PILOT PLANT STUDIES ON THE UTILIZATION ...shodhganga.inflibnet.ac.in/bitstream/10603/19010/8/08...by...
63
Chapter 4 UTILIZATION O? PETROLEUM REFINERY CAUSTIC WASH WASTE FOR THE MANUFACTURE OF INDUSTRIAL BITUMEN
Transcript of PILOT PLANT STUDIES ON THE UTILIZATION ...shodhganga.inflibnet.ac.in/bitstream/10603/19010/8/08...by...
Chapter 4
UTILIZATION O? PETROLEUM REFINERY CAUSTIC WASH WASTE
FOR THE MANUFACTURE OF INDUSTRIAL BITUMEN
61
INTRODUCTION
Industrial bitumen of various grades aremanufactured by the air-blowing polymerization ofpaving bitumen in presence of additives like Phospherous pentoxide, Ferric chloride etc. Pavingbitumen is manufactured mainly by two differentprocesses (1) by the vacuum distillation processand (2) by the propane deasphalting process. Theadditives used for the bitumen air-blowing arecostly and hence the high cost of production ofindustrial bitumen. This necessitated the developmentof cheaper additives that will make the process aneconomic one.
IV(a).1 AIR-BLOWING or BITUMEN WITHOUT ANY ADDITIVE
EXPERIMENTAL
Paving bitumen (80/100 grade) obtained by thevacuum distillation process (Cochin Refinery) andby the propane deasphalting process (Haldia Refinery)were used as the raw materials.
The raw material is heated 10 around IZSCC,
made homogenous by stirring with a glass rod, andone Kg of the material is transferred to the reactoras described in Chapter II. By means of electricalheating the material in the reactor is heated to220°C and made to remain steady at that temperature
62
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by means of a rneostat. Air is then blown into thematerial by means of an air-blowing tube and adjustedthe rate of flow of air to be 51 per min. per kg.sample with the help of the regulator provided on theair-flow meter. Samples are drawn at definite intervalsof time and tested. The process was repeated at 240°Cand 260°C also.
RESULTS AND DISCUSSION
The results are given in Tables 1 to 6. Theeffect of temperature on the softening-point penetrationrelationship are given in Figs.1 & 2.
From tables 1 to 6 it is clear that the polymerization process is very slow and hence not economical.Another observation is that the rate of conversion-ofHaldia bitumen is poor compared to that of Cochin bitumenHence Haldia bitumen requires a longer air-blowing timecompared to Cochin bitumen. It is of course possible toincrease the rate of conversion by raising the tanpera—ture of the process. But it has a drawback that it resulin products of poor softening point—penetration relationship as it is evident from Fig.1 &,2. According tothe IS 702-1961 there are different grades ofindustrial bitumen depending upon the softening pointpenetration relationship. They are mainlyr 75/30.85/25, 85/40, 90/15, 105/25, 115/15, 135/10 and 155/6.
the second one penetration. A grade 75/30 shouldhave the softening point between 70 to 80 and penetration between 25 to 35). From Figs. 1 & 2 it isclear that the manufacture of the different grades ofindustrial bitumen by air-blowing without any additiveis impossible.
IV(a).2 AIR-BLOWING OF BITUMEN IN PRESENCE OF PETROLEUM
REFINERY CAUSTIC WASH wAs1'§
In Petroleum Refineries. hydrogen sulphidepresent in liquified petroleum gas and naphtha fractionsis removed by the caustic washing process. An aqueoussolution of sodium hydroxide of strength 10 to 20% isused for this purpose. Hydrogen sulphide reacts withcaustic soda resulting in the formation of sodium sulphide
below 50°C
2 Na OH + H28 —————9 Nazs + 21-120<:_——above 50°C
Caustic wash is then discharged to the wastewater treatment sytem and then disposed to the inlandwaters. It was thought worthwhile to examine whetherthe sodium sulphide present in the caustic wash wastecould function as an additive in the industrial bitumenmanufacture.
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EXPERINTBTAL
The raw materials are air—blown with
Petroleum refinery caustic wash waste containing 2.0%sodium sulphide at varying temperatures, the air flowrate being 5L/min/kg sample.
