CN102399566B - Method for extracting heavy liquefied oil and kerite substance from residue of direct coal liquefaction - Google Patents
Method for extracting heavy liquefied oil and kerite substance from residue of direct coal liquefaction Download PDFInfo
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Abstract
The invention provides a method for extracting heavy liquefied oil and kerite substances from residues of direct coal liquefaction. The method comprises steps of: a) adding coal residue powder and a first solvent into an extraction apparatus for extraction; b) carrying out solid-liquid separation on an extraction mixture and a raffinate from step a) by a first cyclone separator to obtain a liquid mixture and an underflow mixture; c) sending the underflow mixture from step b) and a second solvent to a re-extraction apparatus for re-extraction to obtain a mixture; d) carrying out a second solid-liquid separation on an extraction mixture and a raffinate from step c) by a second cyclone separator too obtain a liquid mixture and an underflow mixture; e) carrying out precise filtration on a clear liquid mixture from step b) and a re-extracting clear liquid mixture from step e) in a precision filtering device and sending a filtrate to a distillation separator; f) carrying out pressurizing coarse filtration on the underflow mixture from step d) and sending a filtrate part and a clear liquid mixture treated with precise filtration to a distillation separator; g) separating the extraction mixture in the distillation separator.
Description
Technical field
The present invention relates to coal deep processing field, particularly a kind of to the solid-liquid separation after coal liquefaction residue extraction and the method for solvent recuperation.Specifically, the invention provides a kind of method that extracts heavy liquefaction oil and bitumen from coal directly-liquefied residue.
Background technology
Coal direct liquefaction is the important supplement to China's oil shortage of resources, significant to Chinese energy safety.No matter adopt which kind of coal direct liquefaction technique, as IGOR
+technique, NEDOL technique and Shenhua liquefaction process (ZL200410070249.6 and ZL200610090484.9), the transformation efficiency of coal all can not reach 100%, finally always has the liquefied residue by product of 30% left and right that accounts for liquefaction coal input quantity.It is the material of a kind of high-carbon, high ash and high-sulfur, and main mineral substance, catalyzer, the unconverted coal existing with solid form, asphaltene and heavy liquefaction oil in coal forms.Wherein the heavy liquefaction oil in residue, bitumen content account for 50% left and right of level of residue, and unconverted coal accounts for 30% left and right, and ash content and catalyzer account for 20% left and right.
Reclaim the heavy oil product in liquefied residue, to improving the oily yield of whole coal liquefaction craft, thereby improve the economic benefit of liquefaction factory, improve the utilising efficiency of resource, reduce energy dissipation and have very important significance.In addition, bituminous matter in coal directly-liquefied residue is mainly comprised of the condensed aromatics encircling more, there is aromaticity high, carbon content is high, and easily polymerization or crosslinked feature, have the unexistent characteristic of a lot of petroleum pitch matter, be suitable as very much the raw material of preparing carbon materials, be a kind of very valuable and unique resource, the bitum application of gelatin liquefaction is subject to people's attention day by day, is expected to prepare the carbon product of some high added values.Chinese patent ZL200510047800.X discloses a kind ofly take coal hydroliquefaction residue and prepares the method for nano-carbon material as prepared using plasma body.Chinese patent ZL200610012547.9 discloses a kind of method using coal liquefaction residue as road asphalt modifier.Chinese patent ZL200910087907.5 discloses a kind of method of utilizing coal directly-liquefied residue to prepare asphalt base carbon fiber.China ZL200910086158.4 discloses a kind of method of preparing mesophase pitch with coal liquefaction residue.These methods are all that the bitumen of take in coal liquefaction residue is raw material, but from residue, do not isolate heavy liquefaction oil and be used, caused undoubtedly the waste of oil product resource, and the extracting of residue medium pitch class material is all that to take expensive pure chemistry reagent be solvent, cost is relatively high, and research is substantially in the laboratory lab scale stage at present.
Current large approach that utilizes to coal liquefaction residue mainly contains the methods such as burning, coking liquefaction, gasification hydrogen-producing.Coal liquefaction residue directly burns as fuel in boiler or kiln, will affect the economy of gelatin liquefaction undoubtedly, causes the waste of resource, and in liquefied residue higher sulphur content in combustion processes by the problem of bringing aspect environment.Coking liquefaction is that the asphaltene in liquefied residue is converted into mink cell focus and retortable oil, although can increase to a certain extent the liquid oils yield of coal liquefaction craft, but after liquefied residue coking, semi-coke yield is high, oil yield is low, and coking obtains that the sulphur content of semicoke is high and ash content is high, it utilizes approach also very not clear and definite.Patent CN101760220A discloses a kind of method for continuously coking and equipment of coal liquefied residue, coking operation carries out under high temperature, condition of high vacuum degree, but due to high, the easy polymerization of aromaticity content in heavy liquefaction oil, when thermal treatment, having the heavy liquefaction oil polycondensation of significant proportion is coke, and therefore the actual mink cell focus ratio obtaining is not high.The method of liquefied residue being carried out to gasification hydrogen-producing is a kind of effectively extensive approach utilizing, but the high value added utilization potentiality of the bitumen in residue and mink cell focus are embodied.
