CN103723728A - Activated carbon and method for preparing activated carbon from coal-directly liquefied residue - Google Patents
Activated carbon and method for preparing activated carbon from coal-directly liquefied residue Download PDFInfo
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- CN103723728A CN103723728A CN201310685253.2A CN201310685253A CN103723728A CN 103723728 A CN103723728 A CN 103723728A CN 201310685253 A CN201310685253 A CN 201310685253A CN 103723728 A CN103723728 A CN 103723728A
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Abstract
The invention discloses an activated carbon and a method for preparing the activated carbon from coal-directly liquefied residue. The method comprises the following steps: S1, extracting asphalt from the coal-directly liquefied residue, and forming modified coal-liquefied asphalt through a polymerization reaction; S2, smashing the modified coal-liquefied asphalt, mixing the smashed modified coal-liquefied asphalt with coal powder, and then pressing to form lump coal; S3, carbonizing and activating the lump coal, and cooling to obtain the activated carbon. According to the method, after the asphalt is extracted from the coal-directly liquefied residue, the lump coal can be obtained through steps of polymerizing and pressing; then through conventional carbonizing and activating treatments as well as cooling, the activated carbon is obtained. The method is simple in process and low in cost; the development practicability of the modified coal-liquefied asphalt is high, and the modified coal-liquefied asphalt is suitable for serving as a binder for preparing the high-performance activated carbon; the high value-added utilization of the coal-directly liquefied residue is realized.
Description
Technical field
The present invention relates to coal liquefaction residue deep process technology field, in particular to a kind of gac and utilize coal liquefaction residue to prepare the method for gac.
Background technology
Along with the fast development of national economy, modernization and social development process are constantly accelerated, and China constantly increases the consumption of petroleum products, have substantially exceeded the rate of growth of the crude production same period, cause us petroleum import amount all to increase year by year, and exceeded from output.And China is an oil-poor country of rich coal, make full use of abundant coal resources, the advanced persons' such as development of coal direct liquefaction clean coal technology is to reduce external crude oil to depend on unduly, alleviate one of important channel of China's oil shortage of resources, petroleum products supply and demand pressure, also be to improve our coal resources utilization ratio simultaneously, alleviate coal burning pollution, promote the Important Action of the energy, economy, harmonious development.
DCL/Direct coal liquefaction is that coal is passed through to high temperature, high pressure, and under catalyst action, hydrogenation directly changes into a kind of advanced person's of clean transport fuel (petroleum naphtha, diesel oil etc.) or industrial chemicals clean coal technology.The process of DCL/Direct coal liquefaction be generally by coal in advance powder to the granularity below 0.15mm, then be made into coal slurry with solvent, and under certain temperature (approximately 450 ℃) and high pressure hydrogenation, make the macromolecular cleavage in coal be hydrogenated into more micromolecular process.In liquefaction process, except the liquiefied product that obtains needing, go back some hydrocarbon molecules of by-product, CO
xthe liquefaction residue (claiming again coal liquefaction residue) producing Deng gas, process water and solid-liquid separation process.Liquefied residue generally accounts for 30% left and right of coal input quantity.The economy of the efficiency of the utilization of coal liquefaction residue on liquefaction process and whole liquefaction factory and environment protection etc. all have immeasurable impact.Efficient, the feasible method of comprehensive utilization of research coal directly-liquefied residue, extracts value product the economic benefit that improves direct liquefaction process is had important practical significance.
Coal directly-liquefied residue is mainly comprised of inanimate matter and organic two portions, and organic matter comprises liquefaction heavy oil, bitumen and unconverted coal, and inorganic matter (being commonly referred to ash content) comprises mineral substance in coal and additional catalyzer.Liquefaction heavy oil and bitumen in organic material account for 50% of level of residue, and unconverted coal accounts for 30% of level of residue, and ash content accounts for 20% left and right.Therefore, by accounting for 50% bitumen and mink cell focus in liquefied residue, separate and carry out comprehensive development and utilization, it is feasible therefrom extracting or prepare more value product.
Current is mainly some traditional methods to the utilization of coal liquefaction residue, as burning, coking liquefaction and gasification hydrogen-producing etc.As fuel, directly in boiler or kiln, burn, will affect the economy of gelatin liquefaction undoubtedly, and in liquefied residue, higher sulphur content will be brought the problem of environment aspect.Although coking liquefaction has increased the liquid oils yield of coal liquefaction craft, liquefied residue can not obtain the most reasonably utilizing, semicoke and coke utilize approach also very not clear and definite.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 to the bitumen in residue and mink cell focus are embodied, and the ash content in residue is up to more than 20%, this bring very large impact will to the deslagging of vapourizing furnace.
