CN103254933A - Method for separating liquefied heavy oil and asphalt substances from direct coal liquefaction residues - Google Patents
Method for separating liquefied heavy oil and asphalt substances from direct coal liquefaction residues Download PDFInfo
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Abstract
The invention discloses a method for separating liquefied heavy oil and asphalt substances from direct coal liquefaction residues. The method comprises the following steps of: S1, mixing the direct coal liquefaction residues and an extracting solvent, stirring and performing hot-melt extraction to obtain a hot-melt extraction mixture; S2, performing primary solid liquid separation on the hot-melt extraction mixture to obtain primary extraction liquid and a primary extract; S3, performing secondary solid liquid separation on the primary extraction liquid to obtain secondary extraction liquid and a secondary extract; S4, performing solvent recovery on the secondary extraction liquid to obtain an extract; and S5, mixing the extract with a subcritical anti-precipitation solvent, performing subcritical desolvation precipitation and separating to obtain the liquefied heavy oil and the asphalt substances. Due to the dissolution capability difference of the subcritical anti-precipitation solvent on organic matters in the direct coal liquefaction residues and combination of a solid liquid separation process, separation of the liquefied heavy oil and the asphalt substances are effectively realized.
Description
Technical field
The present invention relates to coal liquefaction residue deep process technology field, in particular to the method for from coal directly-liquefied residue, separating liquefaction mink cell focus and bitumen.
Background technology
Along with fast development of national economy, modernization and social development process are constantly accelerated, and China constantly increases the consumption of petroleum products, has substantially exceeded the rate of growth of the crude production same period, cause the China's oil import volume all to increase year by year, and surpassed from output.And China is an oil-poor country of rich coal, take full advantage of the abundant in coal resource, advanced persons' such as development of coal direct liquefaction clean coal technology is to reduce external crude oil is depended on unduly, alleviate one of important channel of China's oil shortage of resources, petroleum products supply and demand pressure, simultaneously also be to improve our coal resources utilization ratio, alleviate coal burning pollution, promote the important behave of the energy, economy, harmonious development.
Coal direct liquefaction be with coal by high temperature, high pressure and under catalyst action hydrogenation directly change into a kind of advanced person's of the transport fuel (petroleum naphtha, diesel oil etc.) of cleaning or industrial chemicals clean coal technology.The process of DCL/Direct coal liquefaction generally be with coal in advance powder be made into coal slurry with solvent again to the granularity below the 0.15mm, and under certain temperature (about 450 ℃) and high pressure hydrogenation, make macromolecular cleavage in the coal be hydrogenated into process than small molecules.Except the liquiefied product that needing to obtain, go back some hydrocarbon molecules of by-product, CO in the liquefaction process
XLiquefaction residue (claiming coal liquefaction residue again) Deng gas, process water and the generation of solid-liquid separation process.Coal liquefaction residue generally accounts for about 30% of coal input quantity; if make good use of coal liquefaction residue then the economy of the efficient of liquefaction process and whole liquefaction factory and environment protection etc. all had immeasurable influence; therefore; efficient, the feasible method of comprehensive utilization of research coal directly-liquefied residue extracts value product the economic benefit that improves the direct liquefaction process is had important practical significance.
Coal liquefaction residue mainly is made up of inanimate matter and organic two portions, and organic matter comprises liquefaction heavy oil, bitumen and unconverted coal, and inorganic matter (being commonly referred to ash content) comprises the mineral substance in the coal and the catalyzer that adds.Liquefaction heavy oil and bitumen in organic class material account for 50% of level of residue, and unconverted coal accounts for 30% of level of residue, and ash content accounts for about 20%.Therefore, 50% bitumen and liquefied heavy are separating of oil comes out to carry out comprehensive development and utilization with accounting in the liquefied residue, and therefrom extracting or prepare more, value product is feasible.
Utilization to coal liquefaction residue now is mainly traditional methods such as burning, coking oil processed and gasification hydrogen-producing.Coal liquefaction residue acted as a fuel directly in boiler or kiln, burn, will influence the economy of gelatin liquefaction undoubtedly, and higher sulphur content will be brought the problem of environment aspect in the liquefied residue.Though coking system oil has increased the liquid oils yield of coal liquefaction craft, liquefied residue can not obtain reasonable use, semicoke and coke utilize approach also very not clear and definite.The method of matchmaker's 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 the bitumen in the coal liquefaction residue and liquefaction heavy oil do not obtain embodying, and the ash content in the coal liquefaction residue is up to more than 20%, and this bring very big influence will for the deslagging of vapourizing furnace.
Patent JP130412 discloses a kind of method of isolating heavy liquefaction oil and bitumen from coal directly-liquefied residue, in this patent the heavy liquefaction oil that separates is carried out secondary hydrocracking and obtain the lightweight liquefaction oil, and bitumen enters the gelatin liquefaction unit and carries out liquefaction reaction again.On the one hand, because the cut of heavy oil product is heavier, aromaticity content is than higher, secondary hydrocracking light Fuel reaction processed is more violent, not only require to carry out deep hydrogenation, cause the hydrogen consumption to increase, and cause catalyzer because of the coking inactivation easily, thereby the performance to hydrocracking catalyst has proposed higher 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 efficient utilization the rationally of bitumen.