Have the separating substances of higher utility value out and respectively to carry out comprehensive processing and utilization the mink cell focus of 50% left and right in residue, asphaltene etc., make it produce larger economic benefit, be a challenging problem in DCL/Direct coal liquefaction field always.One of difficult point is wherein the problem of solid-liquid separation and solvent recuperation.Why these problems are difficult to solve is the feature decision due to liquefied residue.In coal hydroliquefaction residue, the grain graininess of solids is very thin, particle size distribution from less than 1 μ m to several microns, partial suspended is in raffinate, part is colloidal state; Due to the existence of the high viscosity such as preasphaltene, asphaltene material in liquefied residue, and the effect such as swelling therein of unconverted coal, peptization all can determine that the viscosity of liquefied residue is very high; Because liquid phase is comprised of heavy liquefaction oil and bituminous matter substantially, so the density difference between liquid phase and solid particulate is smaller.All these features have caused the difficulty of liquefied residue solid-liquid separation.JP1304182 discloses a kind of method of isolating heavy liquefaction oil and bitumen from direct liquefaction residue.CN101885976A, CN101962560A and CN101962561A disclose a kind of method that heavy-fluid carburetion and bituminous matter difference are fully utilized that extracts from coal directly-liquefied residue.The operational path that above patent provides has farthest been brought into play mink cell focus and the bitum potentiality of utilizing in residue, but does not provide concrete solid-liquid separation and extraction solvent recovery scheme.
Inventor's years of researches are found, select suitable solvent can from liquefied residue, extract heavy liquefaction oil and bitumen, but in residue extraction process, residue solid substrate concentration is large, the concentration of common soluble solid particulate matter accounts for 10～40% of extraction system, and due to the existence of the high-viscosity materials such as bituminous matter, make extraction system viscosity relatively large, bring very large difficulty to the solid-liquid separation of extraction system.Therefore, how to realize the high efficient solid and liquid separation of extraction mixture (extraction solvent, liquefaction mink cell focus and bituminous matter) and extract remainder (solid part in residue), farthest reclaim extraction solvent, thereby improving the technical and economic feasibility of extraction process, is the Main Bottleneck of restriction residue abstraction technique development.Current achievement in research both domestic and external does not address this problem effectively.Patent JP2289684 adopts the method for gravity settling to carry out separated to extraction mixture with extract remainder with patent JP61276889, but the method separation efficiency is relatively low, precipitation apparatus is heavier, and the extract ash content finally obtaining is difficult to reach the requirement lower than 1%, and extraction solvent loss is larger.Kerr-McGee company (U.S. Patent number 3,607,716, U.S. Patent number 3,607,717) adopt light aromatics solvent as toluene etc., under super critical condition, extract liquefied residue, solid-liquid separation still adopts the method for gravity settling, although this technique can obtain the extraction product that ash is less than 1%, solvent recovering rate is higher, but extraction temperature is higher 325～340 ℃, the larger 5.0MPa of pressure ratio, this technique extraction conditions is relatively harsh, plant energy consumption is high, equipment requirements is high, and settlement separate efficiency is not high yet.
Summary of the invention
The present invention proposes a kind of method that extracts heavy liquefaction oil and bitumen from coal hydroliquefaction residue, object is to realize the solid-liquid high efficiency separation of liquefied residue extraction mixture and extract remainder, obtain ash content lower than the residue extract (comprising heavy liquefaction oil and bitumen) of 0.1wt%, this extract will become the high quality raw material of high value added product; Meanwhile, present method can farthest reclaim extraction solvent, improves solvent recovering rate, is beneficial to the long-term stability running of implement device, reduces running cost, thereby improves the Technical Economy of technological process.
A kind of method that extracts heavy liquefaction oil and bitumen from coal hydroliquefaction residue that the present invention proposes, it is characterized in that liquefaction oil (being called the first solvent) by a kind of specific fraction section is as extraction solvent, coal directly-liquefied residue is extracted to obtain to extraction mixture (comprising solvent, extraction heavy liquefaction oil, extraction bituminous matter) and the extract remainder of liquefied residue.
A kind of method that extracts heavy liquefaction oil and bitumen from coal hydroliquefaction residue that the present invention proposes, is characterized in that cyclone separator and filtration unit to be coupled, for the solid-liquid separation of liquefied residue extract and extract remainder.Specifically, the method is first low by cost of investment, reliability is high and applicable continuous run in long period and the high cyclone separator of separation efficiency extract the solid-liquid roughing out of mixture and extract remainder, then for the requirement of subsequent technique, overflow clear liquid to cyclone separator carries out secondary filter, obtains the liquefied residue extract (comprising heavy liquefaction oil and bitumen) that ash is less than 0.1%.
A kind of method that extracts heavy liquefaction oil and bitumen from coal hydroliquefaction residue that the present invention proposes, it is characterized in that, large for solvent residual amount in cyclone separator underflow, and in residue extractable matter not by completely separated problem, with the liquefaction oil (being called the second solvent) of the specific fraction section of another kind as extraction solvent, cyclonic separation underflow is extracted again, and then reclaim solvent and residue extract.
A kind of method that extracts heavy liquefaction oil and bitumen from coal hydroliquefaction residue that the present invention proposes, is characterized in that first the underflow after the second solvent extracts again carries out pressurized raw filtration, reclaims residual solvent and extract; Then to filter residue heating agent blowback, carry out drying treatment, further reclaim and residue in the extraction solvent in filter residue.
