CN101962561A - Extraction method of direct coal liquefaction residues and application of extracts - Google Patents

Extraction method of direct coal liquefaction residues and application of extracts Download PDF

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CN101962561A
CN101962561A CN2010102995637A CN201010299563A CN101962561A CN 101962561 A CN101962561 A CN 101962561A CN 2010102995637 A CN2010102995637 A CN 2010102995637A CN 201010299563 A CN201010299563 A CN 201010299563A CN 101962561 A CN101962561 A CN 101962561A
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extraction
solvent
liquefaction
oil
hydrogenation
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CN2010102995637A
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CN101962561B (en
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吴秀章
李克健
张胜振
舒歌平
李丽
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神华集团有限责任公司
中国神华煤制油化工有限公司
中国神华煤制油化工有限公司北京研究院
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Abstract

The invention relates to an extraction method of direct coal liquefaction residues and application of extracts. The extraction method comprises the following steps: a) adding coal liquefaction residue powder and a first extraction solvent to a stirred tank to undergo primary extraction; b) carrying out solid-liquid separation on the extracted mixture obtained in the step a) and recovering the first extraction solvent from the obtained liquid in a solvent recovery unit and recycling the first extraction solvent; c) obtaining extracts after recovering the first solvent and mixing the extracts with a second extraction solvent to undergo secondary extraction; d) carrying out solid-liquid separation on the extracted mixture obtained in the step c), obtaining heavy liquefied oil after recovering the second extraction solvent from the obtained liquid in the solvent recovery unit and then carrying out moderate hydrogenation on the heavy liquefied oil and other recycled solvents in a coal liquefaction solvent hydrogenation unit and using the product as the recycled solvent in the coal liquefaction process; and e) carrying out heat treatment on the asphaltic substances obtained in the step d) by heating and carbonizing to obtain mesophase asphalt and oils.

Description

The extracting process of coal directly-liquefied residue and the application of extract
Technical field
The present invention relates to coal deep processing field, particularly relate to the application of the extracting process and the extract of coal directly-liquefied residue.
Background technology
Coal direct liquefaction is by high temperature, high pressure with coal, hydrogenation directly changes into the transport liquid fuel (petroleum naphtha, diesel oil etc.) of cleaning or a kind of advanced clean coal technology of industrial chemicals under the effect of catalyzer, is one of important channel of alleviating China's oil shortage of resources, petroleum products supply and demand pressure.The major objective product of DCL/Direct coal liquefaction process is the liquefaction oil product, and the liquefaction residue (claiming coal liquefaction residue again) that produces of gases such as some hydrocarbon gas of by-product, COx, process water and solid-liquid separation process.Liquefied residue generally accounts for about 30% of coal input quantity.How to utilize this part coal liquefaction residue to extract value product, the economy of liquefaction process efficient and whole liquefaction factory and environment protection etc. are all had immeasurable influence.
Coal directly-liquefied residue mainly is made up of inanimate matter and organic two portions, and organic matter wherein comprises heavy liquefaction oil, bitumen and unconverted coal; Inorganic matter comprises coal mineral and the catalyzer that adds.Heavy liquefaction oil in organic class material, bitumen content account for about 50% of level of residue, and unconverted coal accounts for about 30%, and ash content accounts for about 20%.Therefore, about 50% pitch in the residue and mink cell focus separated carry out comprehensive processing and utilization, therefrom extract or prepare more that value product has feasibility.
How effectively to utilize coal liquefaction residue, make it produce bigger economic benefit, be a challenging subject in DCL/Direct coal liquefaction field always.Utilization to coal liquefaction residue now mainly contains traditional methods such as burning, coking system oil, gasification hydrogen-producing.Act as a fuel and directly in boiler or kiln, burn, will influence the economy of gelatin liquefaction undoubtedly, cause the huge waste of resource, and higher sulphur content will be brought the problem of environment aspect in the liquefied residue.Coking system oil is that the asphaltene in the liquefied residue is converted into mink cell focus and retortable oil, though increased the liquid oils yield of coal liquefaction craft, but liquefied residue can not obtain reasonable use, coking obtains semicoke because sulphur content is high and the ash content height, and it utilizes approach also very not clear and definite.The method of liquefied residue being carried out gasification hydrogen-producing is a kind of effectively extensive approach that utilizes, but the high value added utilization potentiality to bitumen in the residue and mink cell focus do not obtain embodying, and ash content is up to more than 20% in the residue, and this brings very big influence will for the deslagging of vapourizing furnace.
It is the method that the raw material plasma body prepares carbon nano-material with the coal direct liquefaction residue that Chinese patent ZL200510047800.X discloses a kind of.Chinese patent ZL200610012547.9 discloses a kind of with the method for coal liquefaction residue as road asphalt modifier.Chinese patent ZL200910087907.5 discloses a kind of method of utilizing coal directly-liquefied residue to prepare asphalt base carbon fiber.China ZL200910086158.4 discloses a kind of method for preparing mesophase pitch with coal liquefaction residue.These methods all are to be raw material with the bitumen in the coal liquefaction residue, do not relate to the utilization of the heavy liquefaction oil in the residue, and the extracting of residue medium pitch class material all is to be solvent with expensive pure chemistry reagent, and cost compares higher.
