CN105754630A - Preparation method of coal liquefied asphalt - Google Patents
Preparation method of coal liquefied asphalt Download PDFInfo
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- CN105754630A CN105754630A CN201610180404.2A CN201610180404A CN105754630A CN 105754630 A CN105754630 A CN 105754630A CN 201610180404 A CN201610180404 A CN 201610180404A CN 105754630 A CN105754630 A CN 105754630A
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- 239000003245 coal Substances 0.000 title claims abstract description 91
- 239000010426 asphalt Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 238000004062 sedimentation Methods 0.000 claims abstract description 123
- 239000007788 liquid Substances 0.000 claims abstract description 82
- 239000000284 extract Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000000203 mixture Substances 0.000 claims abstract description 49
- 238000000926 separation method Methods 0.000 claims abstract description 31
- 238000000199 molecular distillation Methods 0.000 claims abstract description 27
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000002956 ash Substances 0.000 claims description 45
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 claims description 31
- 238000009835 boiling Methods 0.000 claims description 16
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims description 11
- 239000003350 kerosene Substances 0.000 claims description 6
- 238000013461 design Methods 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000002893 slag Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 description 24
- 238000005406 washing Methods 0.000 description 12
- 241000772415 Neovison vison Species 0.000 description 11
- 230000006837 decompression Effects 0.000 description 11
- 230000008901 benefit Effects 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 239000002817 coal dust Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 244000025254 Cannabis sativa Species 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003250 coal slurry Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 235000015114 espresso Nutrition 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/08—Working-up pitch, asphalt, bitumen by selective extraction
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/06—Working-up pitch, asphalt, bitumen by distillation
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention provides a preparation method of coal liquefied asphalt. The preparation method comprises steps as follows: extract liquor of direct coal liquefaction residues is subjected to solid-liquid separation, and a clear liquid and solid residues are obtained; the clear liquid is subjected to natural sedimentation, a sedimentation liquid is obtained, 50vol%-80vol% of the sedimentation liquid located at the upper part is a light sedimentation phase, and 20vol%-50vol% of the sedimentation liquid located at the lower part is a heavy sedimentation phase; an asphalt mixture obtained after solvent recovery from the light sedimentation liquid is subjected to molecular distillation, first liquefied asphalt, second liquefied asphalt and heavy distillate oil with the distillation range of 260-500 DEG C are obtained, the softening point of the first liquefied asphalt is 70-120 DEG C, and the ash content of the first liquefied asphalt is 0.01wt%-0.05wt%; the softening point of the second liquefied asphalt is 200-320 DEG C, and the ash content of the second liquefied asphalt is 0.05wt%-0.5wt%. According to the method, provision of different qualities of raw materials for high-end carbon products is facilitated, and quality-based efficient utilization of the coal liquefied asphalt is realized.
Description
Technical field
The present invention relates to coal chemical technology, in particular to the preparation method of a kind of coal liquefaction Colophonium.
Background technology
Coal directly-liquefied residue is the non-targeted product of DCL/Direct coal liquefaction process, accounts for the 30wt% of coal feeding amount.It is the material of a kind of high ash, high-sulfur and high heating value, is mainly made up of non-distillate carburetion (normal hexane soluble substance), Colophonium (normal hexane insoluble oxolane soluble substance), unconverted coal and inanimate matter.Non-distillate carburetion (heavy coal liquids) and Colophonium account for the 50wt% of coal directly-liquefied residue, are mainly made up of multi-ring condensed aromatics, and it has aromaticity height, carbon content feature high, easily polymerization or crosslinking.Different with the characteristic of asphalt and coal tar asphalt, the bitumen in coal directly-liquefied residue is highly suitable as the raw material preparing carbon material, is the carbon resource of a kind of preciousness and uniqueness；Unconverted coal refers to the organic matter in residue insoluble in oxolane, accounts for the 30wt% of residue total amount, has higher calorific value；Inanimate matter is mainly made up of the mineral in coal and additional catalyst, accounts for the 20wt% of residue total amount.