Patent ZL200510047800.X discloses a kind of method of preparing carbon nano-material take coal hydroliquefaction residue as raw material plasma body.Patent ZL200610012547.9 discloses a kind of method using coal liquefaction residue as road asphalt modifier.ZL200910087907.5 discloses a kind of method of utilizing coal directly-liquefied residue to prepare asphalt base carbon fiber.Patent 200910086158.4 discloses a kind of method of preparing mesophase pitch with coal liquefaction residue.Although but aforesaid method all recycles take the bitumen in coal liquefaction residue as raw material, to the extracting of residue medium pitch class material, all take expensive pure chemistry reagent as solvent, cost is relatively high.
Japanese Patent JP59084977 discloses a kind of method organic in liquefied residue of extracting, the organic matter (comprising heavy liquefaction oil and asphaltene) that extracting is obtained all carries out secondary hydrocracking, obtain light naphtha, although the method improves the yield of total body fluid carburetion, because the existence of bitumen can produce the problem of secondary hydrogenation catalyst coking deactivation.Patent JP130412 discloses a kind of method of isolating heavy liquefaction oil and bitumen from coal directly-liquefied residue, the method is carried out secondary hydrocracking by the heavy liquefaction oil of separation and is obtained lightweight liquefaction oil, and bitumen enters gelatin liquefaction unit, carries out liquefaction reaction again.Although this method has been carried out recycling to residue medium pitch class material, but but exist following problem: on the one hand, because the cut of heavy oil product is heavier, aromaticity content is higher, secondary hydrocracking light Fuel reaction processed is more violent, not only require to carry out deep hydrogenation, cause hydrogen consumption to increase, and easily cause catalyzer because of coking inactivation, thereby the performance of hydrocracking catalyst has been proposed to very high requirement, required hydrocracking catalyst to there is stronger activity, more intense anti-carbon deposition ability.On the other hand, when the bitumen of separating liquefies again, it is liquefaction effect bad again, but also can cause in liquefying reactor the ill effects such as deposition, coking, and therefore the method can not realize the rationally efficient utilization of bitumen.
Patent CN101885976A discloses a kind of method of extracting bitumen and liquefaction heavy oil from coal liquefaction residue, adopt distillate self-produced in DCL/Direct coal liquefaction process as extraction solvent, by bitumen with liquefaction mink cell focus together with extracting and separating out, adopt again the method for destructive distillation, bitumen and liquefaction heavy oil content are opened, obtain the middle phase of pitch, after liquefaction mink cell focus appropriateness hydrogenation, return to gelatin liquefaction unit.Liquefaction mink cell focus is to be mainly greater than the fractions consisting of 350 ℃, more intense with bitumen bonding force, while adopting the method separation of high temperature carbonization, can cause its coking, and be difficult to use as the circulating solvent of gelatin liquefaction.
Patent CN101962560A, CN101962561A disclose a kind of method of utilizing two-stage extraction to extract heavy liquefaction oil and bitumen from coal liquefaction residue, the oil product of two different fractions sections that the method produces take DCL/Direct coal liquefaction process self is as extraction solvent, respectively liquefied residue is carried out to the extraction of two-stage order, obtain heavy liquefaction oil and bitumen.
Although aforesaid method provides the method that the liquefaction mink cell focus in coal liquefaction residue or bitumen are carried out to recycling, but the cost that current these proposed methods have is relatively high, some utilization ratios are low, also have some to have the problem of complex process, this just makes the recycling of coal liquefaction residue also need further research, to provide a kind of technique simple, the recycling method that cost is low.
Summary of the invention
The present invention aims to provide a kind of gac and utilizes coal directly-liquefied residue to prepare the method for gac, so that the recycling method of the simple coal directly-liquefied residue medium pitch of a kind of technique class material to be provided.
To achieve these goals, according to an aspect of the present invention, a kind of method of utilizing coal directly-liquefied residue to prepare gac is provided, has comprised the following steps: the bitumen in S1, extraction coal directly-liquefied residue, has formed modified coal road oil after polyreaction; S2, mix with coal dust after above-mentioned modified coal road oil is pulverized, mixing extrusion forming afterwards, obtains briquetting coal; And S3, by above-mentioned briquetting coal successively through charing, activation treatment, obtain gac after cooling.
Further, the step of extracting bitumen in above-mentioned steps S1 comprises: S11, above-mentioned coal directly-liquefied residue is mixed with extraction solvent, be extracted mixture; S12, above-mentioned extraction mixture is carried out to solid-liquid separation, be extracted liquid and solid part; S13, extraction liquid is carried out to underpressure distillation, obtain bitumen after reclaiming extraction solvent.
Further, above-mentioned steps S11 comprises: coal directly-liquefied residue is mixed according to mass ratio 1:1～1:10 with extraction solvent, obtain mixture; And at N
2or H
2under atmosphere, at pressure, be 0.1～1.0MPa, with the heat-up rate of 10 ℃/h～30 ℃/h, said mixture be warming up to 80 ℃～280 ℃, and with the stir speed (S.S.) of 50～300r/min, constant temperature extracting 5～60min, obtains above-mentioned extraction mixture.