Japanese Patent JP 59084977 discloses a kind of method organic in the liquefied residue of extracting, the organic matter (comprising heavy liquefaction oil and asphaltene) that extracting is obtained all carries out secondary hydrocracking, obtain light naphtha, thereby improve the yield of total body fluid carburetion, but exist because the existence of extract medium pitch class material causes the secondary hydrogenation catalyst to be very easy to the problem of coking deactivation.JP 1304182 discloses a kind of method of isolating heavy liquefaction oil and bitumen from the direct liquefaction residue, this method is carried out secondary hydrocracking with isolating heavy liquefaction oil and is obtained the lightweight liquefaction oil, carries out liquefaction reaction again and bitumen enters the coal liquefaction unit.On the one hand, because the fraction of heavy oil product is heavier, aromaticity content is than higher, reaction is more violent during secondary hydrocracking system light Fuel, not only require to carry out deep hydrogenation, cause having increased the hydrogen consumption, and cause catalyzer easily because of the coking inactivation, thereby the performance to hydrocracking catalyst has proposed very high requirement, requires hydrocracking catalyst to have stronger activity, more intense anti-carbon deposition ability.On the other hand, when the bitumen of separating liquefies again, its effect and bad that liquefies again, but also can cause ill effects such as deposition, coking in liquefying reactor, so this method can not realize that the rationally efficient of asphaltene class material utilizes.
The content of the heavy liquefaction oil in the coal directly-liquefied residue accounts for about 30% of residue weight, and primary structure is the aromatic hydrocarbons and the partial hydrogenation aromatic hydrocarbons of 2~4 rings.Though this part heavy liquefaction oil can obtain the lightweight liquefaction oil after hydrocracking, because this oil product fraction is heavier, aromaticity content is high, need carry out deep hydrogenation, the easy inactivation of catalyzer.And need an amount of heavy fraction of oil in the DCL/Direct coal liquefaction process as solvent.Usually, these solvents only require before use and carry out appropriate hydrotreatment that the aromatic carbon rate before and after the hydrogenation changes between 0.05~0.1, makes the aromatic ring hydrogenation of the easy hydrogenation of part in the oil product, thereby improves the hydrogen supply capacity of solvent.Simultaneously, the heavy solvent in the gelatin liquefaction process not only can improve the dissolving power of solvent to coal and pyrolysis of coal free radical fragment, improves the hydrogen supply performance of solvent, and can alleviate the sedimentation of coal dust at conveying, warm.If the circulating solvent as DCL/Direct coal liquefaction after appropriate hydrogenation of this part heavy oil product in the coal liquefaction residue is used, can substitute out the light component in the former circulating solvent, not only can increase the yield of liquefaction oil product, improve the degree of heaviness of circulating solvent, improve the quality of coal liquefaction solvent, and the desired hydrogenation degree of these mink cell focuses is not high, require not high relatively to catalyzer, can with the common hydrogenation of circulating solvent, need not increase hydrogenation unit newly, therefore, simple relatively, the also mitigation relatively of operational condition of technology.The purpose of DCL/Direct coal liquefaction provides liquid fuel, therefore, thus how as much as possible this part heavy liquefaction oil of recovery is the important topic that is related to the gelatin liquefaction process economy with the oily yield of replacing out lightweight liquefaction oil in the liquefied circulating solvent and improving whole liquefaction process.
The content of the asphaltene class material in the liquefied residue is about about 20% of level of residue, mainly is made up of the polycyclic condensed aromatics, has the aromaticity height, the carbon content height, polymerization or crosslinked characteristics are suitable as the raw material for preparing carbon material very much easily, are a kind of very valuable and unique resources.
Under the usual conditions, liquefied residue is an effluent at the bottom of the still of vacuum distillation apparatus, and therefore heavy liquefaction oil fraction wherein is heavier, is generally the fraction oil of boiling point>350 ℃, and tightr with the bitumen bonded, be difficult to they are separated with common underpressure distillation mode.Heat treating methods such as common destructive distillation, coking, though can realize the purpose of separating, reclaim the heavy liquefaction oil of mink cell focus and pitch coke, but owing to aromaticity content height, aromatic hydrocarbons condensation degree height in the heavy liquefaction oil, violent polycondensation will take place in heat treatment process, the heavy oil content polycondensation of significant proportion is a coke, and therefore the ratio of the actual heavy oil product that obtains is not high.Be difficult to reach the purpose of utilizing gelatin liquefaction heavy liquefaction oil fully, rationally, efficiently.
For these reasons, the present invention proposes a kind of method of utilizing the two-stage extraction from the coal direct liquefaction residue, to extract heavy liquefaction oil and bitumen, this method is an extraction solvent with the oil product of two different fraction sections that DCL/Direct coal liquefaction process self produces, respectively liquefied residue is carried out two-stage and extract in proper order, the method that obtains heavy liquefaction oil and bitumen and rationally utilize.
Summary of the invention
The purpose of this invention is to provide a kind of liquefaction oil product of different fraction sections that utilizes coal liquefaction residue is carried out fractional extraction, the circulating solvent of heavy liquefaction oil in the gelatin liquefaction process that extraction is obtained carries out appropriate hydrogenation to be used as the circulating solvent of gelatin liquefaction later on, and the bitumen that extraction obtains obtains the method for mesophase pitch class material as the raw material of preparation carbon materials through Overheating Treatment.
