CN101864327A - Coal tar hydrogenation modification method - Google Patents
Coal tar hydrogenation modification method Download PDFInfo
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- CN101864327A CN101864327A CN201010159638A CN201010159638A CN101864327A CN 101864327 A CN101864327 A CN 101864327A CN 201010159638 A CN201010159638 A CN 201010159638A CN 201010159638 A CN201010159638 A CN 201010159638A CN 101864327 A CN101864327 A CN 101864327A
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 74
- 239000011280 coal tar Substances 0.000 title claims abstract description 68
- 238000002715 modification method Methods 0.000 title claims abstract description 12
- 239000003921 oil Substances 0.000 claims abstract description 152
- 238000006243 chemical reaction Methods 0.000 claims abstract description 98
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 57
- 239000001257 hydrogen Substances 0.000 claims abstract description 57
- 239000000295 fuel oil Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 38
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003502 gasoline Substances 0.000 claims abstract description 29
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000004821 distillation Methods 0.000 claims abstract description 11
- 238000007670 refining Methods 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 45
- 239000002283 diesel fuel Substances 0.000 claims description 23
- 150000002431 hydrogen Chemical class 0.000 claims description 23
- 239000012535 impurity Substances 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000011269 tar Substances 0.000 claims description 9
- 230000029936 alkylation Effects 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 241000282326 Felis catus Species 0.000 claims description 4
- VKKISSAOCQRXBO-UHFFFAOYSA-N [P].[W].[Mo].[Ni] Chemical compound [P].[W].[Mo].[Ni] VKKISSAOCQRXBO-UHFFFAOYSA-N 0.000 claims description 4
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- 238000000746 purification Methods 0.000 claims description 3
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- 239000002351 wastewater Substances 0.000 claims description 3
- AFTDTIZUABOECB-UHFFFAOYSA-N [Co].[Mo] Chemical compound [Co].[Mo] AFTDTIZUABOECB-UHFFFAOYSA-N 0.000 claims description 2
- FEBFYWHXKVOHDI-UHFFFAOYSA-N [Co].[P][W] Chemical compound [Co].[P][W] FEBFYWHXKVOHDI-UHFFFAOYSA-N 0.000 claims description 2
- CKQGJVKHBSPKST-UHFFFAOYSA-N [Ni].P#[Mo] Chemical compound [Ni].P#[Mo] CKQGJVKHBSPKST-UHFFFAOYSA-N 0.000 claims description 2
- AXFKVYBBROZOGA-UHFFFAOYSA-N [P].[Mo].[Co] Chemical compound [P].[Mo].[Co] AXFKVYBBROZOGA-UHFFFAOYSA-N 0.000 claims description 2
- ACVSDIKGGNSZDR-UHFFFAOYSA-N [P].[W].[Ni] Chemical compound [P].[W].[Ni] ACVSDIKGGNSZDR-UHFFFAOYSA-N 0.000 claims description 2
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- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 2
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 61
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 14
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- 229910052717 sulfur Inorganic materials 0.000 abstract description 14
- 239000011593 sulfur Substances 0.000 abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 12
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 72
- 239000000446 fuel Substances 0.000 description 22
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 13
- 238000009835 boiling Methods 0.000 description 12
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
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- 239000002243 precursor Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 3
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- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
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- 238000011160 research Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a coal tar hydrogenation modification method, which comprises the following steps: cutting coal tar into light oil distillate lower than 205 DEG C and heavy oil distillate higher than 205 DEG C after normal pressure or reduced pressure distillation; mixing the light oil distillate lower than 205 DEG C with hydrogen gas for carrying out demulcent selective hydrogenation refining; then, carrying out alkylation reaction; sending reaction products to a national standard 90# vehicle-use gasoline product outlet device after oil-water separation; carrying out deep hydrogenation refining on the heavy oil distillate higher than 205 DEG C; carrying out cooling, steam stripping and fractionation on obtained hydrogenation generation oil to obtain diesel distillate lower than 360 DEG C and tail oil distillate higher than 360 DEG C; obtaining a national standard 0# diesel product outlet device after treatment on the diesel distillate lower than 360 DEG C; and using the tail oil distillate higher than 360 DEG C as a fuel oil product outlet device. The coal tar hydrogenation modification method provided by the invention can be used for effectively solving the coking problem in the coal tar processing process, realizing the long period operation of a coal tar hydrogenation device, simultaneously reducing the hydrogen consumption of the whole coal tar hydrogenation reaction, controlling the reaction heat, and prolonging the service life of hydrogenation catalysts. The vehicle-use 90# gasoline products and vehicle-use 0# diesel products conforming to the national standard can be obtained, and both the sulfur content and the nitrogen content of the fuel oil products are lower than 500 ppm.
Description
Technical field
The present invention relates to effective utilization of coal tar, particularly relate to the full cut coal tar hydrogenation modification of a kind of basic, normal, high temperature method, belong to and utilize multiple different hydrotreatment process to handle the method for coal tar.
Background technology
Lasting, high speed development along with the integrated of world economy and China's economy have driven the quick growth of China's energy demand.Along with the exhaustion day by day of world petroleum resource and the continuous intensification of China's energy dilemma, seek reasonable, economic substitute energy, change energy consumption structure, become the task of top priority that China faces.
The Energy Situation of China is oil-poor rich coal weak breath, rich coal resources.Therefore, be based on China's Energy Situation, give full play to abundant cheap coal resources advantage, replenish domestic oil, gas inadequate resource, is coal resources chemical industry and cleaning oil product raw material by solid fuel conversion, substitute petrochemical complex, for ensureing the national energy strategic security, have reality and long-range strategic importance.
In addition, along with the fast development of China's iron and steel and Coal Chemical Industry industry, the output of coal tar is increasing, and effective utilization of coal tar also becomes more and more important.At present the working method of coal tar routine has the chemical of extraction, directly is in harmonious proportion oil fuel, delayed coking, hydro-upgrading etc.Coal tar directly burning can cause serious environmental to pollute; extract the chemical process and can produce large amount of sewage; and still there is pollution problem in the resistates behind the extraction chemical; therefore seek the coal tar processing and treating method of a cleaning, environmental protection; quality product for coal tar promotes and environment protection, all is thing highly significant.
