CN103436280B - Coal directly-liquefied residue is utilized to prepare the method for coke - Google Patents
Coal directly-liquefied residue is utilized to prepare the method for coke Download PDFInfo
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Abstract
The invention discloses a kind of method utilizing coal directly-liquefied residue to prepare coke.The method comprises the following steps: S1, coal directly-liquefied residue carried out successively thermosol extraction, a solid-liquid separation and a polymeric modification, obtains gelatin liquefaction modifying asphalt; S2, gelatin liquefaction modifying asphalt to be mixed with coking clean fine coal, pulverize, make cake of press firm by ramming, obtain briquette; And S3, briquette to be delivered in pit kiln at isolated heated under air and be incubated, then through cooling and screening process, obtain coke.Be applied in tamping coking technique by the gelatin liquefaction modifying asphalt that coal directly-liquefied residue is obtained through hot melt extraction, solid-liquid separation and polymeric modification, obtain the coke that indices all reaches country-level metallurgical coke standard, and qualified product yield is up to more than 82%.
Description
Technical field
The present invention relates to coal liquefaction residue deep process technology field, in particular to a kind of method utilizing coal liquefaction residue to prepare coke.
Background technology
Along with the fast development of national economy, modernization and social development process are constantly accelerated, and the consumption of China to petroleum products constantly increases, and greatly exceed the rate of growth of the crude production same period, cause us petroleum import amount all to increase year by year, and exceeded from output.And the country that to be a rich coal oil-poor of China, make full use of abundant coal resources, the clean coal technology of the advanced person such as development of coal direct liquefaction reduces to depend on unduly external crude oil, one of important channel of alleviation China's oil shortage of resources, petroleum products supply and demand pressure, also be improve our coal resources utilization ratio simultaneously, alleviate coal burning pollution, promote the Important Action of the energy, economy, harmonious development.
Coal direct liquefaction is by coal by high temperature, high pressure, and under catalyst action, hydrogenation directly changes into the clean coal technology of a kind of advanced person of clean transport fuel (petroleum naphtha, diesel oil etc.) or industrial chemicals.The process of DCL/Direct coal liquefaction be generally by coal in advance powder to the granularity of below 0.15mm, then be made into coal slurry with solvent, and under certain temperature (about 450 DEG C) and high pressure hydrogenation, make the macromolecular cleavage in coal be hydrogenated into more micromolecular process.In liquefaction process except obtaining the liquiefied product of needs, go back some hydrocarbon molecules of by-product, CO
xdeng the liquefaction residue (also known as coal liquefaction residue) that gas, process water and solid-liquid separation process produce.Liquefied residue generally accounts for about 30% of coal input quantity.The economy and environment protection etc. of utilization on the efficiency of liquefaction process and whole liquefaction factory of coal liquefaction residue all have immeasurable impact.Efficient, the feasible method of comprehensive utilization of research coal directly-liquefied residue, extracts value product and has important practical significance to the economic benefit improving direct liquefaction process.
Coal directly-liquefied residue is primarily of inanimate matter and organic two portions composition, and organic matter comprises liquefaction heavy oil, bitumen and unconverted coal, and inorganic matter (being commonly referred to ash content) comprises mineral substance in coal and additional catalyzer.Liquefaction heavy oil in organic species and bitumen account for 50% of level of residue, and unconverted coal accounts for 30% of level of residue, and ash content accounts for about 20%.Therefore, the bitumen and mink cell focus that account for 50% in liquefied residue are separated and carry out comprehensive development and utilization, it is feasible for therefrom extracting or prepare more value product.
Current utilization mainly some traditional methods to coal liquefaction residue, as burning, coking liquefaction and gasification hydrogen-producing etc.Directly burn in boiler or kiln as fuel, will the economy of gelatin liquefaction be affected undoubtedly, and sulphur content higher in liquefied residue will bring the problem of environment aspect.Although coking liquefaction adds the liquid oil yield of coal liquefaction craft, liquefied residue can not obtain the most reasonably utilizing, and the utilization ways of semicoke and coke is very not clear and definite yet.The method of liquefied residue being carried out gasification hydrogen-producing is a kind of effective extensive approach utilized, but the high value added utilization potentiality of the bitumen in residue and mink cell focus are embodied, and the ash content in residue is up to more than 20%, this brings very large impact will to the deslagging of vapourizing furnace.