Extraction of the two-stage of coal directly-liquefied residue provided by the invention and extract utilize method, it is characterized in that coal directly-liquefied residue with the liquefaction oil (being called first solvent and second solvent) of two kinds of different fraction sections as extraction solvent, extract respectively, obtain heavy liquefaction oil and bitumen, and rationally utilize respectively.
One aspect of the present invention provides a kind of method of utilizing the two-stage extraction to extract heavy liquefaction oil and bitumen from coal directly-liquefied residue, said method comprising the steps of:
A) coal liquefaction residual powder is joined with first extraction solvent carry out one-level extraction in the stirring tank;
B) the extraction mixture to step a) carries out solid-liquid separation, makes the liquid portion that obtains reclaim first extraction solvent through solvent recovery unit and recycles;
C) obtain extract behind recovery first solvent, this extract is mixed with second extraction solvent, carry out the secondary extraction;
D) the extraction mixture to step c) carries out solid-liquid separation, makes the liquid portion that obtains obtain the heavy liquefaction oil after solvent recovery unit reclaims second extraction solvent, enters coal liquefaction solvent hydrogenation unit with other circulating solvent then, carries out appropriate hydrogenation; And
E) to separating the bitumen that obtains in the step d), heat-treat, obtain mesophase pitch and oil product, the oil product that obtains is sent in the described hydrogenation unit of step d) with the pyrogenous method of heating.
The method according to this invention, wherein, described first extraction solvent and second extraction solvent are the liquefaction oil product that directly produces in the DCL/Direct coal liquefaction process.Particularly, first extraction solvent is 220~260 ℃ a fraction, and second extraction solvent is the fraction of IBP~110 ℃.
The method according to this invention, wherein, the extracting operation condition of the one-level extraction in described step a) is: the mass ratio of coal liquefaction residue and described first extraction solvent is 1: 1~10, be preferably 1: 2~8; N 2And/or H 2Atmosphere, pressure is 0.1~3.0MPa, is preferably 0.2~2.5MPa; Extraction temperature is 60~300 ℃, is preferably 80~250 ℃; The extraction time is 5~120min, and stir speed (S.S.) is 50~400r/min.
The method according to this invention, wherein, the extracting operation condition of the secondary extraction in described step c) is: the mass ratio of coal liquefaction residue and described second extraction solvent is 1: 1~10, be preferably 1: 1~6; N 2And/or H 2Atmosphere, pressure is 0.2~3.5MPa, is preferably 0.5~2.5MPa; Extraction temperature is 30~250 ℃, is preferably 40~200 ℃; The extraction time is 5~120min, and stir speed (S.S.) is 50~400r/min.
The method according to this invention, wherein, described solid-liquid separating method can be for comprising filter method, gravity settling separation method, eddy flow centrifugal separation method or the distillation separation method of hot suction filtration mode of vacuum and pressurized heat filter type.
The method according to this invention, wherein, described solvent recovery unit can reclaim extraction solvent for recycling with the method for distillation and/or evaporation.
The method according to this invention, wherein, the hydrogenation reaction temperature in described step d) is 260~370 ℃, is preferably 280~360 ℃; Reaction pressure is 6~19MPa, is preferably 8~15MPa; Reaction solution hourly space velocity LHSV is 0.5~1.5h -1, be preferably 0.7~1.2h -1Vapour-liquid ratio is 300~1200m 3/ t is preferably 500~1000m 3/ t; Hydrogenation catalyst mainly consists of: with two or more of Ni, Mo, Co, W element is active component, and with Alpha-alumina, one or both in gama-alumina, silicon oxide and the molecular sieve etc. are carrier.
The method according to this invention, wherein, the heat treated temperature in described step e) is 200~500 ℃, preferred 300~450 ℃; Heat-treating atmosphere is the inert gas atmosphere that is selected from vacuum or nitrogen, helium.
The method according to this invention, wherein, the thermal treatment oil product that obtains in the heavy liquefaction oil that will obtain in described step d), the step e) other circulating solvent in the gelatin liquefaction process carries out appropriate hydrogenation to be used as the circulating solvent of gelatin liquefaction later on; With the described mesophase pitch class material that obtains in the described step e) raw material as the preparation carbon materials.
Described solvent hydrogenation is that the heavy liquefaction oil of instigating extraction to obtain, the mink cell focus that thermal treatment obtains enter coal liquefaction solvent hydrogenation unit with other circulating solvent, obtains having the gelatin liquefaction circulating solvent of hydrogen supply.
Described thermal treatment process is meant with the pyrogenous method of heating handles bitumen.The heavy oil product that obtains enters solvent hydrogenation unit, as the part of circulating solvent in the gelatin liquefaction process; The mesophase pitch class material that obtains can be used for preparing carbon fiber, needle coke, carbon nanotube and other carbon material etc. as the raw material of preparation carbon materials.
Another aspect of the present invention provides a kind of heavy liquefaction oil and bitumen that is extracted by the method according to this invention.
The circulating solvent of heavy liquefaction oil in the gelatin liquefaction process that the method according to this invention is extracted carries out appropriate hydrogenation to be used as the circulating solvent of gelatin liquefaction later on, and the bitumen that extraction obtains obtains the raw material of mesophase pitch class material as the preparation carbon materials through Overheating Treatment.
Another aspect of the present invention provides the heavy liquefaction oil, the circulating solvent of thermal treatment oil product in the gelatin liquefaction process that are extracted by the method according to this invention to carry out appropriate hydrogenation later on as the application in the circulating solvent of gelatin liquefaction.