Further, the extraction solvent in above-mentioned steps S11 is one or more in tetrahydrofuran (THF), furfural, N-Methyl pyrrolidone, quinoline, liquefied coal coil and distillate thereof and coal tar and distillate thereof.
Further, the solid-liquid separating method in above-mentioned steps S12 is selected from the one in pressurized heat filter method, Vacuum Heat suction filtration method, cyclonic separation method, gravity settling separation method and distillation separation method; Preferably, when above-mentioned solid-liquid separation adopts thermal air pressure filtration, filtration temperature is 50 ℃～250 ℃, is preferably 150 ℃～200 ℃; Filter pressure is 0.02KPa～101.3KPa or 0.2MPa～1.0MPa; Preferably, when above-mentioned solid-liquid separation adopts cyclonic separation, the temperature of cyclonic separation is 50 ℃～250 ℃, and inlet pressure is 0.2MPa～0.6MPa.
Further, the solid part obtaining in above-mentioned steps S12 is through stripping process, reclaim extraction solvent, obtain extract remainder, preferred above-mentioned extraction solvent returns to step S11 and recycles, preferred above-mentioned extract remainder after burning as step S1 in the heat supply source of extractive reaction in polyreaction and/or step S11.
Further, in above-mentioned steps S1, the ash oontent of the bitumen extracting is 0.2～5wt%, and volatile content is 30～60wt%, and β～resin content is 4.45～10.05wt%.
Further, in above-mentioned steps S1, the ash oontent being formed in modified coal road oil is 0.25～6wt%, and volatile content is 25～50wt%, and β～resin content is 18～29.05wt%, and softening temperature is 95～150 ℃.
Further, after above-mentioned modified coal road oil being pulverized in above-mentioned steps S2, mix according to mass ratio 10～20:100 with coal dust, preferred above-mentioned gelatin liquefaction asphalt powder is broken to the particle diameter of 20 μ m～200 μ m, the particle diameter of above-mentioned coal dust is 80 μ m～300 μ m, and preferred formed briquetting coal is of a size of 5～20mm.
Further, in above-mentioned steps S2, the step of extrusion forming is carried out under the pressure of 15～25MPa.
Further, in above-mentioned steps S3, the step of above-mentioned charing processing comprises: it is in the reaction chamber of 290～310 ℃, at N that above-mentioned briquetting coal is put into temperature
2pressure is under 0.05～0.2MPa, and reaction chamber temperature is warming up to 600 ℃～620 ℃ with the speed of 3 ℃～5 ℃/min, then with the speed of 2 ℃～3 ℃/min, is warming up to 630 ℃～650 ℃ and completes charing.
Further, in above-mentioned steps S3, the step of above-mentioned activation treatment comprises: complete after charing step, reaction chamber temperature is further warming up to 900 ℃～950 ℃, and passes into steam, maintenance steam flow is 25～50ml/min, after constant temperature 2～5h, completes activation.
According to another aspect of the present invention, provide a kind of gac of being prepared by above-mentioned preparation method.
Apply a kind of gac of technical scheme of the present invention and utilize coal liquefaction residue to prepare the method for gac, after the bitumen extracting in coal directly-liquefied residue, by the method for polymeric modification, improve the softening temperature of bitumen, β～resin content, volatile matter, the performances such as cohesiveness, obtain modified coal road oil, by modified coal road oil is obtained to briquetting coal with coal dust mixing extrusion forming, to improve its wear strength, then prepare gac take this briquetting coal as raw material simultaneously.This method, after the bitumen extracting in coal directly-liquefied residue, only can be obtained briquetting coal by the step of polymerization, extrusion forming, then adopt conventional charing, activation treatment, obtains gac after cooling.The method not only technique is simple, and cost is low, and the exploitation practicality of the modified coal road oil obtaining is stronger, is suitable as binding agent raw material prepared by high performance active carbon, has realized the high value added utilization of coal liquefaction residue.
Accompanying drawing explanation
The Figure of description that forms the application's a part is used to provide a further understanding of the present invention, and schematic description and description of the present invention is used for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows according to the coal directly-liquefied residue that utilizes of the embodiment of the present invention and prepares the schematic flow sheet of gac.
Embodiment
It should be noted that, in the situation that not conflicting, the feature in embodiment and embodiment in the application can combine mutually.Describe below with reference to the accompanying drawings and in conjunction with the embodiments the present invention in detail.