RESULTS AND DISCUSSION
The results are given in Tables 7 to 12.The softening point penetration relationship of theblown bitumen are given in Fig. 3 & 4.
From Tables 7 to 12 it is evident that thereis a considerable increase in the rate of conversion.Air blowing in presence of 2% sodium sulphide at 220°Creduces the air-blowing time by about 60% as comparedto that without any additive. Another observation isthat, Cochin bitumen requires lesser air blowing timethan Haldia bitumen. A comparative study of Figs. 1 to4 makes it clear that there is considerable improvementin the softening point penetration relationship comparedto the air blown product without any additive. In thiscase also with rise in temperature the softening pointpenetration relationship of the air-blown product deteriorates. This is attributed to the blowing losses of oilthat become considerable as the temperature increases.This is also in agreement with the observations already112 113made by Lockwood and Hoiberg . But by suitablyselecting the temperature of air blowing it is easily
possible to make all the ten different grades ofindustrial bitumen. Another observation is thatcompared to the air-blown products from Haldia bitumenthe Cochin bitumen possesses better softening pointpenetration relationship.
Iv(a).3 AIR-BLOWING OF BITUMEN IN PRESENCE OF
E_E3RIc CHLORIDE
Ferric chloride is a widely used additivefor the manufacture of Industrial Bitumen. So it wasthought worthwhile to compare the efficacy of sodiumsulphide with that of the conventional additive ferricchloride.
EXPERIMENTAL
One kg. of the raw material was heated to220°C added 0.75% ferric chloride and air-blown at the
rate of 51 /minute / kg of raw material. The air-blowingprocess was repeated at temperatures 240 and 260°C in asimilar manner.
RESULTS AFB DI5CU5S§9R
The results are presented in Tables 13 to 18.The softening point penetration relationship of theproducts are given in Figs. 5 and 6. From the resultsit is evident that sodium sulphide is equally effectiveas Ferric chloride in reducing the air blowing period.Figs. 3 to 6 show that Sodium sulphide is equally effective in improving the softening point-penetration
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vation is that in the case of ferric chloride alsothere is deterioration in softening point-penetrationrelationship with rise in temperature. But by suitablyselecting the temperature of the process a-l the tendifferent grades of industrial bitumen could be manufactured.
IV(b) CHARACTERISATION OF THE AIR BLOWN BITUMEN
Iv(b).1 INFRA-RED ANALYSIS
Figs. 7 and 8 show the infrared spectra ofthe air-blown Cochin and Haldia bitumen. An increase
in the intensity of the absorption band at 8.7 micronsand 9.4 microns are observed. The absorption at 8.7nicrons is attributed to the formation of disulphidesand that at 9.4 microns is due to the formation ofthiophenic compounds. Tucker114 after a number of studiesnave confirmed that the absorption band at 8.7 microns is
115flue to the disulphides ,Hartough confirmed the absorption band at 9.4 microns as due to the thiopheniccompounds.
There is the possibility for the formation ofthree types of bonds in this process, the Sulphur-carbonoonds, Carbon-Carbon bonds and Sulphur-hydrogen bonds.
Sulphur is known to react with hydro-carbons in bitumento form polysulphides at asout 125OC.135 A study ofliterature concerning the sulphurization of bitumenreveals that a chemical reaction takes place between
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EFFECT OF ASPHALTENE CONTENT AND ITS MOLECULAR WEIGHT ON
TABLE I 19
SOFTENING POINT - PENETRATION RELATIONSHIP
93
==========—"=====:7====-=======2===-‘==========='=:=€=========$$Q===
Soften- Penetra- Asphal- Molecular wt.Bitumen Air-O ing 0 tion tene of asghaltenesblown @ 220 C point C 1/10 mm content MW Mn(% wt)
withoutany 95 4 26.0 20200 9900additive
fi withI sodium8 sulphide 95 29 33.4 17100 87000
withferricchloride 95 32 34.6 16500 8450Withoutany 95 1 27.2 22400 12100additives
S5 withsodium 95 26 34.4 19000 10450sulphide
withferric 95 29 35.8 18400 10150chloride
=='==F========== i=====-'=—"========== ======1=%=====i=========N
Gaunumawlinolinalau
me 9.GEL PERMEATION CHROMATOGPAPH5 OFTHE ASPHALTENE FRACTIONS OF THEcomm AIR-BLOWN ASPHALTS.
