CA1114764A - Treatment of pyrolysis fuel oil - Google Patents
Treatment of pyrolysis fuel oilInfo
- Publication number
- CA1114764A CA1114764A CA307,976A CA307976A CA1114764A CA 1114764 A CA1114764 A CA 1114764A CA 307976 A CA307976 A CA 307976A CA 1114764 A CA1114764 A CA 1114764A
- Authority
- CA
- Canada
- Prior art keywords
- fuel oil
- pyrolysis fuel
- liquid
- promoter
- fraction
- 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.)
- Expired
Links
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 58
- 239000000295 fuel oil Substances 0.000 title claims abstract description 57
- 239000007788 liquid Substances 0.000 claims abstract description 45
- 238000000926 separation method Methods 0.000 claims abstract description 19
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004821 distillation Methods 0.000 claims abstract description 18
- 239000011331 needle coke Substances 0.000 claims abstract description 16
- 239000003921 oil Substances 0.000 claims abstract description 15
- 239000006229 carbon black Substances 0.000 claims abstract description 10
- 238000004939 coking Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 238000012512 characterization method Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 17
- 230000005484 gravity Effects 0.000 claims description 10
- 239000003350 kerosene Substances 0.000 claims description 6
- 239000010779 crude oil Substances 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 238000009835 boiling Methods 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000002430 hydrocarbons Chemical class 0.000 description 7
- 239000000571 coke Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000011280 coal tar Substances 0.000 description 4
- 150000002790 naphthalenes Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002009 anode grade coke Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- KWKXNDCHNDYVRT-UHFFFAOYSA-N dodecylbenzene Chemical compound CCCCCCCCCCCCC1=CC=CC=C1 KWKXNDCHNDYVRT-UHFFFAOYSA-N 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/003—Solvent de-asphalting
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
Abstract
TREATMENT OF PYROLYSIS FUEL OIL
Abstract of the Disclosure A pyrolysis fuel oil (black oil) is contacted with a promoter liquid having a 5 volume percent distillation temperature of at least 250°F and a 95 volume percent distillation temperature of at least 350°F and no greater than about 750°F, with the liquid having a characterization factor of at least 9.75 to promote the separation of quinoline insolubles and asphaltenes from the fuel oil. A fraction free of quinoline insolubles and having a reduced content of asphaltenes may be subjected to coking to produce a needle coke, or employed directly for the production of carbon black.
-i-
Abstract of the Disclosure A pyrolysis fuel oil (black oil) is contacted with a promoter liquid having a 5 volume percent distillation temperature of at least 250°F and a 95 volume percent distillation temperature of at least 350°F and no greater than about 750°F, with the liquid having a characterization factor of at least 9.75 to promote the separation of quinoline insolubles and asphaltenes from the fuel oil. A fraction free of quinoline insolubles and having a reduced content of asphaltenes may be subjected to coking to produce a needle coke, or employed directly for the production of carbon black.
-i-
Description
1~L147~4 This invention relates to the treatment of pyrolysis fuel oil and more particularly, to a new and improved process of producing needle coke from a pyrolysis fuel oil (black oil).
Needle coke, after calcination and graphitization, is characterized by a low longitudinal coefficient of thermal expansion which is matched by a low electric resistivity and such needle coke is primarily used in producing high quality synthetic graphite electrodes for electrosteel furnaces and for other electro-thermal and chlor-alkali industries.
In accordance with the present invention, a pyrolysis fuel oil is contacted with a liquid promoter which promotes and enhances the separation of non-crystalline substances from the oil in order to recover a pyrolysis fuel oil fraction having a reduced quantity of such non-crystalline substances. Such fraction may then be subjected to coking conditions of temperature and pressure to produce a needle coke or be employed directly for the production of carbon black.
Accordingly, the present invention comprises a process for treating a pyrolysis fuel oil containing asphaltenes comprising:
contacting said pyrolysis fuel oil with a liquid promoter which enhances and promotes the separation of asphaltenes from said pyrolysis fuel oil, said liquid promoter having a 95 volume percent distillation temperature of at least about 350F
and no greater than about 750F, said liquid having a characteri~ation factor of at least 9.75; and separating by gravity difference separation a pyrolysis fuel oil fraction having a reduced ; quantity of asphaltenes, which is substantially free of quinoline insolubles.
J, _ . _ _ . ... _ .. _ . , _ . . . . .. . . . . . . ~ . . _ ....
L47~4 The liquid which is employed to enhance and promote the separation of non-crystalline substances in generally a hydrocarbon liquid having a characterization factor (K) of at least about 9.75 and preferably less than 12.0, wherein:
K = TB
G
wherein TB is the molal average boiling point of liquid (R); and G is specific gravity of the liquid (60F /60F).