CN1147575C discloses the method that a kind of coal tar hydrogenating is produced diesel oil.This method cuts into coal tar＜370 ℃ benzoline and＞370 ℃ last running residual oil, and hydrofining is carried out in＜370 ℃ benzoline, and hydrogenated oil obtains vapour, diesel oil after high score, gas are carried.This method is only applicable to coalite tar, the gasoline fraction benzene content height, the octane value that generate are low, the diesel product cetane value is low, can not directly use as automobile-used vapour, diesel product, and only hydrotreatment has been carried out in＜370 ℃ benzoline, also have＞370 ℃ last running residual oil to need processing separately.
CN101307257A discloses a kind of coal tar hydrogenation modification method of two-stage method.This method is cut into coal tar＜300～380 ℃ benzoline and＞300～380 ℃ heavy distillate, wherein＜300～380 ℃ benzoline is carried out obtaining the petrol and diesel oil product after hydrofining and the hydrocracking after mixing 180～400 ℃ optional thinning oil successively, and＞300～380 ℃ heavy distillate is used to modulate the oil fuel product.This method goes for high, medium and low temperature coal tar, but complex procedures, and hydrofining is carried out in＜300～380 ℃ benzoline under identical conditions, light aromatics saturation exponent height in＜205 ℃ of cuts has increased reactive hydrogen consumption, energy consumption and device running cost, can not handle simultaneously＞300～380 ℃ heavy distillate, and the gasoline fraction benzene content height, the octane value that generate are low, the diesel product cetane value is low, can not directly use as automobile-used vapour, diesel product
US0038990A1 discloses a kind of preparation and application of coal tar system diesel catalytic converter.It is carrier that this method adopts with aluminum oxide, silicon-dioxide, Y zeolite or ZMS-5 etc., MO, Ni, W, P, Co and F etc. are the catalyzer of active ingredient, under 320～400 ℃ of conditions coal tar is carried out a step or two step hydrogenation are produced diesel oil, hydrogenation products can obtain 80～280 ℃ of distillates of 64% through cutting.This method obtains that hydrogenated oil density is big, carbon residue content is high, can't reach the quality standard of automobile-used vapour, diesel oil.
CN101240193A discloses a kind of coal tar multistage hydrogenation treatment technique.This method is carried out hydrofining by pre-hydrogenator, hydrodemetallation (HDM) reactor, deep hydrofinishing reactor successively with the coal tar oil-hydrogen mixture, and refined products is separated water outlet through tripping device, light constituent, heavy constituent.Heavy constituent enter the hydrocracking reaction section.This method complex process, operation are many, and whole coal tar is light, hydro-upgrading is all carried out in last running under the severe condition of High Temperature High Pressure, very easily coking under the high temperature of coal tar on the one hand, and device is not long running period; Make on the other hand in the coal tar lighting end＜205 ℃ of light aromatics saturation exponent height, increased the hydrogen consumption of reaction and the energy consumption of device.And the gasoline fraction benzene content height, the octane value that generate are low, and the diesel product cetane value is low, can not directly use as automobile-used vapour, diesel product.
CN2006100320607 discloses the method that a kind of coal tar is produced oil fuel; after this method removes the full cut coal tar of moisture and ash content and thinning oil and is mixed in proportion; pass through the deep hydrogenation unit that the shallow degree hydrogenation unit of hydrogenation protecting agent, catalyst for pre-hydrogenation is housed and main hydrogenating catalyst is housed successively, the product behind the deep hydrogenation obtains low-sulfur, low nitrogen oil fuel and light-end products through product separation.This method can effectively be controlled temperature runaway and take place, reduce catalyzer coking speed, but the weight cut is blended in and carries out hydrogenation under the identical conditions, cause the whole load of device bigger, light constituent hydrogenation degree of depth height, valuable light aromatics product saturation exponent height has increased aromatic hydrocarbons loss and plant energy consumption, and economic benefit is restricted.And the gasoline fraction benzene content height, the octane value that generate are low, and the diesel product cetane value is low, can not directly use as automobile-used vapour, diesel product,
Summary of the invention
The object of the present invention is to provide and a kind ofly can reduce whole device load, valuable light aromatics product saturation exponent is low, has increased aromatics yield, the method for the coal tar hydrogenation modification of cleaning, environmental protection.
