CN103254933B - 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 being separated liquefaction mink cell focus and bitumen from coal directly-liquefied residue.
Background technology
Along with the fast development of national economy, modernization and social development process are constantly accelerated, and the consumption of China to petroleum products constantly increases, and greatly exceed the rate of growth of the crude production same period, cause China's oil import volume all to increase year by year, and exceeded from output.And the country that to be a rich coal oil-poor of China, make full use of abundant coal resources, the clean coal technology of the advanced person such as development of coal direct liquefaction reduces to depend on unduly external crude oil, one of important channel of alleviation China's oil shortage of resources, petroleum products supply and demand pressure, also be improve our coal resources utilization ratio simultaneously, alleviate coal burning pollution, promote the Important Action of the energy, economy, harmonious development.
Coal direct liquefaction be by coal by high temperature, high pressure and under catalyst action hydrogenation directly change into the clean coal technology of a kind of advanced person of clean transport fuel (petroleum naphtha, diesel oil etc.) or industrial chemicals.The process of DCL/Direct coal liquefaction be generally by coal in advance powder to the granularity of below 0.15mm, then be made into coal slurry with solvent, and under certain temperature (about 450 DEG C) and high pressure hydrogenation, make the macromolecular cleavage in coal be hydrogenated into more micromolecular process.In liquefaction process except obtaining the liquiefied product of needs, go back some hydrocarbon molecules of by-product, CO
xdeng the liquefaction residue (also known as coal liquefaction residue) that gas, process water and solid-liquid separation process produce.Coal liquefaction residue generally accounts for about 30% of coal input quantity; if make good use of coal liquefaction residue, all there is immeasurable impact to the efficiency of liquefaction process and the economy of whole liquefaction factory and environment protection etc.; therefore; efficient, the feasible method of comprehensive utilization of research coal directly-liquefied residue, extracts value product and has important practical significance to the economic benefit improving direct liquefaction process.
Coal liquefaction residue is primarily of inanimate matter and organic two portions composition, and organic matter comprises liquefaction heavy oil, bitumen and unconverted coal, and inorganic matter (being commonly referred to ash content) comprises mineral substance in coal and additional catalyzer.Liquefaction heavy oil in organic species and bitumen 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, out carry out comprehensive development and utilization by separating of oil to the bitumen and liquefied heavy that account for 50% in liquefied residue, it is feasible for therefrom extracting or prepare more value product.
Now the traditional methods such as burning, coking liquefaction and gasification hydrogen-producing are mainly to the utilization of coal liquefaction residue.Coal liquefaction residue is directly burnt as fuel in boiler or kiln, will the economy of gelatin liquefaction be affected undoubtedly, and sulphur content higher in liquefied residue will bring the problem of environment aspect.Although coking liquefaction adds the liquid oil yield of coal liquefaction craft, liquefied residue can not obtain the most reasonably utilizing, and the utilization ways of semicoke and coke is very not clear and definite yet.The method of matchmaker's liquefied residue being carried out gasification hydrogen-producing is a kind of effective extensive approach utilized, but the high value added utilization potentiality of the bitumen in coal liquefaction residue and liquefaction heavy oil are embodied, and the ash content in coal liquefaction residue is up to more than 20%, this brings very large impact will to the deslagging of vapourizing furnace.
Patent JP130412 discloses a kind of method isolating heavy coal liquids and bitumen from coal directly-liquefied residue, in this patent, the heavy coal liquids of separation is carried out secondary hydrocracking and obtain lightweight liquefaction oil, and bitumen enters gelatin liquefaction unit carries out liquefaction reaction again.On the one hand, because the cut of heavy oil product is heavier, aromaticity content is higher, the reaction of secondary hydrocracking light Fuel is more violent, not only require carry out deep hydrogenation, cause hydrogen consumption to increase, and easily cause catalyzer because of coking inactivation, thus higher requirement is proposed to the performance of hydrocracking catalyst, require that hydrocracking catalyst has stronger activity, stronger anti-carbon deposition ability.On the other hand, when the bitumen separated liquefies again, it is liquefaction effect bad again, but also can cause the ill effect such as deposition, coking in liquefying reactor, and therefore the method can not realize the reasonable efficiency utilization of bitumen.
Chinese patent CN101962560A, CN101962561A disclose a kind of two-stage that utilizes and extract the method extracting heavy coal liquids and bitumen from coal liquefaction residue, the oil product of two different fractions sections that the method produces with DCL/Direct coal liquefaction process self is for extraction solvent, respectively the extraction of two-stage order is carried out to liquefied residue, obtain heavy coal liquids and bitumen.Although the method can obtain liquefaction mink cell focus and bitumen, two-stage extraction adds twice two-stage solid-liquid separation, and its technical process is complicated, and product yield is lower, and cost is higher.
Summary of the invention
The present invention aims to provide and a kind ofly from coal directly-liquefied residue, is separated liquefaction mink cell focus and the method for bitumen, complex process when being separated liquefaction mink cell focus and bitumen to solve in prior art and the undesirable technical problem of the bitumen obtained.