It take coal hydroliquefaction residue as the method that raw material plasma body prepares carbon nano-material that patent ZL200510047800.X discloses a kind of.Patent ZL200610012547.9 discloses a kind of using the method for coal liquefaction residue as road asphalt modifier.ZL200910087907.5 discloses a kind of method utilizing coal directly-liquefied residue to prepare asphalt base carbon fiber.Patent 200910086158.4 discloses a kind of method preparing mesophase pitch with coal liquefaction residue.But aforesaid method all with the bitumen in coal liquefaction residue for raw material, do not relate to the modification of pitch, and the extracting of residue medium pitch class material all with expensive pure chemistry reagent for solvent, cost is relatively high.
Patent JP59084977 discloses a kind of method extracting organic matter in liquefied residue, the organic matter (comprising heavy coal liquids and asphaltene) extracting obtained all carries out secondary hydrocracking, obtain light naphtha, thus improve the yield of total body fluid carburetion, but the existence also existed due to bitumen causes secondary hydrogenation catalyst to be very easy to the problem of coking deactivation.Patent JP130412 discloses a kind of method isolating heavy coal liquids and bitumen from coal directly-liquefied residue, the heavy coal liquids of separation is carried out secondary hydrocracking and obtains lightweight liquefaction oil by the method, and bitumen enters gelatin liquefaction unit carries out liquefaction reaction again.On the one hand, because the cut of heavy oil product is heavier, aromaticity content is higher, the reaction of secondary hydrocracking light Fuel is more violent, not only require carry out deep hydrogenation, cause hydrogen consumption to increase, and easily cause catalyzer because of coking inactivation, thus very high requirement is proposed to the performance of hydrocracking catalyst, require that hydrocracking catalyst has stronger activity, stronger anti-carbon deposition ability.On the other hand, when the bitumen separated liquefies again, it is liquefaction effect bad again, but also can cause the ill effect such as deposition, coking in liquefying reactor, and therefore the method can not realize the reasonable efficiency utilization of bitumen.
Patent CN101885976A discloses a kind of method 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 the method for destructive distillation again, bitumen and liquefaction heavy oil content are opened, obtain mesophase pitch, after liquefaction mink cell focus appropriateness hydrogenation, return gelatin liquefaction unit.Liquefaction mink cell focus is mainly greater than the fractions consisting of 350 DEG C, stronger with bitumen bonding force, when adopting the method for high temperature carbonization to be separated, can cause its coking, and the circulating solvent be difficult to as gelatin liquefaction uses.Patent CN101962560A, CN101962561A disclose a kind of two-stage that utilizes and extract the method extracting heavy coal liquids and bitumen from coal liquefaction residue, the oil product of two different fractions sections that the method produces with DCL/Direct coal liquefaction process self is for extraction solvent, respectively the extraction of two-stage order is carried out to liquefied residue, obtain heavy coal liquids and bitumen.
Although coke prepared by the binding agent that the heavy coal liquids obtained in above-mentioned disclosed method and bitumen all can be used as tamping coking, it has, and β-resin content is low, the shortcoming of bad adhesion, to raising coke strenth DeGrain.Twice two-stage solid-liquid separation process is added as have employed two-stage extraction in patent CN101962560A, CN101962561A, make process CIMS complicated, and raw material abstraction solvent source is single and price is higher, product yield is lower, cost is higher, β-the resin content of the bitumen obtained is low, cohesiveness is poor, when coke prepared by binding agent for tamping coking, the physical strength of coke is not made to be improved significantly, therefore, the exploitation suitability of this product is not strong, is not suitable as the binding agent of tamping coking.
Summary of the invention
The present invention aims to provide a kind of method utilizing coal directly-liquefied residue to prepare coke, the intermediate product gelatin liquefaction modifying asphalt obtained is applied in tamping coking by the method prepares coke, save resource, achieve the high value added utilization of coal liquefaction residue medium pitch class material.