The technical solution used in the present invention is as follows: a kind of coal tar hydrogenation modification method is characterized in that may further comprise the steps:
(1) coal tar is cut into＜205 ℃ light oil distillate and＞205 ℃ heavy oil fraction through normal pressure distillation or underpressure distillation;
(2) step (1) is obtained＜205 ℃ of light oil distillates mix with hydrogen that to carry out mild hydrogenation refining after enter one section fixed bed hydrogenation reactor after the process furnace heating, described mild hydrogenation purification condition is: 180～260 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 1.0～3.0MPa, reactive hydrogen oil ratio 200～500, reaction solution hourly space velocity 0.5～3.0h
-1
(3) the generation oil that step (2) is obtained enters flashing tower or stripping tower after cooling, gas-liquid separation, removes reaction and generates the contained gaseous impurities of oil;
(4) reaction that removes gaseous impurities that step (3) is obtained generates oil and carries out alkylated reaction with methanol mixed after enter alkylation reactor after the process furnace heating, the ratio of mixture that described reaction generates oil and methyl alcohol is 1: 1～3, and described alkylation reaction condition is: 350～500 ℃ of temperature of reaction, reaction pressure 0.1～1.0MPa, reaction solution hourly space velocity 0.5～2.0h
-1
(5) resultant of reaction that step (4) is obtained enters gun barrel, and the generation oil that gun barrel top is told enters the motor spirit Mixer pot, goes out device as automobile-used 90# gasoline products after adding oil dope, and waste water is discharged in the gun barrel bottom;
(6) step (1) is obtained＞205 ℃ of heavy oil fractions added by weight 1: 1 and enter two sections fixed bed hydrogenation reactors after thinning oil mixes the back and hydrogen mixes and carry out deep hydrofinishing, described deep hydrofinishing condition is: first reactor: 230～300 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 8.0～15.0MPa, reactive hydrogen oil ratio 800～1500, reaction solution hourly space velocity 0.5～1.5h
-1Second reactor: 300～380 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 8.0～15.0MPa, reactive hydrogen oil ratio 800～1500, reaction solution hourly space velocity 0.5～1.5h
-1
(7) the generation oil that step (6) is obtained enters flashing tower or stripping tower after cooling, gas-liquid separation, generates the contained gaseous impurities of oil to remove reaction;
(8) reaction that removes gaseous impurities that step (7) is obtained generates oil and enters distillation tower, obtains at the distillation tower cat head＜360 ℃ diesel oil distillate, obtains at the bottom of the tower＞360 ℃ tail oil cut;
(9) step (8) is obtained＜a diesel oil distillate part of 360 ℃ returns the reaction inlet as the circulation thinning oil and recycles, and described part of fraction of fuel-oil amount as the circulation thinning oil is 50% of a hydrogenation charge raw material total amount; The remainder diesel oil distillate enters the derv fuel oil Mixer pot, goes out device as automobile-used 0# diesel product after adding oil dope.
Described coal tar is any or several arbitrary proportion mixing oils in any or coal-tar heavy oil and the middle coalite tar of coalite tar, coal-tar middle oil.
Described mild hydrogenation catalyst for refining is that active ingredient is one or more in the catalyzer of molybdenum nickel, molybdenum nickel phosphorus, tungsten nickel, tungsten nickel phosphorus and molybdenum nickel tungsten phosphorus;
Described catalyst for alkylation reaction is conventional ZSM-5 molecular sieve allcylation catalyst.
Described deep hydrofinishing catalyzer is that active ingredient is one or more in the catalyzer of molybdenum cobalt, molybdenum cobalt phosphorus, tungsten cobalt, tungsten cobalt phosphorus and molybdenum nickel tungsten phosphorus.
Oil dope described in the step (5) is respectively conventional octane enhancing additive, oxidation inhibitor, purification agent etc.
Oil dope described in the step (9) is respectively conventional cetane number improver, oxidation inhibitor etc.
Thinning oil described in the step (6) has just begun to adopt commercial Dissel oil, and the normal back that goes into operation adopts in the step (9)＜360 ℃ diesel oil distillate.
Coal tar is a kind of complex mixture of hydrocarbon polymer of high aromaticity, coal tar＜205 ℃ lighting end contains light aromatics and many unsaturated compounds of easy polymerization reaction take place at high temperature such as benzene,toluene,xylene, trimethylbenzene, wherein these light aromatics octane value height are significant contribution components of gasoline products octane value.The coal tar oil properties has determined and need could realize hydro-upgrading under the severe condition of High Temperature High Pressure, and contained unsaturated compound in the coal tar, polymerization reaction take place and generate coking material and cause obstructions such as equipment (as reactor, process furnace, interchanger etc.), pipeline very easily at high temperature such as diolefine, vinylbenzene and cycloolefin particularly, thus the cycle of operation of coal tar hydrogenating unit restricted.Under the harsh reaction conditions of this external High Temperature High Pressure in the coal tar＜light aromatics deep hydrogenation saturated reaction in 205 ℃ of cuts can increase greatly, reactive hydrogen consumption and energy consumption have been increased on the one hand, reduced on the other hand＜octane value of 205 ℃ of gasoline components, reduced economic benefit.In addition, that coal tar hydrogenating is given birth to is olefiant＜205 ℃ of gasoline fractions in benzene content still greater than 20%, can't directly use as motor spirit.
The present invention at first cuts into coal tar＜205 ℃ light oil distillate and＞205 ℃ heavy oil fraction, to contain most diolefine, coking such as vinylbenzene and cycloolefin precursor and benzene, toluene, dimethylbenzene, light aromatics components such as trimethylbenzene＜205 ℃ light oil distillate carries out selective hydrogenation refining under the mitigation condition and alkylated reaction takes off benzene, pass through the mild hydrogenation saturated diolefine of hydrogenation at low temperatures on the one hand in the mild hydrogenation treating process, coking such as vinylbenzene and cycloolefin precursor effectively suppresses coking, thereby prolongs the cycle of operation of coal tar hydrogenating unit; Fully remove impurity such as sulphur nitrogen in the raw material by selective hydrogenation process on the other hand, reduce the saturation exponent of aromatic hydrocarbons in＜205 ℃ of cuts, improve＜205 ℃ of aromatic hydrocarbon product yields, reduce reactive hydrogen consumption and energy consumption, thereby promote economic benefit.Thereby taking off the alkylated reaction of benzene process by benzene and methyl alcohol in alkylation is converted into benzene toluene and reduces benzene content in＜205 ℃ of cuts, improve the octane value of＜205 ℃ of cuts, again by adding the automobile-used 90# gasoline products that an amount of oil dope production meets national standard.
Because easily precursor diolefine, vinylbenzene and the cycloolefin content of coking is seldom in＞205 ℃ of heavy oil fractions, the present invention carried out two section deep hydrofinishings by weight 1: 1 behind the adding thinning oil with＞205 ℃ of heavy oil fractions, slowed down greatly＞at high temperature polymerization coking reaction during 205 ℃ of heavy oil fraction hydrogenation, thereby effectively prolonged the cycle of operation of device; Adding simultaneously thinning oil in＞205 ℃ heavy oil fraction can improve on the one hand＞flowability of 205 ℃ heavy oil fraction by weight 1: 1, the cost and the energy consumption of conservation companion heat, can dilute the reaction heat in the hydrogenation process on the other hand, prevent to react overtemperature, prolong the work-ing life of hydrogenation catalyst.When＞205 ℃ heavy oil fractions enter two sections deep hydrofinishing fixed-bed reactor successively,, react to improve the cetane value of diesel product as far as possible to improve oil quality at the first reactor generation deep desulfuration, denitrogenation, deoxidation and moderate aromatic hydrocarbons saturated reaction at the second reactor generation deepness hydrogenation dearomatization.
