CN104004542A - Method for preparing coal-based high aromatic potential content raw oil - Google Patents
Method for preparing coal-based high aromatic potential content raw oil Download PDFInfo
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- 125000003118 aryl group Chemical group 0.000 title abstract description 5
- 239000003921 oil Substances 0.000 claims abstract description 218
- 239000002994 raw material Substances 0.000 claims abstract description 61
- 239000011280 coal tar Substances 0.000 claims abstract description 57
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 53
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 46
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- 239000003079 shale oil Substances 0.000 claims abstract description 19
- 239000007841 coal based oil Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 62
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 48
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
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Abstract
The invention discloses a method for preparing coal-based high aromatic potential content raw oil. The method includes the first step of preprocessing of raw materials, the second step of distillation separation, the third step of hydrocracking of a suspended bed and the fourth step of hydrogenation upgrading. Coal tar or shale oil can serve as the raw materials, direct coal liquefaction generated oil or coal-oil coprocessing generated oil can also serve as the raw materials, the application range of the raw materials is wide, the method can be used for producing coal-based catalytic reforming raw materials with the high aromatic potential content, another path is provided for utilizing high added value of coal-based oil products, and sources of the catalytic reforming raw materials with the high aromatic potential content are broadened.
Description
Technical field
The invention belongs to coal chemical technology, be specifically related to a kind of preparation method of coal-based high arene underwater content stock oil.
Background technology
Coal tar is taking aromatic hydrocarbon as main organic mixture, it is an important byproduct in pyrolysis of coal/distillation process process, according to the difference of pyrolysis of coal pyrolysis temperature and process approach, coal tar can be divided into coalite tar (500～650 DEG C of pyrolysis temperatures), coal-tar middle oil (700～800 DEG C of pyrolysis temperatures) and coal-tar heavy oil (950～1050 DEG C of pyrolysis temperatures), and its composition difference is larger.
Coal-tar heavy oil derives from coke-oven plant, and annual production is stabilized in 1,200 ten thousand tons of left and right, and 5,000,000 tons/year of actual amount of finish less thaies, serious waste of resources.Mainly contain following three kinds of modes: the one, serve as low heat value industrial fuel oil and come into the market.Can only serve as low value-added primary products.The 2nd, as the raw material of coal tar deep processing, can only therefrom extract the materials such as benzene, phenol, naphthalene, pitch.Be left to carry out burn processing as oil fuel, economic benefit is low.The 3rd, taking coal-tar heavy oil as raw material, adopt hydrofining or hydrocracking process technology, produce oil fuel.
In, coalite tar is mainly derived from the production such as blue charcoal, coal preparing natural gas that middle low temperature pyrogenation produces.The annual blue charcoal in the whole nation is produced coalite tar in by-product and is reached 6,500,000 tons, is mainly distributed in Shan, Shanxi, border land of Meng San province.In addition, extensive coal preparing natural gas project will be built up successively, expect coalite tar in coal preparing natural gas in 2015 and reach 6,000,000 tons, and the year two thousand twenty reaches 2,000 ten thousand tons, is mainly distributed in the resourceful areas such as the brown coal such as Xinjiang, Inner Mongol, long-flame coal.In at present industrialized, the processing mode of coalite tar is to use for reference existing refining of petroleum processing mode to produce oil fuel.
Compared with oil, coal tar has aromatic hydrocarbons and the high feature of naphthene content, for different coal tar, the content of aromatic hydrocarbons and naphthenic hydrocarbon is also different, the large scope about 64%-90%, higher than the aromatic hydrocarbons in petroleum fractions and naphthene content, be applicable to for the preparation of the catalytic reforming raw material of producing aromatic hydrocarbons far away.
And aromatic hydrocarbons chemical domestic needs vigorous (as BTX etc.), being mainly derived from present oil is the aromatic hydrocarbons production process of " catalytic reforming " technology of raw material, Aromatics Production Technology taking oil as raw material is subject to the restriction of Domestic Resources and regional distribution, is difficult to support the development of downstream PTA and PET industry.The petroleum naphtha of preparing coal-based high arene underwater content using coal tar as raw material is produced the raw material of aromatic hydrocarbons as catalytic reforming, not only can solve domestic a large amount of aroamtic hydrocarbon raw material gap problem, can also increase the economic benefit of coal tar processing process.
Chinese patent 201110006659.4 discloses a kind of method of widening catalytic reforming feedstock, this patent is mixed as raw material by 50: 50～70: 30 using FCC stable gasoline and virgin naphtha, through raw material strainer filtering and impurity removing matter, then remove and mix the water carrying in petroleum naphtha through coalescer; Mixing petroleum naphtha enters hydrogenator with hydrogen mixing and contacts with hydrogenation catalyst after process furnace is heated to temperature of reaction, carries out olefin saturated, desulfurization and denitrification reaction; Hydrogenation reaction effluent separates and obtains hydrogen-rich gas and hydrogenated gasoline after condensing cooling, and hydrogen-rich gas recycles, the refining petroleum naphtha that hydrogenated gasoline enters evaporator tower carries out stripping fractionation and be met catalytic reforming feedstock requirement; The mixing petroleum naphtha that present method can exceed mixing proportion 50%FCC stable gasoline carries out hydrotreatment, and acquisition foreign matter content all meets the refining petroleum naphtha of catalytic reforming feedstock requirement, has solved the not enough problem of reformer feed, the source of having widened reformer feed.
