CN104004541A - 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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Abstract
The invention discloses a method for preparing coal-based high aromatic potential content raw oil. The method includes the following steps that (1) raw materials are preprocessed; (2), distillation separation is carried out, wherein direct coal liquefaction generated oil or coal-oil coprocessing generated oil or preprocessed coal tar is divided into carbolic oil or naphtha distillate, diesel distillate and heavy oil distillate through atmospheric distillation or reduced pressure distillation, the cutting temperature of the diesel distillate and the heavy oil distillate ranges from 280 DEG C to 450 DEG C, dephenolization processing is carried out on the carbolic oil or naphtha distillate, then crude phenol oil and dephenolized oil are obtained, light distillate oil is obtained after the dephenolized oil is mixed with the diesel distillate, and hydrofining is carried out on the light distillate oil; (3), hydrofining is carried out, wherein hydrofining generated oil is obtained by carrying out hydrofining on the light distillate oil; (4), the coal-based high aromatic potential content raw oil used for catalytic reforming of production aromatic hydrocarbon is obtained through product fractional distillation. According to the method, not only the coal tar but also the direct coal liquefaction generated oil or the coal-oil coprocessing generated oil can serve as the raw materials, and the application range of the raw materials is wide.
Description
Technical field
The invention belongs to coal chemical technology, particularly, the present invention relates to a kind of coal-based oil product deep processing method.
Background technology
Coal tar is to take 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 ℃ of pyrolysis temperatures), coal-tar middle oil pyrolysis temperature (700～800 ℃) and coal-tar heavy oil (950～1050 ℃ of pyrolysis temperatures), and it is larger that it forms difference.
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 be 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, take coal-tar heavy oil as raw material, adopt hydrofining or hydrocracking process technology, produce oil fuel.
In, coalite tar is mainly derived from the productions such as blue charcoal that middle low temperature pyrogenation produces, coal preparing natural gas.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, Meng San province border land.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.
Compare 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, the Aromatics Production Technology that the oil of take is 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 that the coal tar of usining is prepared coal-based high arene underwater content 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 usingd mixing as raw material by 50: 50～70: 30 of 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 separation after condensing cooling obtains hydrogen-rich gas and hydrogenated gasoline, and hydrogen-rich gas recycles, and hydrogenated gasoline enters evaporator tower and carries out the refining petroleum naphtha that stripping fractionation is met catalytic reforming feedstock requirement; The mixing petroleum naphtha that present method can surpass mixing proportion 50%FCC stable gasoline carries out hydrotreatment, obtains the refining petroleum naphtha that foreign matter content all meets 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 this patent is cut into light benzine cut, middle matter gasoline fraction and heavy gasoline cut by secondary processing of gasoline raw material; 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, the reaction effluent generating carries out cooling, separated, 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, for catalytic reforming provides sulphur, nitrogen content, is all less than the acceptable material of 0.5 Μ G/G.
Chinese patent 200510089848.7 discloses a kind of method of producing catalytic reforming raw material, and this patent is cut into light benzine cut, middle matter gasoline fraction and heavy gasoline cut by secondary processing of gasoline raw material; 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 separation, carry out hydrogenating desulfurization and hydrodenitrification reaction, the reaction effluent generating carries out cooling, separated, 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, for catalytic reforming provides sulphur, nitrogen content, is all less than the acceptable material of 0.5 Μ G/G.
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 enters high-pressure separator through overcooling is laggard; 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 enters high-pressure separator through overcooling is laggard.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 take petroleum base oil product to prepare the method for catalytic reforming raw material 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 after separated, fractionation, obtain meeting the naphtha fraction of the high aromatic hydrocarbon potential content of catalytic reforming charging requirement, and extending catalyst work-ing life.This patent is to take liquefied coal coil as the method for raw material employing ebullated bed for the preparation of the high aromatic hydrocarbons petroleum naphtha of catalytic reforming.