How rationally and efficiently utilizing coal directly-liquefied residue is very important problem in coal liquefaction craft.Now, the method of domestic large-scale application coal directly-liquefied residue is that coal directly-liquefied residue and coal are deployed into water-coal-slurry, prepare synthesis gas and hydrogen as gasification furnace raw material, this have found outlet for coal directly-liquefied residue large-scale application, it is achieved that residue as resources utilizes.But coal directly-liquefied residue, the particularly utilization of the unrealized high added value of oxolane soluble substance (bitumen) therein, thus cause the unrealized maximization of economic benefit of DCL/Direct coal liquefaction industry.Soluble fraction in coal directly-liquefied residue and soluble part are separated, then respectively above-mentioned two parts is reasonably developed, it is possible to produce bigger economic benefit and social benefit.
Existing document describes and a kind of extracts in liquefied residue organic method, and its organic matter extracting obtained (includes heavy coal liquids and asphaltene) and all carries out secondary hydrocracking, obtains light naphtha, thus improving the yield of total body fluid carburetion.Yet with the existence of bitumen, the method is easy to produce the problem that secondary hydrogenation catalyst inactivates because of carbon deposit.
Another section of document provides a kind of method isolating heavy coal liquids and bitumen from coal directly-liquefied residue.The heavy coal liquids of separation is carried out secondary hydrocracking and obtains lightweight liquefaction oil by the method, bitumen enters coal liquefaction unit simultaneously and carries out re-liquefied reaction.The method deposits problem both ways: on the one hand, and owing to the fraction of heavy coal liquids is heavier, arene content is higher, does not require nothing more than and carries out deep hydrogenation, causes that hydrogen consumption increases, and easily causes hydrogenation catalyst and inactivate because of coking；On the other hand, when carrying out re-liquefied to isolated bitumen, its re-liquefied effect is also bad, but also can cause in liquefying reactor the ill effects such as deposition, coking, and therefore the method can not realize rationally efficiently utilizing of bitumen.
Also has a kind of method utilizing two-stage extraction to extract heavy coal liquids and bitumen from coal directly-liquefied residue of bibliographical information, the oil product of two different fractions sections that the method produces with DCL/Direct coal liquefaction process self is for extractant, liquefied residue carries out two-stage order respectively extract, obtain heavy coal liquids and bitumen.But the method adopts two-stage to extract and two-stage solid-liquid separation, thus technological process is complicated, while raw material abstraction solvent source single and price is higher, product yield is relatively low, relatively costly, and the bitumen softening point obtained is high, volatile matter is low, and the product development suitability is not strong.
Summary of the invention
Present invention is primarily targeted at the preparation method that a kind of coal liquefaction Colophonium is provided, develop, with the Colophonium solving to adopt existing method to obtain from coal directly-liquefied residue, the problem that the suitability is not strong.
To achieve these goals, the preparation method that one aspect of the invention provides a kind of coal liquefaction Colophonium, this preparation method includes: the extract of coal directly-liquefied residue carries out solid-liquid separation and obtains clear liquid and solid slag；Clear liquid carrying out natural subsidence and obtains sedimentation liquid, the sedimentation liquid of 50～80vol% above is light phase for sedimentation, and the sedimentation liquid of the 20～50vol% being positioned below is sedimentation heavy phase；And the asphalt mixture obtained after the light phase recycling design of sedimentation is carried out molecular distillation, obtain the first road oil, the second road oil and heavy distillate that boiling range is 260～500 DEG C, the softening point of the first road oil is 70～120 DEG C, and in the first road oil, content of ashes is 0.01～0.05wt%；The softening point of the second road oil is 200～320 DEG C, and in the second road oil, content of ashes is 0.05～0.5wt%.
Further, above-mentioned preparation method also includes the process preparing extract, and this process includes: by coal directly-liquefied residue and extractant mixing by weight with 1:2～6, obtain mixture；And be extract said mixture at 80～200 DEG C in temperature, it is extracted liquid after 30～60min.
Further, the method for solid-liquid separation is selected from centrifugation or isolated by filtration.
Further, the settling temperature in natural subsidence process is 80～200 DEG C, and the sedimentation time is 4～150h.
Further, the separation temperature of molecular distillation process is 300～400 DEG C, and pressure is 0.1～300Pa.
Further, before preparation method is additionally included in natural subsidence process, extract adds the process of stripping solvent.
Further, extract is 1:0.1～1 with the weight ratio of stripping solvent.
Further, stripping solvent is selected from kerosene and/or coal liquefaction light oil.