Another aspect of the present invention provides the bitumen that extracted by the method according to this invention to obtain the application of mesophase pitch class material at the raw material that is used for preparing carbon materials through Overheating Treatment.
Extraction of the two-stage of coal directly-liquefied residue provided by the invention and extract utilize method, its characteristics are, coal directly-liquefied residue is carried out the two-stage extraction under effect under two kinds of extraction solvents, obtain heavy liquefaction oil and bitumen respectively and be used, the whole process flow process is simple, easy and safe to operate, fully reasonable use the characteristic of this material.
Extraction of the two-stage of coal directly-liquefied residue provided by the invention and extract utilize method, its characteristics are that two kinds of extraction solvents are all from the gelatin liquefaction process, the liquefaction oil product for the different fractions section has different dissolving poweies to the organic matter in the liquefied residue.Utilize the difference of its dissolving power, realize heavy liquefaction oil in the residue is separated with bitumen, and the purpose of in addition rationally utilizing.Present method is to isolate the heavy liquefaction oil in the mode of extraction from residue, and bitumen also obtains part heavy liquefaction oil in Overheating Treatment is produced the process of mesophase pitch, therefore utilize the yield of the heavy liquefaction oil that this method obtains higher relatively, can realize heavy liquefaction oil in the residue fully, the efficient utilization.
Extraction of the two-stage of coal directly-liquefied residue provided by the invention and extract utilize method, its characteristics are, two kinds of extraction solvents are all from the gelatin liquefaction process, from the horse's mouth, with low cost, easy recovery.Can substitute out in the former circulating solvent relatively than the light-weight component as the part of the circulating solvent of liquefaction process with the heavy liquefaction oil, improve the degree of heaviness of solvent, improve the overall oily yield of gelatin liquefaction process, thereby improved the economy of liquefaction factory.
Extraction of the two-stage of coal directly-liquefied residue provided by the invention and extract utilize method, its characteristics are, this method extraction obtains the bitumen oleaginousness still less, the condensation degree of aromatic ring is higher, the easier preparation mesophase pitch of heat-treating, the mesophase pitch class material that obtains has higher C/H atomic ratio, lower quinoline insolubles, aromaticity is higher, is the desirable feedstock of preparation carbon materials.
Description of drawings
By the detailed description below in conjunction with accompanying drawing, above-mentioned and further feature of the present invention and advantage will become more obvious, in the accompanying drawing:
Fig. 1 shows a kind of coal directly-liquefied residue and extracts through two-stage, the schema of the method that extraction heavy liquefaction oil and bitumen also are used respectively.
Embodiment
One aspect of the present invention provides a kind of method of utilizing the two-stage extraction to extract heavy liquefaction oil and bitumen from coal directly-liquefied residue, said method comprising the steps of:
A) coal liquefaction residual powder is joined with first extraction solvent carry out one-level extraction in the stirring tank;
B) the extraction mixture to step a) carries out solid-liquid separation, makes the liquid portion that obtains reclaim first extraction solvent through solvent recovery unit and recycles;
C) obtain extract behind recovery first solvent, this extract is mixed with second extraction solvent, carry out the secondary extraction;
D) the extraction mixture to step c) carries out solid-liquid separation, makes the liquid portion that obtains obtain the heavy liquefaction oil after solvent recovery unit reclaims second extraction solvent, enters coal liquefaction solvent hydrogenation unit with other circulating solvent then, carries out appropriate hydrogenation; And
E) to separating the bitumen that obtains in the step d), heat-treat, obtain mesophase pitch and oil product, and the oil product that obtains is sent in the described hydrogenation unit of step d) with the pyrogenous method of heating.
Another aspect of the present invention provides a kind of heavy liquefaction oil and bitumen that is extracted by the method according to this invention.
Another aspect of the present invention provides the heavy liquefaction oil, the circulating solvent of thermal treatment oil product in the gelatin liquefaction process that are extracted by the method according to this invention to carry out appropriate hydrogenation later on as the application in the circulating solvent of gelatin liquefaction.
Another aspect of the present invention provides the bitumen that extracted by the method according to this invention to obtain the application of mesophase pitch class material at the raw material that is used for preparing carbon materials through Overheating Treatment.
Preferably, described method comprises that also thermal treatment oil product other circulating solvent in the gelatin liquefaction process that obtains in the described heavy liquefaction oil that will obtain in the step d), the step e) enters coal liquefaction solvent hydrogenation unit, carry out appropriate hydrogenation, obtain having the gelatin liquefaction circulating solvent of hydrogen supply.
Preferably, described method comprises that also the described bitumen that will obtain in the step e) heat-treats with the pyrogenous method of heating, obtains the raw material of mesophase pitch as the preparation carbon materials, and the oil product of by-product enters the described solvent hydrogenation unit of step d).
In embodiments of the present invention, wherein, described first extraction solvent and second extraction solvent are the liquefaction oil product that directly produces in the DCL/Direct coal liquefaction process.Particularly, first extraction solvent is 220~260 ℃ a fraction, and second extraction solvent is the fraction of IBP~110 ℃.
In embodiments of the present invention, wherein, the extracting operation condition of the one-level extraction in described step a) is: the mass ratio of coal liquefaction residue and described first extraction solvent is 1: 1~10, be preferably 1: 2~and 8; N 2And/or H 2Atmosphere, pressure is 0.1~3.0MPa, is preferably 0.2~2.5MPa; Extraction temperature is 60~300 ℃, is preferably 80~250 ℃; The extraction time is 5~120min, and stir speed (S.S.) is 50~400r/min.