Chinese patent 200510089847.2 discloses a kind of method of hydrotreating of producing catalytic reforming raw material, and secondary processing of gasoline raw material is cut into light benzine cut, middle matter gasoline fraction and heavy gasoline cut by this patent; Middle matter gasoline fraction enters the first reaction zone together with hydrogen, under Hydrobon catalyst effect, react, reaction effluent enters second reaction zone after directly mixing with virgin naphtha without separation, under the effect of Hydrobon catalyst, react, cooling, separation that the reaction effluent generating carries out, isolated hydrogen-rich gas recycles, and isolated liquid enters distillation dehydration tower, obtains petroleum naphtha after imurity-removal.The method can be processed the secondary processing of gasoline that high sulfur-bearing is nitrogenous and olefin(e) centent is high under low pressure condition, is all less than the acceptable material of 0.5 Μ G/G for catalytic reforming provides sulphur, nitrogen content.
Chinese patent 200510089848.7 discloses a kind of method of producing catalytic reforming raw material, and secondary processing of gasoline raw material is cut into light benzine cut, middle matter gasoline fraction and heavy gasoline cut by this patent; Middle matter gasoline fraction, optional virgin naphtha contact with the first Hydrobon catalyst together with hydrogen, carry out olefin saturation, reaction effluent directly contacts with the second Hydrobon catalyst without separating, carry out hydrogenating desulfurization and hydrodenitrification reaction, cooling, separation that the reaction effluent generating carries out, isolated hydrogen-rich gas recycles, and isolated liquid enters distillation dehydration tower, obtains petroleum naphtha after imurity-removal.The method can be processed the secondary processing of gasoline that high sulfur-bearing is nitrogenous and olefin(e) centent is high under low pressure condition, is all less than the acceptable material of 0.5 Μ G/G for catalytic reforming provides sulphur, nitrogen content.
Chinese patent application 200910243462.5 discloses a kind of catalystic reforming method that improves aromatics yield, and its step is as follows: feed naphtha, after heating unit, enters reaction unit; Products therefrom through overcooling laggard enter high-pressure separator; After described high-pressure separator, gained reformate enters stabilizer tower and processes; Overhead extraction dry gas, liquefied gas and a small amount of water; At the bottom of tower, the reformed oil of gained enters extraction system; Described extraction system bottom extraction aromatic hydrocarbons enters respectively diced system with raffinating oil; Diced system bottom extraction is heavily raffinated oil after heating unit, enters another reaction unit, and heavily raffinate oil as diesel oil kerosene or kerosene blend component by pipeline extraction in bottom simultaneously; Gained reaction product through overcooling laggard enter high-pressure separator.The advantage of raising aromatics yield catalystic reforming method of the present invention is: processing power, liquid yield, aromatics yield, hydrogen output improve greatly.
Above patent is all to prepare the method for catalytic reforming raw material taking petroleum base oil product as raw material.
Chinese patent application 201010218009.1 discloses a kind of production method and application of the coal-based naphtha with high potential aromatic content for catalytic reforming, the method comprises: a) hydrogenation step: the full cut liquefaction oil that DCL/Direct coal liquefaction is produced mixes with hydrogen, after mixing, enter expanded bed hydrotreating reactor, contact to occur hydrogenation reaction with hydrotreating catalyst, the logistics that flows out the outlet of expanded bed hydrotreating reactor, after separation, fractionation, is obtained to light ends oil, middle matter cut and heavy distillate; And b) deep hydrofinishing step: after the light ends oil that step a) is obtained, middle matter distillate mix, mix with hydrogen, enter together fixed bed deep hydrofinishing reactor, contact to occur chemical reaction with Hydrobon catalyst, by the logistics that flows out fixed bed deep hydrofinishing reactor outlet through separating, after fractionation, obtain the naphtha fraction of the high aromatic hydrocarbon potential content that meets catalytic reforming charging requirement, and extending catalyst work-ing life.This patent is to adopt the method for ebullated bed for the preparation of the high aromatic hydrocarbons petroleum naphtha of catalytic reforming taking liquefied coal coil as raw material.
Summary of the invention
The object of the invention is to, a kind of preparation method of coal-based high arene underwater content stock oil is provided, the method can coal tar be not only raw material, can also DCL/Direct coal liquefaction generating oil or kerosene refines altogether and generates oil as raw material, applicable raw materials scope is wide, can be used for producing the catalytic reforming raw material of coal-based high aromatic hydrocarbon potential content, for the high value added utilization of coal-based oil product provides another kind of approach, widened the source of the catalytic reforming raw material of high arene underwater content.
