CA2077682A1 - Fuel oil compositions - Google Patents
Fuel oil compositionsInfo
- Publication number
- CA2077682A1 CA2077682A1 CA 2077682 CA2077682A CA2077682A1 CA 2077682 A1 CA2077682 A1 CA 2077682A1 CA 2077682 CA2077682 CA 2077682 CA 2077682 A CA2077682 A CA 2077682A CA 2077682 A1 CA2077682 A1 CA 2077682A1
- Authority
- CA
- Canada
- Prior art keywords
- sulphonic acid
- residuum
- blend
- minutes
- carbon atoms
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2493—Organic compounds containing sulfur, selenium and/or tellurium compounds of uncertain formula; reactions of organic compounds (hydrocarbons, acids, esters) with sulfur or sulfur containing compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
- C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
- C10L1/2437—Sulfonic acids; Derivatives thereof, e.g. sulfonamides, sulfosuccinic acid esters
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
Asphaltene sediment in blends of residual fuel oils is reduced by treating the residuum with an alkylaryl sulphonic acid at 200 ·C
or above before blending.
or above before blending.
Description
C~ ~7t~
WO91/13951 ~ - 2 - PCT/GB91/0033Zp-;
This invention relates to fuel oil compositions and to a ~ethod o~ treating them. More especially it relates to i~proving the compatibility of two or more di~ferent types of fuel oils on blending them, and ~o improving the stability of the resulting blends, and in particular to a ~ethod of in~ibiting the precipitation of asphaltenes from a blend o~ a residual fuel oil with a different fuel.
It is known to prepare residual fuels, i.e., Euels containing residuum, by blending residues, for examp-e the tar from steam craoking (pyrolysis fuel) or thermally cracked (visbroken) residues, and diluents, e.g., ~lashed distillates or gas oils. The residues contain asphal-tenes, carbenesl and resins which are soluble, or colloidally soluble, in the residue but which are likely to precipitate out ~rom the blend either very soon after blending or after long term storage. This precipitation has in the past been largely avoided by blending residual fuels with distillate fro~ the same or similar crudes but, as the need arises to process component fractions more severely and to blend rePidual fuels with distillate from very different crude~, e.g., one having a low aromatic or naphthenic content (and hence less likely to maintain the asphaltenes in solution), it has beco~e increasingly necessary to treat the blend or its com-ponents to prevent or reduce asphaltene precipitation.
Precipitation is likely to occur when the fuel .:
' W~/13951 - 3 - PCTIGB91/0033~
WO91/13951 ~ - 2 - PCT/GB91/0033Zp-;
This invention relates to fuel oil compositions and to a ~ethod o~ treating them. More especially it relates to i~proving the compatibility of two or more di~ferent types of fuel oils on blending them, and ~o improving the stability of the resulting blends, and in particular to a ~ethod of in~ibiting the precipitation of asphaltenes from a blend o~ a residual fuel oil with a different fuel.
It is known to prepare residual fuels, i.e., Euels containing residuum, by blending residues, for examp-e the tar from steam craoking (pyrolysis fuel) or thermally cracked (visbroken) residues, and diluents, e.g., ~lashed distillates or gas oils. The residues contain asphal-tenes, carbenesl and resins which are soluble, or colloidally soluble, in the residue but which are likely to precipitate out ~rom the blend either very soon after blending or after long term storage. This precipitation has in the past been largely avoided by blending residual fuels with distillate fro~ the same or similar crudes but, as the need arises to process component fractions more severely and to blend rePidual fuels with distillate from very different crude~, e.g., one having a low aromatic or naphthenic content (and hence less likely to maintain the asphaltenes in solution), it has beco~e increasingly necessary to treat the blend or its com-ponents to prevent or reduce asphaltene precipitation.
Precipitation is likely to occur when the fuel .:
' W~/13951 - 3 - PCTIGB91/0033~
2~77~82 blend is required to h~ve ~ low sulphur content, w~en the distillate is derived from a low sulphur paraf~inic crude and the residual co~ponent is relatively low - up to 15%
- such blended, intermediate, fuels being very suscep-tible to asphaltene precipitation.