Further, by sedimentation heavy phase return to extract mixing after again carry out solid-liquid separation.
Application technical scheme, adopts natural subsidence method that the extract of coal liquefaction residue is settled, and the extract of coal directly-liquefied residue is divided into diverse two kinds of raw materials of institute's bituminous-settle are light phase and sedimentation heavy phase.Above-mentioned infall process has the advantage such as stability, reproducibility and reliability, it is adaptable to big industrialized production.Then according to actual needs the asphalt mixture obtained after the light phase recycling design of sedimentation is carried out molecular distillation process, obtain the content of ashes the first road oil lower than 0.05wt%, the softening point the second road oil higher than 200 DEG C, this raw material being conducive to providing different quality for high-end carbonaceous product, the coal liquefaction Colophonium sub-prime realized efficiently utilizes, and then improves the overall economic efficiency of DCL/Direct coal liquefaction industry.Can also being separated by the high boiling point heavy distillate that conventional hands be adopted to separate by molecular distillation process, it can be used in DCL/Direct coal liquefaction circulation simultaneously, this economic benefit being conducive to improving coal liquefaction Colophonium preparation technology further.
Accompanying drawing explanation
The Figure of description constituting the part of the application is used for providing a further understanding of the present invention, and the schematic description and description of the present invention is used for explaining the present invention, is not intended that inappropriate limitation of the present invention.
Fig. 1 illustrates the schematic flow sheet of the preparation method of a kind of coal liquefaction Colophonium of a kind of typical embodiment offer of the application.
Detailed description of the invention
It should be noted that when not conflicting, the embodiment in the application and the feature in embodiment can be mutually combined.Describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
Described by background technology, the Colophonium that existing method obtains from coal directly-liquefied residue is adopted to develop the problem that the suitability is not strong.In order to solve above-mentioned technical problem, the preparation method that the invention provides a kind of coal liquefaction Colophonium, as it is shown in figure 1, this preparation method includes: the extract of coal directly-liquefied residue carries out solid-liquid separation and obtains clear liquid and solid slag；Above-mentioned clear liquid carrying out natural subsidence and obtains sedimentation liquid, the sedimentation liquid of 50～80vol% above is light phase for sedimentation, and the sedimentation liquid of the 20～50vol% being positioned below is sedimentation heavy phase；And the asphalt mixture obtained after light phase for above-mentioned sedimentation recycling design is carried out molecular distillation, obtain the first road oil, the second road oil and and heavy distillate that boiling range is 260～500 DEG C, the softening point of the first road oil is 70～120 DEG C, and in described first road oil, content of ashes is 0.01～0.05wt%；The softening point of described second road oil is 200～320 DEG C, and in described second road oil, content of ashes is 0.05～0.5wt%.
Molecular distillation is a kind of special liquid--liquid isolation technics, and it is different from Conventional espresso and relies on boiling-point difference separation principle, but the difference by different material molecular tools realizes separating.When liquid mixture flows along hot plate and is heated, gently, weight molecule can be overflowed liquid level and be entered gas phase, owing to free path light, weight molecule is different, after the molecule of different material is overflowed from liquid level, displacement is different, if one piece of cold plate can be appropriately set, then light molecule reaches cold plate and is condensed discharges, and weight molecule does not reach cold plate along mixed liquor discharge, thus reaching the purpose of separating substances.
The application adopts natural subsidence method that the extract of coal liquefaction residue is settled, and the extract of coal directly-liquefied residue is divided into diverse two kinds of raw materials of institute's bituminous-settle are light phase and sedimentation heavy phase.Above-mentioned infall process has the advantage such as stability, reproducibility and reliability, it is adaptable to big industrialized production.Then according to actual needs the asphalt mixture obtained after the light phase recycling design of sedimentation is carried out molecular distillation process, obtain the content of ashes the first road oil lower than 0.05wt%, the softening point the second road oil higher than 200 DEG C, this raw material being conducive to providing different quality for high-end carbonaceous product, the coal liquefaction Colophonium sub-prime realized efficiently utilizes, and then improves the overall economic efficiency of DCL/Direct coal liquefaction industry.Can also being separated by the high boiling point heavy distillate that conventional hands be adopted to separate by molecular distillation process, it can be used in DCL/Direct coal liquefaction circulation simultaneously, this economic benefit being conducive to improving coal liquefaction Colophonium preparation technology further.
