CN103436280A - Method for preparing coke by using direct coal-liquefied residue - Google Patents
Method for preparing coke by using direct coal-liquefied residue Download PDFInfo
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Abstract
The invention discloses a method for preparing coke by using direct coal-liquefied residue. The method comprises the following steps: S1, orderly carrying out primary hot melt-extraction, primary solid-liquid separation and polymeric modification on the direct coal-liquefied residue, so as to obtain coal-liquefied modified asphalt; S2, mixing the coal-liquefied modified asphalt with cleaned coal for coking, crushing, tamping and pressing into a cake, so as to obtain a coal briquette; and S3, conveying the coal cake to a coke burner to heat and insulate heat in isolated air, and then cooling and screening to obtain the coke. The coal-liquefied modified asphalt which is obtained from the direct coal-liquefied residue in manners of hot melt-extraction, solid-liquid separation and polymeric modification is applied to a tamping coking process, so that the coke of which all indexes achieve the first national metallurgical coke standard is obtained; the yield of qualified products can be up to over 82%.
Description
Technical field
The present invention relates to coal liquefaction residue deep process technology field, in particular to a kind of method of utilizing coal liquefaction residue to prepare coke.
Background technology
Fast development along with 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 the petroleum import amount all to increase year by year, and surpassed from output.And China is an oil-poor country of rich coal, take full advantage of abundant coal resources, the advanced persons' such as development of coal direct liquefaction clean coal technology is to reduce external crude oil is depended on unduly, alleviate one of important channel of China's oil shortage of resources, petroleum products supply and demand pressure, also to 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 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.Except the liquiefied product that obtains needing, go back some hydrocarbon molecules of by-product, CO in liquefaction process
xthe liquefaction residue (claiming again coal liquefaction residue) produced Deng gas, process water and solid-liquid separation process.Liquefied residue generally accounts for 30% left and right of coal input quantity.The utilization of coal liquefaction residue all has immeasurable impact to the economy of the efficiency of liquefaction process and whole liquefaction factory and environment protection etc.Efficient, the feasible method of comprehensive utilization of research coal directly-liquefied residue, extract value product the economic benefit that improves the direct liquefaction process had important practical significance.
Coal directly-liquefied residue mainly is 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 the 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.
To the utilization of coal liquefaction residue, be mainly some traditional methods now, as burning, coking liquefaction and gasification hydrogen-producing etc.Act as a fuel and directly burn in boiler or kiln, will affect undoubtedly the economy of gelatin liquefaction, and in liquefied residue, higher sulphur content will be brought the problem of environment aspect.Although the 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 utilized, 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 ofly take coal hydroliquefaction residue and prepares the method for carbon nano-material as the 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 for preparing mesophase pitch with coal liquefaction residue.But the bitumen that aforesaid method all be take in coal liquefaction residue is raw material, does not relate to the modification of pitch, and the extracting of residue medium pitch class material all to take expensive pure chemistry reagent be solvent, cost is relatively high.
Patent JP59084977 discloses a kind of method organic in liquefied residue of extracting, the organic matter that extracting is obtained (comprising heavy liquefaction oil and asphaltene) all carries out secondary hydrocracking, obtain light naphtha, thereby improve the yield of total body fluid carburetion, but the existence existed due to bitumen causes the secondary hydrogenation catalyst to be very easy to the problem of 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 the lightweight liquefaction oil, and bitumen enters the 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, secondary hydrocracking light Fuel reaction processed is more violent, not only require to carry out deep hydrogenation, cause the hydrogen consumption to increase, and easily cause catalyzer because of the coking inactivation, thereby the performance to hydrocracking catalyst has proposed very high requirement, require 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 the ill effects such as deposition, coking in liquefying reactor, so the method can not realize 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 the 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 the gelatin liquefaction unit.The liquefaction mink cell focus is mainly to be greater than the fractions consisting of 350 ℃, more intense with the 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 two-stage of utilizing and have extracted the method for extracting heavy liquefaction oil and bitumen from coal liquefaction residue, it is extraction solvent that the method be take the oil product of two different fractions sections that DCL/Direct coal liquefaction process self produces, respectively liquefied residue is carried out to two-stage and sequentially extract, obtain heavy liquefaction oil and bitumen.