To achieve these goals, according to an aspect of the present invention, provide a kind of method being separated liquefaction mink cell focus and bitumen from coal directly-liquefied residue, comprise the following steps: S1, coal directly-liquefied residue to be mixed with extraction solvent, stir, thermosol extracts, and obtains thermosol extraction mixture; S2, thermosol is extracted mixture carry out one-level solid-liquid separation, obtain one-level extraction liquid and one-level extract remainder; S3, one-level extraction liquid is carried out secondary solid-liquid separation, obtain secondary extraction liquid and secondary extract remainder; S4, secondary extraction liquid is carried out solvent recuperation, be extracted thing; And S5, extract to be mixed with subcritical anti-precipitation solvent, subcritical anti-solvent precipitation, is separated, obtains liquefaction mink cell focus and bitumen.
Further, extraction solvent is two wires, the normal side oil, first vacuum side stream, one or more in stabilized hydrogenation side line oil that produce in DCL/Direct coal liquefaction process; The boiling range of extraction solvent is 120 ~ 280 DEG C, and preferably, boiling range is 160 DEG C ~ 260 DEG C.
Further, subcritical anti-precipitation solvent be produce in DCL/Direct coal liquefaction process normal top oil, subtract top oil, one or more in stabilized hydrogenation overhead oil, the boiling range of subcritical anti-precipitation solvent is 40 DEG C ~ 160 DEG C, and preferentially, boiling range is 60 DEG C ~ 120 DEG C.
Further, step S1 comprises: S11, mixed according to mass ratio 1:1 ~ 10 with extraction solvent by coal directly-liquefied residue, obtains the first mixed solution; And S12, in the first mixed solution, pass into N
2or H
2, and with 5 DEG C ~ 30 DEG C/h, described mixed solution being warming up to 60 DEG C ~ 300 DEG C under 0.2 ~ 2.0MPa, constant temperature stirs, and thermosol extracts, and is extracted 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, Vacuum Heat suction filtration, 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 DEG C ~ 300 DEG C, and preferably, filtration temperature is 150 DEG C ~ 200 DEG C; 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 DEG C ~ 120 DEG C, and inlet pressure is 0.3MPa ~ 0.6MPa.
Further, the step of subcritical anti-solvent precipitation comprises: extract and anti-solvent are precipitated to send in container and mix, stirring, and the pressure controlling container is 3.3 ~ 5.0MPa, the feeding temperature of subcritical anti-precipitation solvent is 60 DEG C ~ 100 DEG C, and the feeding temperature of extract is 130 DEG C ~ 160 DEG C.
Further, also comprise and steam stripped step is carried out to one-level extract remainder and secondary extract remainder, wherein, the stripping extract remainder that stripping step obtains is gasified or burn processing; And oily water separation is carried out to the liquid portion that stripping step obtains, the extraction solvent obtained through oily water separation step is returned the recycle of thermosol extraction step.
Further, also comprise extraction solvent solvent recovery step obtained and return the process that thermosol extraction step carries out recycle.
Apply technical scheme of the present invention, the oil product of the specific fraction section adopting DCL/Direct coal liquefaction process self to produce is as extraction solvent and subcritical anti-precipitation solvent, single extraction is carried out to coal directly-liquefied residue, two-stage solid-liquid separation, solvent recuperation and subcritical anti-solvent precipitation is carried out to extract, can ensure that subcritical anti-precipitation solvent is in liquid state, be conducive to the extraction to the mink cell focus that liquefies in extract.The oil product that the present invention makes full use of specific fraction section under subcritical state to coal directly-liquefied residue in the difference of organic dissolving power, mink cell focus and bitumen will be liquefied separately.Extraction solvent of the present invention and subcritical anti-precipitation solvent all come from DCL/Direct coal liquefaction process, from the horse's mouth, cheap and recovery facilitates, product liquefaction mink cell focus can be used as component relatively light in circulating solvent Substitute For Partial cycling extraction solvent, improve the degree of heaviness of extraction solvent, improve the overall oily yield of coal liquefaction, thus improve the economic benefit of whole gelatin liquefaction industry; In product bitumen, oleaginousness is low, and aromatic carbon rate is high, easilier prepares mesophase pitch through Overheating Treatment, is the raw material of desirable carbon materials.
Accompanying drawing explanation
The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows the flowage structure schematic diagram being separated liquefaction mink cell focus and bitumen from direct coal liquefaction residue according to exemplary embodiments of the present invention.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
Under the state that " subcritical anti-solvent precipitation " in the present invention instigates solvent to change to gaseous state close to liquid state, utilize it to the difference of solute dissolves ability different in saturated solution, by solute dissolves large for solubleness, by solute precipitates little for solubleness out, thus realize the separation method of different components in solution.
