, %(V/V) -aromatics -saturated Cetane index Viscosity at 40C, at 100C Aromatic content: -monoaromatic -diaromatic -poliaromatic -total Bromine index, (mm2/s) (mm2/s) %(m/m)

gBr/100g

Carbon residue (on 10% distillation residue), %(m/m) Caloric capacity MJ/kg Pour point, V content, Carbon residue, CCR C mg/kg %(m/m)

ISO 3839 ASTM D 1159 EN ISO 10370 ASTM D 4530 ASTM D 240 IP 12 ISO 3016 ASTM D 97 ASTM D 1548 EN ISO 10370 ASTM D 4530

Using the H-Oil process we receive from vacuum residue with 2.5 %(m/m) sulphur content not only desulphurised below 1 % S vacuum residue and vacuum oil cut with 0.4 % (m/m) but also a quite high yield of motor fuel distillates like gas oil and naphtha. A product specification and current market demand decide how to use these products. In the PKN Orlen vacuum fractions from this process are applied directly as plant heaters' fuels. They are preparing to start with sale of a low sulphur heavy fuel oil with maximum 1 % S. The gas oil cut with its very high nitrogen content, rather high sulphur and aromatics content and low cetane number cannot be directed straight for blending of automotive diesel oil as specified by the European Standard EN 590. Mostly it is a component of the light fuel oil. Naphtha in PKN Orlen is fed to ethylene plant. Too high nitrogen and sulphur content in this cut does not allow to process this naphtha on a catalytic reforming plant; a naphtha hydrotreating would be needed. At first after H-Oil plant start-up in PKN Orlen a bad stability of the gas oil fraction hindered to blend it into light fuel oil. Some problems created stability of desulphurised vacuum residue as well and this

problem arisen too at low sulphur residual fuel oils containing vacuum fraction derived from H-Oil process. This situation has been clearly improved by adopting of proper measures in the process itself and by respective product preparation.

4 Stability problems of H-Oil process products in PKN Orlen 4.1 General

Catalytic residue hydrocracking is characterised by the conversion of the higher molecular weight constituents typically boiling above 524 C+ in a feedstock to lower-boiling products. R - CH2 CH2 R + H2 R - CH3 + R - CH3

Such treatment requires severe processing conditions and the use of high hydrogen pressure to minimise polymerisation and condensation reactions that lead to coke formation. In addition, hydrogenation reactions are also taking place that leads to saturation of alkenes and aromatic type compounds, and the removal of heteroatoms such as nitrogen, sulphur and metals. In a mixture as complex as a residue or heavy oil, the reaction pathways can only be discussed in general terms because of difficulties in analysing the complex nature of the molecules that make-up the feedstock and products. In maximising the conversion of residue to distillates, the operator needs to maintain conditions that lead to stable operations, which are generally measured by the level of sediment (ISO 10307 method) in the downstream fractionator bottoms. Stability is a term used to describe the ability of the residue to remain in storage over extended periods of time without appreciable deterioration as measured by the deposition of insoluble solid material, usually referred to as sediment. In lighter distillate fractions, colour degradation and gum formation is an indication of instability. The formation of sediment or insoluble material in a residue hydrocracker is generally thought to occur in one of two ways; (a) condensation of hydrocarbons followed by dehydrogenation to form a coke material, and (b) the precipitation of asphaltenes due to insolubility within the liquid product. The formation of coke in (a) above is irreversible. The later form of sediment (b) is reversible through the addition of solubilisers such as polar aromatics or resins. Maintaining a high ratio of polar aromatics to asphaltenes in the product residue will ensure good operation and minimise possible fouling in downstream fractionation equipment. To obtain a good stable operation, the operator must monitor the relative rate of conversion of both resins (polar aromatics) and asphaltenes as well as the concentration of asphaltenes and resins in the feedstock. Many feedstocks have very low resin to asphaltene ratios and therefore are difficult in maintaining good operability especially when the conversion level is increased. Although a low ratio of resins to asphaltenes in a residue feedstock is an initial indicator of potential fouling in a residue hydrocracker, it is not a universal predictor of sediment formation. Other factors such as the relative reactivity of the asphaltenes and resins, the molecular size of the unconverted asphaltenes and the solubilising power of the unconverted resins are also important. Other feedstocks which have high concentrations of resins relative to asphaltenes, such as the Ural vacuum residue, typically produces high levels of sediment during operations at a moderate conversion level. As previously discussed, the molecular structure of the resin and asphaltene molecules and their relative reaction rates play a critical role with these unique feeds.