Although the heavy liquefaction oil obtained in above-mentioned disclosed method and bitumen all can prepare coke as the binding agent of tamping coking, it has, and β-resin content is low, the shortcoming of bad adhesion, to improving the coke strenth DeGrain.As adopted the two-stage extraction to add the two-stage solid-liquid separation process twice in patent CN101962560A, CN101962561A, make the flow process more 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, while for the binding agent of tamping coking, preparing coke, do not make the physical strength of coke 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 of utilizing coal directly-liquefied residue to prepare coke, the method is applied to the intermediate product gelatin liquefaction modifying asphalt obtained in tamping coking and prepares coke, save resource, realized 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, a kind of method of utilizing coal directly-liquefied residue to prepare coke is provided, comprise the following steps: S1, coal directly-liquefied residue is carried out to the extraction of thermosol, solid-liquid separation and polymeric modification successively, obtain the gelatin liquefaction modifying asphalt; S2, the gelatin liquefaction modifying asphalt is mixed with clean fine coal with coking, pulverize, make cake of press firm by ramming, obtain briquette; And S3, briquette is delivered in pit kiln under isolated air and heat and be incubated, then, through cooling and sieve processing, obtain coke.
Further, the step of preparation gelatin liquefaction modifying asphalt comprises: S11, coal directly-liquefied residue is mixed with extraction solvent, stir, thermosol extracts, and obtains thermosol and extracts mixture; S12, thermosol is extracted to mixture carry out solid-liquid separation, be extracted liquid and extract remainder; S13, extraction liquid is carried out to solvent recuperation, be extracted thing; And S14, extract is carried out to polymeric modification, obtain the gelatin liquefaction modifying asphalt.
Further, step S11 comprises: coal directly-liquefied residue is mixed according to mass ratio 1:1～10 with extraction solvent, obtain mixed solution; And pass into N in mixed solution
2, and with 10 ℃～30 ℃/h, described mixed solution is warming up to 150 ℃～200 ℃ under 0.15～0.3MPa, and constant temperature stirs, and the thermosol extraction 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 the gelatin liquefaction modifying asphalt is 35～46wt%, and β-resin content is 18～29.05wt%, and softening temperature is 95～150 ℃.
Further, in step S2, gelatin liquefaction modifying asphalt and coking are 1～10:99～90 with the mass ratio of clean fine coal; Heating temperature in step S3 is 950 ℃～1050 ℃, 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 a kind of 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 ℃～250 ℃, is preferably 150 ℃～200 ℃; 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 ℃～250 ℃, and inlet pressure is 0.2MPa～0.6MPa.
Further, polymeric modification is selected from a kind of in vacuum flashing polymerization, normal pressure thermopolymerization and pressurized heat polymerization.
Apply technical scheme of the present invention, by by coal directly-liquefied residue through hot melt extract, solid-liquid separation and polymeric modification just can obtain that β-resin content and softening temperature are 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, obtained the coke that indices all reaches country-level metallurgical coke standard, and the 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 stronger, is suitable as the binding agent raw material of tamping coking, has realized the reasonable utilization of coal liquefaction residue.
The 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 the present invention does not form inappropriate limitation of the present invention for explaining.In the accompanying drawings:
The coal directly-liquefied residue that utilizes that Fig. 1 shows a kind of exemplary embodiments according to the present invention prepares the schematic flow sheet of coke.
Embodiment
It should be noted that, in the situation that do not conflict, embodiment and the feature in 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.