The characterization factor is an index of the aromaticity/parafinicity of hydrocarbons and petroleum fractions as disclosed by Watson ~ Nelson Ind. Eng. Chem. 25 880 (1988), with more parafinic materials having higher values for the characterization factor (K). The promoter li~uid which is employed is one which has a characterization factor (K) in excess of 9.75.
, 15 The following table provides representative character-ization factors (K) for various materials: -TABLE
Anthracene 8.3 Napththalene 8.4 20 425-500F Coal Tar Distillate 8.8 550-900F Coal Tar Distillate 9.1 600-900F Coal Tar Distillate 9.0 400-450F Coal Tar Distillate 9.4 Benzene 9.8 25 Tetrahydronaphthalene 9.8 o-xylene 10.3 Decahydronaphthalene 10.6 Cyclohexane 11.0 425-500F Boiling Range Kerosene 11.9 30 n-Dodecylbenzene 12.0 Propylene Oligomers (pentamere) 12.2 Cetene 12.8 Tridecane 12.8 n-Hexane 12.9 35 Hexadecane or cetane 13.0 , , i~L4~4 -The liquid which is used to enhance and promote the separation of non-crystalline substances is further characterized by a 5 volume percent distillation temperature of at least about 250F and a 95 volume percent distillation temperature of at least 5 about 350F and no greater than about 750F. The promoter liquid preferably has a 5 volume percent distillation temperature of at least about 310F and most preferably of at least about 400F.
The 95 volume percent distillation temperature is preferably no greater than about 600F. The most preferred promoter liquid 10 has a 5 volume percent distillation temperature of at least about 425F and a 95 volume percent distillation temperature of no greater than about 500F. It i9 to be understood that the promoter liquid may be a hydrocarbon; e.g. tetrahydronaphthalene, in which case the 5 volume percent and 95 volume percent 15 distillation temperatures are the same; i.e. the hydrocarbon has a single boiling point. In such a case, the boiling point of the hydrocarbon must be at least about 350F in order to meet the requirement of a 5 volume percent distillation temperature of at least about 250F and a 95 volume percent distillation 20 temperature of at least about 350F. The promoter liquid is preferably a blend or mixture of hydrocarbons in which case the 5 volume percent and 95 volume percent distillation temperatures are not the same.
The 5 volume percent and 95 volume percent distillation 25 temperatures may be conveniently determined by ASTM No. D86-67 or No. D~ 1160 with the former being preferred for those liquids having a 95 volume percent distillation temperature below 600F. and the latter for those above 600F. The methods for determining such temperatures are well known in the art 30 and the further details in this respect are not required for a ~ .
full understanding of the invention. It is also to be understood that the reported temperatures are corrected to atmospheric pressure.
As representative examples of such liquids,there may 5 be mentioned: kerosene or kerosene fraction from paraffinic or mixed base crude oils; middle distillates, light gas oils and gas oil fractions from paraffinic or mixed based crude oils;
alkyl benzenes with side chains containing ten or more carbon atoms; paraffinic hydrocarbons containing more than twelve 10 carbon atoms; white oils or white oil fraction derived from crude oils; alphaolefins containing more than twelve carbon atoms;
fully hydrogenated naphthalenes and substituted naphthalenes;
propylene oligomers (pentamer and higher); tetrahydronaphthalene, heavy naphtha fractions, etc. The most preferred liquids are 15 kerosene fractions; white oils; fully hydrogenated naphthalenes and substituted naphthalenes; and tetrahydronaphthalene.
The pyrolysis fuel oil or black oil (the residual heavy black oils boiling above pyrolysis gasolines which are produced as by-products in the steam cracking of virgin petroleum fractions to 20 ethylene) are treated in accordance with the present invention to reduce the asphaltene content thereof in that such asphaitenes detract from the crystallinity of the needle coke product or the quality of carbon black to be produced therefrom.
In treating pyrolysis fuel oils, it is generally not necessary 25 to recover a fraction free of all asphaltenes in that some of the asphaltenes do not detract from the quality of the needle coke or carbon black product to be produced therefrom; accordingly, the promoter -liquid can be employed to separate the asphaltenes which are most harmful to needle coke or carbon black quality, 30 without separating all of the asphaltenes. Thus, the promoter liquid is added in an amount sufficient to reduce the asphaltene content of the pyrolysis fuel oil to thereby provide a pyrolysis ~4~4 fuel oil fraction of reduced asphaltene content suitable for the production of needle coke or carbon black. In general, the promoter liquid is employed in an amount to provide a promoter liquid to pyrolysis fuel oil weight ratio of from 5 0.3:1 to 5:1, and preferably of from 1:1 to 2:1. It is to be understood that the exact ratio will vary with the feedstock and promoter liquid.