For achieving the above object, the present invention has adopted following technical scheme:
A preparation method for coal-based high arene underwater content stock oil, said method comprising the steps of:
1) raw materials pretreatment: when coal-based oil product raw material is that DCL/Direct coal liquefaction generates oil or kerosene and refines altogether while generating oil, this step is omitted, and directly enters fractionation by distillation step;
In the time that coal-based oil product raw material is coal tar or shale oil, the moisture, the solid impurity that remove wherein obtain pretreated coal tar;
2) fractionation by distillation: DCL/Direct coal liquefaction generates oil, kerosene and refines altogether and generate oil or pretreated coal tar, pretreated shale oil are divided into the first light ends oil and heavy distillate through air distillation or underpressure distillation, wherein, the distillation cutting temperature of the first light ends oil and heavy distillate is between 280～370 DEG C; Heavy distillate carries out floating bed hydrocracking;
3) floating bed hydrocracking: at normal pressure, 80～200 DEG C of temperature, catalyzer, vulcanizing agent and solvent oil are mixed to even Kaolinite Preparation of Catalyst slurry oil, again oil-catalyst slurry is mixed and carries out floating bed hydrocracking with heavy distillate and turning oil, crackate obtains liquid-solid phase mixture and the first hydrogen-rich gas through separating, liquid-solid phase mixture is isolated to the second light ends oil and tail oil, or crackate is isolated to low-temperature separator oil, high-temperature separator oil and the second hydrogen-rich gas, high-temperature separator oil enters suspension bed again and carries out hydrocracking;
4) hydrogenation upgrading: step 2) obtain the first light ends oil and step 3) the second light ends oil of obtaining or low-temperature separator oil mixes employing fixed bed or ebullated bed carries out hydrogenation upgrading, hydrogenation upgraded product is carried out product fractionation after cooling, gas-liquid separation, obtain being less than the naphtha fraction of 145 DEG C or be less than naphtha fraction or the cut of 65～145 DEG C or the cut of 65～150 DEG C of 150 DEG C, the cut after above-mentioned fractionation is coal-based high arene underwater content stock oil;
Described solvent oil is one or more in the high-temperature separator oil of tail oil, high-temperature separator oil and Removal of catalyst of heavy distillate, tail oil, Removal of catalyst; Described turning oil is the high-temperature separator oil of tail oil, high-temperature separator oil or the Removal of catalyst of tail oil or Removal of catalyst.
Preferably, described catalyzer is containing one or more active metals in molybdenum, nickel, cobalt, tungsten and iron, and catalyzer is the powdered granule of particle diameter 1～100 μ m.
Preferably, described vulcanizing agent is sulphur or dimethyl disulfide.
Preferably, in described oil-catalyst slurry, solids concn is 20wt%～45wt%.
Preferably, floating bed hydrocracking condition is: 320～480 DEG C of temperature of reaction, reaction pressure 8～25Mpa, volume space velocity 0.3～3.0h
-1, hydrogen to oil volume ratio 500～2000, the add-on of catalyzer taking control active metal total amount with the ratio of heavy ends weight of oil as 0.1:100 to 4:100.
Preferably, floating bed hydrocracking condition is: 350～450 DEG C of temperature of reaction, reaction pressure 10～19Mpa, volume space velocity 0.5～2.0h
-1, hydrogen to oil volume ratio 800～1500, the add-on of catalyzer taking control active metal total amount with the ratio of heavy ends weight of oil as 0.5:100 to 2:100.
Preferably, described step 4) in, in the time adopting fixed bed to carry out hydrogenation upgrading, catalyzer is bar shaped or spherical loaded catalyst, catalyzer contains one or more in active metal iron, nickel, cobalt, molybdenum and tungsten, and support of the catalyst is one or more in aluminum oxide, silicon oxide and titanium oxide;
When adopting ebullated bed while carrying out hydrogenation upgrading, catalyzer is taking inorganic oxide or molecular sieve as carrier, and active metal is one or more in iron, nickel, cobalt, molybdenum and tungsten.
Preferably, described inorganic oxide is one or more in aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, and described molecular sieve is one or more in ZSM zeolite, zeolite L, y-type zeolite, Beta type zeolite.
Preferably, described step 4) in hydrogenation upgrading reaction conditions be: temperature of reaction is 200～440 DEG C, and reaction pressure is 6～17MPa, and volume space velocity is 0.5～4.0h
-1, hydrogen-oil ratio is 300～2000.
The present invention adopts conventional method to remove moisture and the solid impurity of coal tar.
Owing to containing a certain amount of moisture and solid impurity in coal tar, cause serious harm can to distillation, hydrogenation production unit and pipeline, hydrogenation catalyst and quality product, therefore before coal tar deep processing, need coal tar de-slag (solid impurity) pre-treatment of dewatering.Coal tar of the present invention is that in coalite tar, middle coalite tar, coal-tar middle oil, coal-tar heavy oil, any one or two or more coal tar are with the mixing oil of arbitrary proportion, and the present invention can also use shale wet goods.
Coal tar dehydration is divided into preliminary hydro-extraction and final dewatering two steps, and preliminary hydro-extraction adopts heating to leave standstill evaporation, and tar uses coil pipe heating and thermal insulation at 30～90 DEG C in storage tank, and more than standing 36h, tar water content can take off to 2～3%; Also can adopt ultracentrifuge to carry out preliminary hydro-extraction to tar, tar water content can take off to 1%～2%.Final dewatering can adopt batch still evaporation, tube furnace evaporation, film type evaporation and chemical demulsification method etc., and after final dewatering, the water content of coal tar can be down to below 0.5%.
In coal tar, mechanical impurity removes the method that both can adopt solvent extraction and settleability whizzer to combine, also can utilize separately super three-phase centrifugal separation equipment imurity-removal, utilize aforesaid method, can make the coal tar solid impurity content after purifying be less than 0.3%.
The present invention generates oil or kerosene using pretreated purification coal tar, DCL/Direct coal liquefaction and refines altogether and generate one or more in oil and be cut into light ends oil and heavy distillate as stock oil by distillation, light ends removes to be fixed a deep hydrofinishing, and heavy ends goes to floating bed hydrocracking unit to carry out oil product lighting.According to the specific nature of coal tar, preferred, the arbitrary temp of the cutting temperature of light when fractionation by distillation, last running between 280～370 DEG C.Described distillation can be selected air distillation or underpressure distillation.
