The Use Organic Solvents Evaporation Losses System Calculation Control in Tanks of Storage, Productive Systems and Transportation

in Brazil for Prevention of Environmental Impact; Potential Fire and Incidents Risks

Chem Ing. Gilberto Saboia,BsC Gilberto_saboia@hotmail.com

This paper has the intention of supplying subsidies to be a starting point for the Civilian Defense, Fire Brigade and for the personal involved in environmental control; so that they can evaluate an impact caused by the evaporation of solvents, and its inherent potential risks; that may cause fires and environmental accidents. This evaluation can be made even before the project or inspection phase of a new industry, highway or on a new installation of storage tanks in storage parks project or still as a forecast of the evaporation and risk in transport in a route or highway. Besides the theoretical study we will be compare the real measurements data studied theoretical data. Comparing these inventory data with, for instance, the numbers obtained by the mathematical experiment to analyze that an excessive value of losses should be verified, it can indicate need to adapt or to install a system of recovery of the lost steams for the atmosphere as form of control of the environmental emission during storage, transport or process, but it can also indicate the need of larger logistic storage control ( for example it can be having deviation for illicit ends and/or product can being stolen). . We interviewed 70 industries, among them the largest industries of paints and stickers,05 Petroleum Refineries and 02 Petrochemical Plants installed in Brazil whose results will be presented in this summary. The Situation of Tanks of Storage and Transport - The Mathematical Study Model Choice The bulk tanks used for this kind of storage and rake-rail transport of solvents and hidrocarbons ( included ethanol alcohol) in Brazil are steel cylinders manufactured with commercial carbon steel plates or inox steel solded;with many varied capacities, being more common 15, 30 and 50.000 liters. of

physical inventory from 38 industries that answered to the questionnaire with the

Of the technical point of view these tanks are all atmospheric ones, that is, tanks that are opened for the atmosphere through a breath through where the atmospheric air can enter and steams of the solvent stored internally can leave. In Petroleum Refineries and PetroChemical Plants we found storage systems with flotation roof, inert gas or condensation systems for control and reduction of losses for evaporation. Then, we will study the most common situation found in the industries, storage site parks of solvents and fuels, rake-rail transport that are the atmospheric tanks. When the tank is empty after the exit of the solvent, it remains in its interior only mixed atmospheric air with steams of the organic solvent. Being the tank completely full, the whole kept steam will be expelled, for being atmospheric tank this happens with a smaller pressure than 0,36 kPa. Under atmospheric pressure, the mixture gaseous air / solvent steams behave as an ideal gas. Bird et al, 1960. (hypothesis 1) While the tank is being emptied, there will be a fast thermodynamic balance among the phases liquid / steam, exercised by the pressure of steam of each solvent, that it happens for the diffusion in stagnated gas. Bird et al, 1960. When expelling the air of the interior of the tank, in the stuffing operation, actually all the volume of the tanks (of storage, of transport or of production) are equal volume of the tank, in liters, of air with solvent steams will be being expelled, lost for the atmosphere. The thermodynamic balance in the interface liquid-gas grows quickly.

The results below are them obtained as example, for a characteristic campaign found in real situation in most of the brazilian medium or small industries and load

carriers ; that it is the movement of 15.000 liters every 2 days, but higher volumes can be easily estimated.

They express volumes evaporated in liters for a movement of 15.000 liters in stockpiling and production operation in conventional equipments of storage in atmospheric tanks only closed with cover it doesn't stanch. Randomic we had selected a period of the year with medium temperatures in the South of Brazil : nor very high nor very cold

The medium temperatures were collected in the daytime (25 centigrade degrees) and night (13 centigrade degrees) during the first semester of the year for the metropolitan area of Curitiba City, Parana State ( 400 km south from Sao Paulo)

We also selected the main products found in the industries of paints and stickers, the largest consumers of organic solvents.

In terms of fuels, we analyzed the alcohol and we can infer values for gasoline and diesel, that possess many of these solvents in its composition (the gasoline for instance is a hidrocarbons mixture with a distillation strip that is going from 39 to 240 centigrade degrees; this means that it contains in its composition several solvents, as for instance hexane, SPB (Special Boiling Point), toluene, xilens ,white spirits, C9 aromtics.

