CN108048121A - Coal direct liquefaction method and Direct coal liquefaction device - Google Patents
Coal direct liquefaction method and Direct coal liquefaction device Download PDFInfo
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- CN108048121A CN108048121A CN201711203668.6A CN201711203668A CN108048121A CN 108048121 A CN108048121 A CN 108048121A CN 201711203668 A CN201711203668 A CN 201711203668A CN 108048121 A CN108048121 A CN 108048121A
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- 239000003245 coal Substances 0.000 title claims abstract description 219
- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000000047 product Substances 0.000 claims abstract description 157
- 238000006243 chemical reaction Methods 0.000 claims abstract description 116
- 239000001257 hydrogen Substances 0.000 claims abstract description 69
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 69
- 239000007791 liquid phase Substances 0.000 claims abstract description 67
- 239000007789 gas Substances 0.000 claims abstract description 65
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000002904 solvent Substances 0.000 claims abstract description 57
- 239000002994 raw material Substances 0.000 claims abstract description 54
- 238000000926 separation method Methods 0.000 claims abstract description 44
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims abstract description 39
- 239000012263 liquid product Substances 0.000 claims abstract description 30
- 239000003250 coal slurry Substances 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims description 41
- 239000012071 phase Substances 0.000 claims description 40
- 239000000463 material Substances 0.000 claims description 32
- 230000004087 circulation Effects 0.000 claims description 28
- 238000005984 hydrogenation reaction Methods 0.000 claims description 24
- 238000006555 catalytic reaction Methods 0.000 claims description 17
- 238000005292 vacuum distillation Methods 0.000 claims description 17
- 230000001351 cycling effect Effects 0.000 claims description 13
- 239000007792 gaseous phase Substances 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000004821 distillation Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000007790 solid phase Substances 0.000 claims description 7
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000002817 coal dust Substances 0.000 claims description 4
- 230000005587 bubbling Effects 0.000 claims description 3
- 238000004891 communication Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 239000002002 slurry Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 description 44
- 239000007788 liquid Substances 0.000 description 24
- 230000008569 process Effects 0.000 description 17
- 230000008859 change Effects 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 9
- 239000000446 fuel Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- 239000010426 asphalt Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000006837 decompression Effects 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 150000003384 small molecules Chemical class 0.000 description 3
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- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004781 supercooling Methods 0.000 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000002956 ash Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
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- 238000006703 hydration reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004148 unit process Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/006—Combinations of processes provided in groups C10G1/02 - C10G1/08
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a kind of coal direct liquefaction method and Direct coal liquefaction devices.The coal direct liquefaction method comprises the following steps：S1 makes the first raw material for including coal slurry and hydrogen carry out first time liquefaction reaction, obtains the first liquefaction products, and carries out Oil-gas Separation to the first liquefaction products, obtains the first liquid product；S2 makes the second raw material for including the first liquid product, hydrogen and solvent carry out second of liquefaction reaction, obtains the second liquefaction products, and carries out Oil-gas Separation to the second liquefaction products, obtains second liquid phase product；S3, distills part second liquid phase product and catalytic hydrogenation treatment, obtains Coal Liquefaction Products；And S4, above-mentioned steps S1 is repeated to S3, and the first raw material and/or the second raw material further include remainder second liquid phase product during repeating.Lique faction of coal conversion ratio and liquid product yield can be improved using above-mentioned coal direct liquefaction method, resource utilization is obviously improved.
Description
Technical field
The present invention relates to coal chemical technology, in particular to a kind of coal direct liquefaction method and Direct coal liquefaction device.
Background technology
Direct coal liquefaction technology refer to coal in high temperature, high pressure, face hydrogen, solvent and catalyst under the action of, it is straight by being hydrogenated with
Connect the technical process for being converted into fluid product and a small amount of gas products.Direct coal liquefaction process process generally includes four mainly
Part：Coal preparation, Coal Liquefaction reaction, separation of solid and liquid and product upgrading processing and utilization.Coal wears into coal through broken drying
Powder, be configured to together with solvent, catalyst be suitble to conveying and heat transfer coal, coal it is boosted and preheating after be delivered to coal
Hydrogenation liquefaction reactor, the product of pyrolysis and hydrogenation reaction generation liquid occurs for coal under conditions of high temperature and pressure, and reaction is given birth to
Into liquefaction oil separated with bitumen, unconverted coal, catalyst and ash content, recycling design obtains coal liquefaction crude oil,
Coal liquefaction crude oil is subjected to upgrading processing target product again, the scheme difference according to product can produce gasoline, diesel oil, aviation
Kerosene, specialty oil and industrial chemicals etc..