Asphaltenes are separated from the pyrolysis fuel oil at a temperature in the order of from 50C to about 300C, 10 and preferably at a temperature of from 100C to 200C. The separation can be effected at atmospheric pressure; however, higher pressures can be employed. The separation may be effected by any one of a wide variety of techniques, with gravity difference separation techniques beiny preferred, and 15 gravity settling being particularly preferred. In employing gravity settling, a pyrolysis fuel fraction having a reduced content of asphaltenes is recovered as an overflow, and a pyrolysis fuel fraction with an increased content of asphaltenes is recovered as underflow.
In accordance with the present invention, it is possible to recover a pyrolysis fuel oil fraction having an asphaltene content of no greater than 6%, and preferably no greater than 1%, all by weight. In addition, the pyrolysis fuel oil fraction of reduced asphaltene content is generally recovered in a yield 25 of at least 50~, and preferably at least 65%, based on pyrolysis fuel oil feed to the separation operation.
The pyrolysis fuel oil fraction treated in accordance with the present invention also generally includes some small amounts of quinoline insolubles and treatment in accordance with 30 the invention also results in separation of such quinoline insolubles to provide a pyrolysis fuel oil fraction of reduced asphaltene content which is also free of quinoline insolubles.
The recovered treated pyrolysis fuel oil fraction, after separation of promoter liquid therefrom, may then be coked to a needle coke, preferably by a delayed coking technique, although other coking techniques are also possible.
The recovered pyrolysis fuel oil fraction containing an increased content of asphaltenes, after separation of promoter liquid therefrom, may also be coked to produce an anode : grade coke. Alternatively, such fraction may be employed for coke oven charge blending, fuel or the like.
In accordance with an embodiment of the present invention, 10 the treated recovered pyrolysis fuel oil fraction, having a reduced quantity of asphaltenes, can be soaked in the presence of sulfur, prior to coking, as described in U.S. Patent No.
3,687,840.
The invention will be further described with respect 15 to the accompanying drawing, wherein:
The drawing is a simplified schematic flow diagram of an embodiment of the present invention.
;~ Referring now to the drawing, a pyrolysis fuel oil in line 10 is combined with a liquid promoter in line 11 of the type 20 hereinabove described. -The combined stream in line 12 is introduced into a separation zone 13 in order to separate a pyrolysis fuel oil fraction of reduced asphaltene content from a pyrolysis fuel oil fraction, of increased asphaltene content.
As hereinabove noted, the separation zone 13 is preferably a 25 gravity settling zone, containing one or more gravity settlers, whereby the pyrolysis fuel oil fraction of reduced asphaltene content is recovered as an ovexlow, with a pyrolysis fuel oil fraction of increased asphaltene content being recovered as an underflow.
The pyrolysis fuel oil fraction of reduced asphaltene content, which contains promoter liquid, is withdrawn from separation zone 13 through line 14 and introduced into a fractionator, schematically indicated at 15, 7~
in order to recover the promoter liquid therefrom. An overhead of promoter liquid is withdrawn from fractionator 15 through line 16 combined with make-up in line 17 and recycled through line 11 for mixing with the pyrolysis fuel oil feed~
A pyrolysis fuel oil :Eraction of reduced asphaltene content is withdrawn from fractionator 15 through line 21 and introduced into a coker combination fractionating tower 22 of a type known in the art~
In accordance with a preferred embodiment, the 10 pyrolysis fuel oil fraction is introduced into a sulfur soaking :~ zone, schematically indicated as 23, as described in U.S. Patent No. 3,687,840. The pyrolysis fuel oil is withdrawn from soaking zone 23 through line 24 for introduction into the coker combination fractionator 22.
The coker combination fractionating tower 22 is operated as known in the art to recover a gas fraction, a distillate fraction, a light oil fraction, and a heavy oil fraction.
A cokeable bottoms product, having an initial boiling : 20 point of 290 to 430C is withdrawn from coker combination fraction-~ ating tower 22 through line 31 and passed through a coking heater; 32 as known in the art wherein the fraction is heated to a . . temperature in the order of from about 454C to about 515C.
. The heated fraction in line 33 is introduced into a coking 25 drum 34 wherein the fraction is delayed coked to needle coke.
. In general, as known in the art, such coking drums are operated at a pressure of from about 1.05 kg/cm2 (g) to about 6.3 kg/cm2 (g), prefe~ably from about 1.8 to 6.3 kg/cm2 (g), and at an overhead . . temperature of from about 414C to about 475C and preferably -30 from about 460C to about 475C. The coke is withdrawn from the drum 34 through line 35.
' .
-- ~.3L14~4 An overhead is withdrawn from the coke drum 34 through line 36, and such overhead is introduced into the coker combination fractionator 22 to recover various fractions therefrom, as known in the art.