In embodiments of the present invention, wherein, the extracting operation condition of the secondary extraction in described step c) is: the mass ratio of coal liquefaction residue and described second extraction solvent is 1: 1~10, be preferably 1: 1~and 6; N 2And/or H 2Atmosphere, pressure is 0.2~3.5MPa, is preferably 0.5~2.5MPa; Extraction temperature is 30~250 ℃, is preferably 40~200 ℃; The extraction time is 5~120min, and stir speed (S.S.) is 50~400r/min.
In embodiments of the present invention, wherein, described solid-liquid separating method can be for comprising filter method, gravity settling separation method, eddy flow centrifugal separation method or the distillation separation method of hot suction filtration mode of vacuum and pressurized heat filter type.
In embodiments of the present invention, wherein, described solvent recovery unit can reclaim extraction solvent for recycling with the method for distillation and/or evaporation.
In embodiments of the present invention, wherein, the hydrogenation reaction temperature in described step d) is 260~370 ℃, is preferably 280~360 ℃; Reaction pressure is 6~19MPa, is preferably 8~15MPa; Reaction solution hourly space velocity LHSV is 0.5~1.5h -1, be preferably 0.7~1.2h -1Vapour-liquid ratio is 300~1200m 3/ t is preferably 500~1000m 3/ t; Hydrogenation catalyst mainly consists of: with two or more of Ni, Mo, Co, W element is active component, and with Alpha-alumina, one or both in gama-alumina, silicon oxide and the molecular sieve etc. are carrier.
In embodiments of the present invention, wherein, the heat treated temperature in described step e) is 200~500 ℃, preferred 300~450 ℃; Heat-treating atmosphere is the inert gas atmosphere that is selected from vacuum or nitrogen, helium.
In embodiments of the present invention, wherein, the thermal treatment oil product that obtains in the heavy liquefaction oil that will obtain in described step d), the step e) other circulating solvent in the gelatin liquefaction process carries out appropriate hydrogenation to be used as the circulating solvent of gelatin liquefaction later on; With the described mesophase pitch class material that obtains in the described step e) raw material as the preparation carbon materials.
Described solvent hydrogenation is that the heavy liquefaction oil of instigating extraction to obtain, the mink cell focus that thermal treatment obtains enter coal liquefaction solvent hydrogenation unit with other circulating solvent, obtains having the gelatin liquefaction circulating solvent of hydrogen supply.
Described thermal treatment process is meant with the pyrogenous method of heating handles bitumen.The heavy oil product that obtains enters solvent hydrogenation unit, as the part of circulating solvent in the gelatin liquefaction process; The mesophase pitch class material that obtains can be used for preparing carbon fiber, needle coke, carbon nanotube and other carbon material etc. as the raw material of preparation carbon materials.
In the present invention, term " circulating solvent oil carries out appropriate hydrogenation " is meant that the variation of hydrogenation front and back solvent oil aromatic carbon rate is less than 0.1.
In addition, in the present invention, term " aromatic carbon rate " is meant the carbon atom of aromatic structure in the basic structural unit and the ratio of total carbonatoms.
Extraction of the two-stage of coal directly-liquefied residue provided by the invention and extract utilize method, its characteristics are, coal directly-liquefied residue is carried out the two-stage extraction under effect under two kinds of extraction solvents, obtain heavy liquefaction oil and bitumen respectively and be used, the whole process flow process is simple, easy and safe to operate, fully reasonable use the characteristic of this material.
Extraction of the two-stage of coal directly-liquefied residue provided by the invention and extract utilize method, its characteristics are that two kinds of extraction solvents are all from the gelatin liquefaction process, the liquefaction oil product for the different fractions section has different dissolving poweies to the organic matter in the liquefied residue.Utilize the difference of its dissolving power, realize heavy liquefaction oil in the residue is separated with bitumen, and the purpose of in addition rationally utilizing.Present method is to isolate the heavy liquefaction oil in the mode of extraction from residue, and bitumen also obtains part heavy liquefaction oil in Overheating Treatment is produced the process of mesophase pitch, therefore utilize the yield of the heavy liquefaction oil that this method obtains higher relatively, can realize heavy liquefaction oil in the residue fully, the efficient utilization.
Extraction of the two-stage of coal directly-liquefied residue provided by the invention and extract utilize method, its characteristics are, two kinds of extraction solvents are all from the gelatin liquefaction process, from the horse's mouth, with low cost, easy recovery.Can substitute out in the former circulating solvent relatively than the light-weight component as the part of the circulating solvent of liquefaction process with the heavy liquefaction oil, improve the degree of heaviness of solvent, improve the overall oily yield of gelatin liquefaction process, thereby improved the economy of liquefaction factory.
Extraction of the two-stage of coal directly-liquefied residue provided by the invention and extract utilize method, its characteristics are, this method extraction obtains the bitumen oleaginousness still less, the condensation degree of aromatic ring is higher, the easier preparation mesophase pitch of heat-treating, the mesophase pitch class material that obtains has higher C/H atomic ratio, lower quinoline insolubles, aromaticity is higher, is the desirable feedstock of preparation carbon materials.
