CN103468314B - DCL/Direct coal liquefaction circulating solvent and its preparation method and application - Google Patents
DCL/Direct coal liquefaction circulating solvent and its preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of DCL/Direct coal liquefaction circulating solvent and its preparation method and application.This preparation method comprises: step S1, the mixture of refining of petroleum byproduct and coal direct liquefaction oil is carried out hydrogenation, obtains hydrogenation products; Step S2, carries out fractionation by hydrogenation products, obtains light ends oil, middle matter distillate and heavy distillate; Step S3, by matter distillate mixing in heavy distillate and part, obtains DCL/Direct coal liquefaction circulating solvent.In the preparation process in accordance with the present invention, on the one hand owing to containing a large amount of aromatic hydrocarbons in refining of petroleum byproduct, hydrogenation after product is rich in the components such as naphthane, can significantly improve the hydrogen supply capacity of circulating solvent, improves coal direct liquefaction oil yield; On the other hand, utilize refining of petroleum byproduct to replace out the diesel oil distillate being less than the high added value of 350 DEG C in part DCL/Direct coal liquefaction circulating solvent, improve diesel yield, significantly promote the economy of gelatin liquefaction technology; And, existing circulating solvent lighting problem can be alleviated.
Description
Technical field
The present invention relates to gelatin liquefaction field, in particular to a kind of DCL/Direct coal liquefaction circulating solvent and its preparation method and application.
Background technology
DCL/Direct coal liquefaction produces the important channel that liquid fuel is coal cleaning conversion and efficiency utilization, is also one of effective ways making up petroleum resources deficiency.As the strategic reserves technology of the energy, DCL/Direct coal liquefaction is subject to the great attention of developed country always, successfully develops the coal direct liquefaction technique that NEDOL, IGOR and HTI etc. are advanced.Domestic Duo Jia unit has also carried out the research of direct coal liquefaction process aspect.Shenhua Group Co has applied for a kind of Chinese patent CN200410070249 of coal direct liquefaction method for 2004, builds up the coal direct liquefaction demonstration unit of 1,000,000 tons/year of scales, and successfully go into operation in 2008 in Erdos.
In DCL/Direct coal liquefaction process, solvent plays very important effect: solvent and coal are made into coal slurry, is convenient to conveying and the pressurization of coal; The free radical fragment polycondensation can dissolve coal, preventing pyrolysis of coal from producing, thus improve liquefied coal coil yield; Gas phase hydrogen can be dissolved, make hydrogen molecule to coal or catalyst surface diffusion; To the direct hydrogen supply of free radical fragment or hydrogen can be transmitted.According to the principle that similar person mixes, the free radical fragment of the polycyclic aromatic hydrocarbons that structure in solvent and coal molecule are similar to pyrolysis of coal has stronger dissolving power, and solvent has the specific function directly to free radical fragment hydrogen supply.Research finds that partially hydrogenated polycyclic aromatic hydrocarbons (as naphthane, dihydro phenanthrene, dihydroanthracene, tetrahydrochysene anthracene etc.) has very strong hydrogen supply performance.
Realizing in the direct coal liquefaction process of continuous run in long period at present, solvent is from direct coal liquefaction process itself, and namely coal direct liquefaction oil obtains through stabilized hydrogenation, and recycles in DCL/Direct coal liquefaction process, also referred to as circulating solvent.The hydrogen supply performance of current circulating solvent becomes one of emphasis of direct coal liquefaction technology research field, and the solvent of the hydrogen supply performance or exploitation excellent property that improve circulating solvent is further an importance of Technology of direct coal liquefaction progress.