The addition of alkylaryl sulphonic aids to fuel oil compositions to inhibit precipitation has been proposed, for example, in U.S. Patent No. 4,182,613. In this patent, it is noted that although the sulphonic acicls are readily oil soluble heating and agitation may be neces-sary to an extent sufficient to overcome viscosity effects, it being suggested to heat to 90-C or higher with stirrinq until tha additive is dissolved. If incompatibility on blending the components of the fuel oil is expected, the additive may be incorporated into one of the fractions and it is stated, though without gi~ing reasons, that mixing with the residuum fraction is particularly effective.
It has now unexpectedly been found that if, before blending, the residuu~ is treated with the additive at a temperature in excess of 200 C for a prolonged period, the inhibition of sedimentation may be greatly enhanced.
This enhancement is both in relation to pretreatment of the residuum at lower temperatures for the time needed to effect solution and in relation to treat~ent at the same high temperature and f or the same prolonged period carried out on the blend.
WO 91tl3951 2 ~ 7 7 ~ 4 ~ PCT/~B91/00337r~
Accordingly, the present invention provides a method of inhibiting the formation of asp~altene sediment in a blend of fuel oils one of which is a residuu~ which method comprises adding an effective stabilizing amount of an alkylaryl sulphonic acid having from 10 to 70 carbon atoms to the residuum and ~aintaining the residuu~
containing the sulphonic acid at a temperature of at least 200 C for a time sufficient to inhibit sedi~ent formation in the eventual blend, and subsequently blending the residuum with the other component or components of the blend.
The sulphonic acid advantageously contains from 26 to 46 carbon atoms, and the alkyl subs~ituent has or substituents have a total content of 18 to 40, preferably from 22 to 28, carbon atoms, and may be of straight or branched chain structure. Mixtures of two or more sulphonic acids may be used. Especially preferred are those in which there are two alkyl groups m~ to each other on a benzene ring, one alkyl group having from 1 to 14 carbon atoms, the other having from 14 to 36 carbon atoms. Particularly use~ul acids have a molecular weight in the range of from 300 to 750, advantageously fro~ 450 to 700. Mixtures of sulphonic acids with straight and branched chain alkyl groups ~ay be used. As examples of sp~cific acids there may be mentioned the sulphonic acids of tetradecyl ben~ene, hexadecyl benzene, icosyl benzene, ", . .
1tl3951 - 5 - Pc~/GB91/00337 ~77~82 tetracosyl benzene, octacosyl benzene and dotricosyl benzene.
Suitable alkylaromatics may be obtained by numerous techniques and subse~uently sulphonat:ed by any oné of several reagents. For example, benzene, toluene, or naphthalene may be alkylated with an olefinic fraction or a chlorinated alkane using a Friedel~Crafts catalyst.
The olefin may be an oligomer o~ ethylene or a l-alkene.
Alternatively t appropriate natural petroleum products may be used. Sulphonation may be carried out using oleum, concentrated sulphuric acid, sulphur trioxide or chloro-sulphonic acid. The procedures for obtalning the alklyaryl sulphonic acids are well known and will not be detailed here.
The residual fuel oils in which the additive may be incorporated accordingly to the method of the invention are oils containing residua, for example straight residuum, vacuum residuum, steam cracking, and, especially, thermal cracking residuum. The residuum will generally have an initial boiling point of at least 315-C, and advantageously about 345 C at atmospheric pressure.
~ he treated residua may be blended with a variety o~
diluents, more especial~y vacuum, flash or middle distillate e.g., 150 C to 345 C, oils, particularly heavy gas oils e.g., 260-C to 345-C oils.
As indicated above, iD the method o~ the present WO91/13951 2 ~ 7 7 ~ 8 2 6 - PCT/GB91/00337 inventlon, the sulphonic acid is introduced into the residuum at an elevated temperature. The temperature is at least 200 C, and is preferably in t:he range of ~rom 200 C to 350 C. The time of treatment 3t elevated temperature will be at least sufficient to inhibit formation of sedi~ent in the eventual blend, and is generally at least 2 minutes, and is advantageously for lO to 60 minutes, preferably for 15 to 4~ minutes, and most preferably a~out 30 minutes. Generally, for a given treatment, a higher temperature will require a shorter time.
The propensity for a fuel to for~ sediment, and the ability of an additive to inhibit sediment for~ation, are measured by the SHF (Sediment by Hot Filtration) Test, as descri~ed in ~Industrial and Engineering Chemistry", lQ, 678 to 680 t1938). It is a matter of simple routine experiment to ascertain for a given additive at a given treat rate in a given resid~u~ to be blended with a given distillate whether the time/tempera-ture regime of the treatment has reduced the sediment formed by the eventual blend in the SHF test, either to an acceptable level, or to that regarded as economically appropriate. Accordingly, it is not appropriate to lay down here precise treatment regimes, except to say that at higher temperatures the effect of increasing treatment times is greater.