Vulcanizing agent of the present invention can also can generate for other material of hydrogen sulfide under reaction conditions, hydrogen sulfide content in the mixing hydrogen of the add-on of vulcanizing agent in should guarantee system is not less than 1000ppm, the solids concn of oil-catalyst slurry can be controlled in 20wt～45wt%, is preferentially controlled at 25wt～40wt%.
The solvent oil adopting in the present invention is the high-temperature separator oil of tail oil, high-temperature separator oil and the Removal of catalyst of heavy distillate, tail oil, Removal of catalyst, and those skilled in the art can proceed from the reality and select suitable solvent oil for the preparation of oil-catalyst slurry.
Hydrocracking of the present invention adopts the floating bed hydrogenation reactor of one or more series connection to react.
Floating bed hydrogenation reactant of the present invention adopts following several method to separate:
(1) first after separating, gas-liquid separation unit (separating unit can be made up of two or more separators) obtains liquid-solid phase mixture (containing solid liquid phase oil) and hydrogen-rich gas, hydrogen-rich gas is as recycle hydrogen, liquid-solid phase mixture is after atmospheric distillation tower fractionation, tower top obtains light ends oil (egress cutpoint temperature can be the temperature between 300～380 DEG C), at the bottom of tower, be the heavy oil of the normal end (or claiming tail oil) that contains catalyzer, wherein heavy oil of most of (about 2/3rds to 4/5ths) normal end is recycled directly to and in floating bed hydrogenation reactor, further carries out hydrogenation lighting reaction as turning oil, the heavy oil of the normal end of all the other small parts (about 1/3rd to 1/5th) enters solid-liquid separation system and carries out solid-liquid separation, solid-liquid separation can adopt the form of filtration or centrifugation or sedimentation or vacuum fractionation, after separation, obtain catalyst residue and floating bed hydrogenation heavy distillate, the partial solvent that the reaction raw materials of heavy distillate or direct and suspension bed mixes or prepares as oil-catalyst slurry, circulation enters further carries out hydrogenation lighting reaction in floating bed hydrogenation reactor, the catalyzer of deviating from gets rid of outward or regenerates,
(2) hydrocracking reaction material obtains hydrogen-rich gas after gas-liquid separation unit (separating unit can be made up of two or more separators) separates, low-temperature separator oil and high-temperature separator oil, hydrogen-rich gas uses as recycle hydrogen, low-temperature separator oil goes to hydrofining unit to carry out hydrogenation upgrading, the major part (about 2/3rds to 4/5ths) of high-temperature separator oil directly ring enters and in floating bed hydrogenation reactor, further carries out hydrogenation lighting reaction, all the other small parts (about 1/3rd to 1/5th) high-temperature separator oil directly adopts the mode of settling process or centrifugation or filtration or underpressure distillation to carry out solid-liquid separation, floating bed hydrogenation heavy distillate circulation after de-solid enters further carries out hydrogenation lighting reaction in floating bed hydrogenation reactor, the solid-phase catalyst residue of deviating from gets rid of outward or regenerates.
Hydrogenation upgrading of the present invention adopts single hop, two sections or multistage hydrogenation technique.
Hydrogenation upgrading catalyst activity metal of the present invention, except adopting nickel, cobalt, molybdenum or tungsten, can also adopt other metals in periodic table of elements group vib or VIII family.
Hydrogenation upgrading catalyzer pore volume>=0.4ml/g of the present invention, specific surface area>=120m
2/ g, bulk density is 0.4～1.9Kg/m
3.
Advantage of the present invention be mainly reflected in following some:
1. the present invention had both been applicable to coalite tar, middle coalite tar, coal-tar heavy oil, was also applicable to the mixing oil of any two above coal tar, also refined altogether generation oil applicable to DCL/Direct coal liquefaction generation oil and kerosene, and raw material is applied widely.
2. in method provided by the present invention, adopt rational processing process and suitable working depth, by the optimization of processing parameter, taking coal tar full distillate oil as raw material, take heavy distillate floating bed hydrocracking---the catalytic reforming raw material of the high arene underwater content of explained hereafter of-light ends oil fixed bed deep hydrofinishing, technical process is reasonable, and raw material availability is high, the catalytic reforming raw material of the available different high arene underwater content of raw material production.
3. the high value added utilization that the present invention is coal-based oil product provides another kind of approach, has widened the source of the catalytic reforming raw material of high arene underwater content.
4. the catalytic reforming raw material of the high arene underwater content that the present invention produces, arene underwater content is higher than petroleum reformer feed.
Brief description of the drawings
Fig. 1 is the process flow sheet one of the inventive method;
Fig. 2 is the process flow sheet two of the inventive method;
Reference numeral:
Digitized representation material in figure: 1, coal tar or shale oil; 2, hydrogen; 3, pretreated purification coal tar or pretreated purification shale oil or coal direct liquefaction oil or kerosene refine altogether and generate oil; 4, the first light ends oil; 5, heavy distillate; 6, solvent oil; 7, first mixes hydrogen; 8, hydrocracking catalyst and vulcanizing agent; 9, oil-catalyst slurry; 10, second mixes hydrogen; 11, hydrocracking reaction product; 12, the first hydrogen-rich gas; 13, hydrogenation upgraded product; 14, the second hydrogen-rich gas; 15, gas-liquid separation liquid phase material; 16, cut one; 17, cut two; 18, cut three; 19, cut four; 20, the high-temperature separator oil of denitrating catalyst tail oil or denitrating catalyst; 21, catalyst residue; 22, liquid-solid phase mixture; 23, the second light ends oil; 24, tail oil; 25, low-temperature separator oil; 26, high-temperature separator oil;
In figure, letter and number combination represents unit, device or equipment: V1, pretreatment unit; T1, the first fractionation by distillation unit; V2, slurry oil are prepared unit; R1, hydrocracking unit; V3, the first gas-liquid separation unit; T2, after-fractionating unit; R2, hydrogenation upgrading unit; V5, solid-liquid separation unit; V4, the second gas-liquid separation unit; T3, product fractionation unit.
