CN102010741A - Method for directly liquefying coals with function of maximizing utilization of liquefied residues - Google Patents
Method for directly liquefying coals with function of maximizing utilization of liquefied residues Download PDFInfo
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Abstract
The invention relates to a method for directly liquefying coals with a function of maximizing utilization of liquefied residues. The method comprises the following technical steps: preparing coal paste; carrying out hydrotreating and liquefaction on the coal paste; carrying out oil separation treatment on the obtained oil product; carrying out upgrading and hydrotreating on the obtained product; carrying out hot extraction on the residues and then carrying out solid-liquid separation on the residues; and recovering the solvent; and carrying out hydrotreating treatment on the mixture of heavy oils and asphalt materials so as to obtain the final product, then taking the heavy oils as recycled solvent to prepare the coal paste, and the like. The method provided by the invention has the advantages that because of organically combining the liquefaction process and the residue extraction, the utilization of liquefied residues is maximized, the conversion rate of coal is improved, the yields of light and middle oils subjected to coal liquefaction are improved by 10 to 60 percent, and the quality of oil is improved, thereby greatly enhancing the economic benefits of direct coal liquefaction plants and improving environment protection; and the method provided by the invention has important economic and social significances, and can widely be applied to the field of coal direct liquefaction.
Description
Technical field
The invention belongs to the coal chemistry manufacture field, particularly relate to a kind of coal direct liquefaction method that comprises the liquefied residue maximum using.
Background technology
Produced quantity constantly rises because prospective oil descends year by year, and it is soaring to cause oil price to continue in a high position, so worldwide oil shortage crisis will be inevitable.The rich coal of China is oil-poor, and the energy security situation is more serious.Coal direct liquefaction (hereinafter to be referred as coal liquefaction) is under High Temperature High Pressure, by means of hydrogen supply dissolvent and catalyzer, makes protium enter the molecular structure of coal and derivative thereof, thereby coal is converted into the advanced clean coal technology of liquid fuel or industrial chemicals.The development of coal liquefaction technology, it is one of important channel of alleviating China's oil shortage of resources, petroleum products supply and demand pressure, simultaneously also be raising coal resources in China utilization ratio, alleviate coal burning pollution, promote the important measures of the energy, economy, harmonious development.
After the early seventies oil crisis, seek oil substitutes and caused the great attention of each industrially developed country, according to the difference of concrete technical process, various countries have researched and developed many coal liquefaction processes in succession.
The U.S. will have developed H-COAL technology (USP4842719) at the beginning of the end of the year 80 of last century, these technology major technique characteristics are to adopt pump circulation suspended-bed reactor and oil series hydrocatalyst; Adopt spinning liquid to separate and underpressure distillation partitioning cycle solvent.Germany has developed IGOR at the end of the eighties in last century
+Technology, this process using bubbling bed reactor and employing red mud are done deliquescence accelerant; Underpressure distillation partitioning cycle solvent all adopts the hydrogen supply circulating solvent behind the hydrogenation.Japan develops at the end of the nineties in last century and has finished the NEDOL liquefaction process, and the natural pyrite of this process using is done deliquescence accelerant, and adopts the fixed bed hydrogenation reactor of off-line that circulating solvent is carried out hydrogenation; Liquefying reactor is the bubbling bed, underpressure distillation partitioning cycle solvent.U.S. HTI company has researched and developed out the HTI coal liquefaction craft on the basis of H-COAL coal liquefaction craft, this technology is the two-stage catalytic liquefaction process, adopts suspended-bed reactor and HTI to have the ferrum-based catalyst of patent; The online hydrogenation fixed-bed reactor of connecting in the high-temperature separator back; Solid-liquid separation adopts the critical solvent method of extraction, reclaims mink cell focus from liquefied residue to greatest extent.Group of China Shenhua exploitation Firing Shenhua Coal liquefaction process (Chinese patent publication number: CN1438294A and CN1587351A) adopts efficient deliquescence accelerant, hydrogen supply circulating solvent, and solid-liquid separation adopts underpressure distillation.