The main composition of circulating solvent is aromatic hydrocarbons and the hydrogenation of aromatics of 2 ~ 4 rings, and in DCL/Direct coal liquefaction process, the internal circulating load of solvent is comparatively large, and in circulating solvent, 200 ~ 350 DEG C of distillates are more than 50%, and this part mink cell focus can be used to the diesel oil of production high added value.In circulating solvent, part lighter fraction oil can not have impact on the economy of DCL/Direct coal liquefaction process as product, and constantly recycling the further lighting of meeting in process, destroy the stability of coal oil mixture, its consequence is serious in the gasification of DCL/Direct coal liquefaction reactor internal solvent, cause liquid-solid phase excessive concentration and deposit, affect the reaction effect of DCL/Direct coal liquefaction, time serious, also can cause reactor plugs.
(the OrchinM such as Orchin, SrorchM.IndEngChemIEC, 1948,40 (8): 1385) naphthane and cresols are mixed in varing proportions carry out DCL/Direct coal liquefaction Study on Transformation as solvent and show, cresols and naphthane mix, both have mutual promoting action, increase hydrogen supply performance.Yan Ruiping etc. (research [J] of Yanzhou coal and Shijiazhuang vacuum residuum co-processing. coal journal .25 (6) .2000.655-659) have studied reaction conditions in Yanzhou coal and Shijiazhuang vacuum residuum co-processing and Yanzhou coal to be transformed and co-processed product distributes affects Changing Pattern, by with the comparing of coal and residual oil individual curing result, set forth the interaction between coal and residual oil in co-processing.The people such as Steedman (SteedmanW, FlynnT, KempW.InternationalJournalofEnergyResearch, 1994,18:299 ~ 307) use coal and petroleum residual oil co-processing, find the coal liquefaction solvent that pure residual oil has not been, these residual oil are after pre-hydrogenation process, and coal transformation efficiency significantly improves.
Chinese patent application CN100567463C discloses a kind of method of hydrotreating of brown coal directly liquefied circulating solvent, and principal feature is the incomplete saturated hydrogenation realizing coal liquefaction solvent under the processing condition relaxed, and improves the confession hydrogen amount of solvent.Chinese patent application CN200610083582.X describes a kind of preparation method of initiating solvent for direct liquefy of coal, the method describe using boiling range be a kind of petroleum fractions of 220 ~ 538 DEG C as raw material, prepared the initial solvent of DCL/Direct coal liquefaction needs by catalytic hydrogenation.
Sum up prior art and can find still do not have one can either improve gelatin liquefaction economic performance at present, the preparation method of the DCL/Direct coal liquefaction circulating solvent of the hydrogen supply performance of DCL/Direct coal liquefaction circulating solvent can be improved again.
Summary of the invention
The present invention aims to provide a kind of DCL/Direct coal liquefaction circulating solvent and its preparation method and application, has both improve gelatin liquefaction economic performance, turn improves the hydrogen supply performance of DCL/Direct coal liquefaction circulating solvent.
To achieve these goals, according to an aspect of the present invention, provide a kind of preparation method of DCL/Direct coal liquefaction circulating solvent, preparation method comprises: step S1, the mixture of refining of petroleum byproduct and coal direct liquefaction oil is carried out hydrogenation, obtains hydrogenation products; Step S2, carries out fractionation by hydrogenation products, obtains light ends oil, middle matter distillate and heavy distillate; Step S3, by matter distillate mixing in heavy distillate and part, obtains DCL/Direct coal liquefaction circulating solvent.
Further, the boiling range of above-mentioned refining of petroleum byproduct is 220 ~ 500 DEG C, and the boiling range of preferred refining of petroleum byproduct is 250 ~ 460 DEG C; The proportion of refining of petroleum byproduct is 1.0 ~ 1.1g/cm
3, the proportion of preferred refining of petroleum byproduct is 1.01 ~ 1.08g/cm
3; In refining of petroleum byproduct, condensed-nuclei aromatics content is greater than 60wt%, and in preferred refining of petroleum byproduct, condensed-nuclei aromatics content is greater than 70wt%.