To achieve these goals, according to an aspect of the present invention, provide a kind of method utilizing coal directly-liquefied residue to prepare coke, comprise the following steps: S1, coal directly-liquefied residue carried out successively thermosol extraction, a solid-liquid separation and a polymeric modification, obtain gelatin liquefaction modifying asphalt; S2, gelatin liquefaction modifying asphalt to be mixed with coking clean fine coal, pulverize, make cake of press firm by ramming, obtain briquette; And S3, briquette to be delivered in pit kiln at isolated heated under air and be incubated, then through cooling and screening process, obtain coke.
Further, the step of preparation gelatin liquefaction modifying asphalt comprises: S11, mix with extraction solvent by coal directly-liquefied residue, stirs, thermosol extraction, obtains thermosol and extract mixture; S12, thermosol is extracted mixture carry out solid-liquid separation, be extracted liquid and extract remainder; S13, extraction liquid is carried out solvent recuperation, be extracted thing; And S14, polymeric modification is carried out to extract, obtain gelatin liquefaction modifying asphalt.
Further, step S11 comprises: mixed according to mass ratio 1:1 ~ 10 with extraction solvent by coal directly-liquefied residue, obtain mixed solution; And N is passed in mixed solution
2, and with 10 DEG C ~ 30 DEG C/h, described mixed solution being warming up to 150 DEG C ~ 200 DEG C under 0.15 ~ 0.3MPa, constant temperature stirs, and thermosol extracts, and obtains thermosol extraction mixture; The time of thermosol extraction is 27 ~ 50min, and the speed that constant temperature stirs is 50 ~ 300r/min.
Further, the volatile content in gelatin liquefaction modifying asphalt is 35 ~ 46wt%, β-resin content is 18 ~ 29.05wt%, and softening temperature is 95 ~ 150 DEG C.
Further, in step S2, the mass ratio of gelatin liquefaction modifying asphalt and coking clean fine coal is 1 ~ 10:99 ~ 90; Heating temperature in step S3 is 950 DEG C ~ 1050 DEG C, and soaking time is 8 ~ 16 hours.
Further, extraction solvent is one or more in tetrahydrofuran (THF), furfural, N-Methyl pyrrolidone, quinoline, middle distillate from coal liquefaction and dead oil.
Further, solid-liquid separation is selected from the one in thermal air pressure filtration, Vacuum Heat suction filtration, cyclonic separation, gravity settling separation and fractionation by distillation.
Further, when solid-liquid separation adopts thermal air pressure filtration, wherein, the temperature of thermal air pressure filtration is 120 DEG C ~ 250 DEG C, is preferably 150 DEG C ~ 200 DEG C; The pressure of thermal air pressure filtration is 2.9KPa ~ 2.0MPa, is preferably 0.3MPa ~ 1.0MPa.
Further, when solid-liquid separation adopts cyclonic separation, wherein, the temperature of cyclonic separation is 50 DEG C ~ 250 DEG C, and inlet pressure is 0.2MPa ~ 0.6MPa.
Further, polymeric modification is selected from the one in vacuum flashing polymerization, normal pressure thermopolymerization and pressurized heat polymerization.
Apply technical scheme of the present invention, by coal directly-liquefied residue is extracted through hot melt, a solid-liquid separation and polymeric modification just can obtain β-resin content and softening temperature is higher, volatile matter is lower, cohesiveness is better and can meet the gelatin liquefaction modifying asphalt of tamping coking requirement, this gelatin liquefaction modifying asphalt is applied in tamping coking technique, obtain the coke that indices all reaches country-level metallurgical coke standard, and qualified product yield is up to more than 82%.The method not only technique is simple, and cost is low, and the exploitation practicality of the intermediate product gelatin liquefaction modifying asphalt obtained is comparatively strong, is suitable as the binding agent raw material of tamping coking, achieves the Appropriate application of coal liquefaction residue.
Accompanying drawing explanation
The Figure of description forming a application's part is used to provide a further understanding of the present invention, and schematic description and description of the present invention, for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 shows and prepares the schematic flow sheet of coke according to the coal directly-liquefied residue that utilizes of a kind of exemplary embodiments of the present invention.