As background technology part, introduce, the recycling of coal liquefaction residue exists the problem of the relatively high and complex process of cost.In order to improve this problem, inventor has carried out large quantity research to the recycling of coal liquefaction residue, the bitumen that utilization is extracted from coal liquefaction residue, to prepare contenting carbon material, such as tamping coking, gac and Graphite Electrodes molding adhesive, waterproof roll, waterproof paint etc., but because the softening temperature of the bitumen reclaiming in coal liquefaction residue is high, volatile matter is low, bad adhesion, product development suitability is not strong, and its application in these materials is restricted.In once accidental chance, discovery is carried out polymeric modification by the bitumen reclaiming in coal liquefaction residue, can obtain the modified coal road oil that the performances such as softening temperature, volatile matter and cohesiveness are improved, and the briquetting coal that this modified coal road oil obtains with coal dust mixing extrusion forming, can be for the preparation of gac, and prepared Properties of Activated Carbon is better.
The invention provides a kind of method of utilizing coal directly-liquefied residue to prepare gac, as shown in Figure 1, the method comprises the following steps: the bitumen in S1, extraction coal directly-liquefied residue, forms modified coal road oil after polyreaction; S2, mix with coal dust after modified coal road oil is pulverized, afterwards extrusion forming of mixing, obtains briquetting coal; And S3, by briquetting coal successively through charing, activation treatment, obtain gac after cooling.
This method of utilizing coal directly-liquefied residue to prepare gac provided by the present invention, after the bitumen extracting in coal directly-liquefied residue, by the method for polymeric modification, improve the softening temperature of bitumen, volatile matter, the performances such as cohesiveness, obtain modified coal road oil, by modified coal road oil is obtained to briquetting coal with coal dust mixing extrusion forming, to improve its wear strength, then prepare gac take this briquetting coal as raw material simultaneously.This method, after the bitumen extracting in coal directly-liquefied residue, only can be obtained briquetting coal by the step of polymeric modification, extrusion forming, then adopt conventional charing, activation treatment, obtains gac after cooling.The method not only technique is simple, and cost is low, and the exploitation practicality of the modified coal road oil obtaining is stronger, is suitable as binding agent raw material prepared by high performance active carbon, has realized the high value added utilization of coal liquefaction residue.
The step of extracting bitumen in the step S1 of aforesaid method provided by the present invention can adopt conventional means to extract, as long as bitumen is separated from coal liquefaction residue, in a kind of exemplary embodiment of the present invention, extracting the step of bitumen comprises: S11, coal directly-liquefied residue is mixed with extraction solvent, be extracted mixture; S12, extraction mixture is carried out to solid-liquid separation, be extracted liquid and solid part; S13, extraction liquid is carried out to underpressure distillation, obtain bitumen after reclaiming extraction solvent.At employing aforesaid method, extract in the process of bitumen, as long as the extraction solvent adopting can have selective extraction effect to the bitumen in coal liquefaction residue, preferably include in the present invention but be not limited to one or more in tetrahydrofuran (THF), furfural, N-Methyl pyrrolidone, quinoline, liquefied coal coil and distillate thereof and coal tar and distillate thereof.These preferred extraction solvents have percentage extraction high, be easy to the advantages such as recovery.
At employing aforesaid method, extract in the process of bitumen, for the not particular requirement such as the temperature of each step, time, as long as bitumen extracting and separating from coal liquefaction residue out all can, in a kind of preferred implementation of the present invention, above-mentioned steps S11 comprises: coal directly-liquefied residue is mixed according to mass ratio 1:1～1:10 with extraction solvent, obtain mixed solution; And at N
2or H
2under atmosphere, at pressure, be 0.1～1.0MPa, with the heat-up rate of 10 ℃/h～30 ℃/h, mixed solution be warming up to 80 ℃～280 ℃, with the stir speed (S.S.) of 50r/min～300r/min, constant temperature extracting 5～60min, is extracted mixture.
In aforesaid method, by coal directly-liquefied residue and extraction solvent are mixed with and are beneficial to the effect and the solvent recovering rate that improve extraction according to mass ratio 1:1～1:10.If the mass ratio of coal directly-liquefied residue and extraction solvent, may be less because of the consumption of extraction solvent higher than 1:1, cause extraction thorough not, and then reduce effect of extracting; If the mass ratio of coal directly-liquefied residue and extraction solvent, can be excessive because of the consumption of extraction solvent lower than 1:10, and the recycling energy consumption of increase extraction solvent increases cost recovery.Meanwhile, mixed solution is at N
2or H
2under atmosphere protection, can get rid of reactor as the air in stirring tank, reaction is carried out under the condition of anaerobic, prevent that reactant from increasing the danger of pyroreaction in the situation that of aerobic.