Further, the weight content of said mixture PetroChina Company Limited. refining byproduct is 5 ~ 30%, and the weight content of preferred mixture PetroChina Company Limited. refining byproduct is 5 ~ 20%.
Further, above-mentioned refining of petroleum byproduct is selected from one or more in catalytic cracking recycle oil, catalytically cracked oil, Aromatics Extractive Project oil, long residuum, vacuum residuum, lubricating oil extraction aromatic hydrocarbons, visbreaker tar, coking heavy oil.
Further, hydrogenation is carried out in the cascade reaction system that a kind of and fixed-bed reactor of above-mentioned steps S1 in ebullated bed reactor, paste state bed reactor or expanded bed reactor or ebullated bed reactor, paste state bed reactor, expanded bed reactor form.
Further, the hydrogenation in above-mentioned steps S1 carries out under the katalysis of Primary Catalysts and promotor.
Further, above-mentioned Primary Catalysts is made up of active ingredient and carrier, active ingredient is that in the periodic table of elements, VIII race is or/and the oxide compound of VI race's metal, and one or more in the metal oxide of preferred Co, Mo, Ni or W, the weight of active ingredient accounts for 5 ~ 30% of Primary Catalysts weight.
Further, the temperature of reaction of the hydrogenation of above-mentioned steps S1 is between 300 ~ 420 DEG C, and reaction pressure is between 8.0 ~ 20.0MPa, and Primary Catalysts cumulative volume air speed is at 0.5 ~ 4.0h
-1, hydrogen-oil ratio is at 200 ~ 1500V/V.
Further, the cutting temperature of above-mentioned light ends oil and middle matter distillate is between 200 ~ 250 DEG C, and the cutting temperature of preferred light ends oil and middle matter distillate is between 220 ~ 230 DEG C; The cutting temperature of middle matter distillate and heavy distillate is between 300 ~ 350 DEG C, and preferably, the cutting temperature of matter distillate and heavy distillate is between 330 ~ 350 DEG C.
According to a further aspect in the invention, provide a kind of DCL/Direct coal liquefaction circulating solvent, DCL/Direct coal liquefaction circulating solvent adopts above-mentioned preparation method to be prepared from.
Further, in above-mentioned DCL/Direct coal liquefaction circulating solvent, the weight ratio of matter distillate and heavy distillate is 1:1 ~ 1:1.3.
According to another aspect of the invention, the application of a kind of above-mentioned DCL/Direct coal liquefaction circulating solvent in coal liquefaction craft is provided.
Apply technical scheme of the present invention, on the one hand owing to containing a large amount of aromatic hydrocarbons in refining of petroleum byproduct, hydrogenation after product is rich in the components such as naphthane, thus can significantly improve the hydrogen supply capacity of circulating solvent, promotes the conversion of coal, improves coal direct liquefaction oil yield; On the other hand, refining of petroleum byproduct can be utilized to replace out the diesel oil distillate being less than the high added value of 350 DEG C in part DCL/Direct coal liquefaction circulating solvent, thus improve diesel yield, significantly improve the economy of gelatin liquefaction technology; And, existing circulating solvent lighting problem can be alleviated, thus alleviate deposition and the coking of material in direct coal liquefaction process process reactor; Meanwhile, this technical scheme can solve refining of petroleum byproduct owing to being difficult to continue deep processing and the low problem of the utility value that causes containing a large amount of aromatic hydrocarbons.
Accompanying drawing explanation
The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the schematic flow sheet preparing circulating solvent of the embodiment of the present invention 1 to 6.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
In a kind of typical embodiment of the present invention, provide a kind of preparation method of DCL/Direct coal liquefaction circulating solvent, this preparation method comprises: step S1, the mixture of refining of petroleum byproduct and coal direct liquefaction oil is carried out hydrogenation, obtains hydrogenation products; Step S2, carries out fractionation by hydrogenation products, obtains light ends oil, middle matter distillate and heavy distillate; And step S3, by matter distillate mixing in heavy distillate and part, obtain DCL/Direct coal liquefaction circulating solvent.