Embodiment
It should be noted that, when not conflicting, the embodiment in the application and the feature in embodiment can combine mutually.Below with reference to the accompanying drawings and describe the present invention in detail in conjunction with the embodiments.
In order to solve the high value added utilization problem of coal liquefaction residue medium pitch class material, the invention provides a kind of method utilizing coal directly-liquefied residue to prepare coke, as shown in Figure 1, comprise the following steps: S1, coal directly-liquefied residue carried out successively thermosol extraction, a solid-liquid separation and a polymeric modification, obtain gelatin liquefaction modifying asphalt; S2, gelatin liquefaction modifying asphalt to be mixed with coking clean fine coal, pulverize, make cake of press firm by ramming, obtain briquette; Briquette to be delivered in pit kiln at isolated heated under air and be incubated, then through cooling and screening process, obtaining coke.
By coal directly-liquefied residue is extracted through hot melt, a solid-liquid separation and polymeric modification just can obtain β-resin content and softening temperature is higher, volatile matter is lower, cohesiveness is better and can meet the gelatin liquefaction modifying asphalt of tamping coking requirement, this gelatin liquefaction modifying asphalt is applied in tamping coking technique, obtain the coke that indices all reaches country-level metallurgical coke standard, and qualified product yield is up to more than 82%.The method not only technique is simple, and cost is low, and the exploitation practicality of the intermediate product gelatin liquefaction modifying asphalt obtained is comparatively strong, is suitable as the binding agent raw material of tamping coking, achieves the Appropriate application of coal liquefaction residue.
According to a kind of exemplary embodiment of the present invention, the step of preparation gelatin liquefaction modifying asphalt comprises: S11, mix with extraction solvent by coal directly-liquefied residue, stirs, thermosol extraction, obtains thermosol and extract mixture; S12, thermosol is extracted mixture carry out solid-liquid separation, be extracted liquid and extract remainder; S13, extraction liquid is carried out solvent recuperation, be extracted thing; And S14, polymeric modification is carried out to extract, obtain gelatin liquefaction modifying asphalt.
In order to be optimized the technique preparing hot melt extraction mixture, preferably, step S11 comprises: mixed according to mass ratio 1:1 ~ 10 with extraction solvent by coal directly-liquefied residue, obtain mixed solution; And S12, in mixed solution, pass into N
2, and with 10 DEG C ~ 30 DEG C/h, mixed solution being warming up to 150 DEG C ~ 200 DEG C under 0.15 ~ 0.3MPa, constant temperature stirs, and thermosol extracts, and obtains thermosol extraction mixture; Wherein the time of thermosol extraction is 27 ~ 50min, and the speed that constant temperature stirs is 50 ~ 300r/min.Coal directly-liquefied residue is mixed the effect and solvent recovering rate that can ensure to extract with extraction solvent by the present invention according to mass ratio 1:1 ~ 10, if the mass ratio of coal directly-liquefied residue and extraction solvent is higher than 1:1, then may occur that extraction solvent can not, completely by the situation that coal directly-liquefied residue dissolves, cause extraction thorough not; If the mass ratio of coal directly-liquefied residue and extraction solvent is lower than 1:10, then extraction solvent can be caused to waste, increase the cost recovery of follow-up extraction solvent.N is passed in mixed solution
2first can get rid of reactor as the air in stirring tank, reaction is carried out in the absence of oxygen.
A preferred embodiment of the invention, the mass ratio of gelatin liquefaction modifying asphalt and coking clean fine coal is 1 ~ 10:99 ~ 90 in step s 2; Heating temperature in step S3 is 950 DEG C ~ 1050 DEG C, and soaking time is 8 ~ 16 hours.
Preferably, the extraction solvent adopted in above-mentioned preparation technology is one or more in tetrahydrofuran (THF), furfural, N-Methyl pyrrolidone, quinoline, middle distillate from coal liquefaction and dead oil.The present invention preferably but be not limited to above-mentioned extraction solvent, adopt above-mentioned extraction solvent have percentage extraction high, be easy to the advantages such as recovery.