According to a kind of exemplary embodiment of the present invention, as shown in Figure 1, from coal directly-liquefied residue, be separated the method for liquefaction mink cell focus and bitumen, comprise the following steps: S1, coal directly-liquefied residue to be mixed with extraction solvent, stir, thermosol extracts, and is extracted mixture; S2, extraction mixture is carried out one-level solid-liquid separation, obtain one-level extraction liquid and one-level extract remainder; S3, one-level extraction liquid is carried out secondary solid-liquid separation, obtain secondary extraction liquid and secondary extract remainder; S4, secondary extraction liquid is carried out solvent recuperation, be extracted thing; And S5, extract to be mixed with subcritical anti-precipitation solvent, subcritical anti-solvent precipitation, is separated, obtains liquefaction mink cell focus and bitumen.
The oil product of the specific fraction section adopting DCL/Direct coal liquefaction process self to produce is as extraction solvent and subcritical anti-precipitation solvent, single extraction is carried out to coal directly-liquefied residue, two-stage solid-liquid separation, solvent recuperation and subcritical anti-solvent precipitation is carried out to extract, can ensure that subcritical anti-precipitation solvent is in liquid state, be conducive to the extraction to the mink cell focus that liquefies in extract.The oil product that the present invention makes full use of specific fraction section under subcritical state to coal directly-liquefied residue in the difference of organic dissolving power, mink cell focus and bitumen will be liquefied separately.Extraction solvent of the present invention and subcritical anti-precipitation solvent all come from DCL/Direct coal liquefaction process, from the horse's mouth, cheap and recovery facilitates, product liquefaction mink cell focus can be used as component relatively light in circulating solvent Substitute For Partial cycling extraction solvent, improve the degree of heaviness of extraction solvent, improve the overall oily yield of coal liquefaction, thus improve the economic benefit of whole gelatin liquefaction industry; In product bitumen, oleaginousness is low, and aromatic carbon rate is high, easilier prepares mesophase pitch 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 two wires, the normal side oil, first vacuum side stream, one or more in stabilized hydrogenation side line oil that produce in DCL/Direct coal liquefaction process; The boiling range of extraction solvent is 120 ~ 280 DEG C, and preferably, boiling range is 160 DEG C ~ 260 DEG C.Adopt boiling range in above-mentioned scope two wires, normal side oil, first vacuum side stream or stabilized hydrogenation side line oil as extraction solvent, relative to other extraction solvent have percentage extraction high, be easy to recovery advantage.
According to another kind of preferred implementation of the present invention, subcritical anti-precipitation solvent be produce in DCL/Direct coal liquefaction process normal top oil, subtract top oil, one or more in stabilized hydrogenation overhead oil, the boiling range of subcritical anti-precipitation solvent is 40 DEG C ~ 160 DEG C, and preferentially, boiling range is 60 DEG C ~ 120 DEG C.The step of its Subcritical anti-solvent precipitation comprises: sent in container with subcritical anti-precipitation solvent by extract and mix, stir, the pressure controlling container is 3.3 ~ 5.0MPa, and the feeding temperature of subcritical anti-precipitation solvent is 60 DEG C ~ 100 DEG C, and the feeding temperature of extract is 130 DEG C ~ 160 DEG C.Carrying out subcritical anti-solvent precipitation by being mixed with subcritical anti-precipitation solvent by extract, can ensure that solvent is in liquid state, there is the advantage be separated with bitumen by the mink cell focus that liquefies in extract.
DCL/Direct coal liquefaction unit and stabilized hydrogenation unit is mainly divided in direct coal liquefaction process, DCL/Direct coal liquefaction unit realizes being separated of liquidation of coal reaction and reactant, stabilized hydrogenation unit carries out hydrogenation to liquefied coal coil, wherein part oil (the heavier part of cut) returns DCL/Direct coal liquefaction unit as circulating solvent, and another part is delivered to oil hydrogenation reforming unit as product.Gelatin liquefaction unit is provided with an atmospheric tower and a vacuum distillation tower, atmospheric tower establishes normal top line, normal side one line, normal two wires, side and normal bottom line, normal top oil and normal side one line oil, normal two wires, side oil are directly delivered to stabilized hydrogenation unit, oil of the normal end is delivered to vacuum distillation tower and is separated further, vacuum distillation tower is established and is subtracted top line, subtracts side one line, subtract two wires, side and subtract bottom line, subtract top oil, first vacuum side stream, second line of distillation oil delivers to stabilized hydrogenation unit, subtract bottom line discharge coal liquefaction residue.Stabilized hydrogenation establishes an atmospheric tower, and atmospheric tower divides tower top line, tower side line and tower bottom line, overhead oil and part tower side oil send hydro-upgrading unit as product, another part tower side oil and tower at the bottom of oil as circulating solvent send back to gelatin liquefaction unit prepare coal oil mixture.