The current main influence for influencing DCL/Direct coal liquefaction realization industrialization includes Installed capital cost height, lique faction of coal conversion
Rate and oil yield are low, wherein the low economic benefit for being the most key factor, directly affecting Direct coal liquefaction device of oil yield
And the market competitiveness.Since direct coal liquefaction process condition is comparatively harsh, Coal liquefaction temperature is higher, DCL/Direct coal liquefaction
Reaction process mainly includes pyrolysis and hydrogenation, unavoidably causes the second pyrolysis of target product, causes target product oil yield
It reduces, bi-product gas yield is high, while also increases hydrogen consumption, cost increase；In addition, during Coal liquefaction, coal
Activearm component convert first, it is difficult to the component of conversion then needs more harsh conditions, and DCL/Direct coal liquefaction was reacted
Journey is a parallel series reaction system, this also causes the second half in second reactor or reaction, cycles the confession Hydrogen Energy of solvent
Power declines, and hydrogen partial pressure reduces, and reaction severity reduces instead, this is unfavorable for improving lique faction of coal conversion ratio and oil yield.Currently
DCL/Direct coal liquefaction reaction process is a parallel series reaction system in the anti-technique of most DCL/Direct coal liquefaction, thus is had
The problem of like above.
Therefore, in the case where equipment investment amplification is little, reach effective there is an urgent need for developing DCL/Direct coal liquefaction new process at present
Gas yield and hydrogen consumption are reduced, improves lique faction of coal conversion ratio, realizes the purpose for increasing oil yield, is conducive to improve the utilization of resources
Rate enhances DCL/Direct coal liquefaction economic benefit and the market competitiveness.
The content of the invention
It is existing to solve it is a primary object of the present invention to provide a kind of coal direct liquefaction method and Direct coal liquefaction device
The relatively low gentle yield of coal direct liquefaction method liquefying conversion rate in technology is higher, so as to cause oil yield it is poor the problem of.
To achieve these goals, according to an aspect of the invention, there is provided a kind of coal direct liquefaction method, including with
Lower step：S1 makes the first raw material for including coal slurry and hydrogen carry out first time liquefaction reaction, obtains the first liquefaction products, and right
First liquefaction products carry out Oil-gas Separation, obtain the first liquid product；S2 makes to include the first liquid product, hydrogen and solvent
Second raw material carries out second of liquefaction reaction, obtains the second liquefaction products, and carries out Oil-gas Separation to the second liquefaction products, obtains
Second liquid phase product；S3, distills part second liquid phase product and catalytic hydrogenation treatment, obtains Coal Liquefaction Products；And
S4 repeats above-mentioned steps S1 to S3, and the first raw material and/or the second raw material further include residue during repeating
Part second liquid phase product.
Further, the inlet amount of remainder second liquid phase product and the first raw material is than 0.1~1, remainder second
The inlet amount of liquid product and the second raw material is than 0.1~1.
Further, the pressure of first time liquefaction reaction and/or second of liquefaction reaction be each independently 15~
20MPa, reaction temperature are each independently 440~460 DEG C, and the volume of hydrogen and the weight ratio of coal slurry are each independently
800~1200L/Kg.
Further, coal slurry includes coal dust and catalyst for coal liquefaction, and preferably catalyst for coal liquefaction includes nanoscale hydration oxygen
Change any one of iron, natural crystal, the compound of pure state iron and nanoscale ferrous sulfide or a variety of, more preferable coal liquefaction catalysis
Agent is nanoscale hydrated ferric oxide；It is preferred that the dosage of catalyst for coal liquefaction accounts for 0.5~1.5wt% of coal slurry.
Further, in step sl, the temperature for the first liquefaction products being carried out with Oil-gas Separation is 410~440 DEG C, the time
Less than 5min, the preferably time is less than 3min.
Further, in step s 2, the temperature for the second liquefaction products being carried out with Oil-gas Separation is 380~430 DEG C.