According to an aspect of the present invention, provide a kind of method that extracts heavy liquefaction oil and bitumen from coal hydroliquefaction residue, said method comprising the steps of:
A) coal liquefaction residual powder is joined together with the first solvent in residue extraction plant and carry out abundant hybrid extraction, so that comprise heavy liquefaction oil and bitum extractable matter in coal liquefaction residual powder are extracted in the first solvent;
B) utilize the first cyclone separator to carry out solid-liquid separation to comprise the first solvent, heavy liquefaction oil, bitum extraction mixture and the residue extract remainder that obtain in step a), obtain respectively the concentrated underflow mixture of clear liquor phase mixture and bottom of upper strata overflow;
C) the concentrated underflow mixture in the bottom in step b) is sent to together with the second solvent again and in extraction plant, carries out extraction treatment again, the first solvent of carrying secretly in underflow mixture and extractable matter are extracted in the second solvent again, to obtain, extract again mixture;
D) utilize the second cyclone separator to comprise the first solvent, the second solvent, heavy liquefaction oil, bitumly extract again mixture and residue extract remainder carries out solid-liquid separation for the second time what obtain in step c), obtain respectively upper strata overflow extract again clear liquor phase mixture and bottom concentrated extract again underflow mixture;
E) the clear liquor phase mixture that extracts again in the clear liquor phase mixture in step b) and step d) is carried out to secondary filter in precise filtering device, and filtrate is sent in fractionation by distillation device;
F) the concentrated underflow mixture that extracts again in the bottom in step d) is carried out to pressurized raw filtration in pressurized raw filtration unit, filtrate part with extract again clear liquor phase mixture through secondary filter, and gained filtrate is sent into fractionation by distillation device;
G) filtrate of the filtrate of step e) and step f) is carried out separatedly in fractionation by distillation device, to reclaim the first solvent, the second solvent for recycling, and obtain the bitumen that heavy liquefaction oil and ash are less than 0.1wt%.
The method according to this invention, wherein, described method also comprises step h between step f) and step g)): in to step f), after pressurized raw filtration, remaining filter residue carries out drying treatment with heating agent blowback, reclaims residual solvent, sends into fractionation by distillation device.
The method according to this invention, wherein, described the first solvent and the second solvent are in DCL/Direct coal liquefaction process the liquefaction oil product directly producing, and described the first solvent is the fraction of 160～260 ℃, and described the second solvent is the fraction of initial boiling point (IBP)～110 ℃.
The method according to this invention, wherein, the extracting operation condition in described step a) is: the mass ratio of coal liquefaction residual powder and described the first solvent is 1:1～10, is preferably 1:2～8; N
2and/or H
2atmosphere, pressure is 0.1～3.0MPa, is preferably 0.2～2.5MPa; Extraction temperature is 60～300 ℃, is preferably 80～250 ℃; Extraction time is 5～120min, and stir speed (S.S.) is 50～400r/min; After extraction, the solid concentration of system is 5～30%, and system density is 0.95～1.5g/ml.
The method according to this invention, wherein, is 1%～5% at the solid concentration of the clear liquor phase mixture of the upper strata of described step b) overflow, and the solid concentration of the underflow mixture that bottom is concentrated is 40～60%; The solid concentration that extracts again clear liquor phase mixture in the overflow of the upper strata of described step d) is 1%～5%, and the concentrated solid concentration that extracts again underflow mixture in bottom is 40～60%.
The method according to this invention, wherein, in described step c), the condition of extracting operation again of the second solvent is: the mass ratio of coal liquefaction residual powder and described the second solvent is 1:1～10, is preferably 1:1～6; N
2and/or H
2atmosphere, pressure is 0.2～3.5MPa, is preferably 0.5～2.5MPa; Extraction temperature is 30～250 ℃, is preferably 40～150 ℃; Extraction time is 5～120min, and stir speed (S.S.) is 50～400r/min.
The method according to this invention, wherein, the clear liquor phase mixture of the upper strata overflow that cyclonic separation obtains in described step e) obtains solid concentration and is not more than 0.01% filtrate after secondary filter.
The method according to this invention, wherein, the pore size filter of the precise filtering device using in described step e) is 0.5～3 μ m.
The method according to this invention, wherein, in described step f), the concentrated underflow mixture that extracts again obtains solid concentration and is not more than 5% filtrate after pressurized raw is filtered.
The method according to this invention, wherein, the pore size filter of the pressurized raw filtration unit using in described step f) is 10～50 μ m.
The method according to this invention, wherein, in described step f), the solid concentration of pressurized raw filtered filtration residue is 70～90%.
The method according to this invention, wherein, at described step h) in heating agent refer to nitrogen, helium rare gas element and water vapor or their mixture, it is heated in heating unit to 100～300 ℃, for the blowback drying treatment of coarse filtration filter residue.
The method according to this invention, wherein, at described step h) in, reclaim residual solvent and carry out at least one oil-gas separator.
The method according to this invention, wherein, in described step g), fractionation by distillation device is air distillation tripping device, underpressure distillation tripping device or both combinations, preferably both combinations.
The method according to this invention, wherein, the particle diameter of described coal liquefaction residual powder is 0.05～2mm.
The method according to this invention, wherein, described residue extraction plant and again extraction plant are provided with whipping device and recycle pump.
The method according to this invention, wherein, described precise filtering device and pressurized raw filtration unit are provided with pressure equipment and blowback air system are provided.
According to another aspect of the present invention, provide a kind of heavy liquefaction oil and bitumen by extracting according to preceding method.
Heavy liquefaction oil and bitumen that the method according to this invention is extracted, wherein, the boiling range of described heavy liquefaction oil is 260～450 ℃, the ash of described bitumen is less than 0.1wt%.