According to a kind of exemplary embodiment of the present invention, step S1 comprises: S11, mixed according to mass ratio 1:1 ~ 10 with extraction solvent by coal directly-liquefied residue, obtains the first mixed solution; And S12, in the first mixed solution, pass into N
2or H
2, and with 5 DEG C ~ 30 DEG C/h, mixed solution being warming up to 60 DEG C ~ 300 DEG C under 0.2 ~ 2.0MPa, constant temperature stirs, and thermosol extracts, and is extracted mixture; Wherein the time of thermosol extraction is 10 ~ 60min, and the speed that constant temperature stirs is 50 ~ 300r/min.Coal directly-liquefied residue is mixed the effect and solvent recovering rate that can ensure to extract with extraction solvent by the present invention according to mass ratio 1:1 ~ 10, if mass ratio is higher than 1:1, then may occur that extraction solvent can not, completely by the situation that coal directly-liquefied residue dissolves, cause extraction not thorough; 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.N is passed in mixed solution
2or H
2object be first get rid of reactor as the air in stirring tank, make reaction carry out in the absence of oxygen.
In the present invention, the mode of one-level solid-liquid separation and secondary solid-liquid separation comprises thermal air pressure filtration, Vacuum Heat suction filtration, cyclonic separation, gravity settling separation and fractionation by distillation, the present invention preferably but be not limited to above-mentioned solid-liquid separation method, as long as solid-liquid separation can be reached required effect.When adopting the mode of thermal air pressure filtration to carry out solid-liquid separation, the filtration temperature of one-level solid-liquid separation and secondary solid-liquid separation is 80 DEG C ~ 300 DEG C, and preferably, filtration temperature is 150 DEG C ~ 200 DEG C; 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 pressure range and carry out thermal air pressure filtration, can largely by solid-liquid separation.Except thermal air pressure filtration, when one-level solid-liquid separation and secondary solid-liquid separation are cyclonic separation, wherein, the temperature of one-level solid-liquid separation and secondary solid-liquid separation is 60 DEG C ~ 120 DEG C, and inlet pressure is 0.3MPa ~ 0.6MPa.
Solid content in the one-level extract remainder that the present invention obtains after one-level solid-liquid separation and secondary solid-liquid separation and secondary extract remainder is 50 ~ 80wt%, and the solvent that is in one-level extract remainder and secondary extract remainder is 20 ~ 50wt%.Because the solvent in solid phase extraction thing is higher, in order to carry out abundant recycle to reduce costs to extraction solvent, according to a kind of exemplary embodiment of the present invention, also comprise and stripping is carried out to one-level extract remainder and secondary extract remainder and reclaims the step of extraction solvent, wherein, the stripping extract remainder obtained through stripping step carries out gasifying or burn processing; And carry out oily water separation through the liquid portion that stripping step obtains, the extraction solvent obtained through oily water separation step is returned the recycle of thermosol extraction step.Solid content >90wt% in solid phase extraction thing after stripping, extraction solvent content is less than 5wt%.
The present invention also comprises extraction solvent solvent recovery step obtained and returns the process that thermosol extraction step carries out recycle, wherein adopts air distillation, the mode of underpressure distillation and evaporation carries out solvent recuperation to secondary extraction liquid.
The present invention is separated with vacuum distillation tower with the atmospheric tower that solvent directly can enter gelatin liquefaction unit with the liquefaction mink cell focus that two-stage solid-liquid separation obtains through the extraction of one-level thermosol, other solvent oil in isolated liquefaction mink cell focus and liquefaction process carries out hydrogenation reaction, and product can use as circulating solvent.Wherein, the temperature of hydrogenation reaction is 260 DEG C ~ 380 DEG C, is preferably 280 DEG C ~ 370 DEG C; Pressure is 6 ~ 19MPa, and be preferably 10 ~ 18MPa, reaction solution hourly space velocity (LHSV) is 0.5 ~ 1.5h
-1, be preferably 0.8 ~ 1.2h
-1; Vapour-liquid ratio is 300 ~ 1200m
3/ t, is preferably 600 ~ 1000m
3/ t; Hydrogenation catalyst be selected from Ni, Mo, Co and W element two or more, with one or both in Alpha-alumina, gamma oxidation silicon, silicon oxide and molecular sieve etc. for carrier.The ash oontent of the bitumen that secondary extraction liquid obtains after solvent recovery step is 0.05 ~ 10wt%, and sulphur content is less than 0.03%, and solvent oil content is less than 5%, can as the raw material preparing carbon materials.
The ash oontent of the present invention in the bitumen that one-level thermosol extracts and two-stage solid-liquid separation obtains is less than 0.2wt%.Due to its ash oontent and quinoline insolubles low, aromatic carbon rate is high, and the bitumen therefore prepared is the desirable feedstock for high-end carbon materialses such as needle cokes.
Beneficial effect of the present invention is further illustrated below in conjunction with specific embodiment:
Embodiment 1
1) two wires, the normal side oil (boiling range is 160 ~ 260 DEG C) produced in 300kg coal directly-liquefied residue and 750kg coal liquefaction is added in stirring tank, stirs with the speed of 50r/min, in stirring tank, fill N
2to the pressure in stirring tank to 0.2MPa, with after the ramp to 60 of 5 DEG C per hour DEG C, constant temperature stirs, and thermosol extraction 30min, is extracted mixture.