Even gasoline or Diesel fuel oil, however, are not so pure in chemical composition to be a defined product in their compositions, their components percentage varies to much, depending on the petroleum origin and process and for this reason we don't have analytical data at this time that tecnically mathematical study case. allow us to include them in the

Results of the Mathematical Study

We will analyze with more details the first two products, ethyl acetate and ethanol, in the sequence to present other results so that you can do the calculations and reach your conclusions.

Product Ethyl Acetate: Ms Dia Noite Total % Jan 9,13 4,11 13,24 0,088 Fev 9,28 4,22 13,50 0,0900 mar/abr 8,71 3,99 12,70 0,0850 mai/jun 7,67 3,47 11,14 0,0740 jul/ago 5,88 2,96 8,84 0,0590

Analysis :

As expected, the volatile solvent evaporates more during the day where the temperature is larger but you can confirm that it also evaporates during the night even with lower temperatures.

The average January to August of this evaporation is 0,079%, it means that will lose for the atmosphere 0,079% of the whole busy product in this period.

For instance, we will analyze the operation of a company or carrier of loads for a month of 22 days.

It is going in to fill and to empty the tank 11 times; moving 15 000 liters every time, if the tank is a 15.000 liters tank.

That means on that month it moved 165.000 liters. 165.000 x 0,079% = 130,35 liters that evaporated for the atmosphere, in only 22 days.

And if it was a 30.000 liters tank? The calculation would be the same: 22 days are 11 operations x 30.000 liters = 330.000 busy liters in the month x 0,079% = 260,70 liters of loss in the month. And so on. Besides the financial loss for the company, because that is money that is getting lost has some questions that the specialists can answer:

Which is the environment impact? Which is the risk that these steams come to catch fire when/if the fire triangle happens( ignition font, fuel, oxygen)?

Ethanol Ms Dia Noite Total Jan 4,29 1,96 6,25 Fev 4,38 2,02 6,40 mar/abr 4,04 1,90 5,94 mai/jun 3,42 1,62 5,04 Jul/ago 2,96 1,35 4,31

0,0417

0,0427

0,0396

0,0336

0,0287

Evaporation range average % =0,037 An operation of an industry, carrier or gas station , working 22 useful days for a tank of 15.000 liters means that they have 165.000 busy liters in this period. 165.000 x 0,037% =61,47 liters evaporated in 22 days. If the tank is of 30.000 liters it will be 330.000 x 0,037%= 122.95 liters evaporated in only 22 days. How many trucks of alcohol, how many gas stations do have operating, which the volume of busy ethanol in 2 days in our industry, city, State, Country?

Acetone(butanone) Ms Dia Noite Total % Jan 21,69 10,46 32,15 0,0210 Fev 22,08 10,75 32,83 0,0220 Mar/abr 19,57 10,17 29,74 0,1983 Mai/jun 16,88 8,91 25,79 0,1719 Jul/ago 14,85 7,66 22,51 0,1501

Hexane( Aliphatic C6) Ms Dia Noite Total % Toluen Ms Dia Noite Total Jan 2,16 1,08 3,24 Fev 2,20 1,11 3,31 mar/abr 2,05 1,05 3,10 mai/jun 1,77 0,91 2,68 jul/ago 1,56 0,77 2,33 Jan 15,88 8,36 24,24 0,1616 Fev 16,15 8,59 24,74 0,1649 mar/abr 15,09 8,14 23,23 0,1549 mai/jun 13,16 7,16 20,32 0,1355 ul/ago 11,68 6,18 17,86 0,1191

% Xilens Ms Dia Noite Total %

0,0216

0,0221

0,0207

0,0179

0,0155

Jan 0,54 0,25 0,79 0,0053

Fev 0,55 0,25 0,80 0,0053

mar/abr 0,50 0,24 0,74 0,0049

mai/jun 0,43 0,20 0,63 0,0042

Jul/ago 0,37 0,17 0,54 0,0036

Aromatic C9 solvent Ms Dia Noite Total % Jan 0,74 0,35 1,09 0,0073 Fev 0,76 0,36 1,12 0,0075 mar/abr 0,70 0,34 1,04 0,0069 mai/jun 0,60 0,29 0,99 0,0066 jull/ago 0,52 0,24 0,66 0,0044