The method that extracts heavy liquefaction oil and bitumen from coal directly-liquefied residue provided by the invention, adopt that separation efficiency is high, equipment volume is little, flexible operation, the cyclone separator of easily realizing long-term operation extract the solid-liquid separation of mixture and extract remainder, and be coupled and with secondary filter, obtain the extract (heavy liquefaction oil and bitumen) of high quality, low ash; The method that adopts lightweight solvent to extract again, has improved the percentage extraction of liquefied residue and the rate of recovery of the first solvent to greatest extent; After employing coarse filtration, the dry method of blowback has improved the rate of recovery of the second solvent to greatest extent.The method has solved a difficult problem for solid-liquid separation in residue abstraction technique, has farthest reclaimed extraction solvent simultaneously, has reduced solvent loss, has realized the recycle of solvent.The method technological process is simple, workable, be easy to realize long-term operation, improved the oily yield of whole liquefaction process, and provide the raw material of high-quality for the preparation of carbon materials, avoid the waste of liquefied residue resource, to improving the whole economic efficiency of liquefaction factory, there is very important realistic meaning.
Accompanying drawing explanation
With reference to the accompanying drawings, can be easier to understand technical scheme of the present invention.In accompanying drawing:
Fig. 1 shows an a kind of schema of the method from coal directly-liquefied residue extraction heavy liquefaction oil and bitumen.
Embodiment
Below in conjunction with Fig. 1, method provided by the present invention is described in detail, but the present invention is not limited to this.
As shown in Figure 1, the coal liquefaction residual powder after fragmentation 1 and the first solvent 2 are joined in residue extraction plant 3 via the first colvent inlet 32 and coal directly-liquefied residue entrance 31 respectively by a certain percentage, under certain extraction conditions, carry out extracting operation.Then, the solidliquid mixture through extraction that coal liquefaction residue extraction mixture outlet from residue extraction plant 3 33 is discharged is preferably pumped into the first cyclone separator 4 to carry out solid-liquid separation from the coal liquefaction residue extraction mixture outlet 41 of cyclone separator 4 via topping-up pump, thereby it is concentrated to realize the height of gelatin liquefaction solid residue.Wherein, described residue extraction plant 3 also has the residue extraction mixture inlet 34 that is positioned at described residue extraction plant 3 tops, the described coal liquefaction residue extraction mixture outlet 34 of described residue extraction plant 3 is positioned at the bottom of described residue extraction plant 3, and the described coal liquefaction residue extraction mixture outlet 33 of described residue extraction plant 3 is also connected to the described residue extraction mixture inlet 34 on described residue extraction plant 3 tops.Preferably, the clear liquor phase mixture that exports the 43 upper strata overflows of discharging from the clear liquor phase mixture of the first cyclone separator 4 is flow into the first storage tank 6, so that regime flow via the liquid inlet of the first storage tank 6.The liquid of then, the liquid exit from the first storage tank 6 being discharged is pressed into precise filtering device 7 via the clear liquor phase mixture entrance 71 of precise filtering device 7.Preferably, making to export 73 filtrates of discharging from the secondary filter clear filtrate of precise filtering device 7 flow into the second storage tank 8.The concentrated underflow mixture in the bottom of discharging from the concentrated underflow mixture outlet 42 of the first cyclone separator 4 is flow into extraction plant 5 via the concentrated underflow mixture inlet 51 of extraction plant 5 more again, and by a certain percentage the second solvent 19 is joined in extraction plant 5 via the second colvent inlet 52 again, carry out extracting operation more under certain condition.
Then, the solidliquid mixtures of extraction again that solidliquid mixture outlet 53 discharges of extracting again from extraction plant 5 again are preferably pumped into from the second the extracting again solidliquid mixture entrance 121 of cyclone separator 12 via topping-up pump the second cyclone separator 12 to carry out solid-liquid separation, thereby it is concentrated to realize the height of gelatin liquefaction solid residue.Wherein, described extraction plant again 5 also have be positioned at described in again extraction plant 5 tops extract again solidliquid mixture entrance 54, described extraction plant again 5 described extract again solidliquid mixture outlet 53 be positioned at described in the bottom of extraction plant 5 again, and described extraction plant again 5 described extract again solidliquid mixture outlet 53 be also connected to described in the described solidliquid mixture entrance 54 that extracts again on extraction plant 5 tops again.Preferably, make via the liquid inlet of the first storage tank 6, to flow into the first storage tank 6 together with the clear liquor phase mixture that extracts again the upper strata overflows that clear liquor phase mixture discharges with the clear liquor phase mixture outlet 43 from the first cyclone separator 4 that extracts again upper strata overflows that clear liquor phase mixture outlet 123 discharges of the second cyclone separator 12, so that regime flow.Then, the liquid that liquid exit from the first storage tank 6 is discharged is pressed into precise filtering device 7 via the clear liquor phase mixture entrance 71 of precise filtering device 7, and the filtrate of discharging from the secondary filter clear filtrate outlet of precise filtering device 7 is flow into the second storage tank 8.By extract again the concentrated underflow mixture that extracts again in bottom that underflow mixture outlet 122 discharges from the second cyclone separator 12 concentrated, via pressurized raw filtration unit 13 concentrated, extract again underflow mixture inlet 131 and flow into pressurized raw filtration unit 13, carrying out hot pressurized raw filtration.The filtrate of gained is from the coarse filtration filtrate outlet 132 of pressurized raw filtration unit 13 is discharged, via the coarse filtration filtrate entrance 72 of precise filtering device 7, enter in precise filtering device 7, filtrate after filtration flow in the second storage tank 8 via the secondary filter clear filtrate outlet 73 of precise filtering device 7, so that regime flow.