In the preparation method of above-mentioned coal liquefaction Colophonium, it is possible to select extraction temperature commonly used in the art that coal liquefaction Colophonium is extracted, obtain the clear liquid for settling after solid-liquid separation.This process includes: is mixed with the weight ratio of 1:2～6 with extractant by coal directly-liquefied residue, obtains mixture；And be extract said mixture at 80～200 DEG C in temperature, after 30～60min, obtain above-mentioned extract.In extraction process, extraction temperature is not limited to above-mentioned scope, but extraction temperature is limited in above-mentioned scope and is conducive to suppressing extract to lose in the way of being evaporated, said temperature is conducive to improving the dissolubility of material to be extracted simultaneously, thus being conducive to improving the main component extraction efficiency in extract.Extraction time is controlled in above-mentioned scope, be conducive to, while improving coal liquefaction bitumen extraction rate, improving extraction efficiency.In addition coal directly-liquefied residue and extractant are controlled by weight in above-mentioned scope, be conducive to improving the extraction yield of main component in extract further.Preferably, the mode of solid-liquid separation includes but not limited to thermal air pressure filtration, Vacuum Heat sucking filtration, cyclonic separation, gravity settling separation or separated.
In above-mentioned extraction process, extractant can select the organic solvent for extracting coal liquefaction residue commonly used in the art.In a preferred embodiment, extractant includes but not limited to one or more of washing oil, coal direct liquefaction oil or kerosene.Above-mentioned several extractant is the product of DCL/Direct coal liquefaction, thus adopt above-mentioned several material will not introduce new impurity as extractant, and then advantageously reducing the impurity content of follow-up prepared coal liquefaction Colophonium, the properties of product ultimately facilitating the coal liquefaction Colophonium making different batches prepare are relatively stable.
In a preferred embodiment, the process that above-mentioned preparation method also includes carrying out extract solvent recovery and coal dust reclaims.Extract is carried out solvent recovery and coal dust reclaims the effective rate of utilization being conducive to improving resource.
In a preferred embodiment, the mode of solid-liquid separation includes but not limited to centrifugation or isolated by filtration.The method of above-mentioned solid-liquid separation is simple, it is simple to operation, is conducive to simplifying the preparation technology of coal liquefaction Colophonium.
In the preparation method of above-mentioned coal liquefaction Colophonium, those skilled in the art can select temperature and the sedimentation time of sedimentation.In a preferred embodiment, the settling temperature in above-mentioned natural subsidence process is 80～200 DEG C, and the sedimentation time is 4～150h.Settling temperature and sedimentation time control to be conducive to the performance according to required coal liquefaction Colophonium in above-mentioned scope settle out the sedimentation of different component light phase.
In the preparation method of above-mentioned coal liquefaction Colophonium, it is possible to select separation temperature and the pressure of molecular distillation process as required.In a preferred embodiment, the separation temperature of molecular distillation process is 300～400 DEG C, and pressure is 0.1～500Pa.Be conducive to making the light phase Colophonium of sedimentation quickly carry out Component seperation in above-mentioned scope by separation temperature and pressure setting, obtain the coal liquefaction Colophonium that different types of quality is more homogeneous.
In the preparation method of above-mentioned coal liquefaction Colophonium, it is possible to regulate the light phase molecular weight with sedimentation heavy phase medium pitch of sedimentation by processing the temperature of Molecular regulator still-process.In a preferred embodiment, before above-mentioned preparation method is additionally included in natural subsidence process, above-mentioned extract adds the process of stripping solvent.By the dissolubility difference in stripping solvent of each component in Colophonium, above-mentioned extract adds strippant and is conducive to further regulating that sedimentation is light phase and the molecular weight of Colophonium in sedimentation heavy phase.
In a preferred embodiment, extract is 1:0.1～1 with the weight ratio of stripping solvent.The weight ratio of extract and stripping solvent includes but not limited to aforementioned proportion scope, but the weight ratio of the two controls the efficiency being conducive to improving natural subsidence process further in above-mentioned scope.
Preferably, stripping solvent includes but not limited to kerosene and/or coal liquefaction light oil.Above-mentioned substance source is wide, cheap, adopts above-mentioned substance to advantageously reduce process costs as stripping solvent.