4.2 Adjustment of H-Oil process to properties of feed from Ural crude oil
To maximise economic return, the operator is will increase residue conversion in order to maximise distillate yield. However the level of conversion must be weighed with the maximum amount of fouling in downstream equipment which can be tolerated. At the PKN Orlen Plant, a balance approach was taken to minimise the fouling effects. Enhancements were made to the downstream fractionation equipment and a small amount of Heavy FCC Cycle Oil, with its high polar aromatic content, was added to increase the stability of the bottoms product. Figure 2 shows the effect of adding a small amount of Heavy FCC Cycle Oil to the unconverted bottoms.

1 0,9 0,8 0,7 0,6 0,5 0,4 0,3 0,2 0,1 0 0 20 40 60 80 100 Heavy FCC Cycle Oil in Blend with Vacuum Residue from PKN Orlen [%m/m] Simple Dilution Line

Figure 2. Influence of Heavy FCC Cycle Oil on stability of H-Oil vacuum residue Catalyst formerly used in the process was in a next step replaced and ensured higher stability of vacuum residue but caused reduction of the process conversion. Further improvements can be accomplished by minimising reactor severity. This is done by using vacuum bottoms recycle which concentrates the reactants in the reactors system and lowers the reactor weighted average bed temperature for a given level of conversion. Improvements in recycle cup design will lead to better gas/liquid separation and reduce gas hold up in the reactor system thus leading to lower severity at a given level of conversion. Catalyst development is currently focused on balancing the relative reaction rates of resins and asphaltenes in order to minimise sediment formation while achieving high levels of conversion and HDS.

4.3 Evaluation of product stability from the process in PKN Orlen and adopted measures for improvement
Investigation and observed behaviour of particular products from H-Oil process just after the plant in PKN Orlen start-up have shown that gas oil distillate with a boiling range 180-370 oC or even 180o 350 C darkens quickly under influence of atmospheric factors; from this fuel precipitated a considerable amount of deposits. The same phenomena was observed when storing commercial products made with the gas oil distillate from this process. Desulphurised vacuum residue contained substantial quantity of insoluble deposits and also indicated a tendency for asphaltene sedimentation and stratification. It occurred even more intensively at blending of these distillates with other components used for fuel oils.

Stability of gas oils and desulphurised vacuum residue improved considerably by better process control though earlier observed darkening tendency, deposits precipitation and stratification still occur. Stability of naphtha cut meets basic requirements set for motor fuels. Results of stability determination for basic products of this process are indicated in the Table 7. It was found also that stability of gas oil distillate from H-Oil could be additionally improved by lowering the boiling end point of this oil when used for light fuel oil. Satisfactory stability of light fuel oil can be obtained also with H-Oil component reduced to 15-20 %(m/m.) in this fuel. It is confirmed by results shown in the Table 8. Still a problem remains for a long term storage of H-Oil vacuum residue and low sulphur fuel oils made with products from this process. Considerable changes in viscosity of a blend made from 90 %(m/m) of H-Oil vacuum residue and 10 % (m/m) of a Dark Slope Oil kept 40 days at 100 C, are presented as an example in the Table 9. Table 7. Results of stability determination for H-Oil process products in PKN Orlen Gasoline Properties: Oxidation stability, min Gum cont. (solvent washed), mg/100ml Potential residue, mg/100ml Oxidation stability, g/m3 (16h, 95C, 3% O2), Stability, (180 min., 150C) -colour, before/after -reflectance, % Total existent sediment, %(m/m) Potential sediment, ( 24h, 100C) %(m/m) Accelerated sediment (n-C16, 1h,100C) %(m/m) Flocculation ratio, p-Value Compatibility >660 <1 5 3.4 3.0/8.0 70.6 0.31 0.46 0.64 1.2 2 Gas oil Vacuum residue Vacuum oil 50% Vacuum residue 50% 0.17 0.48 ISO 10307-2` 0.50 1.2 3 Scanraff Met. ASTM D 4740 Test Method