A pyrolysis fuel oil fraction, including an increased content of asphaltenes and promoter liquid is withdrawn from separation zone 13 through line 41 and introduced into a fractionator 42 to separate the promoter liquid therefrom. The i separated promoter liquid is withdrawn from fractionator 4210 as an overhead through line 43 for combination with the recycled promotor liquid in line 11.
A heavy pyrolysis fuel oil fraction is withdrawn from fractionator 42 and may be employed, for example, for the production of anode grade coke.
; 15 Alternatively, the heavy pyrolysis fuel oil fraction withdrawn through line 41 may be introduced through line 46 into a flash distillation zone, schematically indicated as 47, to recover the promoter liquid, as overhead through line 48, and a fraction boiling from about 315C to about 538C, as a 20 sidestream through line 49, with the sidestream in line 49 being employed as additional feed for the production of needle coke.
The remaining heavy fraction, withdrawn as bottoms through line 51 may be employed for the production of, for example, anode grade coke.
The invention will be further described with respect of the following example:
A pyrolysis fuel oil (18.2 wt % asphaltenes; 0.09 wt.
% Quinoline Insolubles) is mixed for 0.5 hr. at a temperature 30 of 134F with a promoter liquid having a characterization factor of 11.8,a 5 volume percent distillation temperature of greater - than 310F and an end point of 425F in an amount to provide a promoter liquid to pyrolysis fuel oil wt. ratio 2.0:1Ø
I ~L~4~
The mixture is subjected to gravity settling (220F; atmos-pheric pressure; 2.0 hrs) and the promoter liquid free overflow, contains 6.2wt.% of asphaltenes and 0% guinoline insolubles and is recovered in a yield of 66.6wt.%, based on pyrolysis fuel oil feed.
The recovered pyrolysis fuel oil fraction of reduced asphal-tene content will produce a high grade of needle coke or a superior grade of carbon black.
Preferred embodiments of the present invention have been found to be particularly advantageous in that they make it possib~
to produce a high quality needle coke or carbon black in high yields. Thus, for example, high yieldsof needle coke or carbon black from pyrolysis fuel oil are made possible by the high recovery of non-distillable components having a reduced asphal-tene content. Thus, in preferred embodiments of the present invention, lt is possible to recover in excess of 65% of the non-distillable quinoline soluble components present in the pyrolysis fuel oil, having a reduced content of the asphaltenes which would interfere with the production of crystalline coke to thereby provide a feed suitable for the production of needle I coke.
Needle coke, after calcination and graphitization, is characterized by a low longitudinal coefficient of thermal expansion which is matched by a low electric resistivity and such needle coke is primarily used in producing high quality synthetic graphite electrodes for electrosteel furnaces and for other electro-thermal and chlor-alkali industries.
In accordance with the present invention, a pyrolysis fuel oil is contacted with a liquid promoter which promotes and enhances the separation of non-crystalline substances from the oil in order to recover a pyrolysis fuel oil fraction having a reduced quantity of such non-crystalline substances. Such fraction may then be subjected to coking conditions of temperature and pressure to produce a needle coke or be employed directly for the production of carbon black.
Accordingly, the present invention comprises a process for treating a pyrolysis fuel oil containing asphaltenes comprising:
contacting said pyrolysis fuel oil with a liquid promoter which enhances and promotes the separation of asphaltenes from said pyrolysis fuel oil, said liquid promoter having a 95 volume percent distillation temperature of at least about 350F
and no greater than about 750F, said liquid having a characteri~ation factor of at least 9.75; and separating by gravity difference separation a pyrolysis fuel oil fraction having a reduced ; quantity of asphaltenes, which is substantially free of quinoline insolubles.
J, _ . _ _ . ... _ .. _ . , _ . . . . .. . . . . . . ~ . . _ ....
L47~4 The liquid which is employed to enhance and promote the separation of non-crystalline substances in generally a hydrocarbon liquid having a characterization factor (K) of at least about 9.75 and preferably less than 12.0, wherein:
K = TB
G
wherein TB is the molal average boiling point of liquid (R); and G is specific gravity of the liquid (60F /60F).
The characterization factor is an index of the aromaticity/parafinicity of hydrocarbons and petroleum fractions as disclosed by Watson ~ Nelson Ind. Eng. Chem. 25 880 (1988), with more parafinic materials having higher values for the characterization factor (K). The promoter li~uid which is employed is one which has a characterization factor (K) in excess of 9.75.