No matter above-mentioned these gelatin liquefaction production processes use the sort of coal liquefaction process, and which kind of solid-liquid separating method (underpressure distillation, filtration and solvent extraction etc.) all can produce the liquefied residue that accounts for liquefaction raw coal amount about 30%.It is a kind of high charcoal, high ash and doctor positive material, mainly is made up of mink cell focus, bitumen (asphaltene and preceding asphaltene), unconverted coal, inorganic mineral and catalyst for coal liquefaction.About 50% is heavy liquefaction oil and bitumen in the general liquefied residue, and all the other 50% are unconverted coal, ash content and catalyzer.No matter be economy,, all need liquefied residue is carried out trans-utilization, so the utilization of liquefied residue research tool has very important significance still from the utilization of resources and point of view of environment protection from liquefying plant integral body.
To the more traditional mode of the utilization of liquefied residue mainly is burning, coking and hydrogasification.Residue acts as a fuel and directly burns in boiler or kiln, and is both uneconomical, also can bring the serious environmental pollution problem.Though coking system oil has increased the liquid oils yield of coal liquefaction craft, liquefied residue can not obtain reasonable use, and the quality of semicoke and coke is also bad, and what cause them utilizes approach also very not clear and definite.It is relatively harsh to equipment requirements that liquefied residue is carried out gasification hydrogen-producing, and the high value added utilization potentiality of bitumen in the residue and mink cell focus do not obtain embodying.In above-mentioned HTI liquefaction process, although adopted the technology of critical solvent extraction, just reclaimed the mink cell focus in the residue to greatest extent, bitumen does not reclaim, and does not relate to the comprehensive utilization technique of residue yet.
The massfraction of carbon is about 90% in the liquefied residue, the content of asphaltene class material is about 20%, therefore successively the asphaltene molecule has the aromaticity height, and polymerization or crosslinked characteristics take place easily, and exploitation is used for preparing the method for road asphalt modifier asphalt base carbon fiber mesophase pitch etc.These methods all are to be raw material with the bitumen in the coal liquefaction residue, do not relate to the utilization of mink cell focus in the residue.Japanese Patent JP1304182 discloses a kind of method of isolating mink cell focus and bitumen from coal liquefaction residue, and this method is carried out hydrocracking with the heavy oil content, carries out liquefaction reaction again and bitumen enters the coal liquefaction unit.Because bitumen does not carry out hydrogenation reaction, viscosity is very big, causes the pipeline of liquefaction unit to be easy to stop up.
If can take out the mink cell focus fraction in the residue and carry out appropriate location reason back as the circulating solvent use, this will improve the yield of DCL/Direct coal liquefaction oil product undoubtedly, thereby improve the economic benefit of liquefaction factory.
Summary of the invention
The objective of the invention is to overcome the problem and shortage that above-mentioned prior art exists, the inventor is engaged in the development research and the practice of DCL/Direct coal liquefaction for a long time, the solvent extraction of traditional coal liquefaction craft and liquefied residue and comprehensive utilization are organically combined exploitation a kind of fully at utmost utilize heavy oil fraction and bitumen in the liquefied residue are provided, comprise the novel coal direct liquefaction method of liquefied residue maximum using.
The coal direct liquefaction method that comprises the liquefied residue maximum using provided by the invention comprises the following steps:
(1) coal slurry preparation
Feed coal is carried out drying treatment earlier, make water-content＜4% (massfraction), be broken into granularity (particle dia) then and be the coal dust of 100-200 order (0.149-0.074mm), again with deliquescence accelerant, promotor and circulating solvent are mixed into coal slurry, wherein the deliquescence accelerant addition is the 0.5-5% (massfraction) of dry coal grain weight amount, be preferably 1.5-3%, promotor is sulphur or organic sulfide, addition need satisfy: promotor S/ deliquescence accelerant reactive metal (mol ratio)=0.5-2, be preferably 1.0-2.0, the coal slurry solids concn is 35-50% (massfraction), is preferably 45-50%.
