CN102010741B - 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 PDF

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CN102010741B
CN102010741B CN 201010568218 CN201010568218A CN102010741B CN 102010741 B CN102010741 B CN 102010741B CN 201010568218 CN201010568218 CN 201010568218 CN 201010568218 A CN201010568218 A CN 201010568218A CN 102010741 B CN102010741 B CN 102010741B
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temperature
coal
oil
tower
liquefaction
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CN 201010568218
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CN102010741A (en
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胡发亭
朱晓苏
李文博
张晓静
毛学锋
史士东
石智杰
何平
王雨
李培霖
赵鹏
谷小会
王勇
杜淑凤
张帆
朱肖曼
吴艳
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煤炭科学研究总院
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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

A kind of coal direct liquefaction method that comprises the liquefied residue maximum using
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, causes oil price to continue in a high position soaring, 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, the search for oil substitute has caused the great attention of each industrially developed country, and according to the difference of concrete technology flow process, various countries have researched and developed many coal liquefaction processes in succession.
The U.S. will have developed H-COAL technique (USP4842719) at the beginning of the end of the year 80 of last century, this technique technical characteristics is to adopt pump circulation suspended-bed reactor and petroleum hydrogenation catalyst; Adopt spinning liquid to separate and underpressure distillation partitioning cycle solvent.Germany has developed IGOR at the end of the eighties in last century +Technique, 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 this process using Natural pyrite is done deliquescence accelerant, and adopts the fixed bed hydrogenation reactor of off-line that circulating solvent is carried out hydrogenation; Liquefying reactor is 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, and this technique 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 method for critical solvent extraction, reclaims to greatest extent mink cell focus from liquefied residue.China's Shenhua Group exploitation Firing Shenhua Coal liquefaction process (China Patent Publication No.: 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 the material of a kind of high charcoal, high ash and high-sulfur, mainly is comprised of mink cell focus, bitumen (asphaltene and preasphaltene), 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 the economy from liquefying plant integral body, or from the angle of the utilization of resources and environment protection, all need liquefied residue is carried out trans-utilization, so the utilization of liquefied residue research tool have very important significance.
Mainly be burning, coking and hydrogasification to the more traditional mode of the utilization of liquefied residue.Residue acts as a fuel and directly burns in boiler or kiln, and is both uneconomical, also can bring serious problem of environmental pollution.Although the coking liquefaction has increased the liquid oils yield of coal liquefaction craft, liquefied residue can not obtain the most reasonably utilizing, and the quality of semicoke and coke is also bad, and what cause them utilizes approach also very not clear and definite.Liquefied residue is carried out gasification hydrogen-producing relatively harsh to equipment requirements, and the high value added utilization potentiality of the bitumen in the residue and mink cell focus are embodied.In above-mentioned HTI liquefaction process, although adopted the technology of critical solvent extraction, just reclaimed to greatest extent the mink cell focus in the residue, bitumen does not reclaim, and does not relate to the comprehensive utilization technique of residue yet.
Quality Fraction of Carbonium is about 90% in the liquefied residue, the content of asphaltene class material is about 20%, therefore successively it is high that the asphaltene molecule has aromaticity, and polymerization or crosslinked characteristics easily occur, and exploitation is used for preparing the method for road asphalt modifier asphalt base carbon fiber mesophase pitch etc.These methods all be bitumen in the coal liquefaction residue as raw material, 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 the method is carried out hydrocracking with the heavy oil content, carries out again liquefaction reaction and bitumen enters the coal liquefaction unit.Because bitumen does not carry out hydrogenation reaction, viscosity is very large, 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 suitably process after use as circulating solvent, this will improve the yield of DCL/Direct coal liquefaction oil product undoubtedly, thereby improve the economic benefit of the factory of liquefying.
Summary of the invention
The object of the invention is to overcome the problem and shortage that above-mentioned prior art exists, the inventor is engaged in 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 liquefying 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:
⑴ coal slurry preparation
Feed coal is carried out first drying treatment, make water-content<4%(massfraction), then be broken into granularity (particle dia) 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 pulverized coal weight), be preferably 0.5-3%, 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 the 35-50%(massfraction), be 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 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 ⑴ stirs, and make after continuing to stir and are loaded with Fe(OH on the coal dust) 2The coal slurry of precipitation; The pH value of reaction end is 6.0-12.0, is preferably 6.5-8.5, then will be loaded with Fe(OH) 2The coal slurry of precipitation under 20-50 ℃ of temperature, makes Fe(OH with air or oxygen) 2Be oxidized to γ – FeOOH, and then centrifuging or pressure filtration, obtain the coal dust filter cake catalyzer of load γ – FeOOH.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.
⑵ liquefaction reaction
The coal slurry of step ⑴ preparation is entered reactor (reactor comprises two reactors of connecting, i.e. the first reactor and the second reactor) with the hydrogen mixing by preheating, 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.