Chinese patent CN101962560A, CN101962561A disclose a kind of method of utilizing the two-stage extraction to extract heavy liquefaction oil and bitumen from coal liquefaction residue, this method is extraction solvent with the oil product of two different fractions sections that DCL/Direct coal liquefaction process self produces, respectively liquefied residue is carried out two-stage and extract in proper order, obtain heavy liquefaction oil and bitumen.Though this method can obtain liquefy mink cell focus and bitumen, the two-stage extraction adds the two-stage solid-liquid separation twice, its technical process complexity, and product yield is lower, and cost is higher.
Summary of the invention
The present invention aims to provide a kind of method of separating liquefaction mink cell focus and bitumen from coal directly-liquefied residue, complex process and the undesirable technical problem of bitumen that obtains when separating liquefaction mink cell focus and bitumen to solve in the prior art.
To achieve these goals, according to an aspect of the present invention, a kind of method of separating liquefaction mink cell focus and bitumen from coal directly-liquefied residue is provided, may further comprise the steps: S1, coal directly-liquefied residue is mixed with extraction solvent, stir, the thermosol extraction obtains thermosol extraction mixture; S2, thermosol is extracted mixture carry out the one-level solid-liquid separation, obtain one-level extraction liquid and one-level extract remainder; S3, the one-level extraction liquid is carried out the secondary solid-liquid separation, obtain secondary extraction liquid and secondary extract remainder; S4, the secondary extraction liquid is carried out solvent recuperation, obtain extract; And S5, extract is mixed with subcritical anti-precipitation solvent, subcritical anti-solvent deposition separates, and mink cell focus and bitumen obtain liquefying.
Further, extraction solvent is one or more in the normal side two wires oil that produces in the DCL/Direct coal liquefaction process, first vacuum side stream, the stabilized hydrogenation side line oil; The boiling range of extraction solvent is 120～280 ℃, and preferably, boiling range is 160 ℃～260 ℃.
Further, subcritical anti-precipitation solvent is the normal top oil that produces in the DCL/Direct coal liquefaction process, subtract in top oil, the stabilized hydrogenation overhead oil one or more, and the boiling range of subcritical anti-precipitation solvent is 40 ℃～160 ℃, and preferentially, boiling range is 60 ℃～120 ℃.
Further, step S1 comprises: S11, coal directly-liquefied residue is mixed according to mass ratio 1:1～10 with extraction solvent, obtain first mixed solution; And S12, in first mixed solution, feed N
2Or H
2, and under 0.2～2.0MPa, with 5 ℃～30 ℃/h described mixed solution is warming up to 60 ℃～300 ℃, and constant temperature stirs, and the thermosol extraction obtains extracting mixture; The time of thermosol extraction is 10～60min, and the speed that constant temperature stirs is 50～300r/min.
Further, one-level solid-liquid separation and secondary solid-liquid separation adopt thermal air pressure filtration, the hot suction filtration of vacuum, cyclonic separation, gravity settling separation or fractionation by distillation.
Further, one-level solid-liquid separation and secondary solid-liquid separation adopt thermal air pressure filtration, and wherein, the filtration temperature of one-level solid-liquid separation and secondary solid-liquid separation is 80 ℃～300 ℃, and preferably, filtration temperature is 150 ℃～200 ℃; The filter pressure of one-level solid-liquid separation and secondary solid-liquid separation is 0.02KPa～2.0MPa, and preferably, filter pressure is 0.2MPa～1.0MPa.
Further, one-level solid-liquid separation and secondary solid-liquid separation adopt cyclonic separation, and wherein, the temperature of one-level solid-liquid separation and secondary solid-liquid separation is 60 ℃～120 ℃, and inlet pressure is 0.3MPa～0.6MPa.
Further, the step of subcritical anti-solvent deposition comprises: extract is sent in the container with anti-solvent deposition mixed, stir, and the pressure of control container is 3.3～5.0MPa, the feeding temperature of subcritical anti-precipitation solvent is 60 ℃～100 ℃, and the feeding temperature of extract is 130 ℃～160 ℃.
Further, comprise also one-level extract remainder and secondary extract remainder carried out steam stripped step that wherein, the stripping extract remainder that stripping step is obtained gasifies or burn processing; And the liquid portion that stripping step obtains carried out oily water separation, will return the recycle of thermosol extraction step through the extraction solvent that the oily water separation step obtains.
Further, comprise that also the extraction solvent that solvent recovery step is obtained returns the process that the thermosol extraction step is carried out recycle.
Use technical scheme of the present invention, the oil product of the specific cut section that employing DCL/Direct coal liquefaction process self produces is as extraction solvent and subcritical anti-precipitation solvent, coal directly-liquefied residue is carried out single extraction, the two-stage solid-liquid separation, solvent recuperation and extract carried out subcritical anti-solvent deposition, can guarantee that subcritical anti-precipitation solvent is in liquid state, be conducive to the extraction to liquefaction mink cell focus in the extract.The oil product that the present invention takes full advantage of specific cut section under subcritical state to coal directly-liquefied residue in the difference of organic dissolving power, will liquefy mink cell focus and bitumen separately.Extraction solvent of the present invention and subcritical anti-precipitation solvent all come from the DCL/Direct coal liquefaction process, from the horse's mouth, cheap and recovery makes things convenient for, product liquefaction mink cell focus can be used as circulating solvent and substitutes relative lighter component in the part cycling extraction solvent, improved the degree of heaviness of extraction solvent, improve the overall oily yield of gelatin liquefaction process, thereby improved whole gelatin liquefaction Industrial economic benefit; Oleaginousness is low in the product bitumen, and aromatic carbon rate height prepares mesophase pitch easilier through Overheating Treatment, is the raw material of desirable carbon materials.