Described deliquescence accelerant is Fe series catalysts, Mo system or Ni series catalysts etc., and wherein the Fe series catalysts is for example nanometer ultra-fine grain aqua oxidation iron catalyst (being called for short γ-FeOOH catalyzer), ferric oxide such as Fe
2O
3, FeO, Fe
3O
4, pyrite, rhombohedral iron ore, kakoxene, limonite etc., be preferably nanometer ultra-fine grain aqua oxidation iron catalyst or pyrite, nanometer ultra-fine grain aqua oxidation iron catalyst makes by Chinese patent CN1579623A---with the weakly alkaline solution or the strong alkali solution of a certain amount of hydroxyl-containing ion, for example NaOH, KOH or NH
4OH solution or ammoniacal liquor join in the coal dust that step (1) stirs, and make after continuing to stir and are loaded with Fe (OH) on the coal dust
2Sedimentary coal slurry; The pH value of reaction end is 6.0-12.0, is preferably 6.5-8.5, will be loaded with Fe (OH) then
2Sedimentary coal slurry under 20-50 ℃ of temperature, makes Fe (OH) with air or oxygen
2Be oxidized to γ-FeOOH, and then centrifuging or pressure filtration, the coal dust filter cake catalyzer of γ-FeOOH that obtained load.Mo, Ni series catalysts such as molybdenum oxide, moly-sulfide, ammonium molybdate, nickelous sulfide etc., these catalyzer all are known or commercially available DCL/Direct coal liquefaction catalyzer.Promotor is sulphur or organic sulfide such as dithiocarbonic anhydride, dimethyl disulfide etc.
(2) liquefaction reaction
The coal slurry of step (1) preparation is mixed with hydrogen after preheating enters reactor (reactor comprises two placed in-line reactors, i.e. first reactor and second reactor), carry out liquefaction reaction, temperature of reaction: 400-465 ℃, preferred 450-455 ℃; Reactor pressure is 6-30MPa, is preferably 10-20MPa; Vapour-liquid ratio is 600-1500NL/kg, is preferably 900-1000L/Kg; Described reactor is pump circulation suspension bed, bubbling bed or loop reactor, is preferably loop reactor.
(3) oil product separates
Second reactor outlet material of step (2) is carried out gas-liquid separation through high-temperature separator, and wherein the high-temperature separator controlled temperature is at 350-430 ℃; The liquid phase material of high-temperature separator enters vacuum still, and gaseous phase materials enters the further gas-liquid separation of low-temperature separator, and wherein the temperature of low-temperature separator is a room temperature.
(4) atmospheric and vacuum distillation
Enter atmospheric distillation tower from the low-temperature separator liquid phase, column bottom temperature is 340-360 ℃, tower top temperature is controlled at 60-150 ℃, distill out three strands of materials from atmospheric tower: oil at the bottom of matter oil and the atmospheric tower Atmospheric Tower lightweight oil, the atmospheric tower side line, the oil material enters vacuum still at the bottom of high-temperature separator liquid phase and the atmospheric tower, wherein the VACUUM TOWER BOTTOM temperature is controlled at 330-370 ℃, tower top temperature is controlled at 60-150 ℃, distills out matter oil, decompression side line mink cell focus and VACUUM TOWER BOTTOM liquefied residue the decompression cat head from vacuum distillation tower.
(5) oil product upgrading hydrogenation and fractionating system
Matter oil, decompression overhead oil, vacuum distillation tower side line oil all enter upgrading hydrogenation and fractionating system in the Atmospheric Tower lightweight oil that atmospheric and vacuum distillation comes out, the atmospheric tower side line, carry out hydrogenation and remove impurity and fractionation obtains gasoline, aviation kerosene, diesel oil, heavy wet goods product respectively, wherein mink cell focus is fixed-bed reactor or suspended-bed reactor as circulating solvent deallocation system coal slurry at the unitary hydrogenator of hydrogenation upgrading; Hydrogenation catalyst is the hydrogenation catalyst of Ni-Mo, Ni-Co or Ni-W system; Hydrogenation temperature is 300-390 ℃, is preferably 360-380 ℃, and hydrogenation pressure is 10-19MPa, is preferably 15-16Mpa; Vapour-liquid ratio is 300-1000NL/kg, is the stripping type distillation tower at the separation column of fractionation unit, and column bottom temperature is controlled to be 330-370 ℃, and tower top temperature is 100-240 ℃.