Summary of the invention
The object of the invention is to, a kind of coal-based oil product deep processing method is provided, and the method can coal tar be not only raw material, can also DCL/Direct coal liquefaction generates oil or kerosene and refines altogether and generate 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 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;
When coal-based oil product raw material is coal tar, the moisture, the solid impurity that remove wherein obtain pretreated coal tar;
2) fractionation by distillation: DCL/Direct coal liquefaction generates oil, kerosene refines altogether generation oil or pretreated coal tar is divided into carbolic oil or naphtha fraction, diesel oil distillate and heavy oil fraction through air distillation or underpressure distillation, wherein, the cutting temperature of diesel oil distillate and heavy oil fraction is between 280～450 ℃;
Carbolic oil or naphtha fraction carry out phenol removal and obtain crude phenols and dephenolize oil, after dephenolize oil and diesel oil distillate mix, obtain light ends oil, and light ends oil carries out hydrofining;
3) hydrofining: light ends oil obtains hydrofining by hydrofining and generates oil;
4) product fractionation: when the cutting temperature of diesel oil distillate and heavy oil fraction is between 280～380 ℃, hydrofining generates oil and enter separation column after cooling, gas-liquid separation, according to the requirement of catalytic reforming raw material boiling range, fractionate out and be less than the naphtha fraction of 145 ℃, be less than the naphtha fraction of 150 ℃, the cut of 65～145 ℃ or the cut of 65～150 ℃, above-mentioned fractionation cut is out the coal-based high arene underwater content stock oil of producing aromatic hydrocarbons for catalytic reforming;
When the cutting temperature of diesel oil distillate and heavy oil fraction is between 380～450 ℃, hydrofining generates oil and enter separation column after cooling, gas-liquid separation, according to the fractionation of variant production object, be naphtha fraction or the cut of 65～145 ℃ or the cut of 65～150 ℃ that is less than the naphtha fraction of 145 ℃ or is less than 150 ℃, and tail oil, wherein, be less than the naphtha fraction of 145 ℃ or be less than the naphtha fraction of 150 ℃ or the cut of 65～145 ℃ or the cut of 65～150 ℃ are the coal-based high arene underwater content stock oil of producing aromatic hydrocarbons for catalytic reforming.
Further, described tail oil adopts hydrocracking process to process, and gained hydrocracking generates oil and enter step 3 after cooling, gas-liquid separation) hydrofining.
Preferably, described step 2) in, adopt alkali liquid washing method or solvent extration to extract the phenolic compound in carbolic oil cut or naphtha fraction, obtain crude phenols and dephenolize oil.
Preferably, described step 3) in, hydrofining reactor is fixed-bed reactor, adopts single hop hydrogenation or multistage hydrogenation technique.
Preferably, described step 3) in, it is carrier that hydrogenation catalyst be take one or more in unformed aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, ZSM zeolite, zeolite L, y-type zeolite and Beta zeolite, active metal component comprises base metal component and precious metal component, wherein base metal component comprises one or more in nickel, cobalt, molybdenum and tungsten, and the content in catalyzer is counted 20wt%～80wt% with non-noble metal oxide; Precious metal component comprises platinum and/or palladium, and the content in catalyzer is counted 0.1wt%～20wt% with metal oxide containing precious metals.
Preferably, described step 3) in, Hydrobon catalyst pore volume>=0.4ml/g, specific surface area>=120m
2/ g, bulk density is 0.4～1.9Kg/m
3.
Preferably, described step 3) in, hydrofining reaction condition is: temperature of reaction is 200～440 ℃, and reaction pressure is 6～17MPa, and volume space velocity is 0.5～4.0h
-1, hydrogen-oil ratio is 300～2000.
Preferably, in described hydrocracking process, hydrocracking reactor is fixed-bed reactor, adopts single hop hydrogenation or multistage hydrogenation technique.
Preferably, in described hydrocracking process, it is carrier that hydrogenation catalyst be take one or more in unformed aluminum oxide, silicon oxide, ZSM zeolite, zeolite L, y-type zeolite and Beta zeolite, and active metal component is one or more in group vib and VIII family metallic element
Wherein, group vib metallic element is molybdenum and tungsten;
VIII family metallic element is cobalt and nickel.