The present invention adopts the coal direct liquefaction oil mixing refining of petroleum byproduct as the raw material making DCL/Direct coal liquefaction circulating solvent, on the one hand owing to containing a large amount of aromatic hydrocarbons in refining of petroleum byproduct, hydrogenation after product is rich in the components such as naphthane, thus the hydrogen supply capacity of circulating solvent can be significantly improved, and then promote the conversion of coal, improve coal direct liquefaction oil yield; On the other hand, refining of petroleum byproduct can be utilized to replace out the diesel oil distillate being less than the high added value of 350 DEG C in part DCL/Direct coal liquefaction circulating solvent, thus improve diesel yield, significantly improve the economy of gelatin liquefaction technology; And, existing circulating solvent lighting problem can be alleviated, thus alleviate deposition and the coking of material in direct coal liquefaction process process reactor; Meanwhile, this technical scheme can also solve refining of petroleum byproduct owing to being difficult to continue deep processing and the low problem of the utility value that causes containing a large amount of aromatic hydrocarbons.
In in the DCL/Direct coal liquefaction circulating solvent that technique scheme obtains, the ratio of matter distillate and heavy distillate can be common ratio of mixing different substances together in prior art, also can regulate according to actual product demand, the application a kind of preferred embodiment in order to increase in Coal Liquefaction Products oil the preferred DCL/Direct coal liquefaction circulating solvent of yield in the weight ratio of matter distillate and heavy distillate be 1:1 ~ 1:1.3.Technique scheme is while obtaining DCL/Direct coal liquefaction circulating solvent, light ends oil can export as the thick oil of liquiefied product with matter distillate in remaining part, and be processed as the light liquid fuel such as petroleum naphtha and diesel oil further by methods such as hydro-upgradings.
In a kind of preferred embodiment of the present invention, the boiling range of above-mentioned refining of petroleum byproduct is 220 ~ 500 DEG C, and preferred refining of petroleum byproduct is boiling range is 250 ~ 460 DEG C; The proportion of refining of petroleum byproduct is 1.0 ~ 1.1g/cm
3, the proportion of preferred refining of petroleum byproduct is 1.01 ~ 1.08g/cm
3; In refining of petroleum byproduct, condensed-nuclei aromatics content is greater than 60wt%, and in preferred refining of petroleum byproduct, condensed-nuclei aromatics content is greater than 70wt%.In refining of petroleum byproduct in above-described embodiment, aromaticity content is moderate, can either dissolve coal dust preferably, has again good mobility, is applicable to the requirement of current hydrogenation unit.
The weight content of the mixture PetroChina Company Limited. refining byproduct of above-mentioned preparation method is 5 ~ 30%, and the weight content of preferred mixture PetroChina Company Limited. refining byproduct is 5 ~ 20%.Mixture PetroChina Company Limited. refining byproduct can be different according to selected byproduct source, suitably regulate the consumption of refining of petroleum byproduct, and then obtain desirable mixture, control the performance of prepared circulating solvent from raw material within the scope of above-mentioned weight content.
Refining of petroleum byproduct used in the present invention is selected from catalytic cracking recycle oil, aromatic hydrocarbons extracted out by catalytically cracked oil, Aromatics Extractive Project oil, long residuum, vacuum residuum, lubricating oil, visbreaker tar, one or more in coking heavy oil.After those skilled in the art detect the indices of above-mentioned various byproduct, select the mixing byproduct of suitable a certain byproduct or certain several byproduct composition according to the requirement of the present invention to byproduct.
The present invention's hydrogenator used in hydrogenation process can adopt hydrogenator conventional in prior art, the step S1 of preferred above-mentioned preparation method carries out hydrogenation in ebullated bed reactor, paste state bed reactor or expanded bed reactor, or carries out hydrogenation in the cascade reaction system that forms of any one and the fixed-bed reactor in ebullated bed reactor, paste state bed reactor, expanded bed reactor.Select the cascade reaction system hydrogenation effect of the latter better, but the complicacy of device is higher, those skilled in the art can select according to the working condition of reality.