Among the present invention＜205 ℃ of light oil distillates are refining through mild hydrogenation, the benzene reaction is taken off in alkylation and the oil product harmonic process obtains meeting national standard motor spirit product goes out device;＞205 ℃ heavy oil fraction enters separation column through the generation oil that deep hydrofinishing obtains after gas-liquid separation, stripping or the flash distillation of routine remove gaseous impurities, cat head obtain＜360 ℃ of diesel oil distillates, at the bottom of tower, obtain＞360 ℃ of tail oil cuts.A diesel oil distillate part of＜360 ℃ is got back to reaction inlet as thinning oil and is recycled, and another part goes out device through the automobile-used 0# diesel product that the oil product harmonic process obtains meeting national standard;＞360 ℃ of tail oil cuts oil production that acts as a fuel goes out device.
Advantage of the present invention:
(1) adopts method of the present invention, both can alleviate the environmental pollution that causes in the conventional coal tar processing use, coal tar all can be converted into again cleaning automobile-used vapour, diesel oil and oil fuel product, promoted the comprehensive utilization value of coal tar, to a certain degree having alleviated the pressure of country down, be a kind of cost-effective coal tar processing and utilization means to the petroleum products demand.
(2) during method provided by the invention mainly is applicable to, coalite tar, but in also can handling, coalite tar and the coal-tar heavy oil mixing oil of the two arbitrarily, raw material is applied widely.
(3) the present invention carries out selective hydrogenation refining and alkylated reaction takes off benzene under ℃ light oil distillate of right under the mitigation condition＜205, the mild hydrogenation treating process on the one hand by mild hydrogenation at low temperatures coking precursors such as the saturated diolefine of hydrogenation, vinylbenzene and cycloolefin effectively suppress coking, thereby the cycle of operation of prolongation coal tar hydrogenating unit; Fully remove impurity such as sulphur nitrogen in the raw material by selective hydrogenation process on the other hand, reduce the saturation exponent of aromatic hydrocarbons in＜205 ℃ of cuts, improve＜205 ℃ of aromatic hydrocarbon product yields, reduce reactive hydrogen consumption and energy consumption, thereby promote economic benefit.Thereby taking off the alkylated reaction of benzene process by benzene and methyl alcohol in alkylation is converted into benzene toluene and reduces benzene content in＜205 ℃ of cuts, improve the octane value of＜205 ℃ of cuts, again by adding the motor spirit mediation product that an amount of oil dope production meets national standard.
(4) the present invention carried out deep hydrofinishing by weight 1: 1 behind the adding thinning oil with＞205 ℃ of heavy oil fractions.Since in＞205 ℃ of heavy oil fractions easily precursor diolefine, vinylbenzene and the cycloolefin content of coking seldom, this has just slowed down greatly＞at high temperature polymerization coking reaction during 205 ℃ of heavy oil fraction hydrogenation, thereby has effectively prolonged the cycle of operation of device; Adding thinning oil in＞205 ℃ the heavy oil fraction can improve on the one hand＞flowability of 205 ℃ heavy oil fraction by weight 1: 1, the cost and the energy consumption of conservation companion heat, can dilute the reaction heat in the hydrogenation process on the other hand, prevent to react overtemperature, prolong the work-ing life of hydrogenation catalyst.
The heavy oil fraction of (5) the present invention＞205 ℃ is handled through deep hydrofinishing, can fully remove impurity such as sulphur in the raw material, nitrogen, oxygen, and it is fully saturated that aromatic hydrocarbons is obtained, and helps improving the cetane value of diesel product.
(6) utilize automobile-used vapour, diesel product and sulphur nitrogen content that the present invention can obtain meeting national standard all less than 500ppm＞360 ℃ of oil fuel products.
Description of drawings
Accompanying drawing 1 is a kind of coal tar hydrogenation modification method flow diagram provided by the invention.
Embodiment
From schema Fig. 1 of the present invention as can be known, coal tar 1 is squeezed into often (to subtract) through fresh feed pump 2 and is pressed distillation tower 3, by distillation,＜205 ℃ of light oil distillates 4 mix the laggard selectivity fixed bed hydrogenation reactor of going into new hydrogen 11 and recycle hydrogen 9 after pump 5 boosts, at 180～260 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 1.0～3.0MPa, reactive hydrogen oil ratio 200～500, reaction solution hourly space velocity 0.5～3.0h
-1Condition under carry out selective hydrogenation refining, selective hydrogenation generates oil 6 and enter gas-liquid separator 8 after water-cooled 7, recycle after circulating hydrogen compressor 10 boosts with after new hydrogen 11 mixes through the recycle hydrogen behind the gas-liquid separator 9, liquid 12 enters flashing tower or stripping tower 13, generates the contained gaseous impurities of oil to remove reaction.Gaseous impurities 14 enters the waste gas pipe network, the reaction that removes gaseous impurities generates that oil mixes with methyl alcohol 40 carries out alkylated reaction after enter alkylation reactor 17 behind the pump 15, process furnace 16 heating, and the ratio of mixture that generates oily and methyl alcohol in reaction is 1: 1～3,350～500 ℃ of temperature of reaction, reaction pressure 0.1～1.0MPa, reaction solution hourly space velocity 0.5～2.0h
-1Condition under carry out the alkylated reaction of benzene and methyl alcohol.The alkylated reaction resultant enters gun barrel 19 after water cooler 18 coolings, the generation oil that gun barrel top is told enters motor spirit Mixer pot 20, goes out device as automobile-used 90# gasoline products 21 after adding an amount of oil dope; Waste water is discharged in the gun barrel bottom.