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 of utilizing coal directly-liquefied residue to prepare coke, as shown in Figure 1, comprise the following steps: S1, coal directly-liquefied residue is carried out to the extraction of thermosol, solid-liquid separation and polymeric modification successively, obtain the gelatin liquefaction modifying asphalt; S2, the gelatin liquefaction modifying asphalt is mixed with clean fine coal with coking, pulverize, make cake of press firm by ramming, obtain briquette; Briquette is delivered in pit kiln and heated and be incubated under isolated air, then process through cooling and screening, obtain coke.
By by coal directly-liquefied residue through hot melt extract, solid-liquid separation and polymeric modification just can obtain that β-resin content and softening temperature are 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, obtained the coke that indices all reaches country-level metallurgical coke standard, and the 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 stronger, is suitable as the binding agent raw material of tamping coking, has realized the reasonable utilization 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, coal directly-liquefied residue is mixed with extraction solvent, stir, thermosol extracts, and obtains thermosol and extracts mixture; S12, thermosol is extracted to mixture carry out solid-liquid separation, be extracted liquid and extract remainder; S13, extraction liquid is carried out to solvent recuperation, be extracted thing; And S14, extract is carried out to polymeric modification, obtain the gelatin liquefaction modifying asphalt.
For the technique to preparing hot melt extraction mixture is optimized, preferably, step S11 comprises: coal directly-liquefied residue is mixed according to mass ratio 1:1～10 with extraction solvent, obtain mixed solution; And S12, in mixed solution, pass into N
2, and with 10 ℃～30 ℃/h, mixed solution is warming up to 150 ℃～200 ℃ under 0.15～0.3MPa, and constant temperature stirs, and the thermosol extraction obtains thermosol extraction mixture; Wherein the time of thermosol extraction is 27～50min, and the speed that constant temperature stirs is 50～300r/min.The present invention mixes with extraction solvent coal directly-liquefied residue effect and the solvent recovering rate that can guarantee extraction according to mass ratio 1:1～10, if the mass ratio of coal directly-liquefied residue and extraction solvent is higher than 1:1, the situation that extraction solvent can not dissolve coal directly-liquefied residue fully may occur, cause extraction thorough not; If the mass ratio of coal directly-liquefied residue and extraction solvent lower than 1:10, can cause the extraction solvent waste, increase the cost recovery of follow-up extraction solvent.Pass into N in mixed solution
2can first get rid of reactor as the air in stirring tank, make reaction carry out under the condition of anaerobic.
A preferred embodiment of the invention, in step S2, gelatin liquefaction modifying asphalt and coking are 1～10:99～90 with the mass ratio of clean fine coal; Heating temperature in step S3 is 950 ℃～1050 ℃, 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 advantage such as recovery.
The present invention only adopts one-level hot melt extraction, one-level solid-liquid separation and polymeric modification just can access to meet the gelatin liquefaction modifying asphalt that tamping coking is used.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 reaches required effect.When the mode that adopts thermal air pressure filtration is carried out solid-liquid separation, the temperature of thermal air pressure filtration is 120 ℃～250 ℃, is preferably 150 ℃～200 ℃; 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 ℃～250 ℃, 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%, that is to say that the solvent in extract remainder is 10～50wt%.Because the solvent in the solid phase extraction thing is higher, 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, wherein, the stripping extract remainder obtained through stripping step is gasified or burn processing, or as the raw material of water-permeable brick; And the liquid portion obtained through stripping step carries out oily water separation, the extraction solvent that will obtain through the oily water separation step returns to the recycle of thermosol extraction step.Solid content in solid phase extraction thing after stripping > 90wt%, extraction solvent content is less than 5wt%.
In order to economize on resources, also comprise that the extraction solvent that solvent recovery step is obtained returns to the process that the thermosol extraction step is carried out recycle, wherein adopt the mode of air distillation, underpressure distillation and evaporation to carry out solvent recuperation to extraction liquid.