Similar to the hydrogenation reaction of prior art, hydrogenation of the present invention also carries out under the katalysis of catalyzer, and the hydrogenation in the step S1 of preferred above-mentioned preparation method carries out under the katalysis of Primary Catalysts and promotor.Utilize Primary Catalysts and promotor jointly to carry out hydrogenation, hydrogenation efficiency and hydrogenation effect can be significantly improved, and the proportioning between Primary Catalysts of the present invention and promotor can be selected according to the guidance of hydrogenation catalyst in prior art.
In a kind of preferred embodiment of the present invention, the Primary Catalysts of above-mentioned preparation method is made up of active ingredient and carrier, active ingredient be in the periodic table of elements VIII race or/and the oxide compound of VI race's metal, one or more in the metal oxide of preferred Co, Mo, Ni or W, the weight of active ingredient accounts for 5 ~ 30% of Primary Catalysts weight.Adopt noble metal catalyst as the activeconstituents of the Primary Catalysts of hydrogenation catalyst, hydrogenation effect can be significantly improved.Carrier used in the present invention is porous refractory inorganic oxide or gac, and preferred above-mentioned carrier is aluminum oxide.Utilize the porous performance of aluminum oxide and stronger hydrothermal stability, ensure effective performance of catalyst activity catalytic performance.Promotor used in the present invention is the auxiliary agent that hydrogenation catalyst is conventional, preferred sulphur.
When carrying out hydrogenation to the mixture of coal direct liquefaction oil and refining of petroleum byproduct, consider that in refining of petroleum byproduct, aromaticity content is higher, the temperature of reaction of the hydrogenation of preferred above-mentioned steps S1 is between 300 ~ 420 DEG C, reaction pressure is between 8.0 ~ 20.0MPa, and Primary Catalysts cumulative volume air speed is at 0.5 ~ 4.0h
-1, hydrogen-oil ratio is at 200 ~ 1500V/V.
The cutting temperature of light ends of the present invention oil, middle matter distillate and heavy distillate can be followed and conventionally in prior art cut off temperature, contriver is in order to provide the circulating solvent of hydrogen supply better performances, the cutting temperature of preferred light ends oil and middle matter distillate is between 200 ~ 250 DEG C, and the cutting temperature of preferred light ends oil and middle matter distillate is between 220 ~ 230 DEG C further; The cutting temperature of middle matter distillate and heavy distillate is between 300 ~ 350 DEG C, and the cutting temperature of preferred middle matter distillate and heavy distillate is between 330 ~ 350 DEG C further.
In the another kind of typical embodiment of the present invention, provide a kind of DCL/Direct coal liquefaction circulating solvent, this DCL/Direct coal liquefaction circulating solvent adopts above-mentioned preparation method to be prepared from.Adopt preparation method of the present invention to obtain the component concentration that in DCL/Direct coal liquefaction circulating solvent, the hydrogen supply performance such as naphthane is stronger higher, thus make this DCL/Direct coal liquefaction circulating solvent have higher hydrogen supply capacity.
In another kind of preferred embodiment of the present invention, in above-mentioned DCL/Direct coal liquefaction circulating solvent, the weight ratio of matter distillate and heavy distillate is 1:1 ~ 1:1.3.DCL/Direct coal liquefaction circulating solvent in this embodiment had both had stronger hydrogen supply capacity, the excessive lighting of in use circulating solvent can be avoided again to destroy the stability of coal slurry, thus avoid DCL/Direct coal liquefaction reactor heavy solvent gasification seriously cause liquid-solid phase excessive concentration and deposit, affect the reaction effect of DCL/Direct coal liquefaction, avoid reactor plugs simultaneously, extend the work-ing life of device.