Further, in step s3, the pressure of catalytic hydrogenation treatment is 15~19MPa, and reaction temperature is 350~390
DEG C, volume space velocity is 0.8~2.0h-1, hydrogen-oil ratio is 300~800.
Further, in step s3, catalytic hydrogenation is carried out to the second liquid phase product after distillation using hydrogenation catalyst
Processing, hydrogenation catalyst is loaded catalyst, and preferred vector is aluminium oxide, and the active metal component of loaded catalyst is
Any one of group vib or VIII group are a variety of, and the metal component of more preferable group vib is Mo and W, and the metal component of VIII group is
Ni and Co.
Further, Xun Huan solvent is also obtained in the step of carrying out catalytic hydrogenation treatment to part second liquid phase product,
During repeating, the first raw material includes partly cycling solvent, and the solvent in the second raw material cycles molten for another part
Agent, preferred cycle solvent are more than 220 DEG C of distillate for temperature, and density is 0.92~0.99g/cm3。
Further, the first gas-phase product is obtained in the step of carrying out Oil-gas Separation to the first liquefaction products, and right
Second liquefaction products carry out obtaining the second gas-phase product in the step of Oil-gas Separation, and step S3 further includes procedure below at this time：It is right
The mixture of first gas-phase product and the second gas-phase product carries out Oil-gas Separation, obtains the 3rd liquid product；3rd liquid phase is produced
Object is distilled and catalytic hydrogenation treatment, and preferably the mixture of the 3rd liquid product and second liquid phase product is distilled and urged
Change hydrotreating.
According to another aspect of the present invention, a kind of Direct coal liquefaction device is provided, Direct coal liquefaction device includes：First
Liquefying reactor has first circulation material inlet and the first product exit；Intermediate separator has the first product inlet and the
One liquid-phase outlet, the first product inlet are connected with the first product exit；Second liquefying reactor has the second feed(raw material)inlet, the
Two recycle stock entrances and the second product exit, the second feed(raw material)inlet are connected with the first liquid-phase outlet；First high pressure hot separator,
Exported with the second product inlet and second liquid phase, the second product inlet connect with the second product exit, second liquid phase export and
First circulation material inlet is connected with second circulation material inlet；There is vacuum distillation tower destilling tower entrance, destilling tower oil phase to go out
Mouth and destilling tower solid-phase outlet, destilling tower entrance and second liquid phase outlet；And solvent catalysis hydrogenation unit, with destilling tower
Oil phase outlet.
Further, above-mentioned intermediate separator also has the first gaseous phase outlet, and the first high pressure hot separator also has second
Gaseous phase outlet, Direct coal liquefaction device further include the first cold high pressure separator, and the first cold high pressure separator respectively with the first gas
Mutually outlet, the second gaseous phase outlet are connected with vacuum distillation tower entrance.
Further, above-mentioned first liquefying reactor and the second liquefying reactor are anti-independently selected from forced circulation suspension bed
Device, bubbling bed reactor, paste state bed reactor and the circulation flow reactor with guide shell are answered, is preferably that forced circulation suspension bed is anti-
Answer device.
Further, above-mentioned solvent catalysis hydrogenation unit includes the surge tank of sequential communication and catalytic hydrogenation reaction device, and
Surge tank is connected with vacuum distillation tower, preferred catalytic hydrogenation reactor be fixed bed reactors or fluidized bed reactor, more preferably
For fluidized bed reactor.
It applies the technical scheme of the present invention, provides a kind of coal direct liquefaction method, DCL/Direct coal liquefaction reaction process is drawn
It is divided to two relatively independent reaction systems, due to increasing between first time liquefaction reaction and second of liquefaction reaction to for the first time
Liquefaction products carry out the step of Oil-gas Separation, so as to not only significantly reduce the light oil residence time, avoid secondary cracking
Problem, reduce gas yield and hydrogen consumption, also help reduce second of liquefaction reaction in gas delay, and then improve it is more difficult
The residence time of transformation substance in the reaction, add the hydrogen partial pressure in reaction process；Also, due to anti-in the above-mentioned liquefaction of repetition
In the step of answering, the first raw material and/or the second raw material is made to further include the second liquid that the second liquefaction products obtain after Oil-gas Separation
Phase product, it is achieved thereby that cycling of the high score material in direct coal liquefaction process, the catalyst improved in liquefaction reaction contain
Amount and the reaction time for being relatively difficult to convert coal and bitumen, and then lique faction of coal conversion ratio is improved, finally carry
The oil yield of the high Coal Liquefaction Products obtained through catalytic hydrogenation treatment, resource utilization are obviously improved, and it is direct to enhance coal
The competitiveness of liquefaction technology.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.