2) thermal air pressure filtration mode is adopted to carry out solid-liquid separation to extraction mixture.Wherein filtration temperature is 150 DEG C, and filter pressure is 0.2MPa, and the filter core aperture size of strainer is 50 μm.After single filter, collect one-level extraction liquid and one-level extract remainder, one-level extraction liquid is sent into secondary filter and carries out thermal air pressure filtration, filtration temperature is 150 DEG C, and filter pressure is 0.15MPa, and the filter core aperture size of strainer is 2 μm.After cascade filtration, collect secondary extraction liquid and secondary extract remainder.
3) secondary extraction liquid is sent into vacuum still and carry out solvent recuperation, the extraction solvent recycle of recovered overhead 160 ~ 260 DEG C, at the bottom of tower, collect the mixture of extract liquefaction mink cell focus and bitumen.
4) mixture of liquefy mink cell focus and bitumen is delivered to subcritical anti-solvent precipitation unit to mix with the normal oil (boiling range 60 DEG C ~ 120 DEG C) that pushes up produced in subcritical anti-precipitation solvent and coal liquefaction, pressure during its Subcritical anti-solvent precipitation is 3.3MPa, the feeding temperature of the mixture of liquefaction mink cell focus and bitumen is 130 DEG C, the feeding temperature of subcritical anti-precipitation solvent is 60 DEG C, after subcritical anti-solvent precipitation, obtain liquefaction mink cell focus and bitumen.
5) liquefaction mink cell focus is sent into gelatin liquefaction unit Distallation systm to be separated, liquefaction mink cell focus carries out appropriate hydrogenation together with the circulating solvent of gelatin liquefaction unit, and hydrogenation reaction temperature is 330 DEG C, and pressure is 17MPa, reaction solution hourly space velocity (LHSV) is 0.8h
-1; Vapour-liquid ratio is 700m
3/ t, hydrogenation catalyst mainly consists of: with Ni, Mo for active component, take Alpha-alumina as carrier.
6) one-level extract remainder and secondary extract remainder solid filter residue are fed through steam stripping unit, liquid portion, after oily water separation, is extracted solvent reusable edible, and solid stripping extract remainder can coal blending burning or gasification.
Embodiment 2
1) first vacuum side stream produced in 300kg coal directly-liquefied residue and 3000kg coal liquefaction (boiling range is 180 ~ 220 DEG C) is added in stirring tank, stirs with the speed of 75r/min, in stirring tank, fill N
2to the pressure in stirring tank to 1.0MPa, with after the ramp to 120 of 30 DEG C per hour DEG C, constant temperature stirs, and hot melt extraction 30min, is extracted mixture.
2) thermal air pressure filtration mode is adopted to carry out solid-liquid separation to extraction mixture.Wherein filtration temperature is 200 DEG C, and filter pressure is 0.02MPa, and the filter core aperture size of strainer is 40 μm.After single filter, collect one-level extraction liquid and one-level extract remainder, one-level extraction liquid is sent into secondary filter and carries out thermal air pressure filtration, filtration temperature is 120 DEG C, and filter pressure is 2.0MPa, and the filter core aperture size of strainer is 1 μm.After cascade filtration, collect secondary extraction liquid and secondary extract remainder.
3) secondary extraction liquid is sent into vacuum still and carry out solvent recuperation, the extraction solvent recycle of recovered overhead 120 ~ 250 DEG C, at the bottom of tower, collect the mixture of extract liquefaction mink cell focus and bitumen.
4) liquefaction mink cell focus and the mixture of bitumen are delivered to subcritical anti-solvent precipitation unit to push up oily (boiling range 80 ~ 150 DEG C) with subtracting of producing in subcritical anti-precipitation solvent and coal liquefaction and mix, pressure during its Subcritical anti-solvent precipitation is 5.0MPa, the feeding temperature of liquefaction mink cell focus and bitumen mixture is 160 DEG C, the feeding temperature of subcritical anti-precipitation solvent is 100 DEG C, after subcritical anti-solvent precipitation, obtain liquefaction mink cell focus and bitumen.
5) liquefaction mink cell focus is sent into gelatin liquefaction unit Distallation systm to be separated, liquefaction mink cell focus carries out appropriate hydrogenation together with the circulating solvent of gelatin liquefaction unit, and hydrogenation reaction temperature is 330 DEG C, and pressure is 19MPa, reaction solution hourly space velocity (LHSV) is 0.9h
-1; Vapour-liquid ratio is 700m
3/ t, hydrogenation catalyst mainly consists of: with Ni, Mo for active component, take Alpha-alumina as carrier.
6) one-level extract remainder and secondary extract remainder solid filter residue are fed through steam stripping unit, liquid portion, after oily water separation, is extracted solvent reusable edible, and solid stripping extract remainder can coal blending burning or gasification.