Embodiment
The beneficial effect of further illustrating object of the present invention and having below in conjunction with subordinate list, process flow sheet and specific embodiment, but protection scope of the present invention is not limited to the following example.
Fig. 1 is the embodiment that the sepn process of hydrocracking reaction resultant comprises fractionation by distillation, is described as follows:
In the time that coal-based oil product raw material is coal tar or shale oil, coal tar or shale oil 1 first enter pretreatment unit V1 dewater de-slag (solid impurity) process, pretreated purification coal tar or shale oil 3 enter the first fractionation by distillation unit T1, when coal-based oil product raw material is that DCL/Direct coal liquefaction generates oil or kerosene and refines altogether while generating oil, directly enter fractionation by distillation unit T1 without pre-treatment.
Pretreated purification coal tar, shale oil or coal direct liquefaction oil or kerosene refine altogether and generate oil 3 and in T1, be distilled and be cut into the first light ends oil 4 and heavy distillate 5, the first light ends oil 4 and enter hydrogenation upgrading unit R 2 and carry out hydrofining; After one or more of the tail oil 20 of the part of heavy distillate 5, tail oil 24, Removal of catalyst mix, prepare unit V2 (normal pressure, 80～200 DEG C) Kaolinite Preparation of Catalyst slurry oil as solvent oil 6 slurry that deoils, solvent oil 6 and hydrocracking catalyst and vulcanizing agent 8 are prepared and in unit V2, are mixed with into oil-catalyst slurry 9 at slurry oil; Tail oil 20 mixtures of other parts, oil-catalyst slurry 9, tail oil 24 and the Removal of catalyst of heavy distillate 5 partly or entirely, be mixed to get by hydrogen 2 and the first hydrogen-rich gas 12 second mix to enter after hydrogen 10 mixes in succession and in floating bed hydrocracking unit R 1, carry out cracking reaction.Hydrocracking reaction product 11 carries out gas-liquid separation in the first gas-liquid separation unit V3 (separating unit can include two or three separators), be separated into after the first hydrogen-rich gas 12 and liquid-solid phase mixture 22, the first hydrogen-rich gases 12 mix as recycle hydrogen and hydrogen 2 and go to hydrocracking unit.Liquid-solid phase mixture 22 is distilled and is cut into the second light ends oil 23 and tail oil 24, the second light ends oil 23 go to hydrogenation upgrading unit to carry out hydrofining in after-fractionating unit T2; Tail oil 24 parts go solid-liquid separation unit V5 to carry out solid-liquid separation; After another part of tail oil 24 and the tail oil of Removal of catalyst 20 mix, the slurry that deoils is prepared unit V2 or is directly gone hydrocracking unit R 1 to carry out oil product lighting.Enter solid-liquid separation unit V5 from a part of material of tail oil 24 and carry out solid-liquid separation, be separated into tail oil 20 and the catalyst residue 21 of Removal of catalyst.
After the first mixing hydrogen 7 of the first light ends oil 4, the second light ends oil 23, hydrogen 2 and the second hydrogen-rich gas 14 mixes in succession, enter hydrogenation upgrading unit R 2 and carry out hydrofining, hydrogenation upgraded product 13 is carried out gas-liquid separation in the second gas-liquid separation unit V4, is separated into the second hydrogen-rich gas 14 and gas-liquid separating liquid-phase materials 15.The second hydrogen-rich gas 14 turns back to hydrogenation upgrading unit, gas-liquid separation liquid phase material 15 is in product fractionation unit T3, distillation is cut into cut 1 or cut 2 17 or cut 3 18 or cut 4 19, above-mentioned cut one can be for being less than the cut of 65 DEG C, cut two can be the cut of 65～145 DEG C or the cut of 65～150 DEG C, cut three can be kerosene(oil)fraction, cut four can be diesel oil distillate, those skilled in the art can be according to actual needs, select different cut points, such as above-mentioned cut one and cut two are merged, the naphtha fraction that obtains being less than the naphtha fraction of 145 DEG C or be less than 150 DEG C, wherein be less than the naphtha fraction of 145 DEG C or be less than the naphtha fraction of 150 DEG C or the cut of 65～145 DEG C or the cut of 65～150 DEG C and be the coal-based high arene underwater content stock oil of producing aromatic hydrocarbons for catalytic reforming.
Fig. 2 is the embodiment that the sepn process of hydrocracking reaction resultant does not comprise fractionation by distillation, is described as follows:
In the time that coal-based oil product raw material is coal tar or shale oil, coal tar or shale oil 1 first enter pretreatment unit V1 dewater de-slag (solid impurity) process, pretreated purification coal tar or shale oil 3 enter the first fractionation by distillation unit T1, when coal-based oil product raw material is that DCL/Direct coal liquefaction generates oil or kerosene and refines altogether while generating oil, directly enter fractionation by distillation unit T1 without pre-treatment.