(6) residue extraction heat and solid-liquid separation
Underpressure distillation bottoms material from step (4) is the high-temperature liquid state liquefied residue, directly enters in the extraction kettle that has stirring, and the temperature of extraction kettle is adjusted to suitable temp, adds extraction solvent then.Extraction solvent is N-Methyl pyrrolidone (NMP), N,N-dimethylacetamide, dimethylnaphthalene, tetrahydrofuran (THF), light, the middle matter wet goods of dithiocarbonic anhydride or gelatin liquefaction solvent.The mass ratio of liquefied residue and extraction solvent is: 1: 1-1: 8, and extraction temperature is 50-200 ℃.In the extraction kettle (5 among Fig. 1) behind the extraction certain hour, the mixture of extract in the extraction kettle and extract remainder is pressed in the equipment for separating liquid from solid (6 among Fig. 1) carries out solid-liquid separation.Can adopt the hot suction filtration of vacuum, pressurized heat filtration, gravity settling separation, eddy flow centrifugation or distillation separation method to carry out solid-liquid separation, the extract remainder filter residue that comes out from the equipment for separating liquid from solid bottom burns as boiler oil.
(7) reclaim solvent
Comprise solvent, mink cell focus and the bitumen filtrate that obtain in the equipment for separating liquid from solid from step (6) enter still kettle.Carry out underpressure distillation in still kettle, distilling off solvent returns extraction kettle and makes extraction solvent, and the bottoms material is that the mixture of mink cell focus and bitumen enters downstream hydrogenation fractionating system.
(8) mink cell focus and bitumen hydrotreatment and fractionating system
At high temperature enter high temperature resistant pump from the mink cell focus of step (7) still kettle bottom and the mixture of bitumen, force (forcing) pump is delivered to the floating bed hydrogenation reactor, and temperature of reaction is 400-450 ℃.The product fractionation that hydrogenation obtains is middle matter oil and mink cell focus two portions, and middle matter oil enters step (5) to carry out the secondary hydrogenation and remove to produce the finished product, and mink cell focus is as circulating solvent deallocation system coal slurry.
The advantage of processing method provided by the invention is:
1. the present invention has introduced loop reactor coal direct liquefaction technology first, experiment showed, this reactor inner fluid directed flow through continuous gelatin liquefaction, and circulation liquid speed is very fast, has realized full back-mixing pattern; Gas holdup height in the reactor, the interphase mass transfer coefficient is bigger; Inside does not have inner member, has saved the recycle pump of pump circulation suspended-bed reactor yet, has reduced process cost, has increased the turndown ratio of reactor.
2. processing method of the present invention can make light, the middle matter of gelatin liquefaction give birth to olefiant yield raising 10-60%, and has improved the oil quality of product oil.Thereby improved the economic benefit of DCL/Direct coal liquefaction factory greatly.
3. the extraction solvent of the present invention's employing is a polar solvent, and is strong to the dissolving power of liquefied residue, so amount ratio is less; The percentage extraction height, the percentage extraction of mink cell focus and bitumen can reach more than 95%; Solvent recovering rate also reaches about 95%.
4. liquefied residue can substitute in the former circulating solvent relatively than the light-weight component as circulating solvent preparation coal slurry through extraction, the mink cell focus that obtains after the hydrotreatment, thereby has solved the problem of the solvent lighting that liquefaction factory often runs into, and has improved the transformation efficiency of coal.
5. the present invention utilizes technology organically to combine traditional liquefaction process and residue extraction, has both made full use of the heat of hot residue, has saved the heating installation of extraction kettle; Transportation problem when also having avoided liquefied residue to make other purposes, thus the overall efficiency of liquefaction factory improved.
6. large-scale liquefaction factory can produce a large amount of liquefied residues, and processing method of the present invention has maximally utilised liquefied residue, no matter from the utilization of resources or point of view of environment protection, all has important practical significance.