Below with reference to figure, the present invention is described in further detail.
Description of the drawings
The Figure of description for forming the part of the present invention is used for providing a further understanding of the present invention, and of the invention shows
Meaning property embodiment and its explanation do not constitute improper limitations of the present invention for explaining the present invention.In the accompanying drawings：
Fig. 1 shows a kind of structure diagram for Direct coal liquefaction device that embodiment of the present invention is provided.
Wherein, above-mentioned attached drawing is marked including the following drawings：
110th, coal preparing tank；120th, heating furnace；130th, the first liquefying reactor；140th, intermediate separator；150th,
Two liquefying reactors；160th, the first high pressure hot separator；170th, the first cold high pressure separator；180th, vacuum distillation tower；210th, delay
Rush tank；220th, catalytic hydrogenation reaction device；230th, the second high pressure hot separator；240th, the second cold high pressure separator；250th, fractionating column；
101st, high-pressure coal pulp pump；102nd, coal liquefaction second reactor feed pump；103rd, hydrogenating materials pump.
Specific embodiment
It should be noted that in the case where there is no conflict, the feature in embodiment and embodiment in the present invention can phase
Mutually combination.The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.
In order to which those skilled in the art is made to more fully understand the present invention program, below in conjunction in the embodiment of the present invention
The technical solution in the embodiment of the present invention is clearly and completely described in attached drawing, it is clear that described embodiment is only
The embodiment of a part of the invention, instead of all the embodiments.Based on the embodiments of the present invention, ordinary skill people
Member's all other embodiments obtained without making creative work should all belong to the model that the present invention protects
It encloses.
It should be noted that term " first " in description and claims of this specification and above-mentioned attached drawing, "
Two " etc. be the object for distinguishing similar, without being used to describe specific order or precedence.It should be appreciated that it so uses
Data can exchange in the appropriate case, so as to the embodiment of the present invention described herein.In addition, term " comprising " and " tool
Have " and their any deformation, it is intended that cover it is non-exclusive include, for example, containing series of steps or unit
Process, method, system, product or equipment are not necessarily limited to those steps or unit clearly listed, but may include without clear
It is listing to Chu or for the intrinsic other steps of these processes, method, product or equipment or unit.
As background technology is described, existing overwhelming majority direct coal liquefaction process methods, there are secondary cracking,
The situation that gas yield and hydrogen consumption height and coal liquefaction second reactor severity reduce, oil low so as to cause lique faction of coal conversion ratio
Yield is low.To solve the above-mentioned problems, the present invention provides a kind of coal direct liquefaction method, comprise the following steps：S1 makes to include
First raw material of coal slurry and hydrogen carries out first time liquefaction reaction, obtains the first liquefaction products, and the first liquefaction products are carried out
Oil-gas Separation obtains the first liquid product；S2 makes the second raw material for including the first liquid product, hydrogen and solvent carry out second
Secondary liquefaction reaction obtains the second liquefaction products, and carries out Oil-gas Separation to the second liquefaction products, obtains second liquid phase product；S3,
Part second liquid phase product is distilled and catalytic hydrogenation treatment, obtain Coal Liquefaction Products；And S4, repeat above-mentioned step
Rapid S1 is to S3, and the first raw material and/or the second raw material further include remainder second liquid phase product during repeating.