Preferably, in described hydrocracking process, hydrocracking reaction condition is: temperature of reaction is 200～440 ℃, and reaction pressure is 6～17MPa, and volume space velocity is 0.5～4.0h
-1, hydrogen-oil ratio is 300～2000.
In the present invention, for the higher coal tar of phenol content, in carbolic oil or naphtha fraction oil, contain a considerable number of phenolic compound, if not dephenolize direct hydrogenation, can make the phenolic compound of high added value be converted into aromatic hydrocarbons and enter in the finished product, both reduce product price, increase again process hydrogen consumption.
For the lower coal tar of phenol content, do not consider to propose phenol operation.
In the present invention, light ends oil, by hydrofining, removes detrimental impurity, saturation of olefins and the aromatic hydrocarbons such as sulphur, nitrogen, oxygen and metal in stock oil.
Coal tar of the present invention be in coalite tar, middle coalite tar, coal-tar middle oil, coal-tar heavy oil any one or two or more coal tar with the mixing oil of arbitrary proportion.
In the present invention, while using alkali liquid washing method to carry phenol, alkali cleaning temperature is 30～60 ℃, and the alkali cleaning time is 0.2～1.5min, and concentration of lye is 7%～13%, and water/oil quality ratio is 0.6～1.2, adopts CO
2acidifying sodium phenolate; While using Recovery by Solvent Extraction Methold phenol, extraction agent is ethylene glycol or glycerol, and extraction temperature is normal temperature, and churning time is 10～40min, and dephenolize rate reaches as high as 96%.
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 applicable to DCL/Direct coal liquefaction generation oil and kerosene, refined altogether generation oil, 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, can make the catalytic reforming raw material of the high arene underwater content of light ends oil production of different material.
3. the high value added utilization that the present invention is coal-based oil product provides novel method, has widened the source of the catalytic reforming raw material of high arene underwater content.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, method provided by the present invention is further described,
Fig. 1 is the process flow sheet when the tail oil hydrocracking of the present invention;
Fig. 2 is the process flow sheet of the present invention while containing tail oil hydrocracking;
In figure, omitted the equipment of many necessity, as pump, tank, process furnace, interchanger, valve etc., the shape and size of equipment and pipeline are not subject to the restriction of accompanying drawing, but determine as the case may be.
Reference numeral:
Digitized representation material in Fig. 1 and Fig. 2: 1, fresh hydrogen; 2, coal-based oil product raw material; 3, pretreated coal tar or DCL/Direct coal liquefaction generation oil or kerosene refine altogether and generate oil; 4, carbolic oil or naphtha fraction; 5, diesel oil distillate; 6, heavy ends; 7, crude phenols; 8, dephenolize oil; 9, light ends oil; 10, mix hydrogen; 11, circulating hydrogen; 12, hydrofining generates oil; 13, gas-liquid separation liquid phase; 14, cut one; 15, cut two; 16, cut three; 17, cut four; 18, tail oil; 19, mix hydrogen; 20, circulating hydrogen; 21, tail oil hydrocracking generates oil; 22, gas-liquid separation liquid phase;
Letter and number combination in Fig. 1 and Fig. 2 represents unit, device or equipment: V1, pretreatment unit; T1, fractionation by distillation unit; C1, fresh hydrogen compressor; D1, dephenolize unit; R1, hydrofining unit; C2, circulating hydrogen compressor; V2, hydrofining generate oil-gas-liquid separating unit; T2, product fractionation unit; R2, hydrocracking unit; C3, circulating hydrogen compressor; V3, hydrocracking generate oil-gas-liquid separating unit.
Embodiment
With the drawings and specific embodiments, the present invention is further detailed explanation below.