In another typical embodiment of the present invention, provide the application of a kind of above-mentioned DCL/Direct coal liquefaction circulating solvent in coal liquefaction craft.Utilize DCL/Direct coal liquefaction circulating solvent of the present invention as the circulating solvent in coal liquefaction craft, good dissolving power can be had to coal, stronger hydrogen supply capacity can be provided again; And the excessive lighting of in use circulating solvent can also be avoided to destroy the stability of coal slurry, thus avoid DCL/Direct coal liquefaction reactor heavy solvent gasification seriously cause liquid-solid phase excessive concentration and deposit, affect the reaction effect of DCL/Direct coal liquefaction, avoid reactor plugs simultaneously, extend the work-ing life of device.
Below with reference to embodiment and comparative example, further illustrate beneficial effect of the present invention.
As shown in Figure 1, carry out the refining of petroleum byproduct mixed by a certain percentage and coal direct liquefaction oil adds in material tank 1 as raw material, stock oil is mixed into reactor 2 after raw oil pump and hydrogen measure respectively, the effluent of reactor 2 enters separator 3 and carries out gas-liquid separation, by emptying after the isolated gas dosing in separator 3 top; Liquid efflunent bottom separator 3 enters distillation tower 4, and in distillation tower 4, be cut into light ends oil, middle matter distillate, heavy distillate, circulating solvent as each embodiment after the mixing of matter distillate in heavy distillate and part, slightly oily as liquiefied product after remaining middle matter distillate and the mixing of light ends oil.
DCL/Direct coal liquefaction experiment is carried out in 0.5L stirred autoclave, and entering still coal amount is 28g (dry coal), and the mass ratio of circulating solvent and coal is 1.5:1, and hydrogen first pressing is 10.0MPa, and catalyzer is Fe
2o
3, Fe addition is 3% of dry coal massfraction, and promotor is sulphur, and S/Fe atomic ratio is 2.After being warmed up to temperature of reaction 455 DEG C, constant temperature 60min, after reaction terminates, temperature in the kettle is down to 200 DEG C in 20min.Autoclave product is divided into gas-phase product and liquid-solid mixture two parts, and gas-phase product adopts gas chromatograph to carry out compositional analysis; Liquid-solid phase product carries out soxhlet type with normal hexane and tetrahydrofuran (THF) successively and is separated, definition normal hexane solvend is oil, normal hexane is insoluble and the material that tetrahydrofuran (THF) is solvable is preasphaltene and asphaltene (abbreviation asphaltene fraction), and tetrahydrofuran insoluble is unconverted coal.
In the present invention, PDQI, for supplying hydrogen index (HI), refers to and is positioned at the quality of cycloalkyl β position hydrogen atom and the ratio of solvent quality on cycloalkyl aromatic hydrocarbons, be namely positioned at the milligram number of cycloalkyl β position hydrogen atom on cycloalkyl aromatic hydrocarbons in every gram of hydrogen supply dissolvent.
Embodiment 1 to 5 prepares circulating solvent according to the flow process shown in Fig. 1, and table 1 shows coal direct liquefaction oil and each refining of petroleum byproduct: the parameters of Aromatics Extractive Project oil, visbreaker tar and catalytically cracked oil; Table 2 embodiment 1 to 5 and comparative example 1 to 3 adopt the character of raw material and raw material; Table 3 shows the performance of embodiment 1 to 6 and comparative example 1 to 3 hydrogenation catalyst used and hydrogenation catalyst; Table 4 gives the hydrogenation process conditions of embodiment 1 to 5 and comparative example 1 to 3; Table 5 shows composition and the character of the circulating solvent of embodiment 1 to 5 and comparative example 1 to 3; Table 6 gives the gelatin liquefaction experimental technique condition of embodiment 1 to 6 and comparative example 1 to 3; Table 7 gives the gelatin liquefaction experimental result of embodiment 1 to 5 and comparative example 1 to 3.