In actual use, it is preferable that after sedimentation heavy phase being mixed with above-mentioned extract, again carry out solid-liquid separation and follow-up natural subsidence, molecular distillation process to obtain the first road oil, the second road oil and heavy distillate.This is conducive to that coal liquefaction Colophonium is carried out sub-prime and efficiently utilizes.
Below in conjunction with specific embodiment, the present invention being described in further detail, these embodiments are it is not intended that limit present invention scope required for protection.
Embodiment 1
At 100 DEG C, by weight 1:2, coal liquefaction residue and washing oil being extracted, extraction time is 30min, obtains mixture；It is centrifuged separating by horizontal screw centrifuge by mixture, obtains the extract of solid content 5wt%；
Above-mentioned extract is passed into settling tank and carries out natural subsidence, settling temperature is 150 DEG C, and the sedimentation time is 72h, divides with the volume of sedimentation liquid in settling tank, the sedimentation liquid of the 50vol% that density is less is light phase for sedimentation, and the sedimentation liquid of the 50vol% that density is bigger is sedimentation heavy phase.Carrying out decompression distillation to sedimentation is light phase, obtaining ash is 0.05wt%, and softening point is the road oil of 145 DEG C.This asphalt mixture is delivered in molecular distillation equipment, cut when temperature is 370 DEG C and vacuum is 20Pa, obtaining ash is 0.1wt%, softening point is first road oil of 254 DEG C, ash is 0.01wt%, second road oil of softening point 105 DEG C and boiling range are the mink cell focus of 273 DEG C～489 DEG C, and the weight ratio between three is 60:30:10.
Sedimentation heavy phase is repeated again the process of above-mentioned extraction, solid-liquid separation, natural subsidence and molecular distillation, obtains the first road oil, the second road oil and heavy distillate.
Embodiment 2
At 100 DEG C, by weight 1:2, liquefied residue and washing oil being extracted, extraction time is 30min, obtains mixture；
It is centrifuged separating by horizontal screw centrifuge by mixture, obtains the extract of solid content 5wt%；
Above-mentioned extract and kerosene are passed into settling tank with weight ratio 1:0.7 and carries out natural subsidence, settling temperature is 150 DEG C, sedimentation time is 24h, divide with the volume of sedimentation liquid in settling tank, the sedimentation liquid of the 50vol% that density is less is light phase for sedimentation, and the sedimentation liquid of the 50vol% that density is bigger is sedimentation heavy phase.Carrying out decompression distillation to sedimentation is light phase, obtaining ash is 0.08wt%, and softening point is the road oil of 132 DEG C.This asphalt mixture is delivered in molecular distillation equipment, it it is 370 DEG C in temperature, vacuum is cut under 20Pa, obtaining ash is 0.2wt%, softening point is first road oil of 284 DEG C, ash is 0.01wt%, and softening point is second road oil of 115 DEG C and mink cell focus that boiling range is 273～489 DEG C, and the weight ratio between three is 73:18:9.
Embodiment 3
At 100 DEG C, by weight 1:2, liquefied residue and washing oil being extracted, extraction time is 30min, obtains mixture；
Mixture is carried out cyclonic separation by cyclone separator, obtains the extract of solid content 5wt%；
Above-mentioned extract and kerosene are passed into settling tank with weight ratio 1:0.7 and carries out natural subsidence, settling temperature is 150 DEG C, sedimentation time is 120h, divide with the volume of sedimentation liquid in settling tank, the sedimentation liquid of the 80vol% that density is less is light phase for sedimentation, and the sedimentation liquid of the 20vol% that density is bigger is sedimentation heavy phase.Carrying out decompression distillation to sedimentation is light phase, obtaining ash is 0.06wt%, and softening point is the asphalt mixture of 142 DEG C.
Above-mentioned asphalt mixture is delivered in molecular distillation equipment, it it is 390 DEG C in temperature, vacuum is cut under 10Pa, obtaining ash is 0.15wt%, softening point is first road oil of 264 DEG C, being 0.02wt% with ash, softening point is second road oil of 125 DEG C and mink cell focus that boiling range is 274～479 DEG C, and the weight ratio between three is 56:29:14.