The ~reat rate of the sulphonic acid is ~. ~
.
W~ '/13951 7 PCT/GBæ ~ 76~ 2 advantageously in the range of from 0.0l to 2t, preferably fro~ 0.l to 1.0%, and most: preferably from 0.2 to 0.8%, based on the total weight of the eventual blend.
~hus, for exa~ple, if a blend of l0% residuu~, l0~ gas oil is to be made, a treat rate basecl on the residuum o~
10 times the ranges given above will be appropriate.
In the U.S. patent ~entioned above, it is pointed out that the proportion of additive required to prevent sediment formation depends on the sediment formed by th~
untreated fuel as measured by the SHF Test, and that an addition range of 50 to 250% by weight additive based on the SHF Test sediment result was appropriate, with a treat rate of l00 to 150% being preferred.
The method of the present invention, however, achieves reduction in sedi~ent comparable with that in the above-mentioned U.S. Patent at a treat rate of 30 to 60%.
In addition to measurement of SHF, other measures of the e~fectiveness of an additive are available. One of these is based on the fact that asphaltenes are 501uble in aromatic, but not in aliphatic, solvents. Hence, a comparison of the aromaticity, calculated fro~ density and average boiling point, of a given residual oil as measured by its BMCI with the aromaticity required to retain the asphaltenes present in that oil in solution, as measured by TEF gives a value ~or "solubility WO91/13951 2 ~ 7 7 ~ 8 2 PCT/GBgl/00337f~
reserven. BMCI is the Bureau 9f Mines Correlation Index as described in the paper:
Smith, H. R., "Correlation Index to Aid in Inter-preting Analyses", Bureau of Mines Technical Paper 610, U.S. Dept. of the Interior, U.S. Govt. Printing Office, Washington, D.C. 1940.
TEF is the "Toluene Equivalence Filtered" test, as described in the report of the ASTM Marine Fuels Symposium, Miami, Dec. 8, 1983.
Any treatment that reduces TEF without corres]pond-ingly reducing the ~MCI o~ a product will enable a blend having a higher proportion of gas oil to be ~ormed. It has been found that the treatment method o~ the invention is effective in reduction of TEF and i~proving solubility reserve, and more so than the treatment of the residual oil at lower temperatures.
The following Examples illustrate the invention:
Various residual fuel oil compositions were prepared containing a residuum fro~ therma} cracking and various diluents in several proportions. In the procedure according to the invention, the residuum was treated with a C24 straight chain alkylbenzene sulphonic acid at 200 to 250-C for 30 minutes before blending. In the com-parison procedure, the residuu~ was blended with the diluent and the blend treated with the same sulphonic acid in the same proportions at 200 C for 30 minutes.
WG;~ /13951 ~ 9 ~ ~PCT/GB91/00337 2~77~82 In Table l below, the residuu~ is designat@d VBT;
two different types are used. Type A is a visbroken tar from a vacuum residual feed, TEF 81; 3MCI 85.1: HFS
0.07%; Type D is a visbroken tar, TEF' 69; BMCI 75; HFS
0.06%; Diluent B is paraffinic gas oil from at~ospheric distillation, BMCI 28; Diluent C is a low ~ulphur straight-run heavy fuel oil, BMCI 45; TEF ~ 23;
HFS 0.03~.
.
WO 91/13951 2 ~ 7 7 ~ 8 2 - , o PCI'/GB9t/00337~"
. . . _ ~Ei ~ ooo ~ ~ oo o o o o o o o 3 o o tJ~ i ~ ~I N t~ ~ U') ~ rl 1~1 GL~ O ~ O _~ _1 ~7 V
';;3 O O O O O O O 5 ~ ,~V, ,'~
~ ~ o ~ ~ .~ O
~I ~ O O O O O O O ~ ' ~1. o ~ 0 ':~ . O
~ ,0~ U~ O O ~
_ O ~
o m m m m m '' O
~ O
d~ ,~ ln h U C~ 5 o-. ~ . O Ul U~ O 5 ~J
~ _ I r I ~ Lc'.