Description of drawings
The Figure of description that constitutes the application's a part is used to provide further understanding of the present invention, and illustrative examples of the present invention and explanation thereof are used for explaining the present invention, do not constitute improper restriction of the present invention.In the accompanying drawings:
Fig. 1 shows the flowage structure synoptic diagram that separates liquefaction mink cell focus and bitumen from direct coal liquefaction residue of the exemplary embodiments according to the present invention.
Embodiment
Need to prove that under the situation of not conflicting, embodiment and the feature among the embodiment among the application can make up mutually.Describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
" subcritical anti-solvent deposition " among the present invention instigated under the state that solvent changes to gaseous state close to liquid state, utilize it to the difference of different solute dissolving poweies in the saturated solution, the solute dissolving that solubleness is big, the solute that solubleness is little is precipitated out, thereby realizes the separation method of different components in the solution.
According to a kind of exemplary embodiment of the present invention, as shown in Figure 1, from coal directly-liquefied residue, separate the method for liquefaction mink cell focus and bitumen, may further comprise the steps: S1, coal directly-liquefied residue is mixed with extraction solvent, stir, the thermosol extraction obtains extracting mixture; S2, will extract mixture and carry out the one-level solid-liquid separation, obtain one-level extraction liquid and one-level extract remainder; S3, the one-level extraction liquid is carried out the secondary solid-liquid separation, obtain secondary extraction liquid and secondary extract remainder; S4, the secondary extraction liquid is carried out solvent recuperation, obtain extract; And S5, extract is mixed with subcritical anti-precipitation solvent, subcritical anti-solvent deposition separates, and mink cell focus and bitumen obtain liquefying.
The oil product of the specific cut section that employing DCL/Direct coal liquefaction process self produces is as extraction solvent and subcritical anti-precipitation solvent, coal directly-liquefied residue is carried out single extraction, the two-stage solid-liquid separation, solvent recuperation and extract carried out subcritical anti-solvent deposition, can guarantee that subcritical anti-precipitation solvent is in liquid state, be conducive to the extraction to liquefaction mink cell focus in the extract.The oil product that the present invention takes full advantage of specific cut section under subcritical state to coal directly-liquefied residue in the difference of organic dissolving power, will liquefy mink cell focus and bitumen separately.Extraction solvent of the present invention and subcritical anti-precipitation solvent all come from the DCL/Direct coal liquefaction process, from the horse's mouth, cheap and recovery makes things convenient for, product liquefaction mink cell focus can be used as circulating solvent and substitutes relative lighter component in the part cycling extraction solvent, improved the degree of heaviness of extraction solvent, improve the overall oily yield of gelatin liquefaction process, thereby improved whole gelatin liquefaction Industrial economic benefit; Oleaginousness is low in the product bitumen, and aromatic carbon rate height prepares mesophase pitch easilier through Overheating Treatment, is the raw material of desirable carbon materials.
According to a kind of exemplary embodiment of the present invention, extraction solvent is one or more in the normal side two wires oil that produces in the DCL/Direct coal liquefaction process, first vacuum side stream, the stabilized hydrogenation side line oil; The boiling range of extraction solvent is 120～280 ℃, and preferably, boiling range is 160 ℃～260 ℃.Adopt normal side two wires oil, first vacuum side stream or the stabilized hydrogenation side line oil of boiling range in above-mentioned scope as extraction solvent, have the percentage extraction height, be easy to the recovery advantage with respect to other extraction solvent.
According to another kind of preferred implementation of the present invention, subcritical anti-precipitation solvent is the normal top oil that produces in the DCL/Direct coal liquefaction process, subtract in top oil, the stabilized hydrogenation overhead oil one or more, the boiling range of subcritical anti-precipitation solvent is 40 ℃～160 ℃, and preferentially, boiling range is 60 ℃～120 ℃.Wherein the step of subcritical anti-solvent deposition comprises: extract is sent in the container with subcritical anti-precipitation solvent mixed, stir, the pressure of control container is 3.3～5.0MPa, and the feeding temperature of subcritical anti-precipitation solvent is 60 ℃～100 ℃, and the feeding temperature of extract is 130 ℃～160 ℃.Carry out subcritical anti-solvent deposition by extract is mixed with subcritical anti-precipitation solvent, can guarantee that solvent is in liquid state, have the advantage that liquefaction mink cell focus in the extract is separated with bitumen.