Embodiment 3
1) the stabilized hydrogenation side line oil (boiling range is 130 ~ 260 DEG C) that subtracts produced in 300kg coal directly-liquefied residue and 1500kg coal liquefaction is added in stirring tank, stirs with the speed of 125r/min, in stirring tank, fill N
2to the pressure in stirring tank to 2.0MPa, with after the ramp to 300 of 12.5 DEG C per hour DEG C, constant temperature stirs, and hot melt extraction 60min, is extracted mixture.
2) thermal air pressure filtration is adopted to carry out solid-liquid separation to extraction mixture.Wherein filtration temperature is 300 DEG C, and filter pressure is 2MPa, and filter core aperture size is 45 μm.After single filter, collect one-level extraction liquid and one-level extract remainder, one-level extraction liquid is sent into secondary belt suction filtration, filtration temperature is 180 DEG C, and filter pressure is 0.15MPa, and filter cloth aperture size is 2 μm.After cascade filtration, collect secondary extraction liquid and secondary extract remainder.
3) secondary extraction liquid is sent into vacuum still and carry out solvent recuperation, the extraction solvent recycle of recovered overhead 200 ~ 260 DEG C, at the bottom of tower, collect the mixture of extract liquefaction mink cell focus and bitumen.
4) mixture of liquefy mink cell focus and bitumen is delivered to subcritical anti-solvent precipitation unit to mix with the stabilized hydrogenation overhead oil produced in subcritical anti-precipitation solvent and coal liquefaction (boiling range 70 ~ 120 DEG C), pressure during its Subcritical anti-solvent precipitation is 2.9MPa, the feeding temperature of the mixture of liquefaction mink cell focus and bitumen is 150 DEG C, the feeding temperature of subcritical anti-precipitation solvent is 100 DEG C, after subcritical anti-solvent precipitation, obtain liquefaction mink cell focus and bitumen.
5) liquefaction mink cell focus is sent into gelatin liquefaction unit Distallation systm to be separated, liquefaction mink cell focus carries out appropriate hydrogenation together with the circulating solvent of gelatin liquefaction unit, and hydrogenation reaction temperature is 340 DEG C, and pressure is 19MPa, reaction solution hourly space velocity (LHSV) is 0.9h
-1; Vapour-liquid ratio is 800m
3/ t, hydrogenation catalyst mainly consists of: with Ni, Mo for active component, take silicon oxide as carrier.
6) one-level extract remainder and secondary extract remainder solid filter residue are fed through steam stripping unit, liquid portion, after oily water separation, is extracted solvent reusable edible, and solid stripping extract remainder can coal blending burning or gasification.
Embodiment 4
Operation steps is identical with embodiment 3, and difference is adopted extraction solvent and subcritical anti-precipitation solvent.
Comparative example 1
1) 300kg coal directly-liquefied residue and 600kg first extraction solvent often being pushed up oil (boiling range is 40 DEG C ~ 110 DEG C) adds in stirring tank, stirs, in stirring tank, fill N with the speed of 60r/min
2to the pressure in stirring tank to 0.2MPa, with after the ramp to 100 of 10 DEG C per hour DEG C, constant temperature stirs, and one-level thermosol extraction 30min, obtains the first extraction mixture.
2) adopt hot pressing to cross rate and solid-liquid separation is carried out to the first extraction mixture.Wherein filtration temperature is 80 DEG C, and filter pressure is 0.2MPa, and the filter core aperture size of strainer is 25 μm.After single filter, collect one-level extract remainder and one-level extraction liquid.One-level extraction liquid is sent into one-level vacuum distillation tower and carries out solvent recuperation, column bottom temperature is 250 DEG C, and tower top temperature is 90 DEG C, and tower top pressure is 2KPa, collects liquefaction mink cell focus and the first extraction solvent often pushes up oil, returns one-level thermosol extraction cycle utilize often pushing up oil.
3) one-level extract remainder and the second extraction solvent will be collected subtract side one line oil (boiling range is 180 DEG C ~ 220 DEG C) and be added in stirring tank, and stir with the speed of 55r/min, fill N
2to stirring tank, pressure is 0.3MPa, and after being warming up to 160 DEG C with 30 DEG C per hour, constant temperature stirs, and 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 DEG C, and filter pressure is 1.0MPa, and the filter core aperture size of strainer is 5 μm.After filtering, secondary extract remainder and secondary extraction liquid is collected.Secondary extraction liquid is sent into second depressurized tower and carries out solvent recuperation, column bottom temperature is 320 DEG C, and tower top temperature is 120 DEG C, and tower top pressure is 2.5KPa, collect bitumen and subtract side one line oil (the second extraction solvent), subtract side one line oil and return the extraction of secondary thermosol and carry out recycle.
5) one-level thermosol is extracted the liquefaction mink cell focus obtained to enter hydrogenation unit carry out appropriate hydrogenation together with other circulating solvents of gelatin liquefaction unit, hydrogenation reaction temperature is 330 DEG C, and pressure is 17MPa, reaction solution hourly space velocity LHSV is 0.8h
-1; Vapour-liquid ratio is 700m
3/ t, hydrogenation catalyst mainly consists of: with Ni, Mo for active component, take Alpha-alumina as carrier.