⑶ oil product separates
The second reactor outlet material of step ⑵ is carried out gas-liquid separation through high-temperature separator, and wherein high-temperature separator control 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 room temperature.
⑷ 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 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 Top of Vacuum Tower from vacuum distillation tower.
⑸ oil product upgrading hydrogenation and fractionating system
Matter oil in out Atmospheric Tower lightweight oil of atmospheric and vacuum distillation, the atmospheric tower side line, Top of Vacuum Tower are oily, vacuum distillation tower side line oil all enters upgrading hydrogenation and fractionating system, carry out hydrogenation and imurity-removal and fractionation and obtain respectively gasoline, aviation kerosene, diesel oil, heavy wet goods product, wherein mink cell focus is as circulating solvent deallocation coal slurry processed, and the hydrogenator in hydrogenation upgrading unit is fixed-bed reactor or suspended-bed reactor; 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 ℃.
⑹ residue extraction heat and solid-liquid separation
Underpressure distillation bottoms material from step ⑷ is the high-temperature liquid state liquefied residue, directly enters with in the extraction kettle that stirs, and the temperature of extraction kettle is adjusted to suitable temp, then adds extraction solvent.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, extraction temperature is 50-200 ℃.In the extraction kettle (5 among Fig. 1) behind the extraction certain hour, the mixture of the 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 Vacuum Heat suction filtration, pressurized heat filtration, gravity settling separation, eddy flow centrifugation or distillation separation method to carry out solid-liquid separation, burn as boiler oil from equipment for separating liquid from solid bottom extract remainder filter residue out.
⑺ reclaim solvent
Comprise solvent, mink cell focus and the bitumen filtrate that obtain in the equipment for separating liquid from solid from step ⑹ 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.
⑻ 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 ⑸ to carry out the secondary hydrogenation and remove to produce the finished product, and mink cell focus is as circulating solvent deallocation coal slurry processed.
The advantage of processing method provided by the invention is:
1. the present invention has introduced loop reactor coal direct liquefaction technique 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 is high in the reactor, and the interphase mass transfer coefficient is larger; 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 generate the yield raising 10-60% of oil, and has improved the oil quality of product oil.Thereby greatly improved the economic benefit of DCL/Direct coal liquefaction factory.
3. the extraction solvent of the present invention's employing is polar solvent, and is strong to the dissolving power of liquefied residue, so amount ratio is less; Percentage extraction is high, and 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 the relatively component of lightweight through extraction, the mink cell focus that obtains after the hydrotreatment as circulating solvent preparation coal slurry, 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 technique organically to combine traditional liquefaction process and residue extraction, has both taken full advantage 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 the angle 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. the 2. reactor 3. high-temperature separator 4. vacuum distillation tower 5. extraction kettle 6. equipment for separating liquid from solid 7. distillation still 8. residue hydrogenation fractionating system 9. cold catch pot 10. atmospheric distillation tower 11. oil hydrogenation upgradings of coal slurry tank and new hydrogen 13. coal dust 14. catalyst of fractionating system 12. and co-catalyst 15. recycle hydrogen 16. tail gas 17. gasoline products 18. aviation kerosine product 19. diesel product 20. circulating solvent 21. liquefied residue 22. extracting systems reclaim after solvents 23. extractions the 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 by reference to the accompanying drawings with the following example, but protection scope of the present invention is not limited to the following example.
Embodiment 1
(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 to the Inner Mongol Shengli Brown, obtains 180 purpose coal dusts, and to be dried to water content be the 2%(massfraction).Catalyzer is 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 sulphur, the S/Fe(mol ratio)=2, the Fe/ dry coal is the 1.0%(massfraction), the coal slurry solids concn is the 50%(massfraction), 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, and 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.
Embodiment 2
(40.2%Vdaf, 3.4%Ad, 81.9%C, 5.3%H, 11.2%O) pulverizes to Xinjiang bituminous coal, makes 190 purpose coal dusts, and to be dried to water content be the 1%(massfraction).Catalyzer is molybdenum oxide, and addition is 1.5% of dry pulverized coal quality; Promotor is dithiocarbonic anhydride, and addition is 2.5% of dry pulverized coal quality; The coal slurry solids concn is the 45%(massfraction), 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.
Embodiment 3
(45.8Vdaf, 18.8%Ad, 70.7%C, 4.6%H, 18.8%O) pulverizes to the Gansu brown coal, makes 200 purpose coal dusts, and to be dried to water content be the 2.5%(massfraction).Catalyzer is ferric oxide, and addition is 3% of dry pulverized coal quality; Promotor is dimethyl disulfide, and addition is S/Fe (mol ratio)=2.The coal slurry solids concn is the 45%(massfraction), the coal slurry inlet amount is 10kg/h in the liquefying plant.