Embodiment 4
At 100 DEG C, by weight 1:4, coal liquefaction residue and washing oil being extracted, extraction time is 30min, obtains mixture；
It is filtered separating by pressure filter by mixture, obtains the extract of solid content 2wt%；
Above-mentioned extract is passed into settling tank and carries out natural subsidence, settling temperature is 130 DEG C, and the sedimentation time is 36h, divides with the volume of sedimentation liquid in settling tank, the sedimentation liquid of the 50vol% that density is less is light phase for sedimentation, and the sedimentation liquid of the 50vol% that density is bigger is sedimentation heavy phase.Carrying out decompression distillation to sedimentation is light phase, obtaining ash is 0.03wt%, and softening point is the road oil of 155 DEG C.By in this asphalt delivery to molecular distillation equipment, it it is 350 DEG C in temperature, vacuum is cut under 5Pa, obtaining ash is 0.08wt%, softening point is first road oil of 264 DEG C, ash is 0.01wt%, and softening point is second road oil of 117 DEG C and mink cell focus that boiling range is 245 DEG C～494 DEG C, and the weight ratio between three is 54:30:16.
Embodiment 5
At 80 DEG C, by weight 1:6, coal liquefaction residue and washing oil being extracted, extraction time is 30min, obtains mixture；
It is centrifuged separating by horizontal screw centrifuge by mixture, obtains the extract of solid content 4wt%；
Above-mentioned extract is passed into settling tank and carries out natural subsidence, settling temperature is 200 DEG C, and the sedimentation time is 4h, divides with the volume of sedimentation liquid in settling tank, the sedimentation liquid of the 50vol% that density is less is light phase for sedimentation, and the sedimentation liquid of the 50vol% that density is bigger is sedimentation heavy phase.Carrying out decompression distillation to sedimentation is light phase, obtaining ash is 0.1wt%, and softening point is the road oil of 138 DEG C.By in this asphalt delivery to molecular distillation equipment, it it is 350 DEG C in temperature, vacuum is cut under 5Pa, obtaining ash is 0.3wt%, softening point is first road oil of 301 DEG C, ash is 0.06wt%, and softening point is second road oil of 110 DEG C and mink cell focus that boiling range is 280～410 DEG C, and the weight ratio between three is 62:21:17.
Embodiment 6
At 200 DEG C, by weight 1:6, coal liquefaction residue and washing oil being extracted, extraction time is 30min, obtains mixture；
Mixture is carried out initial gross separation by horizontal screw centrifuge, obtains the extract of solid content 1wt%；
Above-mentioned extract is passed into settling tank and carries out natural subsidence, settling temperature is 80 DEG C, and the sedimentation time is 150h, divides with the volume of sedimentation liquid in settling tank, the sedimentation liquid of the 60vol% that density is less is light phase for sedimentation, and the sedimentation liquid of the 40vol% that density is bigger is sedimentation heavy phase.Carrying out decompression distillation to sedimentation is light phase, obtaining ash is 0.02wt%, and softening point is the road oil of 120 DEG C.By in this asphalt delivery to molecular distillation equipment, it it is 370 DEG C in temperature, vacuum is cut under 1Pa, obtaining ash is 0.05wt%, softening point is first road oil of 320 DEG C, ash is 0.01wt%, and softening point is second road oil of 80 DEG C and mink cell focus that boiling range is 260～590 DEG C, and the weight ratio between three is 55:30:15.
Embodiment 7
At 100 DEG C, by weight 1:4, coal liquefaction residue and washing oil being extracted, extraction time is 30min, obtains mixture；
Mixture is carried out initial gross separation by horizontal screw centrifuge, obtains the extract of solid content 2wt%；
Above-mentioned extract is passed into settling tank and carries out natural subsidence, settling temperature is 130 DEG C, and the sedimentation time is 36h, divides with the volume of sedimentation liquid in settling tank, the sedimentation liquid of the 50vol% that density is less is light phase for sedimentation, and the sedimentation liquid of the 50vol% that density is bigger is sedimentation heavy phase.Carrying out decompression distillation to sedimentation is light phase, obtaining ash is 0.03wt%, and softening point is the asphalt mixture of 155 DEG C.