Fig. 1 shows and utilizes two-stage extraction to extract heavy liquefaction oil and bitumen and the schema of the method that is used respectively from coal directly-liquefied residue.As shown in Figure 1, this method comprise one-level extraction-solid-liquid separation-recovery solvent-hydrogenation-step, and with the solid of solid-liquid separation carry out secondary extraction-solid-liquid separation-recovery solvent-thermal treatment-step.Particularly, said method comprising the steps of: a) coal liquefaction residual powder is joined with first extraction solvent and carry out the one-level extraction in the stirring tank; B) the extraction mixture to step a) carries out solid-liquid separation, makes the liquid portion that obtains reclaim first extraction solvent through solvent recovery unit and recycles; C) obtain extract behind recovery first solvent, this extract is mixed with second extraction solvent, carry out the secondary extraction; D) the extraction mixture to step c) carries out solid-liquid separation, and the liquid portion that obtains obtains the heavy liquefaction oil after solvent recovery unit reclaims second extraction solvent, enter coal liquefaction solvent hydrogenation unit with other circulating solvent then, carries out appropriate hydrogenation; And e) to separating the bitumen that obtains in the step d), heat-treats, obtain mesophase pitch and oil product, oil product is sent into the described hydrogenation unit of step d) with the pyrogenous method of heating.
Further specify the present invention by the following example, but protection scope of the present invention is not limited to the following example.
Embodiment 1
100kg coal directly-liquefied residue and 400Kg first extraction solvent (boiling range is 220~260 ℃) are joined in the stirring tank, make them carry out thorough mixing then.Fill N 2Gas is warming up to 180 ℃ to 2.0MPa, stirs with the stirring velocity of 200r/min and obtains mixture after 30 minutes.Carry out pressurized heat then and filter, obtain the extraction liquid mixture, send into atmospheric distillation tower, cut 220~260 ℃ fraction, reclaim first extraction solvent and recycle, obtain extract miscellany 64.3Kg at the bottom of the tower.This extract mixture and 300Kg second extraction solvent (boiling range is<110 ℃) are carried out thorough mixing, add in the stirring tank.Fill N 2Gas is to 0.5MPa, be warming up to 140 ℃, stirring velocity stirring with 250r/min obtained mixture after 20 minutes, carry out the eddy flow centrifugation then, obtain upper layer of extraction liquid mixture S2, send into atmospheric distillation tower, cut<110 ℃ fraction, reclaim second extraction solvent for recycling, obtain heavy liquefaction oil 32.2kg at the bottom of the tower.Send into hydrogenation unit then with after other circulating solvent and thermal treatment by-product oil product mix, the hydroprocessing condition is 11MPa, 360 ℃, and reaction solution hourly space velocity (LHSV) 0.8h -1, vapour-liquid ratio 700m 3/ t, hydrogenation catalyst are Co-Mo/ γ-Al 2O 3, aromatic carbon rate difference is 0.07 before and after the hydrogenation, satisfies the requirement of DCL/Direct coal liquefaction technology to circulating solvent.
Eddy flow centrifugation underflow obtains bitumen 32.1Kg.Send into thermal treatment unit, under 450 ℃, carry out destructive distillation and handle, obtain heavy oil content 10.2Kg and send into solvent hydrogenation unit, mesophase pitch 21.8Kg, light gas 0.1Kg.The quinoline insolubles of mesophase pitch is 2.0%, and the aromatic carbon rate is 0.81, carbon content 89.7%, and the C/H ratio is 1.70.Can be as the raw material of preparation carbon materials.
Embodiment 2
200kg coal directly-liquefied residue and 600Kg first extraction solvent (boiling range is 220~260 ℃) are joined in the stirring tank, carry out thorough mixing.Fill N 2Gas is warming up to 150 ℃ to 1.0MPa, stirs with the stirring velocity of 150r/min and obtains mixture after 20 minutes.Carry out pressurized heat then and filter, obtain the extraction liquid mixture, send into atmospheric distillation tower, cut 220~260 ℃ fraction, reclaim first extraction solvent and recycle, obtain extract miscellany 112.1Kg at the bottom of the tower.This extract mixture and 300Kg second extraction solvent (boiling range is<110 ℃) are added in the stirring tank, carry out thorough mixing.Fill N 2Gas is to 1.5MPa, be warming up to 100 ℃, stirring velocity stirring with 150r/min obtained mixture after 20 minutes, carrying out the vacuum heat filtering then separates, obtain extraction liquid mixture S2, send into atmospheric distillation tower, cut<110 ℃ fraction, reclaim second extraction solvent for recycling, obtain heavy liquefaction oil 60.2kg at the bottom of the tower.Send into hydrogenation unit then with after other circulating solvent and thermal treatment by-product oil product mix, the hydroprocessing condition is 10.1MPa, 355 ℃, and reaction solution hourly space velocity (LHSV) 0.8h -1, vapour-liquid ratio 900m 3/ t, hydrogenation catalyst are Co-Ni-W/ γ-Al 2O 3, aromatic carbon rate difference is 0.09 before and after the hydrogenation, satisfies the requirement of DCL/Direct coal liquefaction technology to circulating solvent.
Eddy flow centrifugation underflow obtains bitumen 51.9Kg.Send into thermal treatment unit, under 430 ℃, carry out destructive distillation and handle, obtain heavy oil content 15.5Kg and send into solvent hydrogenation unit, mesophase pitch 36.4Kg.The quinoline insolubles of mesophase pitch is 1.9%, and the aromatic carbon rate is 0.82, carbon content 89.0%, and the C/H ratio is 1.68.Can be as the raw material of preparation carbon materials.