6) secondary extract remainder filter residue is sent into steam stripping unit, liquid portion is after oily water separation, and the stripping extract remainder obtained can coal blending burning or gasification, and the second extraction solvent obtained can return the extraction of secondary thermosol and carry out recycle.
Comparative example 2
1) 400kg coal directly-liquefied residue and 1200kg first extraction solvent stabilized hydrogenation overhead oil (boiling range is 40 DEG C ~ 120 DEG C) are added in stirring tank, stir with the speed of 75r/min, in stirring tank, fill N
2to the pressure in stirring tank to 0.4MPa, with after the ramp to 60 of 5 DEG C per hour DEG C, constant temperature stirs, and one-level thermosol extraction 10min, obtains the first extraction mixture.
2) adopt hot pressing to cross rate and carry out solid-liquid separation to the first extraction mixture, filtration temperature is 70 DEG C, and filter pressure is 0.3MPa, and the filter core aperture size of strainer is 15 μm.After single filter, collect one-level extract remainder and one-level extraction liquid.One-level extraction liquid is sent into one-level vacuum distillation tower and carries out solvent recuperation, column bottom temperature is 270 DEG C, tower top temperature is 90 DEG C, tower top pressure is 2KPa(absolute pressure), collect liquefaction mink cell focus and the first extraction solvent stabilized hydrogenation overhead oil, stabilized hydrogenation overhead oil is returned one-level thermosol extraction cycle and utilize.
3) one-level extract remainder will be collected and two wires, the second extraction solvent normal side oil (boiling range is 160 DEG C ~ 260 DEG C) is added in stirring tank, and stir with the speed of 65r/min, fill N
2to stirring tank, pressure is 0.2MPa, and after being warming up to 180 DEG C with 30 DEG C per hour, constant temperature stirs, and 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 DEG C, and filter pressure is 0.02MPa, and the filter core aperture size of strainer is 2 μm.After filtering, obtain secondary extract remainder and secondary extraction liquid.Secondary extraction liquid is sent into second depressurized tower and carries out solvent recuperation, column bottom temperature is 320 DEG C, and tower top temperature is 131 DEG C, and tower top pressure is 3KPa(absolute pressure), collect bitumen and two wires, the second extraction solvent normal side oil, two wires, normal side oil returns the extraction of secondary thermosol and carries out recycle.
5) one-level thermosol is extracted the liquefaction mink cell focus obtained to enter hydrogenation unit carry out appropriate hydrogenation together with other circulating solvents of gelatin liquefaction unit, hydrogenation reaction temperature is 350 DEG C, and pressure is 18.6MPa, and reaction solution hourly space velocity LHSV is 0.9h
-1; Vapour-liquid ratio is 600m
3/ t, hydrogenation catalyst mainly consists of: with Ni, W for active component, take Alpha-alumina as carrier.
6) secondary extract remainder filter residue is sent into steam stripping unit, liquid portion is after oily water separation, and the stripping extract remainder obtained can coal blending burning or gasification, and the second extraction solvent obtained can return the extraction of secondary thermosol and carry out recycle.
The concrete material of embodiment 1 ~ 4 and data refer to table 1, and the concrete material in comparative example 1 ~ 2 and data are in table 2, and wherein adopted raw material provides by China Shenhua Coal to Liquid and Chemical Co., Ltd..
Table 1
Table 2
As can be seen from Table 1, in embodiment 1 ~ 4, adopt two wires, the normal side oil produced in DCL/Direct coal liquefaction process, first vacuum side stream and stabilized hydrogenation side line oil are as extraction solvent, thermosol extraction is carried out to coal liquefaction residue, one-level solid-liquid separation, secondary solid-liquid separation and subcritical anti-solvent precipitation, wherein adopt the normal top oil that the DCL/Direct coal liquefaction that cut is lighter produces, subtract top oil, stabilized hydrogenation overhead oil carries out subcritical anti-solvent precipitation, namely the oil product making full use of specific fraction section under subcritical state to coal directly-liquefied residue in the difference of organic dissolving power, have effectively achieved being separated of liquefaction mink cell focus and bitumen, ash oontent in the bitumen obtained, quinoline insolubles content and mink cell focus content all lower.
As can be seen from Table 2, conventional two-stage extraction process is adopted in comparative example 1 ~ 2, wherein one-level extraction adopts the lighter distillate produced in DCL/Direct coal liquefaction process to extract coal liquefaction residue as extraction solvent, after one-level solid-liquid separation, obtain one-level extraction liquid and one-level extract remainder respectively, one-level extract remainder is extracted by the first vacuum side stream produced in DCL/Direct coal liquefaction process, normal two wires, side oil again, after secondary solid-liquid separation, obtains secondary extract and secondary extract remainder respectively; One-level extraction liquid is obtained after solvent recuperation the mink cell focus that liquefies, secondary extraction liquid obtains bitumen after solvent recuperation.