This green grass or young crops mixture is delivered in molecular distillation equipment, it it is 300 DEG C in temperature, vacuum is cut under 500Pa, obtaining ash is 0.06wt%, softening point is first road oil of 200 DEG C, ash is 0.02wt%, and softening point is second road oil of 80 DEG C and mink cell focus that boiling range is 260～450 DEG C, and the weight ratio between three is 80:10:10.
Embodiment 8
At 100 DEG C, by weight 1:4, coal liquefaction residue and washing oil being extracted, extraction time is 30min, obtains mixture；
Mixture is carried out initial gross separation by horizontal screw centrifuge, obtains the extract of solid content 2wt%；
Above-mentioned extract is passed into settling tank and carries out natural subsidence, settling temperature is 130 DEG C, and the sedimentation time is 36h, divides with the volume of sedimentation liquid in settling tank, the sedimentation liquid of the 50vol% that density is less is light phase for sedimentation, and the sedimentation liquid of the 50vol% that density is bigger is sedimentation heavy phase.Carrying out decompression distillation to sedimentation is light phase, obtaining ash is 0.03wt%, and softening point is the asphalt mixture of 155 DEG C.
Asphalt mixture is delivered in molecular distillation equipment, it it is 400 DEG C in temperature, vacuum is cut under 0.1Pa, obtaining ash is 0.06wt%, softening point is first road oil of 320 DEG C, ash is 0.02wt%, and softening point is second road oil of 120 DEG C and mink cell focus that boiling range is 290～500 DEG C, and the weight ratio between three is 50:32:18.
Comparative example 1
At 100 DEG C, by weight 1:4, coal liquefaction residue and washing oil being extracted, extraction time is 30min, obtains mixture；
Mixture is carried out initial gross separation by horizontal screw centrifuge, obtains the extract of solid content 2wt%；
Above-mentioned extract is passed into settling tank and carries out natural subsidence, settling temperature is 70 DEG C, and the sedimentation time is 2h, divides with the volume of sedimentation liquid in settling tank, the sedimentation liquid of the 10vol% that density is less is light phase for sedimentation, and the sedimentation liquid of the 90vol% that density is bigger is sedimentation heavy phase.Carrying out decompression distillation to sedimentation is light phase, obtaining ash is 1wt%, and softening point is the asphalt mixture of 172 DEG C.
Asphalt mixture is delivered in molecular distillation equipment, it it is 350 DEG C in temperature, vacuum is cut under 5Pa, obtaining ash is 0.06wt%, softening point is first road oil of 65 DEG C, ash is 3.2wt%, and softening point is second road oil of 198 DEG C and mink cell focus that boiling range is 230～390 DEG C, and the weight ratio between three is 85:10:5.
Comparative example 2
At 50 DEG C, by weight 1:1, coal liquefaction residue and washing oil being extracted, extraction time is 30min, obtains mixture；
Mixture is carried out initial gross separation by horizontal screw centrifuge, obtains the extract of solid content 8wt%；
Above-mentioned extract is passed into settling tank and carries out natural subsidence, settling temperature is 130 DEG C, and the sedimentation time is 36h, divides with the volume of sedimentation liquid in settling tank, the sedimentation liquid of the 50vol% that density is less is light phase for sedimentation, and the sedimentation liquid of the 50vol% that density is bigger is sedimentation heavy phase.Carrying out decompression distillation to sedimentation is light phase, obtaining ash is 4wt%, and softening point is the asphalt mixture of 165 DEG C.
Asphalt mixture is delivered in molecular distillation equipment, it it is 350 DEG C in temperature, vacuum is cut under 5Pa, obtaining ash is 8wt%, softening point is first road oil of 262 DEG C, ash is 0.08wt%, and softening point is second road oil of 109 DEG C and mink cell focus that boiling range is 270～460 DEG C, and the weight ratio between three is 64:21:15.
Comparative example 3
At 100 DEG C, by weight 1:4, coal liquefaction residue and washing oil being extracted, extraction time is 30min, obtains mixture；
Mixture is carried out initial gross separation by horizontal screw centrifuge, obtains the extract of solid content 2wt%；
Above-mentioned extract is passed into settling tank and carries out natural subsidence, settling temperature is 130 DEG C, and the sedimentation time is 36h, divides with the volume of sedimentation liquid in settling tank, the sedimentation liquid of the 50vol% that density is less is light phase for sedimentation, and the sedimentation liquid of the 50vol% that density is bigger is sedimentation heavy phase.Carrying out decompression distillation to sedimentation is light phase, obtaining ash is 0.03wt%, and softening point is the asphalt mixture of 155 DEG C.