Field Research Results From 70 consulted companies adhesives industries with Petrochemical Plants. We verified that in their stock risings the real losses of mass are of the order of 0,5% in Refineries, Central and companies with efficient system of evaporation storage control systems like flotation roof, inert gas or condensation systems for control and reduction of losses for evaporation. In the larger industries or those that possess emission reduction systems such an as valves of pressure relief and vacuous this loss only eats evaporation is among 1,8% even to 2,7% in the other facilities where these systems are inexistent. answered this research 38 paint industries and

big, medium and small

sizes, 3 refineries and 2

This percentage is on the total amount volume monthly solvents used ; it is different from the the pictures thet we got in the mathematical formula because the mathematical model doesn't take into account the turbulence generated in the production by the mixers' rotation (usually mixture Cowles equipments- with motor-axis with turbine stirrers) and it doesn't also consider kinetic and thermal energy generated inside these equipments; some heat (in the dispersions mainly) up to 60 degrees centigrade or more. The mathematical formula doesn't also take into account some physical inventory that were used in the production but not written in the production orders such an as solvents used in small cleanings and no thrown as consumption, leaks in the productive equipment inter tranfers, etc.

How can we Reduce the Evaporation Losses With Low Cost We believe that even in the storage systems and transport that commonly we found in the industries of paints, adhesives and similar and also in the solvent and fuels dealers in which the solvents-fuel reservoirs are cylindrical steel tanks atmospherically open, with very low cost it is possible to reduce the losses for evaporation. This could be obtained by the thermal isolation of the storage or transport tank using double walls, for instance; or in quite economical way for the use of simple systems of coils of cooling (some turns in coil in the breath tube with copper serpentine tubes connected in a cheap cold water refrigeration/recirculation system, installed before the relief and vacuous pressure valve. In most used loading systems for the brazilian Petrochemical units and Petroleum Refineries, it is already demanded underneath the shipment from the transporters with equipment of recovery of volatile steams of the interior of the load tank, usually known as Bottom Load System. Another technical environmental recommendation is to install in the exit of the breath for the atmosphere, after the relief and vacuous pressure valves, filters of adsorption of steams, with stuffing of active coal, so that the little of steam of solvents that evaporates from the tanks is absorbed, not being liberated for the atmosphere, as we can see in the

picture 1 below, got in the storage of solvents of the Carbono Qumica Enterprise (a strong Brazilian chemical dealer installed in Bernardo Bernardo do Campo City- Sao Paulo) where this system is being used for more than 8 years with good results.

Top of the Tank

Internal open filter view

For the mixture system and dispersion in industrial production elaborate with Cowles equipment type, for instance, in which we registered the largest index of evaporation of solvents in the industry of paints, a suggestion is the installation of systems of

condensers of steams of solvents, practice already applied in the USA and in Europe. (as the system that we can see in the picture below, of a Cowles dispersor manufactured by Niemann GmbH; of 2001)

In this illustration we can see 4 copper condensers on the cap cover MATHEMATICAL CALCULATION - The BIRD EQUATION Consideration 1 - open Tank Consideration 2 - Diffusion in stagnated gas : Hypotheses: 1. Solubility of the air in the organic liquids in subject is very low to the

atmospheric pressure.

2.

Thermodynamic balance in the interface liquid-gas grows quickly.

Equation: Mass balance:

______________

dN Az dz

(1)

NAz absolute molar flow of the organic in the gaseous phase (mol cm2 s-1) Constituent equation (Ficks Law): dxA NAz = c. DAB . _______ + dz c
molar concentration of the mixture (mol cm-3)

XA .( NAz + NBZ )

(2)

DAB - coefficient of diffusion of the organic in the air (cm2 s-1) xA -fraction molar of the organic in the gaseous phase NBZ absolute molar flow of the air (mol cm-2 s-1) NBZ = 0 hypothesis 1 e 2

Integrating the equation (2) for constant NAz (equation (1)) along an arbitrary diffuse course z:
c. DAB . ________ ________

NA

________ ________
(I-xAO)

(3)

Under atmospheric pressure the gaseous mixture behaves as an ideal gas, soon
C =______

RT

Where P is the pressure, T is the absolute temperature and R is the universal constant of the gases Admitting that far away from the interface the fraction of organic is despicable (XAz = 0).