Preferably, after the heating agent 18 of introducing via the heating agent entrance 151 of heating medium for heating device 15 heats in heating medium for heating device 15, after discharging by the heating agent outlet 152 of heating medium for heating device 15, blowback heating agent entrance 133 via pressurized raw filtration unit 13 enters in pressurized raw filtration unit 13, carries out blowback, drying treatment in pressurized raw filtration unit 13.The gas-oil mixture that gas-oil mixture outlet 134 from pressurized raw filtration unit 13 is discharged is incorporated into gas and oil separating plant 14 via the gas-oil mixture entrance 141 of gas and oil separating plant 14, and this gas-oil mixture carries out separation through gas and oil separating plant 14.Then, the heating agent of gained is discharged from the blowback heating agent outlet 143 of gas and oil separating plant 14, from the heating agent entrance 151 of heating medium for heating device 15, be incorporated into heating medium for heating device 15, for recycling.The oil content that oil content outlet 142 via gas and oil separating plant 14 is discharged is sent in fractionation by distillation device 9 together with the extraction mixture in the second storage tank 8, and the first solvent 2 of recovery and the second solvent 19 are discharged via the first solvent outlet 94 of the recovery of fractionation by distillation device 9 and the second solvent outlet 95 reclaiming.The first solvent reclaiming is fed in residue extraction plant 3 through the first colvent inlet 35 of the recovery of residue extraction plant 3, for recycling.The second solvent 19 reclaiming is fed in extraction plant 5 via the second colvent inlet 55 of the recovery of extraction plant 5 more again, for recycling.And obtain extraction product heavy liquefaction oil 16 and the high-quality asphalt matter 17 of coal liquefaction residue.
Wherein, the particle diameter of described coal liquefaction residual powder is 0.05～2mm, the ash content of coal 10～30%.
Wherein, described residue extraction plant and again extraction plant be provided with whipping device and recycle pump.
Wherein, described the first solvent and the second solvent are the liquefaction oil product directly producing in DCL/Direct coal liquefaction process.Particularly, the first extraction solvent is the fraction of 160～260 ℃, and the second extraction solvent is the fraction of IBP～110 ℃.
Wherein, the extracting operation condition of described the first solvent is: the mass ratio of coal liquefaction residual powder and described the first solvent is 1:1～10, is preferably 1:2～8; N
2and/or H
2atmosphere, pressure is 0.1～3.0MPa, is preferably 0.2～2.5MPa; Extraction temperature is 60～300 ℃, is preferably 80～250 ℃; Extraction time is 5～120min, and stir speed (S.S.) is 50～400r/min; After extraction, the solid concentration of system is 5～30%, and system density is 0.95～1.5g/ml.
Wherein, the solid concentration of the clear liquor phase mixture of the upper strata overflow that described extraction mixture obtains after cyclonic separation is 1%～5%, and the solid concentration of concentrated underflow mixture is 40～60%; The described solid concentration that extracts again clear liquor phase mixture that extracts again the upper strata overflow that mixture obtains after cyclonic separation is 1%～5%, and the concentrated solid concentration that extracts again underflow mixture in bottom is 40～60%.
Wherein, the condition of extracting operation again of described the second solvent is: the mass ratio of coal liquefaction residual powder and described the second solvent is 1:1～10, is preferably 1:1～6; N
2and/or H
2atmosphere, pressure is 0.2～3.5MPa, is preferably 0.5～2.5MPa; Extraction temperature is 30～250 ℃, is preferably 40～150 ℃; Extraction time is 5～120min, and stir speed (S.S.) is 50～400r/min.
The clear liquor phase mixture of the upper strata overflow that wherein, described cyclonic separation obtains obtains solid concentration and is not more than 0.01% filtrate after secondary filter.
Wherein, the pressure-losses of described cyclone separator is 0.1～1.0MPa.
Wherein, the pore size filter that described secondary filter adopts is 0.5～3 μ m.
Wherein, the described concentrated underflow mixture that extracts again obtains solid concentration and is not more than 5% filtrate after pressurized raw is filtered.
Wherein, the pore size filter that described pressurized raw filtration adopts is 10～50 μ m.
Wherein, the solid concentration of described pressurized raw filtered filtration residue is 70～90%.
Wherein, described precise filtering device and pressurized raw filtration unit are provided with pressure equipment and blowback air system are provided.
Wherein, described heating agent refers to nitrogen, helium rare gas element and water vapor or their mixture, it is heated in heating unit to 100～300 ℃, for the blowback drying treatment of coarse filtration filter residue.
Wherein, described fractionation by distillation device is air distillation tripping device, underpressure distillation tripping device or both combinations, preferably both combinations.
Another aspect of the present invention, provides a kind of heavy liquefaction oil and bitumen being extracted by the method according to this invention.
Preferably, the boiling range of the heavy liquefaction oil being extracted by the method according to this invention is 260～450 ℃, is particularly suitable as the solvent of coal direct liquefaction technique, is also that further hydrofining becomes other processed oil, as the high quality raw material of diesel oil, solvent oil.
Preferably, the ash of the bitumen being extracted by the method according to this invention is less than 0.1wt%, and it is the high quality raw material of preparing carbon materials.
Provided by the invention a kind of from coal directly-liquefied residue extraction heavy liquefaction oil and bitum method, its feature is, cyclone separator and filtration unit separation efficiency is high, that be applicable to long-term operation are coupled, for the solid-liquid separation of liquefied residue extract and extract remainder, whole technical process process is simple, easy and safe to operate, separation efficiency is high, facility investment is little, be applicable to long-term operation.