Pretreated purification coal tar or pretreated purification shale oil or coal direct liquefaction oil or kerosene refine altogether and generate oil 3 and in T1, be distilled and be cut into the first light ends oil 4 and heavy distillate 5, the first light ends oil 4 and enter hydrogenation upgrading unit R 2 and carry out hydrofining; After one or more of the high-temperature separator oil 20 of the part of heavy distillate 5, high-temperature separator oil 26, Removal of catalyst mix, prepare unit V2 (normal pressure, 80～200 DEG C) Kaolinite Preparation of Catalyst slurry oil as solvent oil 6 slurry that deoils, solvent oil 6 and hydrocracking catalyst and vulcanizing agent 8 are prepared and in unit V2, are mixed with into oil-catalyst slurry 9 at slurry oil; High-temperature separator oil 20 mixtures of other parts of heavy distillate 5, oil-catalyst slurry 9, high-temperature separator oil 26 and Removal of catalyst partly or entirely, be mixed to get by hydrogen 2 and the first hydrogen-rich gas 12 second mix to enter after hydrogen 10 mixes in succession and in floating bed hydrocracking unit R 1, carry out cracking reaction.Hydrocracking reaction product 11 carries out gas-liquid separation in the first gas-liquid separation unit V3 (separating unit can include two or three separators), be separated into after the first hydrogen-rich gas 12, low-temperature separator oil 25 and high-temperature separator oil 26, the first hydrogen-rich gases 12 mix as recycle hydrogen and hydrogen 2 and go to hydrocracking unit.A part for high-temperature separator oil 26 goes solid-liquid separation unit V5 to carry out solid-liquid separation; After another part of high-temperature separator oil 26 and the high-temperature separator of denitrating catalyst oil 20 mix, as turning oil, the slurry that deoils is prepared unit V2 or is directly gone hydrocracking unit R 1 to carry out hydrocracking lighting reaction.Enter solid-liquid separation unit V5 from a part of material of high-temperature separator oil 26 and carry out solid-liquid separation, be separated into high-temperature separator oil 20 and the catalyst residue 21 of denitrating catalyst.
The mixture 7 of the first light ends oil 4, low-temperature separator oil 25, hydrogen 2 and the second hydrogen-rich gas 14 enters hydrogenation upgrading unit R 2 after in succession mixing and carries out hydrofining, hydrogenation upgraded product 13 is carried out gas-liquid separation in the second gas-liquid separation unit V4, is separated into the second hydrogen-rich gas 14 and gas-liquid separating liquid-phase materials 15.The second hydrogen-rich gas 14 turns back to hydrogenation upgrading unit, gas-liquid separation liquid phase material 15 is in product fractionation unit T3, distillation is cut into cut 1 or cut 2 17 or cut 3 18 or cut 4 19, above-mentioned cut one can be for being less than the cut of 65 DEG C, cut two can be the cut of 65～145 DEG C or the cut of 65～150 DEG C, cut three can be kerosene(oil)fraction, cut four can be diesel oil distillate, those skilled in the art can be according to actual needs, select different cut points, such as above-mentioned cut one and cut two are merged, the naphtha fraction that obtains being less than the naphtha fraction of 145 DEG C or be less than 150 DEG C, wherein be less than the naphtha fraction of 145 DEG C or be less than the naphtha fraction of 150 DEG C or the cut of 65～145 DEG C or the cut of 65～150 DEG C and be the coal-based high arene underwater content stock oil of producing aromatic hydrocarbons for catalytic reforming.
Embodiment 1
Adopt the technical process of Fig. 1, taking a kind of shale oil as raw material, after pre-treatment, pretreated shale oil distills cutting through air distillation or underpressure distillation, cutting temperature is 370 DEG C, after cutting, be divided into and be less than the light ends oil of 370 DEG C and be greater than the heavy distillate of 370 DEG C, the heavy distillate that is greater than 370 DEG C is floating bed hydrocracking stock oil, and the full feedstock oil nature of shale oil is in table 1.The lightweight oil of heavy distillate after hydrocracking and the light ends oil of shale oil fractionation by distillation can obtain the cut of 65～145 DEG C after hydrogenation upgrading, i.e. the catalytic reforming raw material oil of high arene underwater content, and main character is in table 3.Each technique unit technological condition is in table 2.
Vulcanizing agent in the present embodiment is sulphur, and in oil-catalyst slurry, solids concn is 35wt%.
Test is to carry out on the floating bed hydrogenation testing apparatus of 0.2 ton/day, and hydrocracking unit adopts two suspended-bed reactor series connection, and deep hydrofinishing unit adopts two fixed-bed reactor series connection.
Embodiment 2
Adopt the technical process of Fig. 2, taking a kind of coal-tar middle oil as raw material, after pre-treatment, pretreated coal-tar middle oil cuts through air distillation, cutting temperature is 350 DEG C, after cutting, be divided into and be less than the light ends oil of 350 DEG C and be greater than the heavy distillate of 350 DEG C, the heavy distillate that is greater than 350 DEG C is floating bed hydrocracking stock oil, and the full feedstock oil nature of coal-tar middle oil is in table 1.The benzoline that the low-temperature separator oil of heavy distillate after hydrocracking separates with coal tar distillation can obtain the cut of 65～150 DEG C after hydrofining, i.e. the catalytic reforming raw material oil of high arene underwater content, and main character is in table 3.Each technique unit technological condition is in table 2.
Vulcanizing agent in the present embodiment is dimethyl disulfide, and in oil-catalyst slurry, solids concn is 45wt%.