Description of drawings
Fig. 1 is the process flow sheet of coal liquefaction process of the present invention
Illustrate
1. 2. reactors, 3. high-temperature separator 4. vacuum distillation towers, 5. extraction kettle 6. equipment for separating liquid from solid, 7. distillation still 8. residue hydrogenation fractionating systems, 9. cold catch pot 10. atmospheric distillation towers, the 11. oil hydrogenation upgradings of coal slurry tank and fractionating system 12. new hydrogen 13. coal dusts, 14. catalyst and co-catalyst 15. recycle hydrogens 16. tail gas 17. gasoline products 18. aviation kerosine products 19. diesel products 20. circulating solvents 21. liquefied residues 22. extracting systems reclaim after solvent 23. extractions residue matter oil in 24. mink cell focuses and bitumen 25. mink cell focuses 26. that goes to burn
Embodiment
The present invention further specifies the present invention in conjunction with the accompanying drawings with the following example, but protection scope of the present invention is not limited to the following example.
Embodiment 1
To Inner Mongol triumph brown coal (45.7% dry ash-free basis fugitive constituent (Vdaf), 13.2% dry basic ash content (Ad), 71.66%C, 4.75H 21.42%O) pulverizes, and obtains 180 purpose coal dusts, and to be dried to water content be 2% (massfraction).Catalyzer is a diameter 20-50 nanometer, length is γ-hydrous iron oxide (type high reactivity deliquescence accelerant of γ-FeOOH) of the ultra-fine grain of 80-180 nanometer, promotor is a sulphur, S/Fe (mol ratio)=2, the Fe/ dry coal is 1.0% (massfraction), the coal slurry solids concn is 50% (massfraction), and the coal slurry inlet amount is 8kg/h in the liquefying plant.
Residue extraction cells, extraction solvent are N-Methyl pyrrolidone, and residue is 1: 1.5 with the solvent quality ratio, 130 ℃ of extraction temperature, solid-liquid separation method is hot pressure filtration, and solvent recuperation is the underpressure distillation mode, and mink cell focus and bitumen hydrogenation temperature are 420 ℃.
Other processing condition see Table 1, and experimental result sees Table 2.
To Xinjiang bituminous coal (40.2%Vdaf, 3.4%Ad, 81.9%C, 5.3%H 11.2%O) pulverizes, and makes 190 purpose coal dusts, and to be dried to water content be 1% (massfraction).Catalyzer is a molybdenum oxide, and addition is 1.5% of a dry coal opaque amount; Promotor is a dithiocarbonic anhydride, and addition is 2.5% of a dry coal opaque amount; The coal slurry solids concn is 45% (massfraction), and the coal slurry inlet amount is 9kg/h in the liquefying plant.
Residue extraction cells, extraction solvent are N,N-dimethylacetamide, and residue is 1: 3.5 with the solvent quality ratio, and 120 ℃ of extraction temperature, solid-liquid separation are hot pressure filtration, and solvent recuperation is underpressure distillation, and mink cell focus and bitumen hydrogenation temperature are 430 ℃.
Other processing condition see Table 1, and experimental result sees Table 2.
To the Gansu brown coal (45.8Vdaf, 18.8%Ad, 70.7%C, 4.6%H 18.8%O) pulverizes, and makes 200 purpose coal dusts, and to be dried to water content be 2.5% (massfraction).Catalyzer is a ferric oxide, and addition is 3% of a dry coal opaque amount; Promotor is a dimethyl disulfide, and addition is S/Fe (mol ratio)=2.The coal slurry solids concn is 45% (massfraction), and the coal slurry inlet amount is 10kg/h in the liquefying plant.
In the residue extraction cells, extraction solvent is a tetrahydrofuran (THF), and residue is 1: 3 with the solvent quality ratio, and 50 ℃ of extraction temperature, solid-liquid separation are hot pressure filtration, and solvent recuperation is air distillation, and mink cell focus and bitumen hydrogenation temperature are 440 ℃.
Other processing condition see Table 1, and experimental result sees Table 2.