Provided by the invention a kind of from coal directly-liquefied residue extraction heavy liquefaction oil and bitum method, its feature is, the extraction mixture that eddy flow underflow is concentrated extracts with the second solvent again, and carry out coarse filtration, hot blowback drying treatment to extracting again underflow mixture, thereby improve the rate of recovery of solvent, increase the percentage extraction of liquefied residue, thereby improve the economy of extraction process.
Provided by the invention a kind of from coal directly-liquefied residue extraction heavy liquefaction oil and bitum method, its feature is, two kinds of extraction solvents are all from gelatin liquefaction process, for the liquefaction oil product of different fractions section, from the horse's mouth, with low cost, easily reclaim, can be for recycling for a long time.
Provided by the invention a kind of from coal directly-liquefied residue extraction heavy liquefaction oil and bitum method, its feature is, extracts heavy liquefaction oil from liquefied residue, not only can improve the overall oily yield of gelatin liquefaction process, avoid the residue wasting of resources, thereby improve the economy of liquefaction factory; And be suitable coal liquefaction solvent, can improve the degree of heaviness of coal liquefaction solvent, be conducive to Coal liquefaction.
Provided by the invention a kind of from coal directly-liquefied residue extraction heavy liquefaction oil and bitum method, its feature is, the condensation degree of the bitumen aromatic ring extracting from liquefied residue is high, C/H atomic ratio is high, quinoline insolubles is low, and ash content is low, is the high quality raw material of preparing carbon materials.
By the following example, further illustrate the present invention, but protection scope of the present invention is not limited to the following example.
Embodiment
Fundamental test flow process is as follows:
The coal hydroliquefaction residue producing in a kind of 0.1t/d coal direct liquefaction device is selected in this test, and residue character sees attached list 1.First with jaw crusher, residue is crushed to below 2mm.As shown in Figure 1, coal directly-liquefied residue powder after 100Kg fragmentation 1 and 300Kg the first solvent 2 are joined in residue extraction plant 3, by carrying out extracting operation under extraction conditions shown in subordinate list 2, extraction have stir and pump circulation condition under carry out, then extraction solidliquid mixture is pumped into the first cyclone separator 4 and carries out solid-liquid separation, obtain the clear liquor phase mixture 301.5Kg of upper strata overflow, solid concentration is 2.1%, flow into the first storage tank 6, then be pressed into precise filtering device 7, filter pore size is 1 μ m, the solid concentration that obtains filtrate is 0.005%, flow in the second storage tank 8.The underflow mixture 98.5Kg that the first cyclone separator 4 bottoms are concentrated, solid concentration 47.1%, flows in extraction plant 5 again, then adds 200Kg the second solvent 19, by carrying out extracting operation again under extraction conditions again shown in table 2.Extraction have stir and pump circulation condition under carry out, to extract solidliquid mixture is pumped into the second cyclone separator 12 and carries out solid-liquid separation again, what obtain upper strata overflow extracts clear liquor phase mixture 210.1Kg again, solid concentration is 1.9%, flow into the first storage tank 6, then after precise filtering device 7 filters, flow into the second storage tank 8.The second cyclone separator 12 bottoms are concentrated extracts underflow mixture 88.4Kg again, and solid concentration 50.1%, sends into pressurized raw filtration unit 13, carries out hot pressing coarse filtration.Filter pore size is 50 μ m, obtains filtrate 25.8Kg, then through precise filtering device 7, flows into the second storage tank 8.
The character data of table 1 coal directly-liquefied residue
* in soxhlet extraction, oil content refers to the normal hexane soluble part in residue, the bituminous matter insoluble tetrahydrofuran (THF) soluble part of hexane of making a comment or criticism, and insolubles refers to the insoluble part of tetrahydrofuran (THF).
* comprises asphaltene and the preasphaltene in residue.
The main extractant condition of table 2 embodiment
The experimental result of table 3 coal directly-liquefied residue in the method for the invention
Comparative example
In order to further illustrate the technique effect of method of the present invention, comparative example 1 adopts the method for coal directly-liquefied residue same as the previously described embodiments, the first extraction solvent, extraction conditions and identical distillating recovering solvent, adopt conventional hot pressure filtration method to carry out solid-liquid separation, main experimental results is in Table 4.
Comparative example 2 adopts the method for coal directly-liquefied residue same as the previously described embodiments, the first extraction solvent, extraction conditions and identical distillating recovering solvent, adopts conventional settling methods to carry out solid-liquid separation, and main experimental results is in Table 4.
Table 4 is according to the experimental result of the coal directly-liquefied residue of traditional method
Data from table 3 and table 4 can be found out, with according to the experimental result of the coal directly-liquefied residue of traditional method, compare, according to method of the present invention, the percentage extraction of coal directly-liquefied residue, heavy liquefaction oil and bitum yield are high, the rate of recovery of extraction solvent is high, the continuous long-term operation that is conducive to residue extraction process, the economy of raising direct coal liquefaction process.
With reference to embodiment and embodiment, invention has been described.Yet, the aspect that the present invention is not limited to describe in the above-described embodiment and examples, and can carry out various distortion.But should be appreciated that for a person skilled in the art, in the situation that not deviating from the spirit and scope of the present invention, can carry out various modifications and be equal to replacement the present invention.Therefore, the invention is not restricted to the specific embodiment described in this article.More properly, protection scope of the present invention is limited by the accompanying claims.