In aforesaid method, the mixed solution of coal directly-liquefied residue and extraction solvent is warming up to 80 ℃～280 ℃ with the heat-up rate of 10 ℃/h～30 ℃/h, adopt the heat-up rate of this scope both can make mixed solution thermally equivalent to improve extraction efficiency, can prevent that again extraction solvent from reducing extraction efficiency because of the too fast evaporation of being heated, and heat-up rate cross can make slowly the reaction times extend, reduced production efficiency.Mixed solution is warming up to after 80 ℃～280 ℃, with the stir speed (S.S.) of 50r/min～300r/min, constant temperature extracting 5～60min, within the scope of said temperature, extract the extraction activity that can improve extraction solvent, make extraction efficiency higher, lower than 80 ℃ or all make the extraction activity of extraction solvent be restricted higher than the extraction temperature of 280 ℃, and then reduce extraction efficiency.Meanwhile, with the stir speed (S.S.) of 50r/min～300r/min, constant temperature extracting 5～60min.The present invention adopts the stir speed (S.S.) of above-mentioned scope, can either make extraction solvent mix with coal directly-liquefied residue, the risk that can not make because stir speed (S.S.) is too fast again liquid splash out cause insecurity to increase.And extraction time selects 5～60min can make the bitumen in coal directly-liquefied residue extract as much as possible to improve percentage extraction, extraction time exceedes after 60min, also not having more bitumen is extracted out, and extraction time is while being shorter than 5min, too short because of extraction time, the bitumen in coal directly-liquefied residue can not thoroughly be extracted.
S12 at aforesaid method provided by the present invention carries out in the step of solid-liquid separation extraction mixture, method to solid-liquid separation does not have particular requirement, as long as extraction mixture can be carried out to solid-liquid separation, be extracted liquid and solid part, solid-liquid separating method preferably includes but is not limited to be selected from the one in pressurized heat filter method, Vacuum Heat suction filtration method, cyclonic separation method, gravity settling separation method and distillation separation method in the present invention.In a kind of preferred implementation of the present invention, when the mode of adopted pressurized heat filtration is carried out solid-liquid separation, the temperature of thermal air pressure filtration is 120 ℃～250 ℃, more preferably 150 ℃～200 ℃; The pressure that pressurized heat filters is 0.2MPa～1.0MPa.When solid-liquid separation adopts Vacuum Heat suction filtration, the pressure of filtration is 0.02KPa～101.3Kpa.In addition, when solid-liquid separation adopts cyclonic separation, the temperature of cyclonic separation is 50 ℃～250 ℃, and inlet pressure is 0.2MPa～0.6MPa.Adopt in said temperature and pressure range and filter, can both farthest solid-liquid be separated.
In above-mentioned S12 step, carry out the solid part that solid-liquid separation obtains and conventionally contain extract remainder and extraction solvent, the difference of the mode adopting according to solid-liquid separation, in this solid part, solids content also can be distinguished to some extent, but the solid content in solid part is 50～90wt% conventionally, and the solvent in solid part is 10～50wt%.For extraction solvent is carried out to abundant recycle to reduce costs, according to a kind of exemplary embodiment of the present invention, also comprise to extract remainder is carried out stripping and reclaims the step of extraction solvent.The extraction solvent preferably reclaiming returns to step S11 and recycles.Meanwhile, the preferably solid content >95wt% in the extract remainder solid after stripping, extraction solvent content is less than 5wt%.The stripping extract remainder now obtaining through stripping step can gasify or burn processing, or as the raw material of water-permeable brick; Preferably this extract remainder after burning as described step S1 in the heat supply source of extractive reaction in polyreaction and/or step S11.In this preferred implementation by using extract remainder through burning after as heat supply source, can reduce the present invention and utilize coal directly-liquefied residue to prepare the energy consumption of the method for gac, reduce production costs.
In the S13 of aforesaid method provided by the present invention, extraction liquid is carried out to solvent recuperation and extract in the step of extract, its processing parameter is not had to particular requirement, as long as obtain bitumen after can reclaiming extraction solvent.In a kind of preferred implementation of the present invention, the step of this solvent recuperation can adopt the mode of air distillation, underpressure distillation or evaporation to reclaim solvent.
In the above-mentioned S1 of the present invention, will after bitumen polyreaction, form in the step of modified coal road oil, polyreaction adopts common process, preferably includes in the present invention but is not limited to adopt any mode in vacuum flashing polymerization, normal pressure thermopolymerization and pressurized heat polymerization.While wherein adopting vacuum flashing polymerization, a kind of optional mode comprises: by the bitumen of acquisition, in temperature, be that 330～370 ℃, pressure 5～12KPa carry out flash distillation polymerization.When adopting normal pressure thermopolymerization, a kind of optional mode comprises: the bitumen of acquisition is carried out to polymerization under temperature is 400～430 ℃, normal pressure.When adopting pressurized heat polymerization, a kind of optional mode comprises: by the bitumen of acquisition, in temperature, be that 380～430 ℃, pressure 0.8～1.5MPa carry out polymerization.