Comparative Examples 1
To Inner Mongol triumph brown coal (45.7% dry ash-free basis fugitive constituent (Vdaf), 13.2% dry basic ash content (Ad), 71.66%C, 4.75H 21.42%O) is ground into 180 purpose coal dusts, and to be dried to water content be 2% (massfraction).Catalyzer is a diameter 20-50 nanometer, length is γ-hydrous iron oxide (type high reactivity deliquescence accelerant of γ-FeOOH) of the ultra-fine grain of 80-180 nanometer, promotor is a sulphur, S/Fe (mol ratio)=2, the Fe/ dry coal is 1.0% (massfraction), and the coal slurry solids concn is 50% (massfraction).
Other processing condition see Table 1, and experimental result sees Table 2.
Comparative Examples 2
To Xinjiang bituminous coal (40.2%Vdaf, 3.4%Ad, 81.9%C, 5.3%H 11.2%O) pulverizes, and makes 190 purpose coal dusts, and to be dried to water content be 1% (massfraction).Catalyzer is a molybdenum oxide, and addition is 1.5% of a dry coal opaque amount; Promotor is a dithiocarbonic anhydride, and addition is 2.5% of a dry coal opaque amount; The coal slurry solids concn is 45% (massfraction).
Other processing condition see Table 1, and experimental result sees Table 2.
Comparative Examples 3
To the Gansu brown coal (45.8Vdaf, 18.8%Ad, 70.7%C, 4.6%H 18.8%O) pulverizes, and makes 200 purpose coal dusts, and to be dried to water content be 2.5% (massfraction).Catalyzer is a ferric oxide, and addition is 3% of a dry coal opaque amount; Promotor is a dimethyl disulfide, and addition is S/Fe (mol ratio)=2.The coal slurry solids concn is 45% (massfraction).
Other processing condition see Table 1, and experimental result sees Table 2.
The main technique condition of table 1 embodiment 1-3 and Comparative Examples 1-3
The experimental result of table 2 embodiment 1-3 and Comparative Examples 1-3
From the data of table 2 as can be seen, DCL/Direct coal liquefaction processing method provided by the invention improves greatly than liquefaction process coal transformation efficiency and oily yield in the past, and the gas productive rate obviously reduces, and that the hydrogen consumption increases is few; Used liquefied residue extraction solvent consumption is few, the percentage extraction of mink cell focus and asphaltene class material reaches 96-98%, substantially can all extract, and solvent recovering yield is very high, therefore coal liquefaction process of the present invention can be received good liquefaction effect and huge economic benefit.
Claims (3)
1. a coal direct liquefaction method that comprises the liquefied residue maximum using is characterized in that comprising the following steps:
(1) coal slurry preparation
Feed coal is carried out drying treatment earlier, make water-content＜4 quality %, being broken into particle dia then is 100-200 purpose coal dust, be mixed into coal slurry with deliquescence accelerant, promotor and circulating solvent again, wherein the catalyzer addition is the 0.5-5% of dry coal opaque amount, the addition of promotor sulphur need make the mol ratio=0.5-2 of promotor S/ catalyst activity metal, and the coal slurry solids concn is 35-50 quality %;
(2) liquefaction reaction
The coal slurry of step (1) preparation is mixed with hydrogen after preheating enters reactor, carry out liquefaction reaction, described reactor is pump circulation suspension bed, bubbling bed or loop reactor, temperature of reaction 400-465 ℃, reactor pressure is 6-30MPa, and vapour-liquid ratio is 600-1500NL/kg;
(3) oil product separates
The reactor outlet material of step (2) is carried out gas-liquid separation through high-temperature separator, wherein the high-temperature separator controlled temperature is at 350-430 ℃, liquid phase material with high-temperature separator enters vacuum still then, gas phase enters the further gas-liquid separation of low-temperature separator, and wherein the temperature of low-temperature separator is a room temperature;
(4) atmospheric and vacuum distillation