_, 4.. _.. -4,_
9113“
WITHOUT ANY ADDITIVE.1
17.00“
9.03‘
WITH SODIUM SULPHIDE.
17.00"
9.00
WITH FERRIC CHLORIDE.
I
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CONCENTRATION
(SEllnN|_|N)3Wl.L N0|J.N3.l.3l:l
mono. GEL PERMEATION CHROMATOGRAPHS OFTHE ASPHALTENE FRACTIONS or THEHALUIA AIR-BLOWN ASPHALTS.
9.00
WITHOUT ANY ADDITIVE
17.00
9.00
WITH SODIUM SULPHIDE
17.00‘
9.oo—{
WITH FERRIC CHLOREDE
CONCEN'I.‘RATION
96
sulphur and different hydrocarbons constituents ofbitumen Q about 200°C. The reaction proceeds by a freeradical mechanism initiated by the formation of sulphurfree radicals at high temperatures136.
The increase in the intensity of the bands at8.7 microns and 9.4 microns is due to the formation ofdisulphides anithiophenic compounds respectively duringthe air-blowing polymerization in presence of sodiumsulphide.
IV(b).2 MOLECULAR WEIGHT DETERMINATION BY GEL PERMEATIONCHROMATOGRAPHY.
During the bitumen air blowing processNaphthene aromatic fraction present in the bitumen isconverted to polar aromatics which then polymerize tofonn aspha1tenes134. So it was thought worthwhile tofind out the asphaltene contents and their molecularweights in the air-blown bitumen. The results aregiven in Table 19. The gel permeation chromatographsare presented in Figs. 9 and 10.
From Table 19 it can be observed that whenthe air-blown bitumen products possess high asphaltenecontents of low molecular weights (softer asphaltenes),the softening point-penetration relationship will bebetter. It is in agreement with the observations alreadymade by Dark116.
97
IV(b).3 EFFECT OF THE RAW MATERIAL ON SOFTENINGPOINT—PENETRATION RELATIONSHIP
From Table 19 it can be observed that Cochin air
blown bitumen possess better softening point-penetrationrelationship as compared to those of Haldia air blownbitumen. An attempt was made to distinguish theirbehaviour by studying the physical properties of theraw materials. Their physical properties are as givenbelow:
—-.—_—._.__.__.._—_..__..__._._._.__.:—.__—.__..__—_..__.__._.—.—.__..——.—.__.—-——-——————-———-—__.._-—_.._.—_.—_.._——_.._—_.._———_——.......___._._._.._—_.-.._.._—_-_.—._-._—._.—_—.—_.— __
1. Softening point °c 46 442. Penetration 1/10 mm 85 823. Flash point °c 330 3324. Ductility cms. :>10o j>1oo5. Specific gravity 1.007 1.019
As the above physical properties don't give anyclue to the solution of the problem, the chemical composition analyses of the raw materials were carried out bycolumn chromatography (Adsorpticn - elution chromatography)
the results of which are as follows in terms of percentage composition.
98
===-'====:======:=:=:=======::===========:======:====::====Cochin paving Haldia pavingFraction bitumen bitumen
1. saturates 8.9 5.02. Naphthene aromatics 46.6 43.93. Polar aromatics 34.8 38.04. Asphaltenes 9.7 13.1
The inferior softening point-penetration relationship of the air—blown products from Haldia bitumen may beattributed to the presence of lower content of saturates.During the air blowing process the saturates are not affected but the Naphthene-aromatics are transformed to polararomatics which further get polymerised to high molecularweight asphaltenes.
Thus it can be concluded that eventhough thephysical properties of the two different raw materials arepractically the same there is significant difference intheir chemical composition especially as far as the saturatecontents are concerned. This is because they are manufactured by two different processes, Cochin bitumen by thevacuum distillation process and Haldia bitumen by thepropane deasphalting process. However, our studies showthat by suitably adjusting the temperature of the airblowing process it is possible to manufacture all theten different grades of industrial bitumen as per IS 702-1961from both the raw materials.