~rl : W~-1/13951 ~ PCT/GB91/00337 2~77~82 Y~L_2 The effect of treatment time on the SHF results is illustrated in the following Table 2.
Residuum is treated with 0.5% alXylbenzene sulphonic acid for various times at 200 C, then blended to form compositions comprising 25 and 20% gas oil by weight. An untreated blend containing 25% gas oil had an SHF of 1.7%; that containing 20% had an SHF of 0.9%
Table 2 Blend 25% gas oil 20% gas oil Time, minutes 2 0.120 ___ 0.110 0.077 ___ 0.037 0.07 0.012 0.05 ___ Example 3 A further measure of the effectiveness of the treatment according to the invention is the "solvency reserve" .
Table 3 below shows the reduction in TEF by addition o~ a poly(n-butene)benzene sulphonic ~cid, molecular WO 91/13951 2 0 7 7 6 ~3 ~ - l 2 - PCr/GB91/00337f--weight 675, to a VBT of TEF Bl and BMCI 85 . l fuel oil:
treat rate 0.3% at 200 C for 30 minutes. The TEF of the fuel oil blended with a straight run gas oil (BMCI 28) is also reduced.
Table ~
~: VBT 81 VBT + Additive 67 VBT 80%, G0 20S 88 V~ 80%, G0 20% + Additive 73 The solubility reserve is also found to increase with increasing treat rate.
- As has been indicated above, additive treatment methods should improve not only compatibility of blends made immediately after treatment, but also blends ~ade a ' prolonged time after treatment. In this example, one sample of a visbroken tar (TEF = 81) is treated with an alkylbenzene sulphonic acid, 0.5%, at 200 C for 30 minutes, and a second sa~ple is untreated. ~oth samples are stored for 1 month at 50 C, and then formed into a 75%:25% blend with a paraffinic gas oil.
Table 4 below shows the improve~ent in HFS values.
W~1/13951 - 13 - PCT/GB91/00337 Ta~le ~ 2~7682 HFS, %
Blended, Untreated VBT l.7 Blended, Treated VBT ~.05 ExamR~
The effect of temperature on t~e reduction in TEF
achieved by the poly-n-butene benzene sulphonic acid used in Example 3 is shown in Table 5 below. 0 .3% by weight of the acid was used at 50 C and 200 C, for 30 minutes in each case, to treat a VBT (AM413, TEF 81: BHCI 85.l) and the resulting TEF's measured.
Table ~
~E
AM 413, no additi~e 81 AM 413, 50'C treatment 75 AM 413, 200'C ~reatment 67 Exam~le ~ -To ascertain the i~provement in solubility reserve, samples of a VBT (TEF 81; BMCI 85.1) were left untreated, or treated with O.S~ by weight o~ Additive A (90%
solution of a C24 branched chain alky}benzene sulphonic acid), or with 0~5% by weig~t of Additive B (60% solution of the acid used in Example S), in each case for 30 minutes at 200 C. The results are shown in Table 6 below.
, . .
WO 91/13951 2 ~ 7 7 6 8 2- 14 - P~/GB91/00337f~
I~MC I I~EE E~Ye VBT 85.1 81 4.1 VEIT + A85.2 73 12.2 VBT + B85 . 7 67 18 . 7 .~ .. . .
.. . .
- such blended, intermediate, fuels being very suscep-tible to asphaltene precipitation.
The addition of alkylaryl sulphonic aids to fuel oil compositions to inhibit precipitation has been proposed, for example, in U.S. Patent No. 4,182,613. In this patent, it is noted that although the sulphonic acicls are readily oil soluble heating and agitation may be neces-sary to an extent sufficient to overcome viscosity effects, it being suggested to heat to 90-C or higher with stirrinq until tha additive is dissolved. If incompatibility on blending the components of the fuel oil is expected, the additive may be incorporated into one of the fractions and it is stated, though without gi~ing reasons, that mixing with the residuum fraction is particularly effective.
It has now unexpectedly been found that if, before blending, the residuu~ is treated with the additive at a temperature in excess of 200 C for a prolonged period, the inhibition of sedimentation may be greatly enhanced.
This enhancement is both in relation to pretreatment of the residuum at lower temperatures for the time needed to effect solution and in relation to treat~ent at the same high temperature and f or the same prolonged period carried out on the blend.