, 15 The following table provides representative character-ization factors (K) for various materials: -TABLE
Anthracene 8.3 Napththalene 8.4 20 425-500F Coal Tar Distillate 8.8 550-900F Coal Tar Distillate 9.1 600-900F Coal Tar Distillate 9.0 400-450F Coal Tar Distillate 9.4 Benzene 9.8 25 Tetrahydronaphthalene 9.8 o-xylene 10.3 Decahydronaphthalene 10.6 Cyclohexane 11.0 425-500F Boiling Range Kerosene 11.9 30 n-Dodecylbenzene 12.0 Propylene Oligomers (pentamere) 12.2 Cetene 12.8 Tridecane 12.8 n-Hexane 12.9 35 Hexadecane or cetane 13.0 , , i~L4~4 -The liquid which is used to enhance and promote the separation of non-crystalline substances is further characterized by a 5 volume percent distillation temperature of at least about 250F and a 95 volume percent distillation temperature of at least 5 about 350F and no greater than about 750F. The promoter liquid preferably has a 5 volume percent distillation temperature of at least about 310F and most preferably of at least about 400F.
The 95 volume percent distillation temperature is preferably no greater than about 600F. The most preferred promoter liquid 10 has a 5 volume percent distillation temperature of at least about 425F and a 95 volume percent distillation temperature of no greater than about 500F. It i9 to be understood that the promoter liquid may be a hydrocarbon; e.g. tetrahydronaphthalene, in which case the 5 volume percent and 95 volume percent 15 distillation temperatures are the same; i.e. the hydrocarbon has a single boiling point. In such a case, the boiling point of the hydrocarbon must be at least about 350F in order to meet the requirement of a 5 volume percent distillation temperature of at least about 250F and a 95 volume percent distillation 20 temperature of at least about 350F. The promoter liquid is preferably a blend or mixture of hydrocarbons in which case the 5 volume percent and 95 volume percent distillation temperatures are not the same.
The 5 volume percent and 95 volume percent distillation 25 temperatures may be conveniently determined by ASTM No. D86-67 or No. D~ 1160 with the former being preferred for those liquids having a 95 volume percent distillation temperature below 600F. and the latter for those above 600F. The methods for determining such temperatures are well known in the art 30 and the further details in this respect are not required for a ~ .
full understanding of the invention. It is also to be understood that the reported temperatures are corrected to atmospheric pressure.
As representative examples of such liquids,there may 5 be mentioned: kerosene or kerosene fraction from paraffinic or mixed base crude oils; middle distillates, light gas oils and gas oil fractions from paraffinic or mixed based crude oils;
alkyl benzenes with side chains containing ten or more carbon atoms; paraffinic hydrocarbons containing more than twelve 10 carbon atoms; white oils or white oil fraction derived from crude oils; alphaolefins containing more than twelve carbon atoms;
fully hydrogenated naphthalenes and substituted naphthalenes;
propylene oligomers (pentamer and higher); tetrahydronaphthalene, heavy naphtha fractions, etc. The most preferred liquids are 15 kerosene fractions; white oils; fully hydrogenated naphthalenes and substituted naphthalenes; and tetrahydronaphthalene.
The pyrolysis fuel oil or black oil (the residual heavy black oils boiling above pyrolysis gasolines which are produced as by-products in the steam cracking of virgin petroleum fractions to 20 ethylene) are treated in accordance with the present invention to reduce the asphaltene content thereof in that such asphaitenes detract from the crystallinity of the needle coke product or the quality of carbon black to be produced therefrom.
In treating pyrolysis fuel oils, it is generally not necessary 25 to recover a fraction free of all asphaltenes in that some of the asphaltenes do not detract from the quality of the needle coke or carbon black product to be produced therefrom; accordingly, the promoter -liquid can be employed to separate the asphaltenes which are most harmful to needle coke or carbon black quality, 30 without separating all of the asphaltenes. Thus, the promoter liquid is added in an amount sufficient to reduce the asphaltene content of the pyrolysis fuel oil to thereby provide a pyrolysis ~4~4 fuel oil fraction of reduced asphaltene content suitable for the production of needle coke or carbon black. In general, the promoter liquid is employed in an amount to provide a promoter liquid to pyrolysis fuel oil weight ratio of from 5 0.3:1 to 5:1, and preferably of from 1:1 to 2:1. It is to be understood that the exact ratio will vary with the feedstock and promoter liquid.
Asphaltenes are separated from the pyrolysis fuel oil at a temperature in the order of from 50C to about 300C, 10 and preferably at a temperature of from 100C to 200C. The separation can be effected at atmospheric pressure; however, higher pressures can be employed. The separation may be effected by any one of a wide variety of techniques, with gravity difference separation techniques beiny preferred, and 15 gravity settling being particularly preferred. In employing gravity settling, a pyrolysis fuel fraction having a reduced content of asphaltenes is recovered as an overflow, and a pyrolysis fuel fraction with an increased content of asphaltenes is recovered as underflow.
In accordance with the present invention, it is possible to recover a pyrolysis fuel oil fraction having an asphaltene content of no greater than 6%, and preferably no greater than 1%, all by weight. In addition, the pyrolysis fuel oil fraction of reduced asphaltene content is generally recovered in a yield 25 of at least 50~, and preferably at least 65%, based on pyrolysis fuel oil feed to the separation operation.