In the present invention, utilize coal directly-liquefied residue to prepare in the method for gac, as long as adopt aforesaid method to extract the bitumen in coal directly-liquefied residue, and after polyreaction, form modified coal road oil just can be for the preparation of gac, in a kind of preferred implementation of the present invention, the ash oontent of the bitumen extracting in step S1 is 0.2～5wt%, volatile content is 30～60wt%, and β-resin content is 8.45～10.05wt%.More preferably, the ash oontent in the modified coal road oil forming in step S1 is 0.25～6wt%, and volatile content is 25～50wt%, and β-resin content is 18～29.05wt%, and softening temperature is 95～150 ℃.The mentioned component of extracted bitumen is controlled in above-mentioned scope, the each composition that is conducive to control prepared modified coal road oil meets above-mentioned requirements, and by each Composition Control in formed modified coal road oil in above-mentioned scope, be conducive to improve the performance of prepared gac.
In the above-mentioned technique of preparing gac take modified coal road oil as raw material of the present invention, in the step of the formation briquetting coal of step S2, blending ratio between modified coal road oil and coal dust after pulverizing does not have particular requirement, as long as can form briquetting coal in the mode of pressurization after mixing, mass ratio that for example can 5～30:100 mixes, in a kind of preferred implementation of the present invention, in step S2, modified coal road oil mixes according to mass ratio 10～20:100 with coal dust after pulverizing, it is 20 μ m～200 μ m that preferred modified coal road oil is crushed to particle diameter, the particle diameter of coal dust is 80 μ m～300 μ m.When mass ratio is 10～20:100, modified coal road oil and coal dust are in follow-up pressure process, can not need the binding agent just can well compound stalk forming, when mass ratio is less than 10:100, because the consumption of modified coal road oil is very few, cohesiveness is relatively poor, and the molding effect of prepared briquetting coal is not good; Equally, when mass ratio is greater than 20:100, because the consumption of coal modifying asphalt is more, its viscosity is larger, can increase the pressure of compound stalk forming, increases power consumption.Meanwhile, the particle diameter of the gelatin liquefaction asphalt powder through pulverizing is not limited to 20 μ m～200 μ m, the particle diameter of the coal dust using is also not limited to 80 μ m～300 μ m.When both are mixed to interpolation according to such particle diameter, be more conducive to both dispersed mixing, be convenient to moulding.
After above-mentioned modified coal road oil mixes with coal dust, in the step of extrusion forming, pressure can be exerted pressure according to the effect of used raw material and institute's moulding, 1～5min preferably exerts pressure under the pressure of 15～25MPa, under this pressure range, consume energy little, and extrusion forming is effective.The preferred clean fine coal of the present invention's coal dust used.Clean fine coal refers to through washing coal and impurity separated, and obtains ash content and is less than or equal to the coal that 12.5wt%, granularity are less than 100mm.In this clean fine coal, the impurity such as ash content, sulphur content is few, can reduce the discharge of pollutent.The briquetting coal preferably forming is of a size of 5～20mm.Briquetting coal in this size range has the effect that intensity is high, be beneficial to charing, activation.
At the above-mentioned modified coal road oil of the present invention, be that raw material is prepared in the technique of gac, through step S1 and S2, form after briquetting coal, adopt conventional carbonization and activation treatment can obtain gac.In a kind of preferred implementation of the present invention, the step of the charing processing of employing comprises: it is in the reaction chamber of 290～310 ℃, at N that briquetting coal is put into temperature
2pressure is under 0.05～0.2MPa, and reaction chamber temperature is warming up to 600 ℃～620 ℃ with the speed of 3 ℃～5 ℃/min, then with the speed of 2 ℃～3 ℃/min, is warming up to 630 ℃～650 ℃ and completes charing.In this carbonization method, the object difference that points of two temperature stages are carried out charing, be warming up to 600 ℃～620 ℃ take pyrolytic reaction as main with the speed of 3 ℃～5 ℃/min early stage, and alkyl group side chain fracture occurs, and forms free radical, emits light-component gas; Later stage to be warming up to 630 ℃～650 ℃ take hydrogen condensation reaction as main with the speed of 2 ℃～3 ℃/min again, carries out with reaction again, forms gradually the condensed-nuclei aromatics compound that molecular weight is larger.Slowly heating can make reactant be heated evenly, the gac porous nickel of generation.
In a kind of preferred implementation of the present invention, activation treatment step comprises: reaction chamber temperature is further warming up to 900 ℃～950 ℃, and passes into water vapor, maintenance steam flow is 25～50ml/min, after constant temperature 2～5h, completes activation.In this method, activation temperature raises with temperature higher than carbonization temperature, and thermolysis and thermal condensation reaction further occur the polycyclic aromatic hydrocarbons in modified coal road oil and coal, constantly have small molecules to emit during thermolysis, pass into water vapour simultaneously, make the porosity of the gac obtaining higher.Wherein the temperature of activation is not limited to 900 ℃～950 ℃, but while activating under this temperature range, can, under lower energy consumption, obtain the gac that surface-area is larger, and then improves the adsorptive power of gac.In the process of activation, the flow of the water vapor that passes into is not limited to 25～50ml/min, soak time is also not limited to 2～5h, but have within the scope of this, can impel the activation of charcoal piece more complete, and then improve surface-area and the absorption property of prepared gac.