The present invention only adopts the extraction of one-level hot melt, one-level solid-liquid separation and polymeric modification just can obtain meeting the gelatin liquefaction modifying asphalt of tamping coking.Wherein the mode of solid-liquid separation comprises thermal air pressure filtration, Vacuum Heat suction filtration, cyclonic separation, gravity settling separation and fractionation by distillation, the present invention preferably but be not limited to above-mentioned listed solid-liquid separation method, as long as solid-liquid fully can be separated and reach required effect.When adopting the mode of thermal air pressure filtration to carry out solid-liquid separation, the temperature of thermal air pressure filtration is 120 DEG C ~ 250 DEG C, is preferably 150 DEG C ~ 200 DEG C; The pressure of thermal air pressure filtration is 2.9KPa ~ 2.0MPa, is preferably 0.3MPa ~ 1.0MPa.Adopt in said temperature and pressure range and carry out thermal air pressure filtration, can largely solid-liquid be separated.Except thermal air pressure filtration, when solid-liquid separation adopts cyclonic separation, the temperature of cyclonic separation is 50 DEG C ~ 250 DEG C, and inlet pressure is 0.2MPa ~ 0.6MPa.
Solid content in the extract remainder that the present invention obtains after solid-liquid separation is 50 ~ 90wt%, and the solvent that is in extract remainder is 10 ~ 50wt%.Because the solvent in solid phase extraction thing is higher, in order to carry out abundant recycle to reduce costs to extraction solvent, according to a kind of exemplary embodiment of the present invention, also comprise and stripping is carried out to extract remainder and reclaims the step of extraction solvent, wherein, the stripping extract remainder obtained through stripping step carries out gasifying or burn processing, or as the raw material of water-permeable brick; And carry out oily water separation through the liquid portion that stripping step obtains, the extraction solvent obtained through oily water separation step is returned the recycle of thermosol extraction step.Solid content >90wt% in solid phase extraction thing after stripping, extraction solvent content is less than 5wt%.
In order to economize on resources, also comprise extraction solvent solvent recovery step obtained and returning the process that thermosol extraction step carries out recycle, wherein adopt air distillation, the mode of underpressure distillation and evaporation carries out solvent recuperation to extraction liquid.
The extraction liquid obtained after solid-liquid separation is through solvent recovery step, obtaining ash oontent is 0.5 ~ 5wt%, volatilization is divided into 30 ~ 60wt% and β-resin content is the extract bitumen of 7.85 ~ 10.05wt%, by the bitumen of mentioned component after polymeric modification, obtaining volatile content is 35 ~ 46wt%, β-resin content is 18 ~ 29.05wt%, softening temperature is the gelatin liquefaction modifying asphalt of 95 ~ 150 DEG C, its β-resin content visible and softening temperature high, volatile content is lower, during binding agent raw material as tamping coking, cohesiveness is better, the coke that indices all reaches country-level metallurgical coke standard can be prepared as raw material, and qualified product yield is up to more than 82%, it is a kind of desirable feedstock at coal blending tamping coking.Wherein polymeric modification is selected from the one in vacuum flashing polymerization, normal pressure thermopolymerization and pressurized heat polymerization.
Beneficial effect of the present invention is further illustrated below in conjunction with specific embodiment:
Embodiment 1
1) 300kg coal directly-liquefied residue and 750kg naphtalene oil (boiling range is 160 ~ 260 DEG C) are added in stirring tank, stir with the speed of 60r/min, obtain mixed solution, in stirring tank, fill N
2to the pressure in stirring tank to 0.2MPa, after mixed solution being warming up to 150 DEG C with the speed of 10 DEG C per hour, stir with 300r/min constant temperature, thermosol extraction 30min, obtain thermosol extraction mixture.
2) thermal air pressure filtration mode is adopted to carry out solid-liquid separation to thermosol extraction mixture.Wherein filtration temperature is 250 DEG C, and filter pressure is 2.0MPa, and the filter core aperture size of strainer is 50 μm.After single filter, collect the extraction liquid of 867kg and the extract remainder of 180kg.