EN ISO 7536 EN ISO 6246 ASTM D 873 EN ISO 12205 ASTM D 2274 ASTM D 6468 ISO 10307-1 ASTM D 4870 ISO 10307-2

Table 9. Influence of storage time at 100 C temperature on kinematic viscosity of a blend of H-Oil vacuum residue [90 %(m/m)] and Dark Slope Oil [(10 %(m/m)] Time of storage: days 0 10 20 30 40 Viscosity at 100 C, mm2/s Upper layer Lower layer 122.8 122.8 129.2 142.4 134.5 169.0 137.8 173.6 139.2 188.7

Table 8. Influence of storage time on stability of H-Oil gas oil distillate and on commercial basic fuel oil containing this distillate Product: Time of storage**: Properties: Bromine index, gBr/100g Sulphur content, %(m/m) Total Nitrogen content, mg/kg Basic Nitrogen content, %(m/m) Stability by ASTM D 2274 (16h, 95 C, 3% O2) -deposits, g/m3 Stability by ASTM D 6468 (180 min., 150C) -colour, before/after -reflectance Deposits after storage, % g/m3 0 6.0 865 1334 0.085 3.4 gas oil 180-370C 10 days 5.9 857 1308 0.085 4.2 4 weeks 5.6 853 1272 0.085 5.2 6 weeks 5.6 835 1204 0.85 5.4 0 4.4 571 1000 0.056 2.8 gas oil 180-350C 10 days 3.5 4 weeks 4.2 6 weeks 4.3 gas oil 15%(m/m) domestic fuel (base) 85%(m/m) 0 10 days 4 weeks 2.0 632 623 0.024 1.8 (1.4)* 2.0 590 602 0.024 2.0 (1.6)* 1.9 588 593 0.024 4.0 (1.8)*

3.0/8.0 70.65 -

3.5/8.0 63.45 1.4

3.5/8.0L 63.00 2.8

3.5/8.0L 63.7 2.9

2.5/5.5 80.51 -

3.0/6.0 74.13 1.0

3.0/6.0 71.6 2.1

3.0/6.0 71.5 2.2

1.5/3.0 2.0/3.0 2.0/3.0 (1.0/1.5)* (1.0/2.0)* (1.5/2.0)* 88.1 89.75 89.75 (92.1)* (91.9)* (90.2)* 1.3 2.2 (0.3)* (0.6)*

* - 100% domestic fuel **- Stored in glass containers in a laboratory space (temperature 17-20C)

In order to find possibilities for further stability improvement of gas oil from this process, and especially that of basic fuel oils containing this distillate, tests were carried out - to use antioxidation additives - to hydrotreat H-Oil gas oil distillates and basic light fuel oils containing this distillate Effectivity of many additives tested appeared, however, to be insufficient. An interesting experience was gained at hydrotreating process of H-Oil gas oil distillate. The process was carried out on a typical middle distillates hydrodesulphurisation plant with a catalyst bed composed of 15 % NiMo catalyst and 85 % CoMo catalyst. The process parameters during a test run are shown in the table 10. Very drastic severity of process parameters (mode II and III) was used with purpose of determination a possible nitrogen compounds removal from the feed on the existing HDS plant. Table 10. Hydrotreating process parameters for H-Oil gas oil distillate Severity: Average Bed Temperature, C Pressure in the reactor, bar - inlet - P Catalyst Space Velocity, h-1 3 H2/feed, Nm /m2 I 360 40 11 3 135 Process parameters II 380 35 7 2.2 230 III 405 33 4.5 1.4 830

Properties of obtained hydroraffinates are shown in the Table 11. Table 11. Basic properties of H-Oil gas oil hydroraffinates Feed Properties: Boiling range, C Sulphur content, mg/kg Total nitrogen content, mg/kg Basic Nitrogen content, %(m/m) Bromine Index, gBr/100g Aromatics content, %(m/m) - monoaromatics - diaromatics - poliaromatics - total 184-370 865 1334 0.085 6.0 29.2 4.0 1.5 34.7 Process Parameters: I II III 175-370 152-360 146-356 127 <50 <50 1069 921,880 618 0.058 0.047 0.027 2.4 2.4 2.4 33.8 6.4 1.9 42.1 32.0 8.0 2.2 42.2 28.5 9.2 2.2 39.9