Below in conjunction with specific embodiment, further illustrate beneficial effect of the present invention.
In the following example, utilize coal directly-liquefied residue to prepare the step of gac as follows:
(1) take coal directly-liquefied residue as raw material, prepare modified coal road oil:
Coal directly-liquefied residue is mixed with extraction solvent, obtain mixture; This mixture is added in stirring tank, with first rate, stir, fill N
2to the first pressure, with the first heat-up rate, mixture is warming up to the first temperature, constant temperature extracting, is extracted mixture.
Extraction mixture is carried out to solid-liquid separation, be extracted liquid and solid part.
Extraction liquid is sent into vacuum still, and the recycle of recovered overhead extraction solvent, collects bitumen at the bottom of tower.After polymeric modification, obtain modified coal road oil.Solid part after solid-liquid separation is fed through to steam stripping unit, and liquid portion, after oily water separation, is extracted solvent cycle utilization, and the solid extract excess obtaining can coal blending burning or gasification or made water-permeable brick.
(2) take modified coal road oil as raw material, prepare gac
After gelatin liquefaction pitch after above-mentioned modification is pulverized, blend together mixed coal with coal dust, then by mixed coal fragmentation, in the second pressure lower lock block moulding, form briquetting coal.
Question response chambers temp rises to the second temperature, and briquetting coal is dropped in reaction chamber, at N
2pressure is under the 3rd pressure, and reaction chamber temperature is warming up to the 3rd temperature with the second speed, then with third speed, is warming up to the 4th temperature and completes charing.
After charing completes, transfer in active stove, anti-active furnace temperature is further warming up to the 5th temperature, and passes into water vapor, maintenance steam rates is first flow, and constant temperature completes activation, obtains gac after cooling.
Embodiment 1～9: prepare modified coal road oil according to above-mentioned steps (1) with corresponding parameter in table 1, the design parameter of the bitumen that embodiment 1～9 is prepared and modified coal road oil is as shown in table 2, then according to step (2), prepares gac with corresponding parameter in table 3.
Table 1
Table 2
By data in above-mentioned table 1, can be found out, by method provided by the present invention, to the utilization ratio of coal directly-liquefied residue, can be reached more than 32.5%.Wherein, what embodiment 1～6 all adopted is preferred value scope proposed by the invention, within the scope of this, utilization ratio of coal directly-liquefied residue is greater than to the utilization ratio to coal directly-liquefied residue in embodiment 7～9, simultaneously the yield of the prepared modified coal road oil of embodiment 1～6 is apparently higher than the yield of the modified coal road oil in embodiment 7～9.Wherein, the yield of the utilization ratio of embodiment 4 to coal directly-liquefied residue and modified coal road oil is the highest.
Table 3
Properties of Activated Carbon to preparation in above-described embodiment 1～9 detects.Examination criteria is as follows:
Specific area measuring: adopt U.S. health tower AutosorbIQ type physical adsorption appearance to carry out N under liquid nitrogen temperature
2the specific surface area of adsorption/desorption working sample and pore structure.Before mensuration, sample is at 300 ℃, 1.43 × 10
-6degassed processing 3h under MPa pressure.
Adsorptive power is measured: according to GB/T7702.7-2008, measure the adsorptive power of prepared gac to iodine.
Test result is as shown in table 4.
Table 4
| ? | Specific surface area (m 2/g） | Iodine (mg/g) |
| Embodiment 1 | 1460 | 1300 |
| Embodiment 2 | 1431 | 1289 |
| Embodiment 3 | 1455 | 1292 |
| Embodiment 4 | 1432 | 1230 |
| Embodiment 5 | 1214 | 1056 |
| Embodiment 6 | 1192 | 1017 |
| Embodiment 7 | 1020 | 922 |
| Embodiment 8 | 1054 | 979 |
| Embodiment 9 | 534 | 448 |
As can be seen from the above description, the gac of preparing according to method of the present invention of the above embodiments 1～9 all has larger specific surface area and good iodine absorption property, is suitable as gac and uses.Wherein, the Properties of Activated Carbon of embodiment 1～6 is better than embodiment 7～9, and the Properties of Activated Carbon that embodiment 1～4 obtains is better than embodiment 5 and 6.The present invention carries out polymeric modification take coal directly-liquefied residue as waste bitumen and to it, obtained the modified coal road oil that volatile matter is lower and β～resin content improves, the practicality of this gelatin liquefaction pitch is stronger, use it in active charcoal preparing process, obtain high performance gac, improved the high value added utilization of coal directly-liquefied residue medium pitch class material.Processing method provided by the present invention is simple, and cost is low, is applicable to suitability for industrialized production.