WO 91tl3951 2 ~ 7 7 ~ 4 ~ PCT/~B91/00337r~
Accordingly, the present invention provides a method of inhibiting the formation of asp~altene sediment in a blend of fuel oils one of which is a residuu~ which method comprises adding an effective stabilizing amount of an alkylaryl sulphonic acid having from 10 to 70 carbon atoms to the residuum and ~aintaining the residuu~
containing the sulphonic acid at a temperature of at least 200 C for a time sufficient to inhibit sedi~ent formation in the eventual blend, and subsequently blending the residuum with the other component or components of the blend.
The sulphonic acid advantageously contains from 26 to 46 carbon atoms, and the alkyl subs~ituent has or substituents have a total content of 18 to 40, preferably from 22 to 28, carbon atoms, and may be of straight or branched chain structure. Mixtures of two or more sulphonic acids may be used. Especially preferred are those in which there are two alkyl groups m~ to each other on a benzene ring, one alkyl group having from 1 to 14 carbon atoms, the other having from 14 to 36 carbon atoms. Particularly use~ul acids have a molecular weight in the range of from 300 to 750, advantageously fro~ 450 to 700. Mixtures of sulphonic acids with straight and branched chain alkyl groups ~ay be used. As examples of sp~cific acids there may be mentioned the sulphonic acids of tetradecyl ben~ene, hexadecyl benzene, icosyl benzene, ", . .
1tl3951 - 5 - Pc~/GB91/00337 ~77~82 tetracosyl benzene, octacosyl benzene and dotricosyl benzene.
Suitable alkylaromatics may be obtained by numerous techniques and subse~uently sulphonat:ed by any oné of several reagents. For example, benzene, toluene, or naphthalene may be alkylated with an olefinic fraction or a chlorinated alkane using a Friedel~Crafts catalyst.
The olefin may be an oligomer o~ ethylene or a l-alkene.
Alternatively t appropriate natural petroleum products may be used. Sulphonation may be carried out using oleum, concentrated sulphuric acid, sulphur trioxide or chloro-sulphonic acid. The procedures for obtalning the alklyaryl sulphonic acids are well known and will not be detailed here.
The residual fuel oils in which the additive may be incorporated accordingly to the method of the invention are oils containing residua, for example straight residuum, vacuum residuum, steam cracking, and, especially, thermal cracking residuum. The residuum will generally have an initial boiling point of at least 315-C, and advantageously about 345 C at atmospheric pressure.
~ he treated residua may be blended with a variety o~
diluents, more especial~y vacuum, flash or middle distillate e.g., 150 C to 345 C, oils, particularly heavy gas oils e.g., 260-C to 345-C oils.
As indicated above, iD the method o~ the present WO91/13951 2 ~ 7 7 ~ 8 2 6 - PCT/GB91/00337 inventlon, the sulphonic acid is introduced into the residuum at an elevated temperature. The temperature is at least 200 C, and is preferably in t:he range of ~rom 200 C to 350 C. The time of treatment 3t elevated temperature will be at least sufficient to inhibit formation of sedi~ent in the eventual blend, and is generally at least 2 minutes, and is advantageously for lO to 60 minutes, preferably for 15 to 4~ minutes, and most preferably a~out 30 minutes. Generally, for a given treatment, a higher temperature will require a shorter time.
The propensity for a fuel to for~ sediment, and the ability of an additive to inhibit sediment for~ation, are measured by the SHF (Sediment by Hot Filtration) Test, as descri~ed in ~Industrial and Engineering Chemistry", lQ, 678 to 680 t1938). It is a matter of simple routine experiment to ascertain for a given additive at a given treat rate in a given resid~u~ to be blended with a given distillate whether the time/tempera-ture regime of the treatment has reduced the sediment formed by the eventual blend in the SHF test, either to an acceptable level, or to that regarded as economically appropriate. Accordingly, it is not appropriate to lay down here precise treatment regimes, except to say that at higher temperatures the effect of increasing treatment times is greater.
The ~reat rate of the sulphonic acid is ~. ~
.
W~ '/13951 7 PCT/GBæ ~ 76~ 2 advantageously in the range of from 0.0l to 2t, preferably fro~ 0.l to 1.0%, and most: preferably from 0.2 to 0.8%, based on the total weight of the eventual blend.
~hus, for exa~ple, if a blend of l0% residuu~, l0~ gas oil is to be made, a treat rate basecl on the residuum o~
10 times the ranges given above will be appropriate.