As shown in Figure 1, the coal-based oil product stock oil 2 de-slag (solid impurity) that first dewaters in pretreatment unit V1 is processed, pretreated raw material 3 (pretreated coal tar, or, not pretreated DCL/Direct coal liquefaction generate oil or kerosene refine altogether generate oil) enter fractionation by distillation unit T1, carry out fractionation by distillation, be divided into carbolic oil or naphtha fraction 4, diesel oil distillate 5, heavy ends 6.Carbolic oil or naphtha fraction 4 extract after crude phenols 7 through alkali liquid washing method or solvent extration in dephenolize cells D 1, the mixed light ends oil 9 of remaining dephenolize oil 8 and diesel oil distillate 5 and the hydrogen 1 compressing through hydrogen gas compressor C1 or the circulating hydrogen 11 compressing through circulating hydrogen compressor C2 or hydrogen 1 and the mixed mixing hydrogen 10 of circulating hydrogen 11 enter hydrofining unit R 1 simultaneously and carry out hydrofining, from R1 hydrofining out, generate oil 12 and after hydrofining generates oil-gas-liquid separating unit V2, obtain gas-liquid separation phase 13, gas-liquid separation 13 enters product fractionation unit T2 mutually, in T2, material is separated cut 1 or cut 2 15 or cut 3 16 or cut 4 17, above-mentioned cut one can be for being less than the cut of 65 ℃, cut two can be the cut of 65～145 ℃ or the cut of 65～150 ℃, 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 ℃ or be less than 150 ℃, wherein be less than the naphtha fraction of 145 ℃ or be less than the naphtha fraction of 150 ℃ or the cut of 65～145 ℃ or the cut of 65～150 ℃ and be the coal-based high arene underwater content stock oil of producing aromatic hydrocarbons for catalytic reforming.
As shown in Figure 2, the coal-based oil product stock oil 2 de-slag (solid impurity) that first dewaters in pretreatment unit V1 is processed, pretreated raw material 3 (pretreated coal tar, or, not pretreated DCL/Direct coal liquefaction generate oil or kerosene refine altogether generate oil) enter fractionation by distillation unit T1, carry out fractionation by distillation, be divided into carbolic oil or naphtha fraction 4, diesel oil distillate 5, heavy ends 6.Carbolic oil or naphtha fraction 4 extract after crude phenols 7 through alkali liquid washing method or solvent extration in dephenolize cells D 1, the mixed light ends oil 9 of remaining dephenolize oil 8 and diesel oil distillate 5 and the hydrogen 1 compressing through hydrogen gas compressor C1 or the circulating hydrogen 11 compressing through circulating hydrogen compressor C2 or hydrogen 1 and the mixed mixing hydrogen 10 of circulating hydrogen 11 enter hydrofining unit R 1 simultaneously and carry out hydrofining, from R1 hydrofining out, generate oil 12 and after hydrofining generates oil-gas-liquid separating unit V2, obtain gas-liquid separation phase 13, gas-liquid separation 13 enters product fractionation unit T2 mutually, in T2, material is separated cut 1 or cut 2 15 or cut 3 16 or cut 4 17 or tail oil 18, above-mentioned cut one can be for being less than the cut of 65 ℃, cut two can be the cut of 65～145 ℃ or the cut of 65～150 ℃, 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 ℃ or be less than 150 ℃, wherein be less than the naphtha fraction of 145 ℃ or be less than the naphtha fraction of 150 ℃ or the cut of 65～145 ℃ or the cut of 65～150 ℃ and be the coal-based high arene underwater content stock oil of producing aromatic hydrocarbons for catalytic reforming.Tail oil 18 and the hydrogen 1 compressing through hydrogen gas compressor C1 or the circulating hydrogen 11 compressing through circulating hydrogen compressor C2 or the circulating hydrogen 20 compressing through circulating hydrogen compressor C3 or mixing hydrogen 10,19 go hydrocracking unit R 2 to carry out hydrocracking lighting reaction, obtain tail oil hydrocracking and generate oil 21, this oil generates oil-gas-liquid separating unit V3 separation through hydrocracking and obtains gas-liquid separation phase 22, and gas-liquid separation phase 22 can together enter product fractionation unit T2 with R1 hydrofining generation oil out and carry out fractionation by distillation.
The beneficial effect of further illustrating object of the present invention and having below in conjunction with specific embodiment, but protection scope of the present invention is not limited to the following example.