3) extraction liquid is sent into vacuum still and carry out solvent recuperation, the extraction solvent recycle of recovered overhead 120 ~ 210 DEG C, the extract that ash content is 0.35wt% is collected at the bottom of tower, its quinoline insolubles is 0.72wt%, β-resin content 9.33wt%, volatilization is divided into 56%, and softening temperature is 85 DEG C, and sulphur content is 0.03%.
4) above-mentioned extract pitch is passed through normal pressure thermopolymerization modification, obtain gelatin liquefaction modifying asphalt, wherein β-resin content 18wt%, volatilization is divided into 46%, and ash oontent is 0.2wt%, and softening temperature is 95 DEG C.
5) solid extract excess is fed through steam stripping unit, liquid portion, after oily water separation, obtains the extraction solvent of 31.7kg, reusable edible, and obtaining 146.6kg solid can coal blending burning or gasification.
6) gelatin liquefaction modifying asphalt and 1/3 coking coal, Qinghai coal are blended together mixed coal according to the ratio of mass ratio 1:55:44.Mixed coal is broken, and making into depth-width ratio firm by ramming is after the briquette of 9.6:1, delivers in the pit kiln of 5m, be heated to 1050 DEG C of insulations 8 hours when isolated air, carry out coking, after coke maturation, cooling, sieve, >=40mm coke output account for more than 82% of coke ultimate production.Coke indices all reaches country-level metallurgical coke standard.
Embodiment 2
1) 300kg coal directly-liquefied residue and 3000kg middle distillate from coal liquefaction (boiling range is 150 ~ 310 DEG C) are added in stirring tank, stir with the speed of 75r/min, in stirring tank, fill N
2to the pressure in stirring tank to 0.3MPa, with after the ramp to 170 of 30 DEG C per hour DEG C, constant temperature stirs, hot melt extraction 45min, and the speed that constant temperature stirs is 50r/min, obtains thermosol extraction mixture.
2) thermal air pressure filtration mode is adopted to carry out solid-liquid separation to thermosol extraction mixture.Wherein filtration temperature is 120 DEG C, and filter pressure is 0.4MPa, and the filter core aperture size of strainer is 40 μm.After filtering, extraction liquid and extract remainder is collected.
3) extraction liquid is sent into vacuum still and carry out solvent recuperation, the extraction solvent recycle of recovered overhead 120 ~ 210 DEG C, the extract that ash content is 1.6wt% is collected at the bottom of tower, its quinoline insolubles is 1.5wt%, ash oontent is 0.85wt%, and volatilization is divided into 55%, β-resin content 8.21wt%, softening temperature is 105 DEG C, and sulphur content is 0.023%.
4) above-mentioned extract pitch is passed through normal pressure thermopolymerization modification, obtain gelatin liquefaction modifying asphalt, wherein β-resin content 29.05wt%, volatilization is divided into 39%, and softening temperature is 135 DEG C.
5) solid extract excess is fed through steam stripping unit, liquid portion, after oily water separation, is extracted solvent, reusable edible, and obtaining solid can coal blending burning or gasification.
6) gelatin liquefaction modifying asphalt and 1/3 coking coal, Qinghai coal, peaceful coal 3 culm are blended together mixed coal according to the ratio of mass ratio 3:54:25:18.Mixed coal is broken, making into depth-width ratio firm by ramming is after the briquette of 10.74:1 or 11.93:1, deliver in the pit kiln of 5.5m, 950 DEG C of insulations 16 hours are heated to when isolated air, carry out coking, coke is ripe, after cooling, sieve, >=40mm coke output account for more than 86% of coke ultimate production.Coke indices all reaches country-level metallurgical coke standard.Embodiment 3
1) 200kg coal directly-liquefied residue and 800kg carbolineum (boiling range is 220 ~ 405 DEG C) are added in stirring tank, stir with the speed of 85r/min, in stirring tank, fill N
2to the pressure in stirring tank to 0.15MPa, with after the ramp to 200 of 12.5 DEG C per hour DEG C, constant temperature stirs, hot melt extraction 27min, and the speed that constant temperature stirs is 175r/min, obtains thermosol extraction mixture.