In the U.S. patent ~entioned above, it is pointed out that the proportion of additive required to prevent sediment formation depends on the sediment formed by th~
untreated fuel as measured by the SHF Test, and that an addition range of 50 to 250% by weight additive based on the SHF Test sediment result was appropriate, with a treat rate of l00 to 150% being preferred.
The method of the present invention, however, achieves reduction in sedi~ent comparable with that in the above-mentioned U.S. Patent at a treat rate of 30 to 60%.
In addition to measurement of SHF, other measures of the e~fectiveness of an additive are available. One of these is based on the fact that asphaltenes are 501uble in aromatic, but not in aliphatic, solvents. Hence, a comparison of the aromaticity, calculated fro~ density and average boiling point, of a given residual oil as measured by its BMCI with the aromaticity required to retain the asphaltenes present in that oil in solution, as measured by TEF gives a value ~or "solubility WO91/13951 2 ~ 7 7 ~ 8 2 PCT/GBgl/00337f~
reserven. BMCI is the Bureau 9f Mines Correlation Index as described in the paper:
Smith, H. R., "Correlation Index to Aid in Inter-preting Analyses", Bureau of Mines Technical Paper 610, U.S. Dept. of the Interior, U.S. Govt. Printing Office, Washington, D.C. 1940.
TEF is the "Toluene Equivalence Filtered" test, as described in the report of the ASTM Marine Fuels Symposium, Miami, Dec. 8, 1983.
Any treatment that reduces TEF without corres]pond-ingly reducing the ~MCI o~ a product will enable a blend having a higher proportion of gas oil to be ~ormed. It has been found that the treatment method o~ the invention is effective in reduction of TEF and i~proving solubility reserve, and more so than the treatment of the residual oil at lower temperatures.
The following Examples illustrate the invention:
Various residual fuel oil compositions were prepared containing a residuum fro~ therma} cracking and various diluents in several proportions. In the procedure according to the invention, the residuum was treated with a C24 straight chain alkylbenzene sulphonic acid at 200 to 250-C for 30 minutes before blending. In the com-parison procedure, the residuu~ was blended with the diluent and the blend treated with the same sulphonic acid in the same proportions at 200 C for 30 minutes.
WG;~ /13951 ~ 9 ~ ~PCT/GB91/00337 2~77~82 In Table l below, the residuu~ is designat@d VBT;
two different types are used. Type A is a visbroken tar from a vacuum residual feed, TEF 81; 3MCI 85.1: HFS
0.07%; Type D is a visbroken tar, TEF' 69; BMCI 75; HFS
0.06%; Diluent B is paraffinic gas oil from at~ospheric distillation, BMCI 28; Diluent C is a low ~ulphur straight-run heavy fuel oil, BMCI 45; TEF ~ 23;
HFS 0.03~.
.
WO 91/13951 2 ~ 7 7 ~ 8 2 - , o PCI'/GB9t/00337~"
. . . _ ~Ei ~ ooo ~ ~ oo o o o o o o o 3 o o tJ~ i ~ ~I N t~ ~ U') ~ rl 1~1 GL~ O ~ O _~ _1 ~7 V
';;3 O O O O O O O 5 ~ ,~V, ,'~
~ ~ o ~ ~ .~ O
~I ~ O O O O O O O ~ ' ~1. o ~ 0 ':~ . O
~ ,0~ U~ O O ~
_ O ~
o m m m m m '' O
~ O
d~ ,~ ln h U C~ 5 o-. ~ . O Ul U~ O 5 ~J
~ _ I r I ~ Lc'.
~rl : W~-1/13951 ~ PCT/GB91/00337 2~77~82 Y~L_2 The effect of treatment time on the SHF results is illustrated in the following Table 2.
Residuum is treated with 0.5% alXylbenzene sulphonic acid for various times at 200 C, then blended to form compositions comprising 25 and 20% gas oil by weight. An untreated blend containing 25% gas oil had an SHF of 1.7%; that containing 20% had an SHF of 0.9%
Table 2 Blend 25% gas oil 20% gas oil Time, minutes 2 0.120 ___ 0.110 0.077 ___ 0.037 0.07 0.012 0.05 ___ Example 3 A further measure of the effectiveness of the treatment according to the invention is the "solvency reserve" .