Embodiment 1
Adopt the technical process of Fig. 1, it is raw material that the gelatin liquefaction of take generates oil, through distillation unit, is cut into the heavy distillate of 350 ℃ of 230 ℃ of carbolic oil of < or naphtha fraction, 230 ℃～350 ℃ diesel oil distillates and >.230 ℃ of carbolic oil of < or naphtha fraction mix with 230 ℃～350 ℃ diesel oil distillates after dephenolize unit adopts alkali liquid washing method to extract crude phenols product, and mixed light ends oil nature is in Table 1.Light ends oil makes 65～145 ℃ of cuts through deep hydrofinishing, and the catalytic reforming raw material of high arene underwater content is oily, and main character is in Table 3.Above-mentioned each technique unit technological condition is in Table 2.Deep hydrofinishing adopts the fixed bed hydrogenation testing apparatus that inlet amount is 100ml/h, adopts two reactors in series patterns.
Embodiment 2
Adopt the technical process of Fig. 2, take middle coalite tar as raw material, through the de-pretreated purification coal tar of slag (solid impurity) of dehydration, enter distillation unit, be cut into the heavy distillate of 450 ℃ of 230 ℃ of carbolic oil of < or naphtha fraction, 230 ℃～450 ℃ diesel oil distillates and >.230 ℃ of carbolic oil of < or naphtha fraction mix with 230 ℃～450 ℃ diesel oil distillates after dephenolize unit adopts solvent extration to extract crude phenols product, mixed light ends oil nature is in Table 1, light ends oil makes 65～150 ℃ of cuts after deep hydrofinishing, tail oil hydrocracking, be the catalytic reforming raw material oil of high arene underwater content, main character is in Table 3.Above-mentioned each technique unit technological condition is in Table 2.
The present embodiment is to complete on the fixed bed hydrogenation testing apparatus that is 100ml/h by inlet amount, and deep hydrofinishing adopts two reactors in series patterns; Refining reaction device after the fixed bed that tail oil hydrocracking is 100ml/h by the fixed bed hydrogenation cracking case of a 100ml/h and inlet amount, adopts two reactors in series patterns.
Embodiment 3
Adopt the technical process of Fig. 1, take coal-tar heavy oil as raw material, through the de-pretreated purification coal tar of slag (solid impurity) of dehydration, enter distillation unit, be cut into the heavy distillate of 350 ℃ of 230 ℃ of carbolic oil of < or naphtha fraction, 230 ℃～350 ℃ diesel oil distillates and >.230 ℃ of carbolic oil of < or naphtha fraction mix with 230 ℃～350 ℃ diesel oil distillates after dephenolize unit adopts solvent extration to extract crude phenols product, and mixed light ends oil nature is in Table 1.Mixing light distillate can produce through deep hydrofinishing the naphtha fraction that is less than 150 ℃, and the catalytic reforming raw material of high arene underwater content is oily, and main character is in Table 3.Above-mentioned each technique unit technological condition is in Table 2.
Deep hydrofinishing adopts the fixed-bed reactor that inlet amount is 100ml/h, adopts two reactors in series patterns.
The light ends oil nature of table 1 embodiment 1-3 different material
Each unit technological condition of table 2 embodiment 1-3
The main character of the high arene underwater content catalytic reforming raw material of table 3 embodiment 1-3
From the data of table 3, can find out, the high arene underwater content catalytic reforming raw material that the present invention obtains, arene underwater content is high, for catalytic reforming-Aromatics Extractive Project, to produce preferably the stock oil of triphen (benzene,toluene,xylene), its arene underwater content is higher than petroleum reforming raw oil, especially embodiment 3, take coal-tar heavy oil during 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 85.8%, and this is that petroleum reformer feed institute is inaccessiable.