99
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IV(C) KINETIC STUDIES ON BITUMEN AIR—BLOWING
Iv(c) .1 METHOD OF CALCU..ATION or RATE COlISTA;I'I‘S
It is already reported that asphalt air blowingbehaves kinetically as a first order reaction with respectto the hydrocarbon reactants in bitumen 117. The datausually available to the designer and to the operatoras a measure of reaction completion is only the rise insoftening point of the asphaltlle. Thus the designerand operator need a simpler type of analysis using softening point as the variable.
The simplest type of reaction that fits batchair blowing is an irreversible, first order reaction.The differential equation for such a reaction can bewritten as
where C is the concentration of the reactantsin bitumen. Since the concentration of the reactantmaterials is inversely proportional to the softening
point of the asphalt, C = %, where S is the softeningpoint. Substituting this in the differential equationand integrating, the equation becomes,
_ A S_tk — t in so 'where SO is the initial softening point and St is thesoftening point at any time t. The next step is tocheck out this equation with the actual test data andsee how well it fits.
100
TABLE - 20
CCCHIN PAVING BITUHEN AIR—BLOWN WITH DIFFERENT
FLOW RATES or AIR AT 220°C
=========================================================
iiirzefigw ofD1hJ3.-25:3‘; in ggffiinigg rgtiésgozgigxitL/MIN/Km _ _ _hf_>ufS _ _ _ _ _ _ _ _ _ _ _ _ _ _hc_>u§_ _ _
1 51 0.102 57 0.114 3 64 0.114 72 0.115 31 0.111 53 0.142 60 0.143 69 0.14
5 4 77 0.135 as 0.141 54 0.152 62 0.156 3 72 0.154 33 0.155 95 0.15
=============-_-====—“_—===============-_= ======= ===-_.=:=====:-_=
101
TABLE - 21
HALDIA PAVING BITUMEN AIR—BLOWN WITH
DIFFERENT FLOW RATES OF AIR AT 220°C
================ _____ _=== ______ _================aa.=======
ALE f}§‘i'n§f2§e of §‘i‘§31°i3“1n gggggigg raiiriiniidafiisample hours hour‘1 _" ' ' ' ' ' ' ' ' ' 'Z"""Ze"""ofo§"2 53 0.094 3 58 0.094 64 0.095 70 0.091 49 0.112 54 0.105 3 61 0.114 67 0.115 76 0.111 50 0.132 56 0.123 63 0.126 4 70 0.125 79 0.12
102
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104
F|G.11 BITUMEN AIR-BLOWN AT 220°C WITH VARYING AIR-FLOWRATES.
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105
TABLE — 24
COCHIN PAVING BITUMEN AIR—BLOWN WITH VARYING
CONCENTRATIONS or SODIUM SULPHIDE AT 220°C
===========================.===========.============.=====
°°2§e§§§i:i.°“ J§“£i‘Zii2g ggfggnggg raiiriéniéfifiisulphzi.-de % hours hour-11.0 57 0.211.5 64 0.221° % 2.0 70 0.212.5 77 0.213.0 86 0.211.0 61 0.291.5 70 0.282.0% 2.0 80 0.282.5 92 0.283.0 105 0.281.0 62 0.301.5 72 0.30
2 5 2.0 83 0.30. % 2.5 97 9.303.0 112 0.30
106
TABLE - 35
HALDIA PAVING BITUMEN I ~ '
CONCENTRATIONS OF SODIUM SULPHIDE AT 220°C
=========================================================
°°2§e§§§i§i°“ o'§“§"i‘§$i3g Sgfiggiag riiisioiiiiitsulphide % hours hor-11.0 52 0.162.0 61 0.151.5% 3.0 71 0.164.0 32 0.164.5 89 0.16
. . _ . _ _ _ _ . . . _ . _ _ _ . _ _ . _ . _ . - _ , - 1.0 54 0.212.0 67 0.212 , 0% 3 . o 82 0 . 2 14.0 101 0.214.5 112 0.21
1.0 55 0.232.0 69 0.222.5% 3.0 87 0.234.0 109 0.234.5 122 0.23
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110
IV(C).2 BITUMEN AIR—BLOWING WITHOUT ANY ADDITIVB
To find out the optimum rate of flow of airrequired for the process, asphalt is air blown withdifferent rates of flow of air at 220°C. The resultsare given in Tables 20 and 21. It can be observedthat the optimum air flow rate required for the processis 5L,/ min. per kg. sample.