Table 1
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
As can be seen from the data in table 1, in Aromatics Extractive Project oil, visbreaker tar, catalytically cracked oil, total three rings, four cyclic aromatics content are all greater than coal direct liquefaction oil, and circulating solvent its mainly to form be aromatic hydrocarbons and the hydrogenation of aromatics of 2 ~ 4 rings, illustrate that above-mentioned refining of petroleum byproduct compares the raw material being suitable as fabrication cycles solvent.
As can be seen from the data in table 5, by the comparison of the comparison of embodiment 1 and comparative example 1, embodiment 2 and comparative example 2, relatively can the finding out of embodiment 4 and comparative example 3, the confession hydrogen index (HI) of the circulating solvent that the present invention obtains all increases.
As can be seen from the data in table 7, the circulating solvent that embodiment 1 to 5 mixes refining Aromatics Extractive Project oil, visbreaker tar, catalytically cracked oil obtain is carrying out improve coal transformation efficiency when autoclave gelatin liquefaction is tested, add oily yield, demonstrate further mix refining Aromatics Extractive Project oil, hydrogen supply performance that visbreaker tar, catalytically cracked oil can improve circulating solvent.
These are only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (17)
1. a preparation method for DCL/Direct coal liquefaction circulating solvent, is characterized in that, described preparation method comprises:
Step S1, carries out hydrogenation by the mixture of refining of petroleum byproduct and coal direct liquefaction oil, obtains hydrogenation products;
Step S2, carries out fractionation by described hydrogenation products, obtains light ends oil, middle matter distillate and heavy distillate;
Step S3, by described heavy distillate and the described middle matter distillate mixing of part, obtains described DCL/Direct coal liquefaction circulating solvent;
The boiling range of described refining of petroleum byproduct is 250 ~ 460 DEG C; The proportion of described refining of petroleum byproduct is 1.0 ~ 1.1g/cm
3, in described refining of petroleum byproduct, condensed-nuclei aromatics content is greater than 60wt%.
2. preparation method according to claim 1, is characterized in that,
The proportion of described refining of petroleum byproduct is 1.01 ~ 1.08g/cm
3;
In described refining of petroleum byproduct, condensed-nuclei aromatics content is greater than 70wt%.
3. preparation method according to claim 1, is characterized in that, the weight content of refining of petroleum byproduct described in described mixture is 5 ~ 30%.
4. preparation method according to claim 3, is characterized in that, the weight content of refining of petroleum byproduct described in described mixture is 5 ~ 20%.
5. preparation method according to any one of claim 1 to 4, it is characterized in that, described refining of petroleum byproduct is selected from catalytic cracking recycle oil, aromatic hydrocarbons extracted out by catalytically cracked oil, Aromatics Extractive Project oil, long residuum, vacuum residuum, lubricating oil, visbreaker tar, one or more in coking heavy oil.
6. preparation method according to any one of claim 1 to 4, it is characterized in that, in the cascade reaction system that a kind of and fixed-bed reactor of described step S1 in ebullated bed reactor, paste state bed reactor or expanded bed reactor or ebullated bed reactor, paste state bed reactor, expanded bed reactor form, carry out described hydrogenation.
7. preparation method according to any one of claim 1 to 4, is characterized in that, the hydrogenation in described step S1 carries out under the katalysis of Primary Catalysts and promotor.
8. preparation method according to claim 7, is characterized in that, described Primary Catalysts is made up of active ingredient and carrier, described active ingredient be in the periodic table of elements VIII race or/and the oxide compound of VI race's metal.
9. preparation method according to claim 8, is characterized in that, described active ingredient is one or more in the metal oxide of Co, Mo, Ni or W, and the weight of described active ingredient accounts for 5 ~ 30% of described Primary Catalysts weight.