The extraction liquid obtained after solid-liquid separation is through solvent recovery step, having obtained ash oontent is 0.5～5wt%, volatilization is divided into the extract bitumen that 30～60wt% and β-resin content are 7.85～10.05wt%, by the bitumen of mentioned component after polymeric modification, having obtained volatile content is 35～46wt%, β-resin content is 18～29.05wt%, the gelatin liquefaction modifying asphalt that softening temperature is 95～150 ℃, visible its β-resin content and softening temperature are high, volatile content is lower, during as the binding agent raw material of tamping coking, cohesiveness is better, can be used as raw material and prepare the coke that indices all reaches country-level metallurgical coke standard, and the qualified product yield is up to more than 82%, it is a kind of desirable feedstock at the coal blending tamping coking.Wherein polymeric modification is selected from a kind of in vacuum flashing polymerization, normal pressure thermopolymerization and pressurized heat polymerization.
Further illustrate beneficial effect of the present invention below in conjunction with specific embodiment:
Embodiment 1
1) 300kg coal directly-liquefied residue and 750kg naphtalene oil (boiling range is 160～260 ℃) are added in stirring tank, the speed stirring with 60r/min, obtain mixed solution, in stirring tank, fills N
2to the pressure in stirring tank to 0.2MPa, after per hour the speed of 10 ℃ is warming up to 150 ℃ by mixed solution, with 300r/min constant temperature, stir, thermosol extraction 30min, obtain thermosol extraction mixture.
2) adopt the thermal air pressure filtration mode to carry out solid-liquid separation to thermosol extraction mixture.Wherein filtration temperature is 250 ℃, and filter pressure is 2.0MPa, and the filter core aperture size of strainer is 50 μ m.After single filter, collect the extraction liquid of 867kg and the extract remainder of 180kg.
3) extraction liquid is sent into to vacuum still and carried out solvent recuperation, the extraction solvent recycle that recovered overhead is 120～210 ℃, collect the extract that ash content is 0.35wt% 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 ℃, and sulphur content is 0.03%.
4) above-mentioned extract pitch is passed through to normal pressure thermopolymerization modification, obtain the gelatin liquefaction modifying asphalt, wherein β-resin content 18wt%, volatilize and be divided into 46%, and ash oontent is 0.2wt%, and softening temperature is 95 ℃.
5) the solid extract excess is fed through to steam stripping unit, liquid portion, after oily water separation, obtains the extraction solvent of 31.7kg, reusable edible, but obtain 146.6kg solid coal blending burning or gasification.
6) gelatin liquefaction modifying asphalt and 1/3 coking coal, Qinghai coal are blended together to mixed coal according to the ratio of mass ratio 1:55:44.By the mixed coal fragmentation, after the briquette that to make into depth-width ratio firm by ramming be 9.6:1, deliver in the pit kiln of 5m, in the situation that isolated air is heated to 1050 ℃ of insulations 8 hours, carry out coking, after coke is ripe, cooling, sieved, >=40mm coke output account for more than 82% of coke ultimate production.The 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 ℃) are added in stirring tank, with the speed stirring of 75r/min, in stirring tank, fill N
2to the pressure in stirring tank to 0.3MPa, after per hour the speed of 30 ℃ is warming up to 170 ℃, constant temperature stirs, hot melt extraction 45min, and the speed that constant temperature stirs is 50r/min, obtains thermosol extraction mixture.
2) adopt the thermal air pressure filtration mode to carry out solid-liquid separation to thermosol extraction mixture.Wherein filtration temperature is 120 ℃, and filter pressure is 0.4MPa, and the filter core aperture size of strainer is 40 μ m.After filtering, collect extraction liquid and extract remainder.
3) extraction liquid is sent into to vacuum still and carried out solvent recuperation, the extraction solvent recycle that recovered overhead is 120～210 ℃, collect the extract that ash content is 1.6wt% 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 ℃, and sulphur content is 0.023%.
4) above-mentioned extract pitch is passed through to normal pressure thermopolymerization modification, obtain the gelatin liquefaction modifying asphalt, wherein β-resin content 29.05wt%, volatilize and be divided into 39%, and softening temperature is 135 ℃.