2) thermal air pressure filtration is adopted to carry out solid-liquid separation to thermosol extraction mixture.Wherein filtration temperature is 300 DEG C, and filter pressure is 2.9KPa, and filter core aperture size is 30m.After filtering, the extraction liquid of 145kg solid extract excess and 849kg is collected.
3) extraction liquid is sent into vacuum still and carry out solvent recuperation, extraction solvent recycle is reclaimed in tower top and tower side, and collecting ash content at the bottom of tower is respectively 1.2wt% extract, its quinoline insolubles is 3.25wt%, volatilization is divided into 50wt%, and β-resin content is 8.01%, and sulphur content is 0.02%.
4) above-mentioned extract pitch is passed through normal pressure thermopolymerization modification, obtain gelatin liquefaction modifying asphalt, wherein β-resin content 26.70wt%, volatilization is divided into 37%, and softening temperature is 145 DEG C.
5) solid extract excess is fed through steam stripping unit, liquid portion, after oily water separation, obtains the extraction solvent of 19.7kg, reusable edible, and obtaining 124.3kg solid can coal blending burning or gasification.
6) gelatin liquefaction modifying asphalt is blended together coal blending with 1/3 coking coal, Qinghai coal, peaceful coal 3 culm according to mass ratio 4:51:28:17, again that mixed coal is broken, making into depth-width ratio firm by ramming is after the briquette of 12.76:1, deliver in the pit kiln of 6.25m, be heated to 1000 DEG C of insulations when isolated air and carry out coking in 12 hours, coke is ripe, after cooling, sieve, >=40mm coke output account for more than 89% of coke ultimate production.Coke indices all reaches country-level metallurgical coke standard.
Embodiment 4
1) 350kg coal directly-liquefied residue and 1000kg dead oil (boiling range is 200 ~ 260 DEG C) are added in stirring tank, stir with the speed of 55r/min, in stirring tank, fill N
2to the pressure in stirring tank to 0.15MPa, with after the ramp to 180 of 20 DEG C per hour DEG C, stir with 175r/min constant temperature, hot melt extraction 30min, obtain thermosol extraction mixture.
2) adopt cyclonic separation thermosol extraction mixture, separation temperature is 250 DEG C, and pressure is 0.6MPa.After cyclonic separation, collect 303kg underflow dope, 1039kg top stream clear liquid, filtrate is sent into vacuum still, the recycle of recovered overhead extraction solvent, collecting ash content at the bottom of tower is respectively 4.9wt% extract, its quinoline insolubles is 2.57%, volatilization is divided into 52%, β-resin content to be 9.01%, and sulphur content is 0.04%.
4) above-mentioned extract pitch is passed through normal pressure thermopolymerization modification, obtain gelatin liquefaction modifying asphalt, wherein β-resin content 29.05wt%, volatilization is divided into 38%, and softening temperature is 150 DEG C.
5) solid extract excess is fed through steam stripping unit, liquid portion, after oily water separation, obtains the extraction solvent of 132kg, reusable edible, and obtaining 173.6kg solid can coal blending burning or gasification.
6) gelatin liquefaction modifying asphalt and 1/3 coking coal, Qinghai coal, peaceful coal 3 culm are blended together coal blending according to mass ratio 10:44:30:16, again that mixed coal is broken, making into depth-width ratio firm by ramming is after the briquette of 12.76:1, deliver in the pit kiln of 6.25m, be heated to 1000 DEG C of insulations when isolated air and carry out coking in 10 hours, coke is ripe, after cooling, sieve, >=40mm coke output account for more than 83% of coke ultimate production.Coke indices all reaches country-level metallurgical coke standard.