Claims (31)
1. from coal hydroliquefaction residue, extract a method for heavy liquefaction oil and bitumen, said method comprising the steps of:
A) coal liquefaction residual powder is joined together with the first solvent in residue extraction plant and carry out abundant hybrid extraction, so that comprise heavy liquefaction oil and bitum extractable matter in coal liquefaction residual powder are extracted in the first solvent;
B) utilize the first cyclone separator to carry out solid-liquid separation to comprise the first solvent, heavy liquefaction oil, bitum extraction mixture and the residue extract remainder that obtain in step a), obtain respectively the concentrated underflow mixture of clear liquor phase mixture and bottom of upper strata overflow;
C) the concentrated underflow mixture in the bottom in step b) is sent to together with the second solvent again and in extraction plant, carries out extraction treatment again, the first solvent of carrying secretly in underflow mixture and extractable matter are extracted in the second solvent again, to obtain, extract again mixture;
D) utilize the second cyclone separator to comprise the first solvent, the second solvent, heavy liquefaction oil, bitumly extract again mixture and residue extract remainder carries out solid-liquid separation for the second time what obtain in step c), obtain respectively upper strata overflow extract again clear liquor phase mixture and bottom concentrated extract again underflow mixture;
E) the clear liquor phase mixture that extracts again in the clear liquor phase mixture in step b) and step d) is carried out to secondary filter in precise filtering device, and filtrate is sent in fractionation by distillation device;
F) the concentrated underflow mixture that extracts again in the bottom in step d) is carried out to pressurized raw filtration in pressurized raw filtration unit, filtrate part with extract again clear liquor phase mixture through secondary filter, and gained filtrate is sent into fractionation by distillation device;
G) filtrate of the filtrate of step e) and step f) is carried out separatedly in fractionation by distillation device, to reclaim the first solvent, the second solvent for recycling, and obtains the bitumen that heavy liquefaction oil and ash are less than 0.1wt%,
Wherein, described the first solvent is the fraction of 160～260 ℃, and described the second solvent is the fraction of initial boiling point (IBP)～110 ℃, the pore size filter of the precise filtering device using in described step e) is 0.5～3 μ m, and the pore size filter of the pressurized raw filtration unit using in described step f) is 10～50 μ m.
2. method according to claim 1, wherein, described method also comprises step h between step f) and step g)): in to step f), after pressurized raw filtration, remaining filter residue carries out drying treatment with heating agent blowback, reclaims residual solvent, sends into fractionation by distillation device.
3. method according to claim 1, wherein, the extracting operation condition in described step a) is: the mass ratio of coal liquefaction residual powder and described the first solvent is 1:1～10; N
2and/or H
2atmosphere, pressure is 0.1～3.0MPa; Extraction temperature is 60～300 ℃; Extraction time is 5～120min, and stir speed (S.S.) is 50～400r/min; After extraction, the solid concentration of system is 5～30%, and system density is 0.95～1.5g/ml.
4. method according to claim 3, wherein, the extracting operation condition in described step a) is: the mass ratio of coal liquefaction residual powder and described the first solvent is 1:1～10; N
2and/or H
2atmosphere, pressure is 0.1～3.0MPa; Extraction temperature is 80～250 ℃.
5. method according to claim 3, wherein, the extracting operation condition in described step a) is: the mass ratio of coal liquefaction residual powder and described the first solvent is 1:1～10; N
2and/or H
2atmosphere, pressure is 0.2～2.5MPa; Extraction temperature is 60～300 ℃.
6. method according to claim 3, wherein, the extracting operation condition in described step a) is: the mass ratio of coal liquefaction residual powder and described the first solvent is 1:1～10; N
2and/or H
2atmosphere, pressure is 0.2～2.5MPa; Extraction temperature is 80～250 ℃.
7. method according to claim 3, wherein, the extracting operation condition in described step a) is: the mass ratio of coal liquefaction residual powder and described the first solvent is 1:2～8; N
2and/or H
2atmosphere, pressure is 0.1～3.0MPa; Extraction temperature is 60～300 ℃.
8. method according to claim 3, wherein, the extracting operation condition in described step a) is: the mass ratio of coal liquefaction residual powder and described the first solvent is 1:2～8; N
2and/or H
2atmosphere, pressure is 0.1～3.0MPa; Extraction temperature is 80～250 ℃.
9. method according to claim 3, wherein, the extracting operation condition in described step a) is: the mass ratio of coal liquefaction residual powder and described the first solvent is 1:2～8; N
2and/or H
2atmosphere, pressure is 0.2～2.5MPa; Extraction temperature is 60～300 ℃.
10. method according to claim 3, wherein, the extracting operation condition in described step a) is: the mass ratio of coal liquefaction residual powder and described the first solvent is 1:2～8; N
2and/or H
2atmosphere, pressure is 0.2～2.5MPa; Extraction temperature is 80～250 ℃.
11. methods according to claim 1, wherein, are 1%～5% at the solid concentration of the clear liquor phase mixture of the upper strata of described step b) overflow, and the solid concentration of the underflow mixture that bottom is concentrated is 40～60%; The solid concentration that extracts again clear liquor phase mixture in the overflow of the upper strata of described step d) is 1%～5%, and the concentrated solid concentration that extracts again underflow mixture in bottom is 40～60%.