5) the solid extract excess is fed through to steam stripping unit, liquid portion, after oily water separation, is extracted solvent, reusable edible, but obtain solid coal blending burning or gasification.
6) gelatin liquefaction modifying asphalt and 1/3 coking coal, Qinghai coal, peaceful coal 3 culms are blended together to mixed coal according to the ratio of mass ratio 3:54:25:18.By the mixed coal fragmentation, after the briquette that to make into depth-width ratio firm by ramming be 10.74:1 or 11.93:1, deliver in the pit kiln of 5.5m, in the situation that isolated air is heated to 950 ℃ of insulations 16 hours, carry out coking, after coke is ripe, cooling, sieved, >=40mm coke output account for more than 86% of coke ultimate production.The 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 ℃) are added in stirring tank, with the speed stirring of 85r/min, in stirring tank, fill N
2to the pressure in stirring tank to 0.15MPa, after per hour the speed of 12.5 ℃ is warming up to 200 ℃, constant temperature stirs, hot melt extraction 27min, and the speed that constant temperature stirs is 175r/min, obtains thermosol extraction mixture.
2) adopt thermal air pressure filtration to carry out solid-liquid separation to thermosol extraction mixture.Wherein filtration temperature is 300 ℃, and filter pressure is 2.9KPa, and the filter core aperture size is 30m.After filtering, collect the extraction liquid of 145kg solid extract excess and 849kg.
3) extraction liquid is sent into to vacuum still and carried out solvent recuperation, tower top and tower side reclaim the extraction solvent recycle, and collecting respectively ash content at the bottom of tower is the 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 to normal pressure thermopolymerization modification, obtain the gelatin liquefaction modifying asphalt, wherein β-resin content 26.70wt%, volatilize and be divided into 37%, and softening temperature is 145 ℃.
5) the solid extract excess is fed through to steam stripping unit, liquid portion, after oily water separation, obtains the extraction solvent of 19.7kg, reusable edible, but obtain 124.3kg solid coal blending burning or gasification.
6) blend together coal blending by the gelatin liquefaction modifying asphalt and with 1/3 coking coal, Qinghai coal, peaceful coal 3 culms according to mass ratio 4:51:28:17, again by the mixed coal fragmentation, after the briquette that to make into depth-width ratio firm by ramming be 12.76:1, deliver in the pit kiln of 6.25m, in the situation that being heated to 1000 ℃ of insulations, isolated air within 12 hours, carries out coking, after coke is ripe, cooling, sieved, >=40mm coke output account for more than 89% of coke ultimate production.The 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 ℃) are added in stirring tank, with the speed stirring of 55r/min, in stirring tank, fill N
2to the pressure in stirring tank to 0.15MPa, after per hour the speed of 20 ℃ is warming up to 180 ℃, with 175r/min constant temperature, stir, hot melt extraction 30min, obtain thermosol extraction mixture.
2) adopt cyclonic separation thermosol extraction mixture, separation temperature is 250 ℃, and pressure is 0.6MPa.After cyclonic separation, collect 303kg underflow dope, 1039kg top stream clear liquid, filtrate is sent into to vacuum still, the recycle of recovered overhead extraction solvent, collecting respectively ash content at the bottom of tower is the 4.9wt% extract, its quinoline insolubles is 2.57%, it is 9.01% that volatilization is divided into 52%, β-resin content, and sulphur content is 0.04%.
4) above-mentioned extract pitch is passed through to normal pressure thermopolymerization modification, obtain the gelatin liquefaction modifying asphalt, wherein β-resin content 29.05wt%, volatilize and be divided into 38%, and softening temperature is 150 ℃.
5) the solid extract excess is fed through to steam stripping unit, liquid portion, after oily water separation, obtains the extraction solvent of 132kg, reusable edible, but obtain 173.6kg solid coal blending burning or gasification.