Visible, by coal directly-liquefied residue is extracted through hot melt, a solid-liquid separation and polymeric modification just can obtain β-resin content and softening temperature is higher, volatile matter is lower, cohesiveness is better and can meet the gelatin liquefaction modifying asphalt of tamping coking requirement, this gelatin liquefaction modifying asphalt is applied in tamping coking technique, obtain the coke that indices all reaches country-level metallurgical coke standard, and qualified product yield is up to more than 82%.The method not only technique is simple, and cost is low, and the exploitation practicality of the intermediate product gelatin liquefaction modifying asphalt obtained is comparatively strong, is suitable as the binding agent raw material of tamping coking, achieves the Appropriate application of coal liquefaction residue.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. utilize coal directly-liquefied residue to prepare a method for coke, it is characterized in that, comprise the following steps:
S1, described coal directly-liquefied residue carried out successively thermosol extraction, a solid-liquid separation and a polymeric modification, obtain gelatin liquefaction modifying asphalt;
S2, described gelatin liquefaction modifying asphalt to be mixed with coking clean fine coal, pulverize, make cake of press firm by ramming, obtain briquette; And
S3, described briquette to be delivered in pit kiln at isolated heated under air and be incubated, then through cooling and screening process, obtaining coke;
Wherein, the step preparing described gelatin liquefaction modifying asphalt comprises:
S11, to be mixed with extraction solvent by described coal directly-liquefied residue, stir, thermosol extracts, and obtains thermosol extraction mixture, described extraction solvent to be boiling range the be carbolineum of 220 ~ 405 DEG C;
S12, described thermosol extraction mixture is carried out solid-liquid separation, be extracted liquid and extract remainder;
S13, described extraction liquid is carried out solvent recuperation, be extracted thing; And
S14, polymeric modification is carried out to described extract, obtain gelatin liquefaction modifying asphalt.
2. method according to claim 1, is characterized in that, described step S11 comprises:
Described coal directly-liquefied residue is mixed according to mass ratio 1:1 ~ 10 with described extraction solvent, obtains mixed solution; And
N is passed in described mixed solution
2, and with 10 DEG C ~ 30 DEG C/h, described mixed solution being warming up to 150 DEG C ~ 200 DEG C under 0.15 ~ 0.3MPa, constant temperature stirs, and thermosol extracts, and obtains described thermosol extraction mixture;
The time of described thermosol extraction is 27 ~ 50min, and the speed that described constant temperature stirs is 50 ~ 300r/min.
3. method according to claim 1, is characterized in that,
Volatile content in described gelatin liquefaction modifying asphalt is 35 ~ 46wt%, β-resin content is 18 ~ 29.05wt%, and softening temperature is 95 ~ 150 DEG C.
4. method according to claim 1, is characterized in that, the mass ratio of gelatin liquefaction modifying asphalt described in described step S2 and described coking clean fine coal is 1 ~ 10:99 ~ 90; Heating temperature in described step S3 is 950 DEG C ~ 1050 DEG C, and soaking time is 8 ~ 16 hours.
5. method according to claim 1, is characterized in that, described solid-liquid separation is selected from the one in thermal air pressure filtration, Vacuum Heat suction filtration, cyclonic separation, gravity settling separation and fractionation by distillation.
6. method according to claim 5, is characterized in that, when described solid-liquid separation adopts thermal air pressure filtration, wherein,
The temperature of described thermal air pressure filtration is 120 DEG C ~ 250 DEG C;
The pressure of described thermal air pressure filtration is 2.9KPa ~ 2.0MPa.
7. method according to claim 6, is characterized in that, when described solid-liquid separation adopts thermal air pressure filtration, wherein, the temperature of described thermal air pressure filtration is 150 DEG C ~ 200 DEG C.
8. method according to claim 6, is characterized in that, when described solid-liquid separation adopts thermal air pressure filtration, wherein, the pressure of described thermal air pressure filtration is 0.3MPa ~ 1.0MPa.
9. the method according to any one of claim 5 to 8, is characterized in that, when described solid-liquid separation adopts cyclonic separation, wherein,
The temperature of described cyclonic separation is 50 DEG C ~ 250 DEG C, and inlet pressure is 0.2MPa ~ 0.6MPa.
10. method according to claim 1, is characterized in that, described polymeric modification is selected from the one in vacuum flashing polymerization, normal pressure thermopolymerization and pressurized heat polymerization.
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| CN104694147B (en) * | 2015-03-19 | 2017-03-15 | 中国矿业大学(北京) | The method that supercritical solvent extraction coal directly-liquefied residue prepares mesophase pitch |
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