Table 1 and table 2 are carried out contrast can find out, percentage extraction in comparative example 1 ~ 2 will lower than the percentage extraction in embodiment 1 ~ 4, separating effect due to one-level extraction liquid and one-level extract remainder in comparative example 1 is bad, partial liquefaction mink cell focus remains in one-level extract remainder, causes the liquefaction heavy oil-contg higher (more than 37%) in secondary extract remainder bitumen.Therefore the separating effect of conventional secondary extraction to the liquefaction mink cell focus in coal liquefaction residue and bitumen is adopted to be not so good as to adopt the technique good separating effect that one-level extracts and subcritical anti-solvent precipitated phase combines in the present invention.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. from coal directly-liquefied residue, be separated a method for liquefaction mink cell focus and bitumen, it is characterized in that, comprise the following steps:
S1, to be mixed with extraction solvent by described coal directly-liquefied residue, stir, thermosol extracts, and obtains thermosol extraction mixture;
S2, described thermosol extraction mixture is carried out one-level solid-liquid separation, obtain one-level extraction liquid and one-level extract remainder;
S3, described one-level extraction liquid is carried out secondary solid-liquid separation, obtain secondary extraction liquid and secondary extract remainder;
S4, described secondary extraction liquid is carried out solvent recuperation, be extracted thing; And
S5, mixed with subcritical anti-precipitation solvent by described extract, subcritical anti-solvent precipitation, is separated, obtains liquefaction mink cell focus and bitumen; Wherein,
Described extraction solvent is two wires, the normal side oil, first vacuum side stream, one or more in stabilized hydrogenation side line oil that produce in DCL/Direct coal liquefaction process; The boiling range of described extraction solvent is 120 ~ 280 DEG C;
Described subcritical anti-precipitation solvent be produce in DCL/Direct coal liquefaction process normal top oil, subtract top oil, one or more in stabilized hydrogenation overhead oil, the boiling range of described subcritical anti-precipitation solvent is 40 DEG C ~ 160 DEG C;
In the process of described subcritical anti-precipitin reaction, pressure is 3.3 ~ 5.0MPa, and the feeding temperature of described subcritical anti-precipitation solvent is 60 DEG C ~ 100 DEG C, and the feeding temperature of described extract is 130 DEG C ~ 160 DEG C.
2. method according to claim 1, is characterized in that, the boiling range of described extraction solvent is 160 DEG C ~ 260 DEG C.
3. method according to claim 1, is characterized in that, the boiling range of described subcritical anti-precipitation solvent is 60 DEG C ~ 120 DEG C.
4. method according to claim 1, is characterized in that, described step S1 comprises:
S11, described coal directly-liquefied residue to be mixed according to mass ratio 1:1 ~ 10 with described extraction solvent, obtain the first mixed solution; And
S12, in described first mixed solution, pass into N
2or H
2, and with 5 DEG C ~ 30 DEG C/h, described mixed solution being warming up to 60 DEG C ~ 300 DEG C under 0.2 ~ 2.0MPa, constant temperature stirs, and thermosol extracts, and 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, Vacuum Heat suction filtration, 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 DEG C ~ 300 DEG C;
The filter pressure of described one-level solid-liquid separation and described secondary solid-liquid separation is 0.02KPa ~ 2.0MPa.
7. method according to claim 6, is characterized in that, the filtration temperature of described one-level solid-liquid separation and described secondary solid-liquid separation is 150 DEG C ~ 200 DEG C; The filter pressure of described one-level solid-liquid separation and described secondary solid-liquid separation is 0.2MPa ~ 1.0MPa.
8. 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 DEG C ~ 120 DEG C, and inlet pressure is 0.3MPa ~ 0.6MPa.
9. method according to claim 1, is characterized in that, also comprises and carries out steam stripped step to described one-level extract remainder and described secondary extract remainder, wherein,
The stripping extract remainder that described stripping step obtains is gasified or burn processing; And
Oily water separation is carried out to the liquid portion that described stripping step obtains, the described extraction solvent obtained through described oily water separation step is returned the recycle of described thermosol extraction step.
10. method according to claim 1, is characterized in that, also comprises the described extraction solvent described solvent recovery step obtained and returns the process that described thermosol extraction step carries out recycle.
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| CN103937542B (en) * | 2014-04-14 | 2016-06-29 | 辽宁科技大学 | A kind of analysis method of mink cell focus and Colophonium composition in hydrogenation liquefaction solid residue |
| CN108774547B (en) * | 2018-05-02 | 2021-05-11 | 国家能源投资集团有限责任公司 | System and method for preparing synthesis gas from coal liquefaction residues |
| CN111040808B (en) * | 2018-10-12 | 2022-06-28 | 中国石油化工股份有限公司 | Inferior oil upgrading method and system for high-yield heavy upgraded oil |
| CN112029527B (en) * | 2020-08-14 | 2022-05-31 | 中国神华煤制油化工有限公司 | Method for treating coal direct liquefaction residues, coal direct liquefaction method and application thereof |
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