6) gelatin liquefaction modifying asphalt and 1/3 coking coal, Qinghai coal, peaceful coal 3 culms are blended together to coal blending according to mass ratio 10:44:30:16, again by the mixed coal fragmentation, after the briquette that to make into depth-width ratio firm by ramming be 12.76:1, deliver in the pit kiln of 6.25m, in the situation that being heated to 1000 ℃ of insulations, isolated air within 10 hours, carries out coking, after coke is ripe, cooling, sieved, >=40mm coke output account for more than 83% of coke ultimate production.The coke indices all reaches country-level metallurgical coke standard.
Visible, by by coal directly-liquefied residue through hot melt extract, solid-liquid separation and polymeric modification just can obtain that β-resin content and softening temperature are 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, obtained the coke that indices all reaches country-level metallurgical coke standard, and the 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 stronger, is suitable as the binding agent raw material of tamping coking, has realized the reasonable utilization 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 modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (10)
1. a method of utilizing coal directly-liquefied residue to prepare coke, is characterized in that, comprises the following steps:
S1, described coal directly-liquefied residue is carried out to the extraction of thermosol, solid-liquid separation and polymeric modification successively, obtain the gelatin liquefaction modifying asphalt;
S2, described gelatin liquefaction modifying asphalt is mixed with clean fine coal with coking, pulverize, make cake of press firm by ramming, obtain briquette; And
S3, described briquette is delivered in pit kiln under isolated air and heat and be incubated, then, through cooling and sieve processing, obtain coke.
2. method according to claim 1, is characterized in that, the step for preparing described gelatin liquefaction modifying asphalt comprises:
S11, described coal directly-liquefied residue is mixed with extraction solvent, stir, the thermosol extraction, obtain thermosol extraction mixture;
S12, described thermosol extraction mixture is carried out to solid-liquid separation, be extracted liquid and extract remainder;
S13, described extraction liquid is carried out to solvent recuperation, be extracted thing; And
S14, described extract is carried out to polymeric modification, obtain the gelatin liquefaction modifying asphalt.
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 1:1～10 with described extraction solvent, obtain mixed solution; And
Pass into N in described mixed solution
2, and with 10 ℃～30 ℃/h, described mixed solution is warming up to 150 ℃～200 ℃ under 0.15～0.3MPa, and constant temperature stirs, and the thermosol extraction 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.
4. method according to claim 1, is characterized in that,
Volatile content in described gelatin liquefaction modifying asphalt is 35～46wt%, and β-resin content is 18～29.05wt%, and softening temperature is 95～150 ℃.
5. method according to claim 1, is characterized in that, gelatin liquefaction modifying asphalt described in described step S2 and described coking are 1～10:99～90 with the mass ratio of clean fine coal; Heating temperature in described step S3 is 950 ℃～1050 ℃, and soaking time is 8～16 hours.
6. method according to claim 2, is characterized in that, described extraction solvent is one or more in tetrahydrofuran (THF), furfural, N-Methyl pyrrolidone, quinoline, middle distillate from coal liquefaction and dead oil.
7. method according to claim 1, is characterized in that, described solid-liquid separation is selected from a kind of in thermal air pressure filtration, Vacuum Heat suction filtration, cyclonic separation, gravity settling separation and fractionation by distillation.
8. method according to claim 7, 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 ℃～250 ℃, is preferably 150 ℃～200 ℃;
The pressure of described thermal air pressure filtration is 2.9KPa～2.0MPa, is preferably 0.3MPa～1.0MPa.
9. method according to claim 7, is characterized in that, when described solid-liquid separation adopts cyclonic separation, wherein,
The temperature of described cyclonic separation is 50 ℃～250 ℃, and inlet pressure is 0.2MPa～0.6MPa.
10. method according to claim 1, is characterized in that, described polymeric modification is selected from a kind of in vacuum flashing polymerization, normal pressure thermopolymerization and pressurized heat polymerization.
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