Mainly be divided into DCL/Direct coal liquefaction unit and stabilized hydrogenation unit in the DCL/Direct coal liquefaction technology, separating of liquidation of coal reaction and reactant realized in the DCL/Direct coal liquefaction unit, the stabilized hydrogenation unit carries out hydrogenation to liquefied coal coil, wherein part oil (the heavier part of cut) returns the DCL/Direct coal liquefaction unit as circulating solvent, and another part is delivered to the oil hydrogenation reforming unit as product.The gelatin liquefaction unit is provided with an atmospheric tower and a vacuum distillation tower, atmospheric tower is established normal top line, normal side one line, normal side two wires and normal bottom line, normal top oil and normal side one line oil, normal side two wires oil directly are delivered to the stabilized hydrogenation unit, oil of the normal end is delivered to vacuum distillation tower and is further separated, vacuum distillation tower is established and is subtracted top line, subtracts side one line, subtracts the side two wires and subtract bottom line, subtract top oil, first vacuum side stream, second line of distillation oil is delivered to the stabilized hydrogenation unit, subtracts bottom line discharge coal liquefaction residue.Stabilized hydrogenation is established an atmospheric tower, and atmospheric tower divides cat head line, tower side line and tower bottom line, and overhead oil and part tower side oil send the hydro-upgrading unit as product, and oil is sent the gelatin liquefaction unit coal slurry that makes up oil back to as circulating solvent at the bottom of another part tower side oil and the tower.
According to a kind of exemplary embodiment of the present invention, step S1 comprises: S11, coal directly-liquefied residue is mixed according to mass ratio 1:1～10 with extraction solvent, obtain first mixed solution; And S12, in first mixed solution, feed N
2Or H
2, and under 0.2～2.0MPa, with 5 ℃～30 ℃/h mixed solution is warming up to 60 ℃～300 ℃, and constant temperature stirs, and the thermosol extraction obtains extracting mixture; Wherein the time of thermosol extraction is 10～60min, and the speed that constant temperature stirs is 50～300r/min.The present invention mixes coal directly-liquefied residue and extraction solvent according to mass ratio 1:1～10 can guarantee the effect and the solvent recovering rate that extract, if mass ratio is higher than 1:1, extraction solvent then may occur can not cause extraction not thorough fully with the situation of coal directly-liquefied residue dissolving; If mass ratio is lower than 1:10, then can cause the waste of extraction solvent, increase the cost recovery of follow-up extraction solvent.In mixed solution, feed N
2Or H
2Purpose be the air of at first getting rid of in reactor such as the stirring tank, make and to carry out under the condition be reflected at anaerobic.
The mode of one-level solid-liquid separation and secondary solid-liquid separation comprises thermal air pressure filtration, the hot suction filtration of vacuum, cyclonic separation, gravity settling separation and fractionation by distillation among the present invention, the present invention is preferred but be not limited to above-mentioned solid-liquid separation method, as long as can and reach required effect with solid-liquid separation.When the mode that adopts thermal air pressure filtration was carried out solid-liquid separation, the filtration temperature of one-level solid-liquid separation and secondary solid-liquid separation was 80 ℃～300 ℃, and preferably, filtration temperature is 150 ℃～200 ℃; The filter pressure of one-level solid-liquid separation and secondary solid-liquid separation is 0.02KPa～2.0MPa, and preferably, filter pressure is 0.2MPa～1.0MPa.Adopt in said temperature and the pressure range and carry out thermal air pressure filtration, can be largely with solid-liquid separation.Except thermal air pressure filtration, when one-level solid-liquid separation and secondary solid-liquid separation were cyclonic separation, wherein, the temperature of one-level solid-liquid separation and secondary solid-liquid separation was 60 ℃～120 ℃, and inlet pressure is 0.3MPa～0.6MPa.
The one-level extract remainder that the present invention obtains after one-level solid-liquid separation and secondary solid-liquid separation and the solid content in the secondary extract remainder are 50～80wt%, that is to say that the solvent in one-level extract remainder and the secondary extract remainder is 20～50wt%.Because the solvent in the solid phase extraction thing is higher, for extraction solvent is carried out abundant recycle to reduce cost, according to a kind of exemplary embodiment of the present invention, also comprise one-level extract remainder and secondary extract remainder are carried out stripping and reclaim the step of extraction solvent, wherein, the stripping extract remainder that obtains through stripping step gasifies or burn processing; And carry out oily water separation through the liquid portion that stripping step obtains, will return the recycle of thermosol extraction step through the extraction solvent that the oily water separation step obtains.Solid content in the solid phase extraction thing behind stripping〉90wt%, extraction solvent content is less than 5wt%.
The present invention comprises that also the extraction solvent that solvent recovery step is obtained returns the process that the thermosol extraction step is carried out recycle, wherein adopts the mode of air distillation, underpressure distillation and evaporation that the secondary extraction liquid is carried out solvent recuperation.
The present invention separates with vacuum distillation tower with the atmospheric tower that solvent can directly enter the gelatin liquefaction unit with the liquefaction mink cell focus that the two-stage solid-liquid separation obtains through the extraction of one-level thermosol, other solvent oil in isolated liquefaction mink cell focus and the liquefaction process carries out hydrogenation reaction, and product can be used as circulating solvent and uses.Wherein, the temperature of hydrogenation reaction is 260 ℃～380 ℃, is preferably 280 ℃～370 ℃; Pressure is 6～19MPa, is preferably 10～18MPa, and reaction solution hourly space velocity (LHSV) is 0.5～1.5h
-1, be preferably 0.8～1.2h
-1Vapour-liquid ratio is 300～1200m
3/ t is preferably 600～1000m
3/ t; Hydrogenation catalyst is selected from two or more in Ni, Mo, Co and the W element, is carrier with in Alpha-alumina, gamma oxidation silicon, silicon oxide and the molecular sieve etc. one or both.The ash oontent of the bitumen that the secondary extraction liquid obtains after solvent recovery step is 0.05～10wt%, and sulphur content is less than 0.03%, and solvent oil content can be used as the raw material of preparation carbon materials less than 5%.