Embodiment 3
150kg coal directly-liquefied residue and 500Kg first extraction solvent (boiling range is 220~260 ℃) are joined in the stirring tank, carry out thorough mixing.Fill N 2Gas is warming up to 140 ℃ to 0.5MPa, stirs with the stirring velocity of 180r/min and obtains mixture after 120 minutes.Carry out pressurized heat then and filter, obtain the extraction liquid mixture, send into atmospheric distillation tower, cut 220~260 ℃ fraction, reclaim first extraction solvent and recycle, obtain extract miscellany 75.6Kg at the bottom of the tower.This extract mixture and 250Kg second extraction solvent (boiling range is<110 ℃) are added in the stirring tank, carry out thorough mixing.Fill N 2Gas is to 1.5MPa, be warming up to 110 ℃, stirring velocity stirring with 180r/min obtained mixture after 40 minutes, carry out the pressurized heat filtering separation then, obtain extraction liquid mixture S2, send into atmospheric distillation tower, cut<110 ℃ fraction, reclaim second extraction solvent for recycling, obtain heavy liquefaction oil 35.0kg at the bottom of the tower.Send into hydrogenation unit then with after other circulating solvent and thermal treatment by-product oil product mix, the hydroprocessing condition is 9.1MPa, 355 ℃, and reaction solution hourly space velocity (LHSV) 1.0h -1, vapour-liquid ratio 1000m 3/ t, hydrogenation catalyst are Co-Ni-W/ γ-Al 2O 3, aromatic carbon rate difference is 0.08 before and after the hydrogenation, satisfies the requirement of DCL/Direct coal liquefaction technology to circulating solvent.
Eddy flow centrifugation underflow obtains bitumen 45.6Kg.Send into thermal treatment unit, under 440 ℃, carry out destructive distillation and handle, obtain heavy oil content 12.8Kg and send into solvent hydrogenation unit, mesophase pitch 32.7Kg, light gas 0.1Kg.The quinoline insolubles of mesophase pitch is 2.1%, and the aromatic carbon rate is 0.83, carbon content 89.9%, and the C/H ratio is 1.71.Can be as the raw material of preparation carbon materials.
Embodiment 4
100kg coal directly-liquefied residue and 600Kg first extraction solvent (boiling range is 220~260 ℃) are joined in the stirring tank, carry out thorough mixing.Fill N 2Gas is warming up to 200 ℃ to 2.0MPa, stirs with the stirring velocity of 100r/min and obtains mixture after 30 minutes.Carry out pressurized heat then and filter, obtain the extraction liquid mixture, send into atmospheric distillation tower, cut 220~260 ℃ fraction, reclaim first extraction solvent and recycle, obtain extract miscellany 50.8Kg at the bottom of the tower.This extract mixture and 200Kg second extraction solvent (boiling range is<110 ℃) are added in the stirring tank, carry out thorough mixing.Fill N 2Gas is to 1.0MPa, be warming up to 60 ℃, stirring velocity stirring with 200r/min obtained mixture after 120 minutes, carrying out the vacuum heat filtering then separates, obtain extraction liquid mixture S2, send into atmospheric distillation tower, cut<110 ℃ fraction, reclaim second extraction solvent for recycling, obtain heavy liquefaction oil 25.1kg at the bottom of the tower.Send into hydrogenation unit then with after other circulating solvent and thermal treatment by-product oil product mix, the hydroprocessing condition is 9.0MPa, 340 ℃, and reaction solution hourly space velocity (LHSV) 0.8h -1, vapour-liquid ratio 750m 3/ t, hydrogenation catalyst are Co-Ni-Mo-W/ γ-Al 2O 3, aromatic carbon rate difference is 0.09 before and after the hydrogenation, satisfies the requirement of DCL/Direct coal liquefaction technology to circulating solvent.
Eddy flow centrifugation underflow obtains bitumen 25.7Kg.Send into thermal treatment unit, under 420 ℃, carry out destructive distillation and handle, obtain heavy oil content 6.5Kg and send into solvent hydrogenation unit, mesophase pitch 19.2Kg.The quinoline insolubles of mesophase pitch is 2.3%, and the aromatic carbon rate is 0.81, carbon content 89.1%, and the C/H ratio is 1.69.Can be used as the raw material of preparation carbon materials.
By the result of embodiments of the invention 1-4 as can be known, from residue, isolate the heavy liquefaction oil by the mode of two-stage extraction of utilizing of the present invention, and bitumen also obtains part heavy liquefaction oil in Overheating Treatment is produced the process of mesophase pitch, therefore utilize the yield of the heavy liquefaction oil that this method obtains higher relatively, can realize heavy liquefaction oil in the residue fully, the efficient utilization.And two kinds of extraction solvents are all from the gelatin liquefaction process, from the horse's mouth, with low cost, easy recovery.Can substitute out in the former circulating solvent relatively than the light-weight component as the part of the circulating solvent of liquefaction process with the heavy liquefaction oil, improve the degree of heaviness of solvent, improve the overall oily yield of gelatin liquefaction process, thereby improved the economy of liquefaction factory.
In addition, this method extraction obtains the bitumen oleaginousness still less, the condensation degree of aromatic ring is higher, the easier preparation mesophase pitch of heat-treating, the mesophase pitch class material that obtains has higher C/H atomic ratio, lower quinoline insolubles, aromaticity is higher, is the desirable feedstock of preparation carbon materials.