The pyrolysis fuel oil fraction treated in accordance with the present invention also generally includes some small amounts of quinoline insolubles and treatment in accordance with 30 the invention also results in separation of such quinoline insolubles to provide a pyrolysis fuel oil fraction of reduced asphaltene content which is also free of quinoline insolubles.
The recovered treated pyrolysis fuel oil fraction, after separation of promoter liquid therefrom, may then be coked to a needle coke, preferably by a delayed coking technique, although other coking techniques are also possible.
The recovered pyrolysis fuel oil fraction containing an increased content of asphaltenes, after separation of promoter liquid therefrom, may also be coked to produce an anode : grade coke. Alternatively, such fraction may be employed for coke oven charge blending, fuel or the like.
In accordance with an embodiment of the present invention, 10 the treated recovered pyrolysis fuel oil fraction, having a reduced quantity of asphaltenes, can be soaked in the presence of sulfur, prior to coking, as described in U.S. Patent No.
3,687,840.
The invention will be further described with respect 15 to the accompanying drawing, wherein:
The drawing is a simplified schematic flow diagram of an embodiment of the present invention.
;~ Referring now to the drawing, a pyrolysis fuel oil in line 10 is combined with a liquid promoter in line 11 of the type 20 hereinabove described. -The combined stream in line 12 is introduced into a separation zone 13 in order to separate a pyrolysis fuel oil fraction of reduced asphaltene content from a pyrolysis fuel oil fraction, of increased asphaltene content.
As hereinabove noted, the separation zone 13 is preferably a 25 gravity settling zone, containing one or more gravity settlers, whereby the pyrolysis fuel oil fraction of reduced asphaltene content is recovered as an ovexlow, with a pyrolysis fuel oil fraction of increased asphaltene content being recovered as an underflow.
The pyrolysis fuel oil fraction of reduced asphaltene content, which contains promoter liquid, is withdrawn from separation zone 13 through line 14 and introduced into a fractionator, schematically indicated at 15, 7~
in order to recover the promoter liquid therefrom. An overhead of promoter liquid is withdrawn from fractionator 15 through line 16 combined with make-up in line 17 and recycled through line 11 for mixing with the pyrolysis fuel oil feed~
A pyrolysis fuel oil :Eraction of reduced asphaltene content is withdrawn from fractionator 15 through line 21 and introduced into a coker combination fractionating tower 22 of a type known in the art~
In accordance with a preferred embodiment, the 10 pyrolysis fuel oil fraction is introduced into a sulfur soaking :~ zone, schematically indicated as 23, as described in U.S. Patent No. 3,687,840. The pyrolysis fuel oil is withdrawn from soaking zone 23 through line 24 for introduction into the coker combination fractionator 22.
The coker combination fractionating tower 22 is operated as known in the art to recover a gas fraction, a distillate fraction, a light oil fraction, and a heavy oil fraction.
A cokeable bottoms product, having an initial boiling : 20 point of 290 to 430C is withdrawn from coker combination fraction-~ ating tower 22 through line 31 and passed through a coking heater; 32 as known in the art wherein the fraction is heated to a . . temperature in the order of from about 454C to about 515C.
. The heated fraction in line 33 is introduced into a coking 25 drum 34 wherein the fraction is delayed coked to needle coke.
. In general, as known in the art, such coking drums are operated at a pressure of from about 1.05 kg/cm2 (g) to about 6.3 kg/cm2 (g), prefe~ably from about 1.8 to 6.3 kg/cm2 (g), and at an overhead . . temperature of from about 414C to about 475C and preferably -30 from about 460C to about 475C. The coke is withdrawn from the drum 34 through line 35.
' .
-- ~.3L14~4 An overhead is withdrawn from the coke drum 34 through line 36, and such overhead is introduced into the coker combination fractionator 22 to recover various fractions therefrom, as known in the art.
A pyrolysis fuel oil fraction, including an increased content of asphaltenes and promoter liquid is withdrawn from separation zone 13 through line 41 and introduced into a fractionator 42 to separate the promoter liquid therefrom. The i separated promoter liquid is withdrawn from fractionator 4210 as an overhead through line 43 for combination with the recycled promotor liquid in line 11.
A heavy pyrolysis fuel oil fraction is withdrawn from fractionator 42 and may be employed, for example, for the production of anode grade coke.
; 15 Alternatively, the heavy pyrolysis fuel oil fraction withdrawn through line 41 may be introduced through line 46 into a flash distillation zone, schematically indicated as 47, to recover the promoter liquid, as overhead through line 48, and a fraction boiling from about 315C to about 538C, as a 20 sidestream through line 49, with the sidestream in line 49 being employed as additional feed for the production of needle coke.