The ash oontent of the present invention in the bitumen that the one-level thermosol extracts and the two-stage solid-liquid separation obtains is less than 0.2wt%.Because its ash oontent and quinoline insolubles are low, aromatic carbon rate height, therefore the bitumen of preparation is the desirable feedstock for high-end carbon materialses such as needle cokes.
Further specify beneficial effect of the present invention below in conjunction with specific embodiment:
Embodiment 1
1) the normal side two wires oil (boiling range is 160～260 ℃) that produces in 300kg coal directly-liquefied residue and the 750kg gelatin liquefaction process is added in the stirring tank, with the speed stirring of 50r/min, in stirring tank, fills N
2Pressure to the stirring tank is to 0.2MPa, and after per hour 5 ℃ speed was warming up to 60 ℃, constant temperature stirred, and thermosol extraction 30min obtains extracting mixture.
2) adopt the thermal air pressure filtration mode that the extraction mixture is carried out solid-liquid separation.Wherein filtration temperature is 150 ℃, and filter pressure is 0.2MPa, and the filter core aperture size of strainer is 50 μ m.After one-level is filtered, collect one-level extraction liquid and one-level extract remainder, the one-level extraction liquid to be sent into secondary filter carry out thermal air pressure filtration, filtration temperature is 150 ℃, and filter pressure is 0.15MPa, and the filter core aperture size of strainer is 2 μ m.Through behind the cascade filtration, collect secondary extraction liquid and secondary extract remainder.
3) the secondary extraction liquid is sent into vacuum still and carry out solvent recuperation, the mixture of extract liquefaction mink cell focus and bitumen is collected in the extraction solvent recycle that recovered overhead is 160～260 ℃ at the bottom of the tower.
4) will liquefy that to deliver to subcritical anti-solvent deposition unit be that the normal top oil (60 ℃～120 ℃ of boiling ranges) that produces in the gelatin liquefaction process mixes with subcritical anti-precipitation solvent for the mixture of mink cell focus and bitumen, wherein the pressure during subcritical anti-solvent deposition is 3.3MPa, the feeding temperature of the mixture of liquefaction mink cell focus and bitumen is 130 ℃, the feeding temperature of subcritical anti-precipitation solvent is 60 ℃, and mink cell focus and bitumen obtain liquefying behind subcritical anti-solvent deposition.
5) mink cell focus that will liquefy is sent into gelatin liquefaction unit Distallation systm and is separated, and the liquefaction mink cell focus carries out appropriate hydrogenation with the circulating solvent of gelatin liquefaction unit, and the hydrogenation reaction temperature is 330 ℃, and pressure is 17MPa,, reaction solution hourly space velocity (LHSV) is 0.8h
-1Vapour-liquid ratio is 700m
3/ t, hydrogenation catalyst mainly consists of: being active component with Ni, Mo, is carrier with the Alpha-alumina.
6) one-level extract remainder and secondary extract remainder solid filter residue are fed through steam stripping unit, liquid portion obtains the extraction solvent reusable edible after oily water separation, but solid stripping extract remainder coal blending burning or gasification.
Embodiment 2
1) first vacuum side stream (boiling range is 180～220 ℃) that produces in 300kg coal directly-liquefied residue and the 3000kg gelatin liquefaction process is added in the stirring tank, with the speed stirring of 75r/min, in stirring tank, fills N
2Pressure to the stirring tank is to 1.0MPa, and after per hour 30 ℃ speed was warming up to 120 ℃, constant temperature stirred, and hot melt extraction 30min obtains extracting mixture.
2) adopt the thermal air pressure filtration mode that the extraction mixture is carried out solid-liquid separation.Wherein filtration temperature is 200 ℃, and filter pressure is 0.02MPa, and the filter core aperture size of strainer is 40 μ m.After one-level is filtered, collect one-level extraction liquid and one-level extract remainder, the one-level extraction liquid to be sent into secondary filter carry out thermal air pressure filtration, filtration temperature is 120 ℃, and filter pressure is 2.0MPa, and the filter core aperture size of strainer is 1 μ m.Through behind the cascade filtration, collect secondary extraction liquid and secondary extract remainder.
3) the secondary extraction liquid is sent into vacuum still and carry out solvent recuperation, the mixture of extract liquefaction mink cell focus and bitumen is collected in the extraction solvent recycle that recovered overhead is 120～250 ℃ at the bottom of the tower.
4) will liquefy that to deliver to subcritical anti-solvent deposition unit be that the top oil (80～150 ℃ of boiling ranges) that subtracts that produces in the gelatin liquefaction process mixes with subcritical anti-precipitation solvent for the mixture of mink cell focus and bitumen, wherein the pressure during subcritical anti-solvent deposition is 5.0MPa, the feeding temperature of liquefaction mink cell focus and bitumen mixture is 160 ℃, the feeding temperature of subcritical anti-precipitation solvent is 100 ℃, and mink cell focus and bitumen obtain liquefying behind subcritical anti-solvent deposition.