Asphalt mixture is delivered in molecular distillation equipment, it it is 260 DEG C in temperature, vacuum is cut under 5Pa, obtaining ash is 0.05wt%, softening point is first road oil of 187 DEG C, ash is 0.01wt%, and softening point is second road oil of 56 DEG C and mink cell focus that boiling range is 210～280 DEG C, and the weight ratio between three is 90:5:5.
As can be seen from the above description, the above embodiments of the present invention achieve following technique effect:
By embodiment 1 to 3 and comparative example 1 are compared; under similarity condition; when settle light phase and sedimentation heavy phase volume ratio in the scope that the application protects time; in final products the content of ashes in the first road oil substantially reduce, the softening point of the second road oil significantly raised; this raw material being conducive to providing different quality for high-end carbonaceous product, it is achieved coal liquefaction Colophonium sub-prime efficiently utilize；
By embodiment 1 to 8 and comparative example 2 are compared it can be seen that controlled by extraction conditions in above-mentioned scope, in final products the content of ashes in the first road oil be significantly reduced, the softening point of the second road oil significantly raised；
By embodiment 1 to 8 and comparative example 3 are compared; the temperature and pressure of molecular distillation is limited in the scope that the application protects, again such that in final products the content of ashes in the first road oil be significantly reduced, the softening point of the second road oil significantly raised.Thus adopt the method that the application provides to be conducive to providing the raw material of different quality for high-end carbonaceous product, it is achieved coal liquefaction Colophonium sub-prime efficiently utilize, thus being conducive to improving further the economic benefit that coal liquefaction residue is recycled；
By by embodiment 2 and 3 and embodiment 1 compare it can be seen that after adding stripping solvent in extract in natural subsidence process, it is possible to effectively regulate the proportionate relationship of the first road oil, the second road oil and heavy distillate.
The foregoing is 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.All within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (9)
1. the preparation method of a coal liquefaction Colophonium, it is characterised in that described preparation method includes:
The extract of coal directly-liquefied residue is carried out solid-liquid separation and obtains clear liquid and solid slag；
Described clear liquid carrying out natural subsidence and obtains sedimentation liquid, the described sedimentation liquid of 50～80vol% above is light phase for sedimentation, and the described sedimentation liquid of the 20～50vol% being positioned below is sedimentation heavy phase；And
The asphalt mixture obtained after light phase for described sedimentation recycling design is carried out molecular distillation, obtain the first road oil, the second road oil and heavy distillate that boiling range is 260～500 DEG C, the softening point of described first road oil is 70～120 DEG C, and in described first road oil, content of ashes is 0.01～0.05wt%；The softening point of described second road oil is 200～320 DEG C, and in described second road oil, content of ashes is 0.05～0.5wt%.
2. preparation method according to claim 1, it is characterised in that above-mentioned preparation method also includes the process preparing described extract, and described process includes:
Described coal directly-liquefied residue is mixed with the weight ratio of 1:2～6 with extractant, obtains mixture；And
It is extract described mixture at 80～200 DEG C in temperature, after 30～60min, obtains described extract.
3. preparation method according to claim 1 and 2, it is characterised in that the method for described solid-liquid separation is selected from centrifugation or isolated by filtration.
4. preparation method according to claim 1, it is characterised in that the settling temperature in described natural subsidence process is 80～200 DEG C, the sedimentation time is 4～150h.
5. preparation method according to any one of claim 1 to 4, it is characterised in that the separation temperature of described molecular distillation process is 300～400 DEG C, pressure is 0.1～300Pa.
6. preparation method according to claim 5, it is characterised in that described preparation method adds the process of stripping solvent before being additionally included in described natural subsidence process in described extract.
7. preparation method according to claim 6, it is characterised in that the weight ratio of described extract and described stripping solvent is 1:0.1～1.
8. preparation method according to claim 6, it is characterised in that described stripping solvent is selected from kerosene and/or coal liquefaction light oil.
9. preparation method according to claim 1, it is characterised in that again carry out described solid-liquid separation with described extract after described sedimentation heavy phase being mixed.
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