Test is to carry out on the floating bed hydrogenation testing apparatus of 0.2 ton/day, and hydrocracking unit adopts two suspended-bed reactor series connection, and deep hydrofinishing unit adopts two ebullated bed reactor series connection.
Embodiment 3
Adopt the technical process of Fig. 1, taking coalite tar in one as raw material, after pre-treatment, pretreated middle coalite tar cuts through distillation, 370 DEG C of cutting temperatures, after cutting, be divided into and be less than the light ends oil of 370 DEG C and be greater than the heavy distillate of 370 DEG C, the stock oil of the raw material that the heavy distillate that is wherein greater than 370 DEG C is floating bed hydrocracking, the full feedstock oil nature of middle coalite tar is in table 1.The light ends oil that the light oil fraction of heavy distillate after hydrocracking separates with coal tar distillation can obtain the naphtha fraction that is less than 145 DEG C together after hydrofining, i.e. the catalytic reforming raw material oil of high arene underwater content, and main character is in table 3.Each technique unit technological condition is in table 2.
Vulcanizing agent in the present embodiment is sulphur, and in oil-catalyst slurry, solids concn is 30wt%.
Test is to carry out on the floating bed hydrogenation testing apparatus of 0.2 ton/day, and hydrocracking unit adopts two suspended-bed reactor series connection, and deep hydrofinishing unit adopts two fixed-bed reactor series connection.
Embodiment 4
Adopt the technical process of Fig. 2, taking a kind of coal-tar heavy oil as raw material, after pre-treatment, pretreated coal-tar heavy oil cuts through underpressure distillation, cutting temperature is 300 DEG C, after cutting, be divided into and be less than the light ends oil of 280 DEG C and be greater than the heavy distillate of 300 DEG C, be wherein greater than the heavy distillate of 300 DEG C as the stock oil of floating bed hydrocracking, the full feedstock oil nature of coal-tar heavy oil is in table 1.The light ends oil that the low-temperature separator oil of heavy distillate after hydrocracking separates with coal tar distillation can obtain the naphtha fraction that is less than 150 DEG C together after hydrofining, i.e. the catalytic reforming raw material oil of high arene underwater content, and main character is in table 3.Each technique unit technological condition is in table 2.
Vulcanizing agent in the present embodiment is dimethyl disulfide, and in oil-catalyst slurry, solids concn is 20wt%.
Test is to carry out on the floating bed hydrogenation testing apparatus of 0.2 ton/day, and hydrocracking unit adopts two suspended-bed reactor series connection, and deep hydrofinishing unit adopts two ebullated bed reactor series connection.
Table 1 embodiment 1-4 coal tar raw material oil nature
Table 2 embodiment 1-4 hydrocracking and hydrogenation upgrading unit technological condition
The main character of the high arene underwater content catalytic reforming raw material that table 3 embodiment 1-4 obtains
The high arene underwater content catalytic reforming raw material that the present invention obtains, arene underwater content is high, the stock oil of producing preferably triphen (benzene,toluene,xylene) for catalytic reforming-Aromatics Extractive Project, its arene underwater content is higher than petroleum reforming raw oil, especially embodiment 4, during taking coal-tar heavy oil as raw material of the present invention, the high arene underwater content catalytic reforming raw material that the present invention obtains, arene underwater content is up to 87.2%, and this is that petroleum reformer feed institute is inaccessiable.
Claims (9)
1. a preparation method for coal-based high arene underwater content stock oil, said method comprising the steps of:
1) raw materials pretreatment: when coal-based oil product raw material is that DCL/Direct coal liquefaction generates oil or kerosene and refines altogether while generating oil, this step is omitted, and directly enters fractionation by distillation step;
In the time that coal-based oil product raw material is coal tar or shale oil, the moisture, the solid impurity that remove wherein obtain pretreated coal tar;
2) fractionation by distillation: DCL/Direct coal liquefaction generates oil, kerosene and refines altogether and generate oil or pretreated coal tar, pretreated shale oil are divided into the first light ends oil and heavy distillate through air distillation or underpressure distillation, wherein, the distillation cutting temperature of the first light ends oil and heavy distillate is between 280～370 DEG C; Heavy distillate carries out floating bed hydrocracking;
3) floating bed hydrocracking: at normal pressure, 80～200 DEG C of temperature, catalyzer, vulcanizing agent and solvent oil are mixed to even Kaolinite Preparation of Catalyst slurry oil, again oil-catalyst slurry is mixed and carries out floating bed hydrocracking with heavy distillate and turning oil, crackate obtains liquid-solid phase mixture and the first hydrogen-rich gas through separating, liquid-solid phase mixture is isolated to the second light ends oil and tail oil, or crackate is isolated to low-temperature separator oil, high-temperature separator oil and the second hydrogen-rich gas, high-temperature separator oil enters suspension bed again and carries out hydrocracking;
4) hydrogenation upgrading: step 2) obtain the first light ends oil and step 3) the second light ends oil of obtaining or low-temperature separator oil mixes employing fixed bed or ebullated bed carries out hydrogenation upgrading, hydrogenation upgraded product is carried out product fractionation after cooling, gas-liquid separation, obtain being less than the naphtha fraction of 145 DEG C or be less than naphtha fraction or the cut of 65～145 DEG C or the cut of 65～150 DEG C of 150 DEG C, be coal-based high arene underwater content stock oil;
Described solvent oil is one or more in the high-temperature separator oil of tail oil, high-temperature separator oil and Removal of catalyst of heavy distillate, tail oil, Removal of catalyst; Described turning oil is the high-temperature separator oil of tail oil, high-temperature separator oil or the Removal of catalyst of tail oil or Removal of catalyst.