5) mink cell focus that will liquefy is sent into gelatin liquefaction unit Distallation systm and is separated, and the liquefaction mink cell focus carries out appropriate hydrogenation with the circulating solvent of gelatin liquefaction unit, and the hydrogenation reaction temperature is 330 ℃, and pressure is 19MPa,, reaction solution hourly space velocity (LHSV) is 0.9h
-1Vapour-liquid ratio is 700m
3/ t, hydrogenation catalyst mainly consists of: being active component with Ni, Mo, is carrier with the Alpha-alumina.
6) one-level extract remainder and secondary extract remainder solid filter residue are fed through steam stripping unit, liquid portion obtains the extraction solvent reusable edible after oily water separation, but solid stripping extract remainder coal blending burning or gasification.
Embodiment 3
1) the stabilized hydrogenation side line oil (boiling range is 130～260 ℃) that subtracts that produces in 300kg coal directly-liquefied residue and the 1500kg gelatin liquefaction process is added in the stirring tank, with the speed stirring of 125r/min, in stirring tank, fills N
2Pressure to the stirring tank is to 2.0MPa, and after per hour 12.5 ℃ speed was warming up to 300 ℃, constant temperature stirred, and hot melt extraction 60min obtains extracting mixture.
2) adopt thermal air pressure filtration that the extraction mixture is carried out solid-liquid separation.Wherein filtration temperature is 300 ℃, and filter pressure is 2MPa, and the filter core aperture size is 45 μ m.After one-level is filtered, collect one-level extraction liquid and one-level extract remainder, the one-level extraction liquid is sent into secondary belt suction filtration, filtration temperature is 180 ℃, and filter pressure is 0.15MPa, and the filter cloth aperture size is 2 μ m.Through behind the cascade filtration, collect secondary extraction liquid and secondary extract remainder.
3) the secondary extraction liquid is sent into vacuum still and carry out solvent recuperation, the mixture of extract liquefaction mink cell focus and bitumen is collected in the extraction solvent recycle that recovered overhead is 200～260 ℃ at the bottom of the tower.
4) will liquefy that to deliver to subcritical anti-solvent deposition unit be that the stabilized hydrogenation overhead oil (70～120 ℃ of boiling ranges) that produces in the gelatin liquefaction process is mixed with subcritical anti-precipitation solvent for the mixture of mink cell focus and bitumen, wherein the pressure during subcritical anti-solvent deposition is 2.9MPa, the feeding temperature of the mixture of liquefaction mink cell focus and bitumen is 150 ℃, the feeding temperature of subcritical anti-precipitation solvent is 100 ℃, and mink cell focus and bitumen obtain liquefying behind subcritical anti-solvent deposition.
5) mink cell focus that will liquefy is sent into gelatin liquefaction unit Distallation systm and is separated, and the liquefaction mink cell focus carries out appropriate hydrogenation with the circulating solvent of gelatin liquefaction unit, and the hydrogenation reaction temperature is 340 ℃, and pressure is 19MPa,, reaction solution hourly space velocity (LHSV) is 0.9h
-1Vapour-liquid ratio is 800m
3/ t, hydrogenation catalyst mainly consists of: being active component with Ni, Mo, is carrier with the silicon oxide.
6) one-level extract remainder and secondary extract remainder solid filter residue are fed through steam stripping unit, liquid portion obtains the extraction solvent reusable edible after oily water separation, but solid stripping extract remainder coal blending burning or gasification.
Embodiment 4
Operation steps is identical with embodiment 3, and difference is the extraction solvent and the subcritical anti-precipitation solvent that adopt.
Comparative Examples 1
1) 300kg coal directly-liquefied residue and 600kg first extraction solvent are often pushed up in oil (boiling range is 40 ℃～110 ℃) the adding stirring tank, with the speed stirring of 60r/min, in stirring tank, fill N
2Pressure to the stirring tank is to 0.2MPa, and after per hour 10 ℃ speed was warming up to 100 ℃, constant temperature stirred, and one-level thermosol extraction 30min obtains the first extraction mixture.
2) adopt hot pressing to cross rate the first extraction mixture is carried out solid-liquid separation.Wherein filtration temperature is 80 ℃, and filter pressure is 0.2MPa, and the filter core aperture size of strainer is 25 μ m.After one-level is filtered, collect one-level extract remainder and one-level extraction liquid.The one-level extraction liquid is sent into the one-level vacuum distillation tower carry out solvent recuperation, column bottom temperature is 250 ℃, and tower top temperature is 90 ℃, and tower top pressure is 2KPa, collects liquefaction mink cell focus and first extraction solvent and often pushes up oil, will often push up oil and return the utilization of one-level thermosol extraction cycle.
3) will collect one-level extract remainder and second extraction solvent and subtract side one line oil (boiling range is 180 ℃～220 ℃) and be added in the stirring tank, stir with the speed of 55r/min, fill N
2Pressure is 0.3MPa to the stirring tank, with per hour 30 ℃ be warming up to 160 ℃ after, constant temperature stirs, secondary thermosol extraction 45min obtains the second extraction mixture.
4) the second extraction mixture is sent into strainer and carry out thermal air pressure filtration, filtration temperature is 120 ℃, and filter pressure is 1.0MPa, and the filter core aperture size of strainer is 5 μ m.After filtering, collect secondary extract remainder and secondary extraction liquid.The secondary extraction liquid is sent into the second depressurized tower carry out solvent recuperation, column bottom temperature is 320 ℃, and tower top temperature is 120 ℃, and tower top pressure is 2.5KPa, collect bitumen and subtract side one line oil (second extraction solvent), subtract side one line oil and return the extraction of secondary thermosol and carry out recycle.