＞205 ℃ of heavy oil fractions 22 when device goes into operation, add the commercial Dissel oil (deep hydrogenation that just often adds 1: 1 (weight ratio) at device generates oil＜360 ℃ of diesel oil distillate turning oils 35) of 1: 1 (weight ratio) after pump 23 boosts back and enter first deep hydrogenation fixed-bed reactor 25 after newly hydrogen 11 and recycle hydrogen 24 mix, at 230～300 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 8.0～15.0MPa, reactive hydrogen oil ratio 800～1500, reaction solution hourly space velocity 0.5～1.5h
-1Condition under carry out the first step hydrofining, the first step hydrofined oil 26 enters second deep hydrogenation fixed-bed reactor 27, at 300～380 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 8.0～15.0MPa, reactive hydrogen oil ratio 800～1500, reaction solution hourly space velocity 0.5～1.5h
-1Condition under carry out second the step hydrofining, the second step hydrofined oil enters gas-liquid separator 29 after water cooler 28 coolings, carry out gas-liquid separation here, after circulating hydrogen compressor 30 boosts with after new hydrogen mixes, recycle through the hydrogen behind the gas-liquid separator 24.Liquid enters flashing tower or stripping tower 31, generates the contained gaseous impurities of oil to remove reaction.Gaseous impurities 32 enters the waste gas pipe network, the reaction that removes gaseous impurities generates oil 33 and enters separation column 34, obtain at cat head＜360 ℃ of diesel oil, wherein a part of 360 ℃ of diesel oil distillates 35 are got back to reactor inlet as the circulation thinning oil and are recycled, 360 ℃ of diesel oil distillates 36 of another part enter derv fuel oil Mixer pot 37, go out device as automobile-used 0# diesel product 38 after adding an amount of oil dope; At the bottom of the tower＞360 ℃ of oil fuel products 39 go out device.
Following embodiment will further specify.The used hydrogenation catalyst kind of embodiment sees Table 1.The used benzene alkylation reaction catalyzer of embodiment is conventional ZSM-5 molecular sieve allcylation catalyst.
Table 1 embodiment hydrogenation catalyst kind
Embodiment 1
With a kind of coalite tar is raw material, its raw material,＜205 ℃ of light oil distillates,＞205 ℃ of heavy oil fraction character see Table 2,＜205 ℃ of light oil distillate selective hydrogenation conditions are: 180 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 1.0MPa, reactive hydrogen oil ratio 200, reaction solution hourly space velocity 0.5h
-1Alkylation reaction condition is: the ratio of mixture of＜205 ℃ of light oil distillate hydrogenated oils and methyl alcohol is 1: 1,350 ℃ of temperature of reaction, reaction pressure 0.1MPa, reaction solution hourly space velocity 0.5h
-1＞205 ℃ of heavy oil fraction deep hydrofinishing reaction conditionss are: 230 ℃ of the first reactor reaction temperature, reactive hydrogen dividing potential drop 8.0MPa, reactive hydrogen oil ratio 800, reaction solution hourly space velocity 0.5h
-1300 ℃ of the second reactor reaction temperature, reactive hydrogen dividing potential drop 8.0MPa, reactive hydrogen oil ratio 800, reaction solution hourly space velocity 0.5h
-1The gasoline of gained, diesel oil, oil fuel product property see Table 3.
Embodiment 2
With a kind of coal-tar middle oil is raw material, its raw material,＜205 ℃ of light oil distillates,＞205 ℃ of heavy oil fraction character see Table 4,＜205 ℃ of light oil distillate selective hydrogenation conditions are: 220 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 1.5MPa, reactive hydrogen oil ratio 350, reaction solution hourly space velocity 1.75h
-1Alkylation reaction condition is: the ratio of mixture of＜205 ℃ of light oil distillate hydrogenated oils and methyl alcohol is 1: 2,430 ℃ of temperature of reaction, reaction pressure 0.5MPa, reaction solution hourly space velocity 1.25h
-1＞205 ℃ of heavy oil fraction deep hydrofinishing reaction conditionss are: 265 ℃ of the first reactor reaction temperature, reactive hydrogen dividing potential drop 11.5MPa, reactive hydrogen oil ratio 1150, reaction solution hourly space velocity 1.0h
-1340 ℃ of the second reactor reaction temperature, reactive hydrogen dividing potential drop 11.5MPa, reactive hydrogen oil ratio 1150, reaction solution hourly space velocity 1.0h
-1The gasoline of gained, diesel oil, oil fuel product property see Table 5.
Embodiment 3
(coalite tar: coal-tar middle oil: coal-tar heavy oil) Pei Zhi mixed coal tar was a raw material by weight 1: 1: 1 with a kind of, its raw material,＜205 ℃ of light oil distillates,＞205 ℃ of heavy oil fraction character see Table 6,＜205 ℃ of light oil distillate selective hydrogenation conditions are: 260 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 3.0MPa, reactive hydrogen oil ratio 500, reaction solution hourly space velocity 3.0h
-1Alkylation reaction condition is: the ratio of mixture of＜205 ℃ of light oil distillate hydrogenated oils and methyl alcohol is 1: 3,500 ℃ of temperature of reaction, reaction pressure 1.0MPa, reaction solution hourly space velocity 2.0h
-1＞205 ℃ of heavy oil fraction deep hydrofinishing reaction conditionss are: 300 ℃ of the first reactor reaction temperature, reactive hydrogen dividing potential drop 15.0MPa, reactive hydrogen oil ratio 1500, reaction solution hourly space velocity 1.5h
-1380 ℃ of the second reactor reaction temperature, reactive hydrogen dividing potential drop 15.0MPa, reactive hydrogen oil ratio 1500, reaction solution hourly space velocity 1.5h
-1The gasoline of gained, diesel oil, oil fuel product property see Table 7.