In the residue extraction cells, extraction solvent is 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
(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 to the Inner Mongol Shengli Brown, and to be dried to water content be the 2%(massfraction).Catalyzer is 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 sulphur, the S/Fe(mol ratio)=2, the Fe/ dry coal is the 1.0%(massfraction), the coal slurry solids concn is the 50%(massfraction).
Other processing condition see Table 1, and experimental result sees Table 2.
Comparative Examples 2
(40.2%Vdaf, 3.4%Ad, 81.9%C, 5.3%H, 11.2%O) pulverizes to Xinjiang bituminous coal, makes 190 purpose coal dusts, and to be dried to water content be the 1%(massfraction).Catalyzer is molybdenum oxide, and addition is 1.5% of dry pulverized coal quality; Promotor is dithiocarbonic anhydride, and addition is 2.5% of dry pulverized coal quality; The coal slurry solids concn is the 45%(massfraction).
Other processing condition see Table 1, and experimental result sees Table 2.
Comparative Examples 3
(45.8Vdaf, 18.8%Ad, 70.7%C, 4.6%H, 18.8%O) pulverizes to the Gansu brown coal, makes 200 purpose coal dusts, and to be dried to water content be 2.5% (massfraction).Catalyzer is ferric oxide, and addition is 3% of dry pulverized coal quality; Promotor is 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 technological 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
Can find out from the data of table 2, direct coal liquefaction process 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 the hydrogen consumption increases seldom; 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 the rate of recovery of solvent 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:
⑴ coal slurry preparation
Feed coal is carried out first drying treatment, make water-content<4 quality %, then being broken into particle dia is 100-200 purpose coal dust, be mixed into coal slurry with deliquescence accelerant, promotor and circulating solvent again, wherein said deliquescence accelerant is Fe series catalysts, Mo series catalysts or Ni series catalysts, the deliquescence accelerant addition is the 0.5-5% of dry pulverized coal quality, described promotor is mol ratio=0.5-2 that the addition of sulphur or organic sulfide promotor sulphur need make promotor S/ catalyst activity metal, and the coal slurry solids concn is 35-50 quality %;
⑵ liquefaction reaction
The coal slurry of step ⑴ preparation mixed by preheating with hydrogen enter 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;
⑶ oil product separates
The reactor outlet material of step ⑵ is carried out gas-liquid separation through high-temperature separator, wherein high-temperature separator control temperature is at 350-430 ℃, then the liquid phase material with high-temperature separator enters vacuum still, gas phase enters the further gas-liquid separation of low-temperature separator, and wherein the temperature of low-temperature separator is room temperature;
⑷ 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 Top of Vacuum Tower from vacuum still;
⑸ oil product upgrading hydrogenation and fractionating system
In out Atmospheric Tower lightweight oil of atmospheric and vacuum distillation, the atmospheric tower side line in matter oil, the Top of Vacuum Tower matter oil, vacuum distillation tower side line mink cell focus all enter upgrading hydrogenation and fractionating system, carry out hydrogenation and imurity-removal and fractionation and obtain respectively gasoline, aviation kerosene, diesel oil and mink cell focus, wherein mink cell focus is as circulating solvent deallocation coal slurry processed, 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 ℃;
⑹ residue extraction heat and solid-liquid separation
Directly enter with in the extraction kettle that stirs from liquefied residue at the bottom of the vacuum still of step ⑷, the temperature of extraction kettle is adjusted to suitable temp, then add extraction solvent, 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 the 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 Vacuum Heat suction filtration, pressurized heat filters, gravity settling separation, eddy flow centrifugation or distillation separation method carry out solid-liquid separation, burn as boiler oil from filter bottom extract remainder filter residue out;
⑺ reclaim solvent
Enter still kettle from the filtrate that obtains in the step ⑹ 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;
⑻ mink cell focus and bitumen hydrotreatment and fractionating system
The mink cell focus of step ⑺ 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, middle matter oil enters step ⑸ and atmospheric and vacuum distillation material out to carry out together the secondary hydrogenation and removes to produce the finished product, and mink cell focus is as circulating solvent deallocation coal slurry processed.
2. according to claim 1 method, it is characterized in that described step ⑴, the deliquescence accelerant addition is the 0.5-3 quality % of dry pulverized coal weight, and 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 ⑵ reactor is 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 ⑹ is matter oil in N-Methyl pyrrolidone, N,N-dimethylacetamide, dimethylnaphthalene, tetrahydrofuran (THF), dithiocarbonic anhydride, liquefaction lightweight oil or the liquefaction.
3. according to claim 2 method 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.
CN 201010568218 2010-11-26 2010-11-26 Method for directly liquefying coals with function of maximizing utilization of liquefied residues CN102010741B (en)

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