5) the liquefaction mink cell focus that one-level thermosol extraction is obtained enters hydrogenation unit with other circulating solvents of gelatin liquefaction unit and carries out appropriate hydrogenation, and the hydrogenation reaction temperature is 330 ℃, and pressure is 17MPa,, reaction solution hourly space velocity LHSV is 0.8h
-1Vapour-liquid ratio is 700m
3/ t, hydrogenation catalyst mainly consists of: being active component with Ni, Mo, is carrier with the Alpha-alumina.
6) secondary extract remainder filter residue is sent into steam stripping unit, liquid portion is after oily water separation, but the stripping extract remainder coal blending burning or the gasification that obtain, and second extraction solvent that obtains can return the extraction of secondary thermosol and carry out recycle.
Comparative Examples 2
1) 400kg coal directly-liquefied residue and the 1200kg first extraction solvent stabilized hydrogenation overhead oil (boiling range is 40 ℃～120 ℃) are added in the stirring tank, with the speed stirring of 75r/min, in stirring tank, fill N
2Pressure to the stirring tank is to 0.4MPa, and after per hour 5 ℃ speed was warming up to 60 ℃, constant temperature stirred, and one-level thermosol extraction 10min obtains the first extraction mixture.
2) adopt hot pressing to cross rate the first extraction mixture is carried out solid-liquid separation, filtration temperature is 70 ℃, and filter pressure is 0.3MPa, and the filter core aperture size of strainer is 15 μ m.After one-level is filtered, collect one-level extract remainder and one-level extraction liquid.The one-level extraction liquid is sent into the one-level vacuum distillation tower carry out solvent recuperation, column bottom temperature is 270 ℃, tower top temperature is 90 ℃, tower top pressure is the 2KPa(absolute pressure), collect liquefaction mink cell focus and the first extraction solvent stabilized hydrogenation overhead oil, the stabilized hydrogenation overhead oil is returned the utilization of one-level thermosol extraction cycle.
3) will collect the one-level extract remainder and the normal side of second extraction solvent two wires oil (boiling range is 160 ℃～260 ℃) is added in the stirring tank, stir with the speed of 65r/min, fill N
2Pressure is 0.2MPa to the stirring tank, with per hour 30 ℃ be warming up to 180 ℃ after, constant temperature stirs, secondary thermosol extraction 35min obtains the second extraction mixture.
4) the second extraction mixture is sent into strainer and carry out thermal air pressure filtration, filtration temperature is 210 ℃, and filter pressure is 0.02MPa, and the filter core aperture size of strainer is 2 μ m.After filtering, obtain secondary extract remainder and secondary extraction liquid.The secondary extraction liquid is sent into the second depressurized tower carry out solvent recuperation, column bottom temperature is 320 ℃, and tower top temperature is 131 ℃, and tower top pressure is the 3KPa(absolute pressure), collect bitumen and the normal side of second extraction solvent two wires oil, normal side two wires oil returns the extraction of secondary thermosol and carries out recycle.
5) the liquefaction mink cell focus that one-level thermosol extraction is obtained enters hydrogenation unit with other circulating solvents of gelatin liquefaction unit and carries out appropriate hydrogenation, and the hydrogenation reaction temperature is 350 ℃, and pressure is 18.6MPa, and reaction solution hourly space velocity LHSV is 0.9h
-1Vapour-liquid ratio is 600m
3/ t, hydrogenation catalyst mainly consists of: being active component with Ni, W, is carrier with the Alpha-alumina.
6) secondary extract remainder filter residue is sent into steam stripping unit, liquid portion is after oily water separation, but the stripping extract remainder coal blending burning or the gasification that obtain, and second extraction solvent that obtains can return the extraction of secondary thermosol and carry out recycle.
Concrete material and the data of embodiment 1～4 see table 1 for details, and concrete material and data in the Comparative Examples 1～2 see Table 2, and the raw material that wherein adopts provides by China Shenhua Coal to Liquid and Chemical Co., Ltd..
Table 1
Table 2
As can be seen from Table 1, among the embodiment 1～4, adopt the normal side two wires oil that produces in the DCL/Direct coal liquefaction process, first vacuum side stream and stabilized hydrogenation side line oil are as extraction solvent, coal liquefaction residue is carried out the thermosol extraction, the one-level solid-liquid separation, secondary solid-liquid separation and subcritical anti-solvent deposition, the normal top oil that wherein adopts the lighter DCL/Direct coal liquefaction of cut to produce, subtract top oil, the stabilized hydrogenation overhead oil is carried out subcritical anti-solvent deposition, the oil product that namely takes full advantage of specific cut section under subcritical state to coal directly-liquefied residue in the difference of organic dissolving power, that has realized liquefaction mink cell focus and bitumen effectively separates ash oontent in the bitumen that obtains, quinoline insolubles content and mink cell focus content are all lower.