Table 3 below shows the reduction in TEF by addition o~ a poly(n-butene)benzene sulphonic ~cid, molecular WO 91/13951 2 0 7 7 6 ~3 ~ - l 2 - PCr/GB91/00337f--weight 675, to a VBT of TEF Bl and BMCI 85 . l fuel oil:
treat rate 0.3% at 200 C for 30 minutes. The TEF of the fuel oil blended with a straight run gas oil (BMCI 28) is also reduced.
Table ~
~: VBT 81 VBT + Additive 67 VBT 80%, G0 20S 88 V~ 80%, G0 20% + Additive 73 The solubility reserve is also found to increase with increasing treat rate.
- As has been indicated above, additive treatment methods should improve not only compatibility of blends made immediately after treatment, but also blends ~ade a ' prolonged time after treatment. In this example, one sample of a visbroken tar (TEF = 81) is treated with an alkylbenzene sulphonic acid, 0.5%, at 200 C for 30 minutes, and a second sa~ple is untreated. ~oth samples are stored for 1 month at 50 C, and then formed into a 75%:25% blend with a paraffinic gas oil.
Table 4 below shows the improve~ent in HFS values.
W~1/13951 - 13 - PCT/GB91/00337 Ta~le ~ 2~7682 HFS, %
Blended, Untreated VBT l.7 Blended, Treated VBT ~.05 ExamR~
The effect of temperature on t~e reduction in TEF
achieved by the poly-n-butene benzene sulphonic acid used in Example 3 is shown in Table 5 below. 0 .3% by weight of the acid was used at 50 C and 200 C, for 30 minutes in each case, to treat a VBT (AM413, TEF 81: BHCI 85.l) and the resulting TEF's measured.
Table ~
~E
AM 413, no additi~e 81 AM 413, 50'C treatment 75 AM 413, 200'C ~reatment 67 Exam~le ~ -To ascertain the i~provement in solubility reserve, samples of a VBT (TEF 81; BMCI 85.1) were left untreated, or treated with O.S~ by weight o~ Additive A (90%
solution of a C24 branched chain alky}benzene sulphonic acid), or with 0~5% by weig~t of Additive B (60% solution of the acid used in Example S), in each case for 30 minutes at 200 C. The results are shown in Table 6 below.
, . .
WO 91/13951 2 ~ 7 7 6 8 2- 14 - P~/GB91/00337f~
I~MC I I~EE E~Ye VBT 85.1 81 4.1 VEIT + A85.2 73 12.2 VBT + B85 . 7 67 18 . 7 .~ .. . .
.. . .
Claims (13)
1. A method of inhibiting the formation of asphaltene sediment in a blend of fuel oils one of which is a residuum which method comprises adding an effective stabilizing amount of an alkylaryl sulphonic acid having from 10 to 70 carbon atoms to the residuum and maintain-ing the residuum containing the sulphonic acid at a temperature of at least 200°C for a time sufficient to inhibit sediment formation in the eventual blend, and subsequently blending the residuum with the other component or components of the blend.
2. A method as claimed in claim, wherein the sulphonic acid contains from 26 to 46 carbon atoms.
3. A method as claimed in claim 1 or claim 2, wherein the alkyl substituent or substituents on the aryl sulphonic acid has or have a total content of 18 to 40 carbon atoms.
4. A method as claimed in claim 1, wherein the sulphonic acid has a molecular weight in the range of from 300 to 750.
5. A method as claimed in any one of claims 1 to 4, wherein the residuum is treated with the sulphonic acid at a temperature in the range of from 200°C to 350°C.
6. A method as claimed in any one of claims 1 to 5, wherein the treatment time is at least 2 minutes.
7. A method as claimed in claim 6, wherein the treatment time is 10 to 60 minutes.
8. A method as claimed in claim 7, wherein the treatment time is 15 to 45 minutes.
9. A method as claimed in any one of claims 1 to 8, wherein the treat rate of the sulphonic acid is in the range of from 0.01 to 2% based on the total weight of the eventual blend.