EFFECT OF TEMPERATURE ON THE VELOCITY CONSTANTS
In order to determine the temperature coefficientsof the process, the process was carried out at varyingtemperatures. Using the mean velocity constants obtained,the Arrhenius plots are drawn as in Figs.14 and 15. Theactivation energies in Kcal per male for Cochin bitumenand Haldia bitumen are found to be 8.78 and 7.86 respectively.
Iv(c).3 BITUMEN AIR BLONN NII‘H SODIUM SULPI-IIDE
In order to find the optimum concentration ofsodium sulphide required for the process, the raw materialsare air blown at 5L/min per kg. sample at 220°C in presenceof varying concentrations of sodium sulphide. The resultsare given in Tables 24 and 25. It can be seen that theoptimum concentration of sodium sulphide required forthe process is 2.0%.
EFFECT OF TEMEERATURE OH THE VELQCITY CONSTXKTS
The process was carried out at varying temperatures. The results are presented in Tables 26 & 27.The Arrhenius plots are drawn using the mean velocityconstants. The activation energies in Kcal/mole for
111
Cochin bitumen and Haldia bitumen are found to be
6.50 and 6.04 respectively.
Based on the above experimental results thefollowing reaction mechanism is suggested.
(1)
(2)
(3)
R+
RH + 02
R + 02
Formation of free radicals
———>
———>
R00’ + H25 ———>0
HS + 02ROOH
0RH + HOO
H O22RH+6H
RH + S
RI-2+}-IS.
—>—?>———>
———>————>
?—>———>
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Ii R'H+R' ‘H
R R'H R"H
———e P? R'H R"I-I
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R00’
noon + Hs
H00’ + ’s'
Rd -+ 5H
R7 + H20
2 6H
fi + H20fl + H§
£5 + H28
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disproportionation
Crosslinking reaction
X/(a) formation of disulphides
stable products
112ll19 1 C
R-S + R - s -———————> R-S-S-R
(b) Formation of thiophenic compounds.
Qt. I\‘- _____9 _+_1«12s
+ esgjjgfi
EOE}; UPSulphur is report:d to be fore powerful than oxygen
(Naphtheyiccompound}
~ostraction of hydrogen from hydrocarbozs inbitumen13 . The effect of sodium sulphide in the polyin the
\)
merization of bitumen is attributed to the formation ofsulphur free radicals.
I\/(C) .4 BIT‘JI»I.'_’IZ3 .?:.IR E3-LOJLT '.-.'I 331 F__RI~1IC CI~ILC)ILZDE
In order to find the optimum concentration of
ferric chloride required for the process the raw materialswere air blown with sl/hdn per kg. at 220°C with varying
113
TABLE - 28
COCHIN BITUMEN.AIR-BLOWN WITH VARYING
CONCENTRATIONS OF FERRIC CHLORIDE AT 220°C
Concentration Duration Softening First orderof ferric of blowing Point °C rate constantchloride hours hour"11 j 1 Q 1 ; j 1 j 1 Z 1 1 1 1 1 Z 1 I I i I I I I ’ 1 1 1 11.0 58 0.231.5 63 0.210.5% 2.0 73 0.232.5 81 0.233.0 91 0.23
1.0 62 0.311.5 73 0.290.75% 2.0 86 0.312.5 99 0.313.0 116 0.31. . . . . . . . . _ _ . . . . _ . _ _ _ _ . . . - - , _ .. _1.0 64 0.331.5 77 0.341.0% 2.0 89 0.332.5 106 0.333.0 125 0.33-T-=-.'_'==== -‘J==Z-'=='=".=="—='=='=='=2:==='==_‘?_'=a=‘———.——"==2==r_.'_.___.""—*_§_.—"" '—._-—"====
114
TABLE - 39
HALDIA BITUMEN AIR-BLOWN WITH VARYING
CONCENTRATIONS OF FERRIC CHLORIDE AT 220°C
Concentration Duration Softening First orderof ferric of blowing Point °C rate const tchloride hours hour‘1.0 52 0.172.0 62 0.170.5% 3.0 74 0.173.5 79 0.174.0 87 0.171.0 56 0.232.0 70 0.230.75% 3.0 89 0.233.5 97 0.234.0 112 0.231.0 56 0.242.0 72 0.251.0% 3.0 92 0.253.5 105 0.254.0 118 0.25
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115
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F|G.13 BITUMEN AIR-BLOWN AT 220°C WITH VARYING CONCENTRATIONS OF FERRIC CHLORIDE ‘
0.35 -_
0.30
)-1
1_0.25
First order k( h
0.20
1 10.5 0.75
A. COCHIN BITUMENB. HALDIA BITUMEN
1.0
CONCENTRATION OF FERRIC CHLORIDE (vawt)
118
Concentrations of ferrichloride. The results aregiven in fables 28 and 2?.