10. preparation method according to claim 7, is characterized in that, the temperature of reaction of the hydrogenation of described step S1 is between 300 ~ 420 DEG C, and reaction pressure is between 8.0 ~ 20.0MPa, and Primary Catalysts cumulative volume air speed is at 0.5 ~ 4.0h
-1, hydrogen-oil ratio is at 200 ~ 1500V/V.
11. preparation methods according to any one of claim 1 to 4, is characterized in that,
The cutting temperature of described light ends oil and described middle matter distillate is between 200 ~ 250 DEG C, and the cutting temperature of described middle matter distillate and described heavy distillate is between 300 ~ 350 DEG C.
12. preparation methods according to claim 11, is characterized in that, the cutting temperature of described light ends oil and described middle matter distillate is between 200 ~ 250 DEG C, and the cutting temperature of described middle matter distillate and described heavy distillate is between 330 ~ 350 DEG C.
13. preparation methods according to claim 11, is characterized in that, the cutting temperature of described light ends oil and described middle matter distillate is between 220 ~ 230 DEG C; The cutting temperature of described middle matter distillate and described heavy distillate is between 300 ~ 350 DEG C.
14. preparation methods according to claim 11, is characterized in that, the cutting temperature of described light ends oil and described middle matter distillate is between 220 ~ 230 DEG C; The cutting temperature of described middle matter distillate and described heavy distillate is between 330 ~ 350 DEG C.
15. 1 kinds of DCL/Direct coal liquefaction circulating solvents, is characterized in that, described DCL/Direct coal liquefaction circulating solvent adopts the preparation method according to any one of claim 1 to 14 to be prepared from.
16. DCL/Direct coal liquefaction circulating solvents according to claim 15, is characterized in that, in described in described DCL/Direct coal liquefaction circulating solvent, the weight ratio of matter distillate and described heavy distillate is 1:1 ~ 1:1.3.
The application of DCL/Direct coal liquefaction circulating solvent in coal liquefaction craft described in 17. 1 kinds of claims 15 or 16.
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| CN104194830B (en) * | 2014-08-29 | 2017-01-11 | 神华集团有限责任公司 | Direct coal liquefaction circulating solvent and processing method thereof as well as direct coal liquefaction method utilizing direct coal liquefaction circulating solvent |
| CN104910961B (en) * | 2015-06-03 | 2017-04-12 | 神华集团有限责任公司 | Direct-coal-liquefied circulating hydrogen-donor solvent and preparation method thereof |
| CN104845670A (en) * | 2015-06-03 | 2015-08-19 | 神华集团有限责任公司 | Circular hydrogen supply solvent for direct coal liquefaction and preparation method thereof |
| CN105018140B (en) * | 2015-07-14 | 2016-08-17 | 程志宇 | A kind of high temperature coal-tar wash oil fraction combinational processing method |
| CN105400537B (en) * | 2015-10-23 | 2018-03-20 | 北京中科诚毅科技发展有限公司 | A kind of method using mixed refining technique processing oil and coal |
| CN109852419B (en) * | 2019-03-14 | 2021-10-15 | 国家能源投资集团有限责任公司 | Coal liquefaction circulating solvent and preparation method thereof |
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| CN101649220B (en) * | 2009-09-15 | 2013-04-17 | 中国科学院山西煤炭化学研究所 | Method for simultaneously producing liquid fuel and asphalt paving materials by coprocessing coal and heavy oil |
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| CN1865399A (en) * | 2006-06-09 | 2006-11-22 | 神华集团有限责任公司 | Preparation method of initiating solvent for direct liquefy of coal |
| CN101333448A (en) * | 2008-07-09 | 2008-12-31 | 煤炭科学研究总院 | Direct liquefaction process of coal by replacing circling solvent with petroleum or petroleum refining byproduct |
| CN102517071A (en) * | 2011-12-26 | 2012-06-27 | 神华集团有限责任公司 | Method for mixing and processing wash oil and direct coal liquefaction oil |
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