As can be seen from Table 2, adopt conventional two-stage extraction process in the Comparative Examples 1～2, wherein the one-level extraction adopts the lighter distillate that produces in the DCL/Direct coal liquefaction process as extraction solvent coal liquefaction residue to be extracted, after the one-level solid-liquid separation, obtain one-level extraction liquid and one-level extract remainder respectively, the one-level extract remainder is first vacuum side stream, the oil extraction of normal side two wires by producing in the DCL/Direct coal liquefaction process again, after the secondary solid-liquid separation, obtains secondary extract and secondary extract remainder respectively; The one-level extraction liquid is obtained the mink cell focus that liquefies through after the solvent recuperation, and the secondary extraction liquid obtains bitumen through after the solvent recuperation.
Table 1 and table 2 are compared as can be seen, percentage extraction in the Comparative Examples 1～2 will be lower than the percentage extraction among the embodiment 1～4, in the Comparative Examples 1 because the separating effect of one-level extraction liquid and one-level extract remainder is bad, the partial liquefaction mink cell focus remains in the one-level extract remainder, causes the liquefaction heavy oil-contg higher (more than 37%) in the secondary extract remainder bitumen.Therefore adopt conventional secondary extraction that the separating effect of the liquefaction mink cell focus in the coal liquefaction residue and bitumen is not so good as to adopt among the present invention one-level extraction and subcritical anti-solvent deposition process combined good separating effect.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a method of separating liquefaction mink cell focus and bitumen from coal directly-liquefied residue is characterized in that, may further comprise the steps:
S1, described coal directly-liquefied residue is mixed with extraction solvent, stir, the thermosol extraction obtains thermosol extraction mixture;
S2, described thermosol extraction mixture is carried out the one-level solid-liquid separation, obtain one-level extraction liquid and one-level extract remainder;
S3, described one-level extraction liquid is carried out the secondary solid-liquid separation, obtain secondary extraction liquid and secondary extract remainder;
S4, described secondary extraction liquid is carried out solvent recuperation, obtain extract; And
S5, described extract is mixed with subcritical anti-precipitation solvent, subcritical anti-solvent deposition separates, and mink cell focus and bitumen obtain liquefying.
2. method according to claim 1 is characterized in that, described extraction solvent is one or more in the normal side two wires oil that produces in the DCL/Direct coal liquefaction process, first vacuum side stream, the stabilized hydrogenation side line oil; The boiling range of described extraction solvent is 120～280 ℃, and preferably, described boiling range is 160 ℃～260 ℃.
3. method according to claim 1, it is characterized in that, described subcritical anti-precipitation solvent is the normal top oil that produces in the DCL/Direct coal liquefaction process, subtract in top oil, the stabilized hydrogenation overhead oil one or more, the boiling range of described subcritical anti-precipitation solvent is 40 ℃～160 ℃, preferentially, described boiling range is 60 ℃～120 ℃.
4. method according to claim 1 is characterized in that, described step S1 comprises:
S11, described coal directly-liquefied residue is mixed according to mass ratio 1:1～10 with described extraction solvent, obtain first mixed solution; And
S12, in described first mixed solution, feed N
2Or H
2, and under 0.2～2.0MPa, with 5 ℃～30 ℃/h described mixed solution is warming up to 60 ℃～300 ℃, and constant temperature stirs, and the thermosol extraction obtains described extraction mixture;
The time of described thermosol extraction is 10～60min, and the speed that described constant temperature stirs is 50～300r/min.
5. method according to claim 1 is characterized in that, described one-level solid-liquid separation and described secondary solid-liquid separation adopt thermal air pressure filtration, the hot suction filtration of vacuum, cyclonic separation, gravity settling separation or fractionation by distillation.
6. method according to claim 5 is characterized in that, described one-level solid-liquid separation and described secondary solid-liquid separation adopt thermal air pressure filtration, wherein,
The filtration temperature of described one-level solid-liquid separation and described secondary solid-liquid separation is 80 ℃～300 ℃, and preferably, described filtration temperature is 150 ℃～200 ℃;
The filter pressure of described one-level solid-liquid separation and described secondary solid-liquid separation is 0.02KPa～2.0MPa, and preferably, described filter pressure is 0.2MPa～1.0MPa.
7. method according to claim 5 is characterized in that, described one-level solid-liquid separation and described secondary solid-liquid separation adopt cyclonic separation, wherein,
The temperature of described one-level solid-liquid separation and described secondary solid-liquid separation is 60 ℃～120 ℃, and inlet pressure is 0.3MPa～0.6MPa.
8. method according to claim 1 is characterized in that, the step of described subcritical anti-solvent deposition comprises:
Described extract sent in the container with described anti-solvent deposition mix, stir, and the pressure of controlling described container is 3.3～5.0MPa, and the feeding temperature of described subcritical anti-precipitation solvent is 60 ℃～100 ℃, and the feeding temperature of described extract is 130 ℃～160 ℃.
9. method according to claim 1 is characterized in that, also comprise described one-level extract remainder and described secondary extract remainder are carried out steam stripped step, wherein,
The stripping extract remainder that described stripping step is obtained gasifies or burn processing; And
The liquid portion that described stripping step is obtained carries out oily water separation, will return the recycle of described thermosol extraction step through the described extraction solvent that described oily water separation step obtains.
10. method according to claim 1 is characterized in that, comprises that also the described extraction solvent that described solvent recovery step is obtained returns the process that described thermosol extraction step is carried out recycle.
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