EFFECT OF TEJPERADUR; ON THE VELOCITY CQNJTAITS
The process was carried out at varying temperatures. The mean velocity constants wer: used for makingthe Arrhenius plots. The activation energi;s in Kcal/molefor Lochin and Haldia bitumen are found to be 6.23 and
5.77 respectively.
Based on the above experimental results thefollowing reaction mechanism is suggested.
1. The formation of free radicals as a result of valencyconversions of iron.
0r1
FeCl3 + RH ._____;> R + Feclz + HCl
FeCl3 + I-I20 —~9 FeCl2 + HCl + OH2+ F 3+ 0 ._H_:sFeCl2 + 02 .__._;> Fe ..... O2.___g> e .... 2 ¢___3 0Fe + + H00
2. Increase in the probability of hydrocarbon raiicalscoming in contact with oxygen as a result of theincrease in their concentration in the startingperioi of oxidation.
n+o2?9RooR00’ + 1:3: *9 R00}! + '31
220011’ _% no + o:—:R1lH + 024 _9 R 11 + 2-120
1H + HOO —————€> R + H2 02
119
H202 ———> 2 OH.R1}! + on ——9 R1 + H20
Besides ordinary decomposition of hydropcroxide andperoxide radicals with the formation of aldehydes,ketones and alcohols, they interact with bivalentiron.PeCl2 ?> FeCl2OI-I + R0R00 + FeC12 —-——> ROO FeCl2
+ ROOH
Interaction of trivalent iron with the oxidationproducts having reducing properties with the
2+regeneration of Fe and with the separation of water.
FeCl2OH + RC1-IO —% Feclz + H O + RCO‘2
Acceleration of decomposition of peroxides withbivalent iron.
F-e2+ +H2O2 ———> Fe3+ + OH + 01:
Fe3+ + OH’ —% Fe2+ + OH
RH + OH —-——9 R + I-I20Polymerization
.R+ RIH ——————> R R1H(unsaturatedcompound)
1R R H + R11H ——> R R11-*1 R111-I
disproportionationR R113. R1121’ 9 stable products
1.60
1.50
1.40
2+logk
1.30
1.20
FIG.l4 ARRHENIUS PLOTS OF AIR-BLOWN COCHIN BITUMEN
120
A. WITHOUT ANY ADDITIVE
B. WITH SODIUM SULPHIDE
C. WITH FERRIC CHLORIDE1 .1.90 1-95
FIG.l5 ARRHENIUS PLOTS OF AIR-BLOWN HALDIA BITUMEN
1.50 _C
1.40 _ 81.30 _
XU32+(‘I
1020 "
1.10 _
A. WITHOUT ANY ADDITIVE
B. WITH SODIUM SULPHIDE \\0. WITH FERRIC CHLORIDE \\4 1- ! \C
1.90 3 1.95 2.00x 10
122
SUMMARY
Petroleum refinery caustic wash waste isfound to be an excellent additive for bitumen air
blowing. This additive in concentrations of theorder of 2.0% reduces the blowing time to the extentof about 6 % and is economically advantageous inindustrial bitumen manufacture. Since there is atremendous increase in the production of industrialbitumen in the recent years it is important to knowthe mechanism of air-blowing in detail. The presentstudy also gives the physico-chemical characteristicsof the reactions involved.
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