Invention has been described with reference to embodiment and embodiment.Yet, the aspect that the present invention is not limited to describe in the above-described embodiment and examples, and can carry out various distortion.But should be appreciated that for a person skilled in the art, under the situation that does not deviate from the spirit and scope of the present invention, can carry out various modifications and be equal to replacement the present invention.Therefore, the invention is not restricted to the specific embodiment described in this article.More properly, protection scope of the present invention is limited by the accompanying claims.

Claims (13)

1. one kind is utilized two-stage to extract the method for extracting heavy liquefaction oil and bitumen from coal directly-liquefied residue, said method comprising the steps of:
A) coal liquefaction residual powder is joined with first extraction solvent carry out one-level extraction in the stirring tank;
B) the extraction mixture to step a) carries out solid-liquid separation, makes the liquid portion that obtains reclaim first extraction solvent through solvent recovery unit and recycles;
C) obtain extract behind recovery first solvent, this extract is mixed with second extraction solvent, carry out the secondary extraction;
D) the extraction mixture to step c) carries out solid-liquid separation, makes the liquid portion that obtains obtain the heavy liquefaction oil after solvent recovery unit reclaims second extraction solvent, enters coal liquefaction solvent hydrogenation unit with other circulating solvent then, carries out appropriate hydrogenation; And
E) to separating the bitumen that obtains in the step d), heat-treat, obtain mesophase pitch and oil product, the oil product that obtains is sent in the described hydrogenation unit of step d) with the pyrogenous method of heating.
2. method according to claim 1, wherein, described first extraction solvent and described second extraction solvent are the liquefaction oil product that directly produces in the DCL/Direct coal liquefaction process.
3. method according to claim 2, wherein, described first extraction solvent is 220~260 ℃ a fraction, and described second extraction solvent is the fraction of IBP~110 ℃.
4. method according to claim 1, wherein, the extracting operation condition of the one-level extraction in described step a) is: the mass ratio of coal liquefaction residue and described first extraction solvent is 1: 1~10, be preferably 1: 2~8; N 2And/or H 2Atmosphere, pressure is 0.1~3.0MPa, is preferably 0.2~2.5MPa; Extraction temperature is 60~300 ℃, is preferably 80~250 ℃; The extraction time is 5~120min, and stir speed (S.S.) is 50~400r/min.
5. method according to claim 1, wherein, the extracting operation condition of the secondary extraction in described step c) is: the mass ratio of coal liquefaction residue and described second extraction solvent is 1: 1~10, be preferably 1: 1~6; N 2And/or H 2Atmosphere, pressure is 0.2~3.5MPa, is preferably 0.5~2.5MPa; Extraction temperature is 30~250 ℃, is preferably 40~200 ℃; The extraction time is 5~120min, and stir speed (S.S.) is 50~400r/min.
6. according to each described method among the claim 1-4, wherein, described solid-liquid separating method can be for comprising filter method, gravity settling separation method, eddy flow centrifugal separation method or the distillation separation method of hot suction filtration mode of vacuum and pressurized heat filter type.
7. according to each described method among the claim 1-4, wherein, described solvent recovery unit can reclaim extraction solvent for recycling with the method for distillation and/or evaporation.
8. method according to claim 1, wherein, the hydrogenation reaction temperature in described step d) is 260~370 ℃, is preferably 280~360 ℃; Reaction pressure is 6~19MPa, is preferably 8~15MPa; Reaction solution hourly space velocity LHSV is 0.5~1.5h -1, be preferably 0.7~1.2h -1Vapour-liquid ratio is 300~1200m 3/ t is preferably 500~1000m 3/ t; Hydrogenation catalyst mainly consists of: with two or more of Ni, Mo, Co, W element is active component, and with Alpha-alumina, one or both in gama-alumina, silicon oxide and the molecular sieve etc. are carrier.
9. method according to claim 1, wherein, the heat treated temperature in described step e) is 200~500 ℃, preferred 300~450 ℃; Heat-treating atmosphere is the inert gas atmosphere that is selected from vacuum or nitrogen, helium.
10. method according to claim 1, wherein, the heavy liquefaction oil that will obtain in described step d), thermal treatment oil product other circulating solvent in the gelatin liquefaction process that step e) obtains carry out that the circulating solvent as gelatin liquefaction uses after the appropriate hydrogenation; With the described mesophase pitch class material that obtains in the described step e) raw material as the preparation carbon materials.
11. heavy liquefaction oil and mesophase pitch class material according to each described method extraction among the claim 1-9.
12. heavy liquefaction oil, thermal treatment oil product other circulating solvent in the gelatin liquefaction process of extracting according to each described method among the claim 1-9 carry out appropriate hydrogenation later on as the application in the circulating solvent of gelatin liquefaction.
13. the mesophase pitch class material that extracts according to each described method among the claim 1-9 is in the application of the raw material that is used for preparing carbon materials.
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CN104745219A (en) * 2015-03-23 2015-07-01 神华集团有限责任公司 Modified asphalt and preparation method thereof
CN104845652A (en) * 2015-06-10 2015-08-19 神华集团有限责任公司 Treatment method for direct coal liquefaction residues
CN104845652B (en) * 2015-06-10 2018-06-26 神华集团有限责任公司 The processing method of coal directly-liquefied residue
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