Table 2 embodiment 1 raw material,＜205 ℃ of light oil distillates,＞205 ℃ of heavy oil fraction character
| Analysis project | Raw material | ＜205 ℃ of light oil distillates | ＞205 ℃ of heavy oil fractions |
| Outward appearance | Black | Yellow | Black |
| Analysis project | Raw material | ＜205 ℃ of light oil distillates | ＞205 ℃ of heavy oil fractions |
| 20 ℃ of density, kg/m 3 | ??939 | ??834 | ??951 |
| Condensation point, ℃ | ??11 | ??18 | |
| Boiling range, ℃ | |||
| ??HK～10％ | ??66～134 | ??65～71 | ??201～232 |
| ??30％～ | ??196～231 | ??95～121 | ??276～308 |
| ??70％～ | ??266～344 | ??155～191 | ??324～386 |
| ??KK | ??＞400 | ??205 | ??＞400 |
| Total N, ppm | ??10800 | ??7911 | ??12670 |
| Total S, ppm | ??8810 | ??5765 | ??9341 |
| Carbon residue, w% | ??2.15 | ??2.33 | |
| Benzene content, w% | ??22.7 |
Table 3 embodiment 1 gasoline products character
| Project | ＜205 ℃ of gasoline | ??GB???17930-2006 | Project | ＜205 ℃ of gasoline | ??GB???17930-2006 |
| Research octane number (RON) | ??90.1 | ??≮90 | Mercaptan sulfur content/% (massfraction) | ??0.0002 | ??≯0.001 |
| Anti-knock index | ??85.6 | ??≮85 | Manganese content, g/l | Do not have | ??≯0.016 |
| Lead content, g/l | ??0.001 | ??≯0.005 | Water soluble acid or alkali | Do not have | Do not have |
| Total sulfur, % (massfraction) | ??0.0005 | ??≯0.015 | Mechanical impurity and moisture | Do not have | Do not have |
| Inductive phase, min | ??560 | ??≮480 | Iron level, g/l | ??0.005 | ??≯0.01 |
| Boiling range, ℃ 10% 50% 90% KK residual quantity/v% | ???63??118??187??205??0.5 | ???≯70??≯120??≯190??≯205??≯2 | Benzene content, w% aromaticity content, w% olefin(e) centent, w% oxygen level, w% methanol content, w% | 0.5 38.5 1.2 2.1 do not have | ???≯1??≯40??≯30??≯2.7??≯0.3 |
| Project | ＜205 ℃ of gasoline | ??GB???17930-2006 | Project | ＜205 ℃ of gasoline | ??GB???17930-2006 |
| Vapour pressure, Kpa November 1 to May 1 April 30 was to October 31 | ???81???69? | ???≯88???≯72? | Copper corrosion (50 ℃, 3h)/the level existent gum, mg/100ml | ???1???2? | ???≯1???≯5? |
Table 4 embodiment 1 diesel product character
| Project | Diesel product | ??GB??252-2000 | Project | Diesel product | ??GB??252-2000 |
| Cetane value | ??45.2 | ??≮45 | 10% carbon residue, w% | ??0.01 | ??≯0.3 |
| Total insoluble substance, mg/100ml | ??1.0 | ??≯2.5 | Ash content, w% | ??0.01 | ??≯0.01 |
| Acidity, mgKOH/100ml | ??2.7 | ??≯7 | Condensation point, ℃ | ??20 | ??≯0 |
| Total sulfur, ppm | ??0.0045 | ??≯0.2 | Moisture, v% | Vestige | ≯ vestige |
| Colourity, number | ??2.1 | ??≯3.5 | Kinematic viscosity (20 ℃) mm 2/s | ??3.9 | ??3.0～8.0 |
| Boiling range, ℃ 50% 90% 95% | ???275??316??359 | ???≯300??≯355??≯365 | Cold filter clogging temperature, ℃ flash-point (remaining silent), ℃ density (20 ℃) kg/m 3Copper corrosion (50 ℃, 3h)/level | ??18??65??821??1 | ≯ 4 ≮ 55 actual measurements ≯ 1 |
Table 5 embodiment 1 oil fuel product property
| Project | ＞360 ℃ of oil fuel | Project | ＞360 ℃ of oil fuel |
| 20 ℃ of density, kg/m 3 | ??894 | Boiling range, ℃ | |
| Total sulfur, ppm | ??298 | ??HK～10％ | ??361～399 |
| Total nitrogen, ppm | ??146 | ??30％～50％ | ??415～431 |
| Condensation point, ℃ | ??36 | ??70％～90％ | ??466～499 |
| Ash content, % | ??0.01 | Flash-point (remaining silent), ℃ | ??80 |
Table 6 embodiment 2 raw materials,＜205 ℃ of light oil distillates,＞205 ℃ of heavy oil fraction character
| Analysis project | Raw material | ＜205 ℃ of light oil distillates | ＞205 ℃ of heavy oil fractions |
| Outward appearance | Black | Yellow | Black |
| 20 ℃ of density, kg/m 3 | ??993 | ??847 | ??998 |
| Condensation point, ℃ | ??17 | ??22 | |
| Boiling range, ℃ | |||
| ??HK??～ | ??70～154 | ??69～73 | ??206～262 |
| ??30％～ | ??226～285 | ??99～123 | ??289～334 |
| ??70％～ | ??306～425 | ??157～201 | ??366～421 |
| ??KK | ??451 | ??205 | ??454 |
| Total N, ppm | ??8900 | ??6900 | ??10100 |
| Total S, ppm | ??7500 | ??5400 | ??9941 |
| Carbon residue, w% | ??1.47 | ??2.54 | |
| Benzene content, w% | ??19.8 |
Table 7 embodiment 2 gasoline products character
| Project | ＜205 ℃ of gasoline | ??GB??17930-2006 | Project | ＜205 ℃ of gasoline | ??GB??17930-2006 |
| Research octane number (RON) | ??90.4 | ??≮90 | Mercaptan sulfur, % | ??0.0005 | ??≯0.001 |
| Anti-knock index | ??85.1 | ??≮85 | Manganese content, g/l | Do not have | ??≯0.016 |
| Lead content, g/l | ??0.001 | ??≯0.005 | Water-soluble soda acid | Do not have | Do not have |
| Total sulfur, ppm | ??0.0015 | ??≯0.015 | Mechanical impurity and moisture | Do not have | Do not have |
| Inductive phase, min | ??510 | ??≮480 | Iron level, g/l | ??0.008 | ??≯0.01 |
| Project | ＜205 ℃ of gasoline | ??GB??17930-2006 | Project | ＜205 ℃ of gasoline | ??GB??17930-2006 |