Enter atmospheric distillation tower from the low-temperature separator liquid phase, column bottom temperature is 340-360 ℃, tower top temperature is controlled at 100-150 ℃, distill out Atmospheric Tower lightweight oil, the atmospheric tower side line mink cell focus at the bottom of the matter oil and atmospheric tower from atmospheric tower, oil enters vacuum still at the bottom of high-temperature separator liquid phase and the atmospheric tower, wherein the underpressure distillation column bottom temperature is controlled at 330-370 ℃, tower top temperature is controlled at 60-150 ℃, distills out matter oil, decompression side line mink cell focus and VACUUM TOWER BOTTOM liquefied residue the decompression cat head from vacuum still;
(5) oil product upgrading hydrogenation and fractionating system
Matter oil, vacuum distillation tower side line mink cell focus all enter upgrading hydrogenation and fractionating system in matter oil in the Atmospheric Tower lightweight oil that atmospheric and vacuum distillation comes out, the atmospheric tower side line, the decompression cat head, carry out hydrogenation and remove impurity and fractionation obtains gasoline, aviation kerosene, diesel oil and mink cell focus respectively, wherein mink cell focus is as circulating solvent deallocation system coal slurry, is fixed-bed reactor or suspended-bed reactor at the hydrogenator of upgrading hydrogenation unit; Hydrogenation catalyst is the hydrogenation catalyst of Ni-Mo, Ni-Co or Ni-W system; Hydrogenation temperature is 300-390 ℃, and hydrogenation pressure is 10-19MPa, and vapour-liquid ratio is 300-1000NL/kg; Separation column at fractionation unit is the stripping type distillation tower, and column bottom temperature is controlled to be 330-370 ℃, and tower top temperature is 100-240 ℃;
(6) residue extraction heat and solid-liquid separation
Directly enter in the extraction kettle that has stirring from liquefied residue at the bottom of the vacuum still of step (4), the temperature of extraction kettle is adjusted to suitable temp, add extraction solvent then, the mass ratio of liquefied residue and extraction solvent is: 1: 1-1: 8, extraction temperature is 50-220 ℃, after in extraction kettle, extracting certain hour, the mixture of extract in the extraction kettle and extract remainder is pressed into carries out solid-liquid separation in the equipment for separating liquid from solid, can adopt the hot suction filtration of vacuum, pressurized heat filters, gravity settling separation, eddy flow centrifugation or distillation separation method carry out solid-liquid separation, and the extract remainder filter residue that comes out from filter bottom burns as boiler oil;
(7) reclaim solvent
Enter still kettle from the filtrate that obtains in step (6) equipment for separating liquid from solid and carry out underpressure distillation, distilling off solvent returns extraction kettle and makees extraction solvent, and the bottoms material is the mink cell focus that extracts from liquefied residue and the mixture of bitumen;
(8) mink cell focus and bitumen hydrotreatment and fractionating system
The mink cell focus of step (7) and the mixture of bitumen are at high temperature entered high temperature resistant pump, force (forcing) pump is delivered to the floating bed hydrogenation reactor, temperature of reaction is 400-450 ℃, the product fractionation that hydrogenation obtains is middle matter oil and mink cell focus two portions, in matter oil enter material that step (5) and atmospheric and vacuum distillation come out and carry out the secondary hydrogenation together and remove to produce the finished product, mink cell focus is as circulating solvent deallocation system coal slurry.
2. according to the method for claim 1, it is characterized in that described step (1) deliquescence accelerant is Fe series catalysts, Mo or Ni series catalysts, the deliquescence accelerant addition is the 0.5-3 quality % of dry coal grain weight amount, described promotor is sulphur or organic sulfide, the promotor addition is that the mol ratio of S/ catalyst activity metal in the promotor is 1.0-2.0, and the coal slurry solids concn is 45-50 quality %;
Described step (2) reactor is a loop reactor, and temperature of reaction is 450-455 ℃, and reactor pressure is 10-20MPa, and vapour-liquid ratio is 900-1500NL/Kg; The extraction solvent of described step (6) is N-Methyl pyrrolidone, N,N-dimethylacetamide, dimethylnaphthalene, tetrahydrofuran (THF), dithiocarbonic anhydride or liquefaction lightweight or middle matter oil.