NAZ

-P = _______ RT

DAB _______
z

In (I-xAO)

(4)

Integrating the flow along the free surface from the tank during a complete period of emptying, it is obtained the evaporated total mass:

MT

1 = 2L _____ DAB In _______ RT

) In (2 ) . t . M

(5)

MT evaporated total mass (kg) L - length of the tank (5,4m) P - atmospheric pressure (Pa) R universal gas constant (8,314,0 Pa m3 Kmol-1 k-1) T - absolute temperature (k) DAB diffusion coefficientof the organics in the air (m2 s-1) xAO molar fraction of organic in the interface (psat/p) psat pressure of saturation pressure of the organic in T (Pa) t time (s) MA molecular mass of the organics in (kg Kmol-1) To convert the mass evaporated in liters of organic liquid that were originally in the tank is enough to divide her/it for the specific mass of the organic liquid:

VT

T = _____ Pa

VT - liquid total volume organic lost for evaporation in liters Pa specific mass of the organic liquid (kg litro-1)

The critical properties, density, parameters for Wagner's equation for calculation of the pressures of saturation of the pure organic liquids were solitary of Reid, et al, 1986.

These data are shown in the table 1.

Table 1. MA TC K PC x 10-5 Pa Toluol Haxane Acetone Ethano Xilen Ethyl Acetate C9 128,26 568,0 23,3 -7,80573 1,68023 -4,50859 -0,78808 0,717 92,14 86,18 58,08 46,07 106,17 88,11 591,8 507,5 508,1 513,9 630,3 523,2 41,0 30,1 47,0 61,4 37,3 38,3 -7,28607 -7,46765 -7,45514 -8,51838 -7,53357 -7,68521 1,38091 1,44211 1,20200 0,34163 1,40968 1,36511 -2,83433 -3,28222 -2,43926 -5,73683 -3,10985 -4,08980 -2,79168 -2,50947 -3,35590 8,32581 -2,85992 -1,75342 0,863 0,659 0,790 0,789 0,880 0,901 VPa VPb VPc VPd PA Kg/litro

Wagner's equation for calculation of the steam pressures is:

1,5 3 1Tc 6 + VPD

( ) ( )[ (
= 1 _______ VPA

t ___ psa

1-

Tc

) (
+VPB

1- Tc

) (
+VPC

1Tc

)]

1Where:

psat- saturation pressure (Pa) Pc- critical pressure (Pa) Tc- critical temperature (K) T temperature (K) VPA, VPB, VPC E VPD - they are parameters of Wagner's equation. All the necessary data are presented in the table 1.

The coefficients of diffusion of the organic steams in the air were calculated using the methodology proposed by Fuller, et al, 1966.

10-7 T1,75 DAB

=

1+ 1 MA MB ___________________________ P

1 2

[(

VA

) (V ) ]
+
B

1 3

1 3

Where: DAB coefficient of diffusion of the organic in the air (m2s-1) MA molecular mass of the organic product (g mol-1) MB molecular mass of the air 28,9 g mol-1 VA volume of diffusion of the organic product (cm3mol-1) VB volume of diffusion of the air = 20,1cm3mol-1 P pressure (atm) T temperature (K) The data of VA are shown in the table 2.

Table 2. DifusionVolumes for the air difisivity components calculation . Componente Toluen (C7H8) Hexane (C6H6) Acetone(C34H60) Ethanol (C2H6) Xilens (C8H10) Ethyl Acetate (C4H10O2) Solvent C9 (C9H20) VA cm3mol-1 131,34 126,72 66,86 50,36 151,80 96,76 188,10

Bibliography:

Avaliao Terica Das Perdas por Evaporao em Tanques de Armazenamento de Solventes; Anais do 8o. Congresso Internacional de Tintas da ABRAFATI, 2003; eng. Gilberto Sabia e eng. Paulo Auriquio (Petrobras S.A) Controle das perdas por evaporao de solventes orgnicos em sistemas produtivos de unidades industriais de tintas no Brasil,Anais do 9. Congresso Internacional de Tintas da Abrafati 2005. eng.Gilberto Sabia e Dr Roberto Giannini. BIRD, R.B., Stewart, W.E e Lightfoot, E.N., Transport Phenomena, 1 ed., John Wiley Sons, Singapura, 1960. PERRY, R.H., Green, D.W. e Maloney, J.O., Perrys Chemical EngineersHandbook, 6 ed.,McGrawHill, USA, 1984. REID, R.C., Praunitz, J..M. e Poling, B.E., The Properties of Gases and Liquids, 4 ed., Mc Graw-Hill, USA, 1987. &

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