| Boiling range, ℃ 10% 50% 90% KK residual quantity/v% | ???70??120??189??205??0.9 | ???≯70??≯120??≯190??≯205??≯2 | Benzene content, w% aromaticity content, w% olefin(e) centent, w% oxygen level, w% methanol content, w% | 0.4 39.1 2.0 2.5 do not have | ???≯1??≯40??≯30??≯2.7??≯0.3 |
| Vapour pressure, Kpa 11/1～4,/30 5/1～10/30 | ???86???70? | ???≯88???≯72? | Copper corrosion (50 ℃, 3h)/the level existent gum, mg/100ml | ???1???3.5? | ???≯1???≯5? |
Table 8 embodiment 2 diesel product character
| Project | Diesel product | ??GB??252-2000 | Project | Diesel product | ??GB??252-2000 |
| Cetane value | ??45.0 | ??≮45 | 10% carbon residue, w% | ??0.05 | ??≯0.3 |
| Total insoluble substance, mg/100ml | ??1.6 | ??≯2.5 | Ash content, w% | ??0.01 | ??≯0.01 |
| Acidity, mgKOH/100ml | ??3.9 | ??≯7 | Condensation point, ℃ | ??17 | ??≯0 |
| Total sulfur, ppm | ??0.0061 | ??≯0.2 | Moisture, v% | Vestige | ≯ vestige |
| Colourity, number | ??2.0 | ??≯3.5 | Kinematic viscosity (20 ℃) mm 2/s | ??4.1 | ??3.0～8.0 |
| Boiling range, ℃ 50% 90% 95% | ???277??321??358 | ???≯300??≯355??≯365 | Cold filter clogging temperature, ℃ flash-point (remaining silent), ℃ density (20 ℃) kg/m 3Copper corrosion (50 ℃, 3h)/level | ??14??69??837??1 | ≯ 4 ≮ 55 actual measurements ≯ 1 |
Table 9 embodiment 2 oil fuel product properties
| Project | ＞360 ℃ of oil fuel | Project | ＞360 ℃ of oil fuel |
| 20 ℃ of density, kg/m 3 | ??901 | Boiling range, ℃ | |
| Total sulfur, ppm | ??313 | ??HK～10％ | ??360～392 |
| Project | ＞360 ℃ of oil fuel | Project | ＞360 ℃ of oil fuel |
| Total nitrogen, ppm | ??179 | ??30％～50％ | ??415～439 |
| Condensation point, ℃ | ??38 | ??70％～90％ | ??456～489 |
| Ash content, % | ??0.01 | Flash-point (remaining silent), ℃ | ??85 |
Table 10 embodiment 3 raw materials,＜205 ℃ of light oil distillates,＞205 ℃ of heavy oil fraction character
| Analysis project | Raw material | ＜205 ℃ of light oil distillates | ＞205 ℃ of heavy oil fractions |
| Outward appearance | Black | Yellow | Black |
| 20 ℃ of density, kg/m 3 | ??1029 | ??840 | ??1034 |
| Condensation point, ℃ | ??22 | ??32 | |
| Boiling range, ℃ | |||
| ??HK??～ | ??70～194 | ??70～73 | ??206～271 |
| ??30％～ | ??298～385 | ??88～119 | ??307～394 |
| ??70％～ | ??413～479 | ??139～200 | ??429～498 |
| ??KK | ??＞500 | ??205 | ??＞500 |
| Total N, ppm | ??5800 | ??3800 | ??7600 |
| Total S, ppm | ??12000 | ??8560 | ??12339 |
| Carbon residue, w% | ??1.99 | ??3.01 | |
| Benzene content, w% | ??17.9 |
Table 11 embodiment 3 gasoline products character
| Project | ＜205 ℃ of gasoline | ??GB??17930-2006 | Project | ＜205 ℃ of gasoline | ??GB??17930-2006 |
| Research octane number (RON) | ??90 | ??≮90 | Mercaptan sulfur, % | ??0.0009 | ??≯0.001 |
| Anti-knock index | ??85 | ??≮85 | Manganese content, g/l | Do not have | ??≯0.016 |
| Lead content, g/l | ??0.001 | ??≯0.005 | Water-soluble soda acid | Do not have | Do not have |
| Total sulfur, ppm | ??0.002 | ??≯0.015 | Mechanical impurity and moisture | Do not have | Do not have |
| Inductive phase, min | ??590 | ??≮480 | Iron level, g/l | ??0.009 | ??≯0.01 |
| Boiling range, ℃ 10% 50% 90% KK residual quantity/v% | ???70??119??189??205??1.3 | ???≯70??≯120??≯190??≯205??≯2 | Benzene content, w% aromaticity content, w% olefin(e) centent, w% oxygen level, w% methanol content, w% | 0.3 37.9 3.9 2.6 do not have | ???≯1??≯40??≯30??≯2.7??≯0.3 |
| Vapour pressure, Kpa 11/1～4,/30 5/1～10/30 | ??86??70 | ??≯88??≯72 | Copper corrosion (50 ℃, 3h)/the level existent gum, mg/100ml | ??1??4.1 | ??≯1??≯5 |
Table 12 embodiment 3 diesel product character
| Project | Diesel product | ??GB??252-2000 | Project | Diesel product | ??GB??252-2000 |
| Cetane value | ??45.1 | ??≮45 | 10% carbon residue, w% | ??0.1 | ??≯0.3 |
| Total insoluble substance, mg/100ml | ??2.0 | ??≯2.5 | Ash content, w% | ??0.01 | ??≯0.01 |
| Acidity, mgKOH/100ml | ??5.1 | ??≯7 | Condensation point, ℃ | ??18 | ??≯0 |
| Total sulfur, ppm | ??0.0089 | ??≯0.2 | Moisture, v% | Vestige | ≯ vestige |
| Colourity, number | ??2.5 | ??≯3.5 | Kinematic viscosity (20 ℃) mm 2/s | ??5.0 | ??3.0～8.0 |
| Boiling range, ℃ 50% 90% 95% | ???287??323??359 | ???≯300??≯355??≯365 | Cold filter clogging temperature, ℃ flash-point (remaining silent), ℃ density (20 ℃) kg/m 3Copper corrosion (50 ℃, 3h)/level | ??-11??71??851??1 | ≯ 4 ≮ 55 actual measurements ≯ 1 |
Table 13 embodiment 3 oil fuel product properties
| Project | ＞360 ℃ of oil fuel | Project | ＞360 ℃ of oil fuel |
| 20 ℃ of density, kg/m 3 | ??948 | Boiling range, ℃ | |
| Total sulfur, ppm | ??499 | ??HK～10％ | ??359～402 |
| Total nitrogen, ppm | ??117 | ??30％～50％ | ??419～451 |
| Condensation point, ℃ | ??37 | ??70％～90％ | ??459～496 |
| Ash content, % | ??0.02 | Flash-point (remaining silent), ℃ | ??88 |
Claims (6)
1. a coal tar hydrogenation modification method is characterized in that: comprise the steps:
(1) coal tar is cut into＜205 ℃ light oil distillate and＞205 ℃ heavy oil fraction through normal pressure distillation or underpressure distillation;
(2) step (1) is obtained＜205 ℃ of light oil distillates mix with hydrogen that to carry out mild hydrogenation refining after enter one section fixed bed hydrogenation reactor after the process furnace heating, described mild hydrogenation purification condition is: 180～260 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 1.0～3.0MPa, reactive hydrogen oil ratio 200～500, reaction solution hourly space velocity 0.5～3.0h
-1
(3) the generation oil that step (2) is obtained enters flashing tower or stripping tower after cooling, gas-liquid separation, removes reaction and generates the contained gaseous impurities of oil;
(4) reaction that removes gaseous impurities that step (3) is obtained generates oil and carries out alkylated reaction with methanol mixed after enter alkylation reactor after the process furnace heating, the ratio of mixture that described reaction generates oil and methyl alcohol is 1: 1～3, and described alkylation reaction condition is: 350～500 ℃ of temperature of reaction, reaction pressure 0.1～1.0MPa, reaction solution hourly space velocity 0.5～2.0h
-1
(5) resultant of reaction that step (4) is obtained enters gun barrel, the generation oil that gun barrel top is told enters the motor spirit Mixer pot, go out device as the automobile-used 90# gasoline products of GB after adding oil dope, waste water is discharged in the gun barrel bottom;
(6) step (1) is obtained＞205 ℃ of heavy oil fractions added by weight 1: 1 and enter two sections fixed bed hydrogenation reactors after thinning oil mixes the back and hydrogen mixes and carry out deep hydrofinishing, described deep hydrofinishing condition is: first reactor: 230～300 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 8.0～15.0MPa, reactive hydrogen oil ratio 800～1500, reaction solution hourly space velocity 0.5～1.5h
-1Second reactor: 300～380 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 8.0～15.0MPa, reactive hydrogen oil ratio 800～1500, reaction solution hourly space velocity 0.5～1.5h
-1
(7) the generation oil that step (6) is obtained enters flashing tower or stripping tower after cooling, gas-liquid separation, generates the contained gaseous impurities of oil to remove reaction;
(8) reaction that removes gaseous impurities that step (7) is obtained generates oil and enters distillation tower, obtains at the distillation tower cat head＜360 ℃ diesel oil distillate, obtains at the bottom of the tower＞360 ℃ tail oil cut;
(9) step (8) is obtained＜a diesel oil distillate part of 360 ℃ returns the reaction inlet as the circulation thinning oil and recycles, and described part of fraction of fuel-oil amount as the circulation thinning oil is 50% of a hydrogenation charge raw material total amount; The remainder diesel oil distillate enters the derv fuel oil Mixer pot, goes out device as the automobile-used 0# diesel product of GB after adding oil dope.
2. according to the described coal tar hydrogenation modification method of claim 1, it is characterized in that: described coal tar is any or several arbitrary proportion mixing oils in any or coal-tar heavy oil and the middle coalite tar of coalite tar, coal-tar middle oil.
3. according to the described coal tar hydrogenation modification method of claim 1, it is characterized in that: described mild hydrogenation catalyst for refining is that active ingredient is one or more in the catalyzer of molybdenum nickel, molybdenum nickel phosphorus, tungsten nickel, tungsten nickel phosphorus and molybdenum nickel tungsten phosphorus.
4. according to the described coal tar hydrogenation modification method of claim 1, it is characterized in that: described catalyst for alkylation reaction is conventional ZSM-5 molecular sieve allcylation catalyst.
5. according to the described coal tar hydrogenation modification method of claim 1, it is characterized in that: described deep hydrofinishing catalyzer is that active ingredient is one or more in the catalyzer of molybdenum cobalt, molybdenum cobalt phosphorus, tungsten cobalt, tungsten cobalt phosphorus and molybdenum nickel tungsten phosphorus.
6. according to the described coal tar hydrogenation modification method of claim 1, it is characterized in that: adopt commercial Dissel oil when the thinning oil described in the step (5) goes into operation for the first time, the normal back that goes into operation adopts＞260 ℃ heavy oil fraction deep hydrogenation to generate the diesel oil distillate of oil content distilled＜360 ℃, thinning oil recycles, and adding proportion is 1: 1.
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