A mild hydrotreating process conducted at typical middle distillate hydrodesulphurisation conditions ensures an effective sulphur removal, eliminates however nitrogen compounds in a rather very small range. A radical increase in the process severity, elevated temperature and increased hydrogen flow rate with reduced feed space velocity (severity III) allows to reduce nitrogen content by only about 50 %. At the same time, due to hydrocracking and cyclisation reactions occurring at more severe mode of plant operation an increase of polycyclic aromatic hydrocarbons content in the hydroraffinate and considerable decrease of its yield could be seen. An influence of hydrotreating process on hydroraffinate stability is presented in the Table 12. Tests were made during 6-week storage period of samples in glass containers at laboratory conditions

Table 12. Test results for stability of H-Oil gas oil distillate hydroraffinates during 6-week storage time Process parameters: Time of storage: Properties: Stability by ASTM D 2274, (16h, 95C, 3% O2), - deposits, g/m3 Stability by ASTM D 6468, (180 min., 150C) - colour, before/after - reflectance, % Deposits after storage, g/m3 0 I 10 days 4 weeks 6 weeks 0 II 10 days 4 weeks 6 weeks 0 III 10 days 4 weeks 6 weeks

3.4 2.0/3.5 90.70 -

6.2 2.5/4.5 69.25 7.9

5.4 3.0/4.5 80.25 26.7

6.8 3.5L/5.0 70.7 24.9

3.5 1.5/2.5 89.5 -

10.6 2.0/4.0 63.2 11.5

7.1 2.0/3.5 74.45 37.4

8.8 2.5L/4.0 68.6 27.0

4.0 1.5/2.0 88.7 -

16.9 1.5/3.5 58.3 18.0

11.8 1.5/3.0 69.7 47.9

13.5 2.0L/3.5 61.9 36.8

Hydrotreating processing influenced very beneficial on colour stability of H-Oil gas oil distillate but did not improved however its tendency to sedimentation of deposits under atmospheric factors acting during storage period. Increased process severity had decidedly negative effect on stability of hydrotreated H-Oil product. A solution allowing for safe utilisation of H-Oil gas oil distillate in blending into light fuel oil (at a quantity of 15-30 %9m/m)) is a mild hydrotreating of the basic fuel made with H-Oil distillate. Results obtained from tests on stability of hydroraffinate containing 15 % of H-Oil gas oil distillate on HDS plant with severity mode I are shown in the Table 13 (the stability results for feedstock as of the Table 7). Table 13. Stability results of light fuel oil hydroraffinate containing 15 % of gas oil distillate from H-Oil process Time of storage: Properties: Bromine index, gBr/100g Sulphur content, %(m/m) Total nitrogen content, mg/kg Basic Nitrogen content, %(m/m) Stability by ASTM D 2274 (16h, 95C, 3% O2), - deposits, g/m3 Stability by ASTM D 6468 (180 min, 150C) - colour, before/after - reflectance, % Deposits after storage, g/m3 0 0.8 0.0087 437 0.016 1.3 1.0/1.5 91.8 10 days 1.7 1.0/2.0 91.5 0.4 4 weeks 1.7 1.0/2.0 91.4 0.6 6 weeks 2.0 1.5/2.5 90.1 0.9

A tendency of H-Oil vacuum residue for stratification and asphaltene deposits sedimentation (the Table 9) was found. It hinders long term storage and does not allow to sell the product outside of the refinery. Attempts to correct these faults were made by blending with proper selected distillates containing considerable quantities of polar aromatic hydrocarbons. PKN Orlen refinery has for disposal highly aromatic gas oil distillate from FCC (LCO), Steam Cracking Fuel Oil (SCO) and Heavy FCC Cycle Oil (HCO). Compatibility of these streams with H-Oil vacuum residuum was evaluated. Results obtained are presented in the Table 14. Table 14. Compatibility evaluation of blends of H-Oil vacuum residue (VR H-Oil) with high aromatic hydrocarbon cuts and stability evaluation of these blends in 50:50 ratio with H-Oil vacuum residue Component: Light Cycle Oil (LCO) Steam Cracking Oil (SCO) Heavy FCC Cycle Oil (HCO) Flocculation Ratio p-Value 1.7 1.8 1.6 Compatibility ASTM D 4740-95 2 1 2