12. methods according to claim 1, wherein, in described step c), the condition of extracting operation again of the second solvent is: the mass ratio of coal liquefaction residual powder and described the second solvent is 1:1～10; N
2and/or H
2atmosphere, pressure is 0.2～3.5MPa; Extraction temperature is 30～250 ℃; Extraction time is 5～120min, and stir speed (S.S.) is 50～400r/min.
13. methods according to claim 12, wherein, in described step c), the condition of extracting operation again of the second solvent is: the mass ratio of coal liquefaction residual powder and described the second solvent is 1:1～10; N
2and/or H
2atmosphere, pressure is 0.2～3.5MPa; Extraction temperature is 40～150 ℃.
14. methods according to claim 12, wherein, in described step c), the condition of extracting operation again of the second solvent is: the mass ratio of coal liquefaction residual powder and described the second solvent is 1:1～10; N
2and/or H
2atmosphere, pressure is 0.5～2.5MPa; Extraction temperature is 30～250 ℃.
15. methods according to claim 12, wherein, in described step c), the condition of extracting operation again of the second solvent is: the mass ratio of coal liquefaction residual powder and described the second solvent is 1:1～10; N
2and/or H
2atmosphere, pressure is 0.5～2.5MPa; Extraction temperature is 40～150 ℃.
16. methods according to claim 12, wherein, in described step c), the condition of extracting operation again of the second solvent is: the mass ratio of coal liquefaction residual powder and described the second solvent is 1:1～6; N
2and/or H
2atmosphere, pressure is 0.2～3.5MPa; Extraction temperature is 30～250 ℃.
17. methods according to claim 12, wherein, in described step c), the condition of extracting operation again of the second solvent is: the mass ratio of coal liquefaction residual powder and described the second solvent is 1:1～6; N
2and/or H
2atmosphere, pressure is 0.2～3.5MPa; Extraction temperature is 40～150 ℃.
18. methods according to claim 12, wherein, in described step c), the condition of extracting operation again of the second solvent is: the mass ratio of coal liquefaction residual powder and described the second solvent is 1:1～6; N
2and/or H
2atmosphere, pressure 0.5～2.5MPa; Extraction temperature is 30～250 ℃.
19. methods according to claim 12, wherein, in described step c), the condition of extracting operation again of the second solvent is: the mass ratio of coal liquefaction residual powder and described the second solvent is 1:1～6; N
2and/or H
2atmosphere, pressure is 0.5～2.5MPa; Extraction temperature is 40～150 ℃; Extraction time is 5～120min, and stir speed (S.S.) is 50～400r/min.
20. methods according to claim 1, wherein, the clear liquor phase mixture of the upper strata overflow that cyclonic separation obtains in described step e) obtains solid concentration and is not more than 0.01% filtrate after secondary filter.
21. methods according to claim 1, wherein, in described step f), the concentrated underflow mixture that extracts again obtains solid concentration and is not more than 5% filtrate after pressurized raw is filtered.
22. methods according to claim 1, wherein, in described step f), the solid concentration of pressurized raw filtered filtration residue is 70～90%.
23. methods according to claim 2, wherein, at described step h) in heating agent refer to nitrogen, helium rare gas element and water vapor or their mixture, described heating agent is heated to 100～300 ℃ in heating unit, for the blowback drying treatment of coarse filtration filter residue.
24. methods according to claim 2, wherein, at described step h) in, reclaim residual solvent and carry out at least one oil-gas separator.
25. methods according to claim 1, wherein, in described step g), described fractionation by distillation device is atmospheric distillation tower, vacuum still or both combinations.
26. methods according to claim 25, wherein, in described step g), described fractionation by distillation device is the combination of atmospheric distillation tower, vacuum still.
27. methods according to claim 1, wherein, the particle diameter of described coal liquefaction residual powder is 0.05～2mm.
28. methods according to claim 1, wherein, described residue extraction plant and again extraction plant are provided with whipping device and recycle pump.
29. methods according to claim 1, wherein, described precise filtering device and pressurized raw filtration unit are provided with pressure equipment and blowback air system are provided.
30. 1 kinds by the heavy liquefaction oil and the bitumen that extract according to the method described in any one in claim 1-29.
31. heavy liquefaction oil according to claim 30 and bitumens, wherein, the boiling range of described heavy liquefaction oil is 260～450 ℃, and the ash of described bitumen is less than 0.1wt%.
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| CN114702978B (en) * | 2022-04-08 | 2023-12-08 | 山东明君新材料科技有限公司 | High-purity slurry oil and production method of impregnating asphalt and binder asphalt |
| CN115572615B (en) * | 2022-09-30 | 2024-01-12 | 中国神华煤制油化工有限公司 | Separation process and separation system for directly liquefying asphaltene from coal |
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| CN101580729B (en) * | 2009-06-11 | 2012-12-05 | 煤炭科学研究总院 | Method for preparing mesophase asphalt by coal liquefaction residue |
| CA2679908A1 (en) * | 2009-09-23 | 2011-03-23 | Shell Internationale Research Maatschappij B.V. | Closed loop solvent extraction process for oil sands |
| CN101962560B (en) * | 2010-09-29 | 2013-08-14 | 神华集团有限责任公司 | Extraction method of direct coal liquefaction residues and application of extracts |
| CN101962561B (en) * | 2010-09-29 | 2013-08-14 | 神华集团有限责任公司 | Extraction method of direct coal liquefaction residues and application of extracts |
| CN102010741B (en) * | 2010-11-26 | 2013-04-10 | 煤炭科学研究总院 | Method for directly liquefying coals with function of maximizing utilization of liquefied residues |
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