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 modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (13)
1. utilize coal directly-liquefied residue to prepare a method for gac, it is characterized in that, the method comprises the following steps:
S1, extract the bitumen in described coal directly-liquefied residue, after polyreaction, form modified coal road oil;
S2, mix with coal dust after described modified coal road oil is pulverized, mixing extrusion forming afterwards, obtains briquetting coal; And
S3, by described briquetting coal successively through charing, activation treatment, obtain described gac after cooling.
2. method according to claim 1, is characterized in that, the step of extracting bitumen in described step S1 comprises:
S11, described coal directly-liquefied residue is mixed with extraction solvent, extraction is extracted mixture;
S12, described extraction mixture is carried out to solid-liquid separation, be extracted liquid and solid part;
S13, described extraction liquid is carried out to underpressure distillation, obtain described bitumen after reclaiming described extraction solvent.
3. method according to claim 2, is characterized in that, described step S11 comprises:
Described coal directly-liquefied residue is mixed according to mass ratio 1:1～1:10 with described extraction solvent, obtain mixture; And at N
2or H
2under atmosphere, under 0.1～1.0MPa pressure condition, with the heat-up rate of 10 ℃/h～30 ℃/h, described mixture is warming up to 80 ℃～280 ℃, with the stir speed (S.S.) of 50～300r/min, constant temperature extracting 5～60min, obtains described extraction mixture.
4. method according to claim 2, is characterized in that, extraction solvent described in described step S11 is one or more in tetrahydrofuran (THF), furfural, N-Methyl pyrrolidone, quinoline, liquefied coal coil and distillate thereof and coal tar and distillate thereof.
5. method according to claim 2, is characterized in that, the solid-liquid separating method in described step S12 is selected from the one in pressurized heat filter method, Vacuum Heat suction filtration method, cyclonic separation method, gravity settling separation method and distillation separation method;
Preferably, when described solid-liquid separation adopts pressurized heat to filter, filtration temperature is 50 ℃～250 ℃, is preferably 150 ℃～200 ℃; Filter pressure is 0.2MPa～1.0MPa;
Preferably, when described solid-liquid separation adopts Vacuum Heat suction filtration method, filter pressure is 0.02KPa～101.3KPa;
Preferably, when described solid-liquid separation adopts cyclonic separation, the temperature of cyclonic separation is 50 ℃～250 ℃, and inlet pressure is 0.2MPa～0.6MPa.
6. method according to claim 2, it is characterized in that, the solid part obtaining in described step S12 is through stripping process, reclaim extraction solvent, obtain extract remainder, preferred described extraction solvent returns to described step S11 and recycles, preferred described extract remainder after burning as described step S1 in the heat supply source of extractive reaction in polyreaction and/or described step S11.
7. method according to claim 1, is characterized in that, in described step S1, the ash oontent of described bitumen is 0.2～5wt%, and volatile content is 30～60wt%, and β-resin content is 4.45～10.05wt%.
8. method according to claim 1, is characterized in that, in described step S1, the ash oontent forming in described modified coal road oil is 0.25～6wt%, volatile content is 25～50wt%, and β-resin content is 18～29.05wt%, and softening temperature is 95～150 ℃.
9. method according to claim 1, it is characterized in that, after described modified coal road oil being pulverized in described step S2, mix according to mass ratio 10:100～25:100 with coal dust, it is 20 μ m～200 μ m that preferred described gelatin liquefaction asphalt powder is broken to particle diameter, the particle diameter of described coal dust is 80 μ m～300 μ m, and preferred formed briquetting coal is of a size of 5～20mm.
10. method according to claim 1, is characterized in that, extrusion forming described in described step S2 is to carry out under the pressure of 15～25MPa.
11. methods according to claim 1, is characterized in that, described in described step S3, the step of charing processing comprises:
It is in the reaction chamber of 290 ℃～310 ℃, at N that described briquetting coal is put into temperature
2pressure is under 0.05～0.2MPa, and reaction chamber temperature is warming up to 600 ℃～620 ℃ with the speed of 3 ℃/min～5 ℃/min, then is warming up to 630～650 ℃ and completes charing with 2 ℃/min～3 ℃/speed of min.
12. methods according to claim 1, is characterized in that, described in described step S3, the step of activation treatment comprises:
Complete after charing step, reaction chamber temperature is further warming up to 900 ℃～950 ℃, and passes into water vapor, maintenance steam flow is 25～50ml/min, after constant temperature 2～5h, completes activation.
13. 1 kinds of gacs, is characterized in that, adopt the method described in any one in claim 1 to 12 to be prepared from.
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