The remaining heavy fraction, withdrawn as bottoms through line 51 may be employed for the production of, for example, anode grade coke.
The invention will be further described with respect of the following example:
A pyrolysis fuel oil (18.2 wt % asphaltenes; 0.09 wt.
% Quinoline Insolubles) is mixed for 0.5 hr. at a temperature 30 of 134F with a promoter liquid having a characterization factor of 11.8,a 5 volume percent distillation temperature of greater - than 310F and an end point of 425F in an amount to provide a promoter liquid to pyrolysis fuel oil wt. ratio 2.0:1Ø
I ~L~4~
The mixture is subjected to gravity settling (220F; atmos-pheric pressure; 2.0 hrs) and the promoter liquid free overflow, contains 6.2wt.% of asphaltenes and 0% guinoline insolubles and is recovered in a yield of 66.6wt.%, based on pyrolysis fuel oil feed.
The recovered pyrolysis fuel oil fraction of reduced asphal-tene content will produce a high grade of needle coke or a superior grade of carbon black.
Preferred embodiments of the present invention have been found to be particularly advantageous in that they make it possib~
to produce a high quality needle coke or carbon black in high yields. Thus, for example, high yieldsof needle coke or carbon black from pyrolysis fuel oil are made possible by the high recovery of non-distillable components having a reduced asphal-tene content. Thus, in preferred embodiments of the present invention, lt is possible to recover in excess of 65% of the non-distillable quinoline soluble components present in the pyrolysis fuel oil, having a reduced content of the asphaltenes which would interfere with the production of crystalline coke to thereby provide a feed suitable for the production of needle I coke.
Claims (11)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for treating a pyrolysis fuel oil containing asphaltenes, comprising:
contacting said pyrolysis fuel oil with a liquid promoter which enhances and promotes the separation of asphaltenes from said pyrolysis fuel oil, said liquid promoter having a 95 volume percent distillation temperature of at least about 350°F
and no greater than about 750°F, said liquid having a characteriza-tion factor of at least 9.75; and separating by gravity difference separation a pyrolysis fuel oil fraction having a reduced quantity of asphaltenes, which is substantially free of quinoline insolubles.
contacting said pyrolysis fuel oil with a liquid promoter which enhances and promotes the separation of asphaltenes from said pyrolysis fuel oil, said liquid promoter having a 95 volume percent distillation temperature of at least about 350°F
and no greater than about 750°F, said liquid having a characteriza-tion factor of at least 9.75; and separating by gravity difference separation a pyrolysis fuel oil fraction having a reduced quantity of asphaltenes, which is substantially free of quinoline insolubles.
2. The process of claim 1 wherein the promoter liquid is added in an amount to provide a promoter liquid to pyrolysis fuel oil weight ratio of from 0.3:1 to 5:1.
3. The process of claim 2 wherein the promoter liquid has a 5 volume percent distillation temperature of at least 310°F and no greater than about 600°F.
4. The process of claim 2 wherein the recovered pyrolysis fuel oil fraction contains at least 50° of the pyrolysis fuel oil.
5. The process of claim 4 wherein the recovered fraction is recovered by gravity settling.
6. The process of claim 5 wherein at least a portion of the recovered pyrolysis fuel oil fraction is coked to needle coke.
7. The process of claim 6 wherein the recovered fraction is heat soaked in the presence of sulfur prior to the coking.
8. The process of claim 2 wherein the promoter liquid is at least one member selected from the group consisting of kerosene, kerosene fractions, light gas oils, gas oil fractions, heavy naphthas, white oils and white oil fractions from crude oils.
9. The process of claim 2 wherein the recovered pyrolysis fuel oil fraction has an asphaltene content of no greater than 6%, by weight.
10. The process of claim 1 wherein at least a portion of the recovered pyrolysis fuel oil fraction is employed directly for the production of carbon black.