2. the preparation method of coal-based high arene underwater content stock oil according to claim 1, is characterized in that, described catalyzer is containing one or more active metals in molybdenum, nickel, cobalt, tungsten and iron, and catalyzer is the powdered granule of particle diameter 1～100 μ m.
3. the preparation method of coal-based high arene underwater content stock oil according to claim 1, is characterized in that, described vulcanizing agent is sulphur or dimethyl disulfide.
4. the preparation method of coal-based high arene underwater content stock oil according to claim 1, is characterized in that, in described oil-catalyst slurry, solids concn is 20wt%～45wt%.
5. the preparation method of coal-based high arene underwater content stock oil according to claim 1, is characterized in that, floating bed hydrocracking condition is: 320～480 DEG C of temperature of reaction, reaction pressure 8～25Mpa, volume space velocity 0.3～3.0h
-1, hydrogen to oil volume ratio 500～2000, the add-on of catalyzer taking control active metal total amount with the ratio of heavy ends weight of oil as 0.1:100 to 4:100.
6. the preparation method of coal-based high arene underwater content stock oil according to claim 5, is characterized in that, floating bed hydrocracking condition is: 350～450 DEG C of temperature of reaction, reaction pressure 10～19Mpa, volume space velocity 0.5～2.0h
-1, hydrogen to oil volume ratio 800～1500, the add-on of catalyzer taking control active metal total amount with the ratio of heavy ends weight of oil as 0.5:100 to 2:100.
7. the preparation method of coal-based high arene underwater content stock oil according to claim 1, it is characterized in that, described step 4) in, in the time adopting fixed bed to carry out hydrogenation upgrading, catalyzer is bar shaped or spherical loaded catalyst, catalyzer contains one or more in active metal iron, nickel, cobalt, molybdenum and tungsten, and support of the catalyst is one or more in aluminum oxide, silicon oxide and titanium oxide;
When adopting ebullated bed while carrying out hydrogenation upgrading, catalyzer is taking inorganic oxide or molecular sieve as carrier, and active metal is one or more in iron, nickel, cobalt, molybdenum and tungsten.
8. the preparation method of coal-based high arene underwater content stock oil according to claim 7, it is characterized in that, described inorganic oxide is one or more in aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, and described molecular sieve is one or more in ZSM zeolite, zeolite L, y-type zeolite, Beta type zeolite.
9. the preparation method of coal-based high arene underwater content stock oil according to claim 1, it is characterized in that, described step 4) in hydrogenation upgrading reaction conditions be: temperature of reaction is 200～440 DEG C, and reaction pressure is 6～17MPa, and volume space velocity is 0.5～4.0h
-1, hydrogen-oil ratio is 300～2000.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106065336A (en) * | 2016-08-16 | 2016-11-02 | 北京神雾环境能源科技集团股份有限公司 | A kind of system and method for fast pyrogenation coal tar |
| CN108048132A (en) * | 2017-12-29 | 2018-05-18 | 中海油天津化工研究设计院有限公司 | It is a kind of to prepare C by the BTX aromatics containing polycyclic and double ring arene6~C8The method of aromatic hydrocarbons |
| CN110396427A (en) * | 2018-04-25 | 2019-11-01 | 北京华石联合能源科技发展有限公司 | A kind of processing technology of full fraction coal tar |
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| CN101885982A (en) * | 2010-06-23 | 2010-11-17 | 煤炭科学研究总院 | Hydrogenation method for coal tar suspension bed of heterogeneous catalyst |
| CN103305265A (en) * | 2013-06-18 | 2013-09-18 | 煤炭科学研究总院 | Coal-based military fuel and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101885982A (en) * | 2010-06-23 | 2010-11-17 | 煤炭科学研究总院 | Hydrogenation method for coal tar suspension bed of heterogeneous catalyst |
| CN103305265A (en) * | 2013-06-18 | 2013-09-18 | 煤炭科学研究总院 | Coal-based military fuel and preparation method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106065336A (en) * | 2016-08-16 | 2016-11-02 | 北京神雾环境能源科技集团股份有限公司 | A kind of system and method for fast pyrogenation coal tar |
| CN106065336B (en) * | 2016-08-16 | 2017-11-24 | 神雾科技集团股份有限公司 | A kind of system and method for fast pyrogenation coal tar |
| CN108048132A (en) * | 2017-12-29 | 2018-05-18 | 中海油天津化工研究设计院有限公司 | It is a kind of to prepare C by the BTX aromatics containing polycyclic and double ring arene6~C8The method of aromatic hydrocarbons |
| CN110396427A (en) * | 2018-04-25 | 2019-11-01 | 北京华石联合能源科技发展有限公司 | A kind of processing technology of full fraction coal tar |
| CN110396427B (en) * | 2018-04-25 | 2021-09-03 | 北京华石联合能源科技发展有限公司 | Processing technology of full-range coal tar |
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Effective date of registration: 20160329 Address after: 100013 Beijing, Hepingli Youth ditch East Road, No. 5, No. Applicant after: Co., Ltd of coal science and technology academy Address before: 100013 Beijing, Hepingli Youth ditch East Road, No. 5, No. Applicant before: General Research Institute of Coal Science |
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Application publication date: 20140827 |
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