Claims (10)
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;
When coal-based oil product raw material is coal tar, the moisture, the solid impurity that remove wherein obtain pretreated coal tar;
2) fractionation by distillation: DCL/Direct coal liquefaction generates oil, kerosene refines altogether generation oil or pretreated coal tar is divided into carbolic oil or naphtha fraction, diesel oil distillate and heavy oil fraction through air distillation or underpressure distillation, wherein, the cutting temperature of diesel oil distillate and heavy oil fraction is between 280～450 ℃;
Carbolic oil or naphtha fraction carry out phenol removal and obtain crude phenols and dephenolize oil, after dephenolize oil and diesel oil distillate mix, obtain light ends oil, and light ends oil carries out hydrofining;
3) hydrofining: light ends oil obtains hydrofining by hydrofining and generates oil;
4) product fractionation: when the cutting temperature of diesel oil distillate and heavy oil fraction is between 280～380 ℃, hydrofining generates oil and enter separation column after cooling, gas-liquid separation, according to the requirement of catalytic reforming raw material boiling range, fractionate out and be less than the naphtha fraction of 145 ℃, be less than the naphtha fraction of 150 ℃, the cut of 65～145 ℃ or the cut of 65～150 ℃, be the coal-based high arene underwater content stock oil of producing aromatic hydrocarbons for catalytic reforming;
When the cutting temperature of diesel oil distillate and heavy oil fraction is between 380～450 ℃, hydrofining generates oil and enter separation column after cooling, gas-liquid separation, according to the fractionation of variant production object, be naphtha fraction or the cut of 65～145 ℃ or the cut of 65～150 ℃ that is less than the naphtha fraction of 145 ℃ or is less than 150 ℃, and tail oil, wherein, be less than the naphtha fraction of 145 ℃ or be less than the naphtha fraction of 150 ℃ or the cut of 65～145 ℃ or the cut of 65～150 ℃ are the coal-based high arene underwater content stock oil of producing aromatic hydrocarbons for catalytic reforming.
2. method according to claim 1, is characterized in that, described step 4) in tail oil adopt hydrocracking process to process, gained hydrocracking generates oil and enter step 3 after cooling, gas-liquid separation) hydrofining.
3. method according to claim 1 and 2, is characterized in that, described step 2) in, adopt alkali liquid washing method or solvent extration to extract the phenolic compound in carbolic oil cut or naphtha fraction, obtain crude phenols and dephenolize oil.
4. method according to claim 1 and 2, is characterized in that, described step 3) in, hydrofining reactor is fixed-bed reactor, adopts single hop hydrogenation or multistage hydrogenation technique.
5. method according to claim 1 and 2, it is characterized in that, described step 3) in, it is carrier that hydrogenation catalyst be take one or more in unformed aluminum oxide, silicon oxide, titanium oxide, magnesium oxide, ZSM zeolite, zeolite L, y-type zeolite and Beta zeolite, active metal component comprises base metal component and precious metal component, wherein base metal component comprises one or more in nickel, cobalt, molybdenum and tungsten, and the content in catalyzer is counted 20wt%～80wt% with non-noble metal oxide; Precious metal component comprises platinum and/or palladium, and the content in catalyzer is counted 0.1wt%～20wt% with metal oxide containing precious metals.
6. method according to claim 1 and 2, is characterized in that, described step 3) in, Hydrobon catalyst pore volume>=0.4ml/g, specific surface area>=120m
2/ g, bulk density is 0.4～1.9Kg/m
3.
7. method according to claim 1 and 2, is characterized in that, described step 3) in, hydrofining reaction condition is: temperature of reaction is 200～440 ℃, and reaction pressure is 6～17MPa, and volume space velocity is 0.5～4.0h
-1, hydrogen-oil ratio is 300～2000.
8. method according to claim 2, is characterized in that, in described hydrocracking process, hydrocracking reactor is fixed-bed reactor, adopts single hop hydrogenation or multistage hydrogenation technique.
9. method according to claim 2, it is characterized in that, in described hydrocracking process, it is carrier that hydrogenation catalyst be take one or more in unformed aluminum oxide, silicon oxide, ZSM zeolite, zeolite L, y-type zeolite and Beta zeolite, active metal component is one or more in group vib and VIII family metallic element
Wherein, group vib metallic element is molybdenum and tungsten;
VIII family metallic element is cobalt and nickel.
10. method according to claim 2, is characterized in that, in described hydrocracking process, hydrocracking reaction condition is: temperature of reaction is 200～440 ℃, 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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