11. The process of claim 6 wherein the promoter liquid to pyrolysis fuel oil weight ratio is from 1:1 to 2:1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US82573077A | 1977-08-18 | 1977-08-18 | |
| US825,730 | 1977-08-18 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1114764A true CA1114764A (en) | 1981-12-22 |
Family
ID=25244787
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA307,976A Expired CA1114764A (en) | 1977-08-18 | 1978-07-24 | Treatment of pyrolysis fuel oil |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS5432502A (en) |
| CA (1) | CA1114764A (en) |
| DE (1) | DE2834475A1 (en) |
| FR (1) | FR2400548B1 (en) |
| GB (1) | GB1601644A (en) |
| IT (1) | IT1107957B (en) |
| NL (1) | NL184788C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013170358A1 (en) * | 2012-05-17 | 2013-11-21 | Wong Wing-Yam | Pyrolytic oil for the manufacturing of carbon black |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4686027A (en) * | 1985-07-02 | 1987-08-11 | Foster Wheeler Usa Corporation | Asphalt coking method |
| CN1142259C (en) * | 2000-09-25 | 2004-03-17 | 中国石油化工股份有限公司 | Combined process of initial solvent asphalt elimination and delayed coking |
| US8083930B2 (en) | 2006-08-31 | 2011-12-27 | Exxonmobil Chemical Patents Inc. | VPS tar separation |
| WO2008027139A1 (en) | 2006-08-31 | 2008-03-06 | Exxonmobil Chemical Patents Inc. | Method for upgrading steam cracker tar using pox /cocker |
| WO2008027131A1 (en) | 2006-08-31 | 2008-03-06 | Exxonmobil Chemical Patents Inc. | Disposition of steam cracked tar |
| US7846324B2 (en) | 2007-03-02 | 2010-12-07 | Exxonmobil Chemical Patents Inc. | Use of heat exchanger in a process to deasphalt tar |
| EP2240554B1 (en) | 2008-01-28 | 2017-09-13 | Corina Projahn | Method and device to perform a pyrolysis |
| DE202008008767U1 (en) | 2008-06-27 | 2008-09-11 | Projahn, Corina | Apparatus for carrying out a pyrolysis |
| DE102008030983B4 (en) | 2008-06-27 | 2012-06-06 | Corina Projahn | Method and device for carrying out a pyrolysis and its use for smoldering waste tires and biomass |
| DE102008039817A1 (en) | 2008-08-22 | 2010-02-25 | Corina Projahn | Pyrolysis coke obtained by pyrolysis process, where the process after loading the furnace with pyrolyzable goods e.g. tires, comprises heating single or all heating element of the pyrolysis ovens, useful as e.g. heat insulating agent |
| DE102012109874A1 (en) | 2012-10-16 | 2014-04-17 | Merenas Trust Reg. | Apparatus and process for the material handling of raw materials |
| JP6553959B2 (en) * | 2015-06-23 | 2019-07-31 | 株式会社ブリヂストン | Carbon black, method for producing carbon black, rubber composition and tire |
| EP3472272A1 (en) | 2016-06-20 | 2019-04-24 | Exxonmobil Research And Engineering Company | Deasphalting and hydroprocessing of steam cracker tar |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE584763C (en) * | 1925-12-12 | 1933-10-16 | I G Farbenindustrie Akt Ges | Process for the processing of the products that arise when the coal is liquefied by hydrogenation |
| US2988501A (en) * | 1958-08-18 | 1961-06-13 | Union Oil Co | Hydrorefining of crude oils |
| US3326796A (en) * | 1964-06-22 | 1967-06-20 | Great Lakes Carbon Corp | Production of electrode grade petroleum coke |
| US3687840A (en) * | 1970-04-28 | 1972-08-29 | Lummus Co | Delayed coking of pyrolysis fuel oils |
| US3856675A (en) * | 1972-11-07 | 1974-12-24 | Lummus Co | Coal liquefaction |
| US3989803A (en) * | 1975-06-23 | 1976-11-02 | Phillips Petroleum Company | Concentration of carbonaceous solids in fuel oil stream in a carbon black procus |
-
1978
- 1978-05-19 GB GB20920/78A patent/GB1601644A/en not_active Expired
- 1978-07-24 CA CA307,976A patent/CA1114764A/en not_active Expired
- 1978-08-05 DE DE19782834475 patent/DE2834475A1/en active Granted
- 1978-08-10 IT IT50691/78A patent/IT1107957B/en active
- 1978-08-14 JP JP9897878A patent/JPS5432502A/en active Granted
- 1978-08-17 FR FR7823992A patent/FR2400548B1/en not_active Expired
- 1978-08-17 NL NLAANVRAGE7808537,A patent/NL184788C/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013170358A1 (en) * | 2012-05-17 | 2013-11-21 | Wong Wing-Yam | Pyrolytic oil for the manufacturing of carbon black |
| US9453130B2 (en) | 2012-05-17 | 2016-09-27 | Wing-Yam Wong | Pyrolytic oil for the manufacturing of carbon black |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2400548B1 (en) | 1985-10-11 |
| JPS5432502A (en) | 1979-03-09 |
| NL7808537A (en) | 1979-02-20 |
| DE2834475C2 (en) | 1987-05-21 |
| DE2834475A1 (en) | 1979-03-01 |
| JPH0144272B2 (en) | 1989-09-26 |
| GB1601644A (en) | 1981-11-04 |
| NL184788C (en) | 1989-11-01 |
| NL184788B (en) | 1989-06-01 |
| IT7850691A0 (en) | 1978-08-10 |
| IT1107957B (en) | 1985-12-02 |
| FR2400548A1 (en) | 1979-03-16 |
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