Best results were obtained in case of the blend composed of vacuum residue with steam cracking fuel oil though in mixtures with 50 % of this component it failed to achieve floculation factor pV min. 2.0 which - according to adopted criteria - ensures a proper product stability. Further increasing of high aromatic component content in the mixture with H-Oil vacuum residue brought expected results. It is illustrated by data shown in the Table 15.

Table 15. Stability improvement for H-Oil vacuum residue by blending with high aromatic hydrocarbon streams. Composition:, % (m/m) VR H-Oil LCO Properties: SCO Flocculation ratio, p-Value 2.3 Compatibility 1 Total existent sediment, % (m/m) 0.05 Potential sediment (24h, 100C), % (m/m) 0.02 Accelerated sediment, % (m/m) 0.06 30 20 50 VR H-Oil SCO 2.3 1 0.06 0.03 0.04 30 70 Scanraff Met. ASTM D 4740-95 ISO 10307-1 ISO 10307-2 ISO 10307-2 Test Method

By utilisation of available refinery highly aromatic components from crude oil processing we succeeded to obtain stable products containing H-Oil low sulphur vacuum residue. It was also confirmed by stability test results obtained for stored blends as shown in the Table 16. At current refinery operation state we managed to introduce up to 40 % of H-Oil vacuum residue to commercial fuel oils. Table 16. Changes in stability and viscosity of blends containing H-Oil vacuum residue during storage at 50C within 14 days Composition:, %(m/m) VR H-Oil LCO SCO Properties : before storage Total existent sediment %(m/m) 0.05 Viscosity in 50C mm2/s 33.93 30 20 50 after storage 0.04 34.48 VR H-Oil SCO before storage 0.06 101.9 30 70 after storage 0.04 106.68

5 Resume
Putting into operation of the H-Oil plant in PKN Orlen enabled to solve very important issue of high sulphur vacuum residua which were used to blend fuel oils with sulphur content up to 3.0 % (m/m). At the moment H-Oil low sulphur vacuum residue is being used as a fuel in power station and the refinery succeeded in lowering SO2, emission; excess of this stream will be blended into low sulphur commercial fuel oils which are now demanded by customers. Gas oil distillate is utilised mainly for blending of light fuel oil and problems with its stability are avoided by reducing the boiling end of the distillate and hydrotreating in a mixture with other fuel components. Naphtha is now directed to steam cracker and increases feedstock pool for petrochemical complex of the PKN Orlen. Despite of troubles created by feed used for processing obtained from the Ural crude oil a majority of technical obstacles was removed. Final products made from stream obtained on the H-Oil plant are stable, do not have any tendency for deposits precipitation and darkening.

References 1. Colyar, J.J. and Wisdom, L.I., Second Generation Ebullated-Bed Technology, JPI Petroleum
Refining Conference, Tokyo, Japan (1994).

2. Colyar, J.J. and Wisdom, L.I., The H-Oil Process: A Worldwide Leader in Vacuum Residue 3. 4. 5.

Processing, 1997 National Petroleum Refiners Association Annual Meeting, San Antonio, TX, (1997). Colyar, J.J. and Wisdom, L.I., Upgrading vacuum Residua from Mexican Crudes for Petroleos Mexicanos Hydrodesulfurization Residue Complex Miguel Hidalgo Refinery, Japan Petroleum Institute, Tokyo, (1992). Lubowicz, J., Skret, I., Duda, A., Ocena jakosci i mozliwosci wykorzystania frakcji oleju napedowego z instalacji HOG, dokumentacja ITN, Krakow, 2000. Duda, A. Skret, I., Badanie stabilnosci produktow instalacji HOG po wymianie katalizatora, dokumentacja ITN, Krakow 2002.