3. according to the method for claim 2, it is characterized in that described deliquescence accelerant is nanometer ultra-fine grain aqua oxidation iron catalyst, ferric oxide, pyrite, rhombohedral iron ore, molybdenum oxide, moly-sulfide, ammonium molybdate or nickelous sulfide; Described organic sulfide is dithiocarbonic anhydride or dimethyl disulfide.
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| CN102399566A (en) * | 2011-09-30 | 2012-04-04 | 神华集团有限责任公司 | Method for extracting heavy liquefied oil and kerite substance from residue of direct coal liquefaction |
| CN103074097A (en) * | 2013-01-31 | 2013-05-01 | 煤炭科学研究总院 | Method and system for direct coal liquefaction |
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| CN103275744A (en) * | 2013-05-30 | 2013-09-04 | 神华集团有限责任公司 | Asphalt substance separated from direct coal liquefaction residues and method and application thereof |
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| CN103074097B (en) * | 2013-01-31 | 2015-07-01 | 煤炭科学研究总院 | Method and system for direct coal liquefaction |
| CN103074097A (en) * | 2013-01-31 | 2013-05-01 | 煤炭科学研究总院 | Method and system for direct coal liquefaction |
| CN104004536B (en) * | 2013-02-22 | 2017-01-11 | 神华集团有限责任公司 | Mesophase pitch and preparation method thereof |
| CN104004536A (en) * | 2013-02-22 | 2014-08-27 | 神华集团有限责任公司 | Mesophase pitch and preparation method thereof |
| CN103173025A (en) * | 2013-03-15 | 2013-06-26 | 长安大学 | Method for preparing road asphalt by direct coal liquefaction residue |
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| CN103436280B (en) * | 2013-09-11 | 2015-11-04 | 神华集团有限责任公司 | Coal directly-liquefied residue is utilized to prepare the method for coke |
| CN103436280A (en) * | 2013-09-11 | 2013-12-11 | 神华集团有限责任公司 | Method for preparing coke by using direct coal-liquefied residue |
| CN103977822A (en) * | 2014-05-21 | 2014-08-13 | 煤炭科学研究总院 | Oil solubility compound-type suspended bed hydrocracking catalyst as well as preparation method thereof |
| CN103977822B (en) * | 2014-05-21 | 2016-08-31 | 煤炭科学技术研究院有限公司 | A kind of compound hydrocracking catalyst for suspension bed of oil-soluble and preparation method thereof |
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| CN105233829A (en) * | 2015-11-18 | 2016-01-13 | 陕西延长石油（集团）有限责任公司 | Method for preparing hydrocracking catalyst from iron-containing waste residue and application of hydrocracking catalyst from iron-containing waste residue |
| WO2017124767A1 (en) * | 2016-01-19 | 2017-07-27 | 肇庆市顺鑫煤化工科技有限公司 | Method and apparatus for separating product of direct coal liquefaction |
| CN108048121A (en) * | 2017-11-24 | 2018-05-18 | 神华集团有限责任公司 | Coal direct liquefaction method and Direct coal liquefaction device |
| CN108048121B (en) * | 2017-11-24 | 2020-12-08 | 神华集团有限责任公司 | Direct coal liquefaction method and direct coal liquefaction device |
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| CN109082292A (en) * | 2018-09-04 | 2018-12-25 | 福建海峡能源集团股份有限公司 | A kind of technique for extracting pitch from putty slag |
| CN109233890A (en) * | 2018-09-04 | 2019-01-18 | 新奥科技发展有限公司 | A kind of oil gas coproduction gasification process and device |
| CN109082292B (en) * | 2018-09-04 | 2019-10-25 | 福建海峡能源集团股份有限公司 | A kind of technique for extracting pitch from putty slag |
| CN110229690A (en) * | 2019-04-21 | 2019-09-13 | 宁波市化工研究设计院有限公司 | Containing solid oils or oil-containing solid phase solvent extraction recycling and processing device and method |
| CN114517110A (en) * | 2020-11-18 | 2022-05-20 | 中科合成油技术股份有限公司 | Method for co-producing high-quality liquid fuel and system for implementing method |
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