10. A method as claimed in claim 9, wherein the treat rate is from 0.1 to 1.0%.
11. A method as claimed in claim 9, wherein the treat rate is from 0.2 to 0.8%.
12. A method as claimed in claim 1, carried out substantially as described in any one of the Examples herein.
13. Any new and novel feature hereinbefore described, or any new and novel combination of hereinbefore described features.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9004867.9 | 1990-03-05 | ||
| GB909004867A GB9004867D0 (en) | 1990-03-05 | 1990-03-05 | Fuel oil compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2077682A1 true CA2077682A1 (en) | 1991-09-06 |
Family
ID=10672007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2077682 Abandoned CA2077682A1 (en) | 1990-03-05 | 1991-03-05 | Fuel oil compositions |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0524195A1 (en) |
| AU (1) | AU7453691A (en) |
| CA (1) | CA2077682A1 (en) |
| GB (1) | GB9004867D0 (en) |
| WO (1) | WO1991013951A1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9800442D0 (en) * | 1998-01-10 | 1998-03-04 | Bp Chem Int Ltd | Marine diesel fuel additive |
| US7906010B2 (en) | 2006-01-13 | 2011-03-15 | Exxonmobil Chemical Patents Inc. | Use of steam cracked tar |
| US8083930B2 (en) | 2006-08-31 | 2011-12-27 | Exxonmobil Chemical Patents Inc. | VPS tar separation |
| US8083931B2 (en) | 2006-08-31 | 2011-12-27 | Exxonmobil Chemical Patents Inc. | Upgrading of tar using POX/coker |
| US7560020B2 (en) | 2006-10-30 | 2009-07-14 | Exxonmobil Chemical Patents Inc. | Deasphalting tar using stripping tower |
| US7744743B2 (en) | 2006-10-30 | 2010-06-29 | Exxonmobil Chemical Patents Inc. | Process for upgrading tar |
| US7846324B2 (en) | 2007-03-02 | 2010-12-07 | Exxonmobil Chemical Patents Inc. | Use of heat exchanger in a process to deasphalt tar |
| EP3360949B1 (en) * | 2015-08-13 | 2020-01-29 | Exxonmobil Research And Engineering Company | Modification of fuel oils for compatibility |
| US11788017B2 (en) | 2017-02-12 | 2023-10-17 | Magëmã Technology LLC | Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil |
| US10604709B2 (en) | 2017-02-12 | 2020-03-31 | Magēmā Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials |
| US20180230389A1 (en) | 2017-02-12 | 2018-08-16 | Magēmā Technology, LLC | Multi-Stage Process and Device for Reducing Environmental Contaminates in Heavy Marine Fuel Oil |
| US12281266B2 (en) | 2017-02-12 | 2025-04-22 | Magẽmã Technology LLC | Heavy marine fuel oil composition |
| US12025435B2 (en) | 2017-02-12 | 2024-07-02 | Magēmã Technology LLC | Multi-stage device and process for production of a low sulfur heavy marine fuel oil |
| US12071592B2 (en) | 2017-02-12 | 2024-08-27 | Magēmā Technology LLC | Multi-stage process and device utilizing structured catalyst beds and reactive distillation for the production of a low sulfur heavy marine fuel oil |
| EP3795661B1 (en) * | 2019-09-17 | 2022-03-09 | Infineum International Limited | Asphaltene solvation and dispersion process |
| EP3795660B1 (en) * | 2019-09-17 | 2022-03-09 | Infineum International Limited | Refinery antifoulant process |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1523597A (en) * | 1975-03-06 | 1978-09-06 | Shell Int Research | Residual fuel oils |
| US4182613A (en) * | 1976-11-24 | 1980-01-08 | Exxon Research & Engineering Co. | Compatibility additive for fuel oil blends |
| US4441890A (en) * | 1982-09-29 | 1984-04-10 | Exxon Research And Engineering Co. | Method for improving stability of residual fuel oils |
-
1990
- 1990-03-05 GB GB909004867A patent/GB9004867D0/en active Pending
-
1991
- 1991-03-05 AU AU74536/91A patent/AU7453691A/en not_active Abandoned
- 1991-03-05 EP EP19910905489 patent/EP0524195A1/en not_active Withdrawn
- 1991-03-05 CA CA 2077682 patent/CA2077682A1/en not_active Abandoned
- 1991-03-05 WO PCT/GB1991/000337 patent/WO1991013951A1/en not_active Application Discontinuation
Also Published As
| Publication number | Publication date |
|---|---|
| AU7453691A (en) | 1991-10-10 |
| GB9004867D0 (en) | 1990-05-02 |
| WO1991013951A1 (en) | 1991-09-19 |
| EP0524195A1 (en) | 1993-01-27 |
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