In above-mentioned coal direct liquefaction method provided by the present invention, due to liquefying in first time liquefaction reaction and second
Increase the step of Oil-gas Separation is carried out to the first liquefaction products between reaction, Coal liquefaction is divided into two by a system
Relatively independent reaction system so as to not only significantly reduce the light oil residence time, avoids secondary cracking problem, reduces gas
Body yield and hydrogen consumption, also help the delay for reducing gas in second of liquefaction reaction, and then improve more difficult transformation substance and exist
Residence time in reaction adds the hydrogen partial pressure in reaction process；Also, due to repeat above-mentioned liquefaction reaction the step of
In, the first raw material and/or the second raw material is made to further include the second liquid phase product that the second liquefaction products obtain after Oil-gas Separation, from
And cycling of the high score material in direct coal liquefaction process is realized, improve catalyst content in liquefaction reaction and more difficult
To convert the reaction time of coal and bitumen, and then lique faction of coal conversion ratio is improved, finally improved through catalysis
The oil yield for the Coal Liquefaction Products that hydrotreating obtains, improves the level of resources utilization, enhances the competing of direct coal liquefaction technology
Strive power.
In coal direct liquefaction method provided by the present invention, the second gas is obtained after carrying out Oil-gas Separation to the second liquefaction products
Phase product (gas phase portion) and second liquid phase product (liquid-solid phase part), during above-mentioned steps S1 to S3 is repeated
One raw material and/or the second raw material further include part second liquid phase product, and another part obtains liquefied coal coil and residue after distillation.
Preferably, the second liquefaction products is controlled to carry out the temperature of Oil-gas Separation as 380~430 DEG C；Also, remainder second liquid phase produces
The inlet amount of object and the first raw material is than 0.1~1, and the inlet amount of remainder second liquid phase product and the second raw material is than 0.1~1.
By controlling above-mentioned inlet amount than can more effectively improve the catalyst content in liquefaction reaction and relatively be difficult to convert coal
With the residence time of bitumen, so as to improve lique faction of coal conversion ratio and oil yield.
Those skilled in the art may be employed in coal direct liquefaction method provided by the present invention, during liquefaction reaction to exist
Common catalyst during DCL/Direct coal liquefaction.In a preferred embodiment, the catalysis used during liquefaction reaction
Agent is water synthesis nano hydrated ferric oxide.Using hydrated ferric oxide as the catalyst of liquefaction reaction, production cost is low, and liquefaction is lived
Property it is high, catalyst loading can be reduced, improve the reaction rate of liquefaction reaction, promote the conversion of coal, improve oil yield, improved
The economy of the technique reduces coal liquefaction residue amount.In addition, those skilled in the art can select the specific use of the catalyst
Amount.Preferably, the dosage of above-mentioned catalyst is 0.5~1.5wt% of dry coal weight.
In coal direct liquefaction method provided by the present invention, liquefaction reaction process may be employed common in coal liquefaction
Process conditions.In a preferred embodiment, the pressure of first time liquefaction reaction and/or second of liquefaction reaction can be each
From 15~20MPa independently is, reaction temperature is 440~460 DEG C, and second of liquefaction reaction temperature should be with first time liquefaction reaction
Temperature is identical or slightly higher, and the ratio of hydrogen and coal is 800~1200L/kg.By each process regulation of liquefaction reaction upper
Scope is stated, Installed capital cost can be reduced, and Coal liquefaction can be made more abundant, there is higher coal during guarantee liquefaction reaction
Conversion ratio and liquid fuel yield.
In coal direct liquefaction method provided by the present invention, increase between first time liquefaction reaction and second of liquefaction reaction
Add and Oil-gas Separation is carried out to the first liquefaction products, Coal liquefaction is divided into two relatively independent reactants by a system
System, the first liquefaction products are carried out with the temperature of Oil-gas Separation needs as far as possible close to the temperature of first time liquefaction reaction.A kind of excellent
In the embodiment of choosing, the first liquefaction products are carried out with the temperature of Oil-gas Separation for 410~440 DEG C, the liquid phase residence time is less than 5
Minute, it is preferably less than 3 minutes, while the note disturbance measures such as hydrogen or cooling oil (cycling solvent) can be used, it can effectively control object
There is a situation where cokings during Oil-gas Separation for material.
In coal direct liquefaction method provided by the present invention, Xun Huan solvent catalysis hydrogenation process may be employed oil refining industry and urge
Change the process conditions of hydrogenation process.In a preferred embodiment, in above-mentioned steps S3, the pressure of catalytic hydrogenation treatment
For 15~19MPa, reaction temperature is 350~390 DEG C, and volume space velocity is 0.8~2.0h-1, hydrogen-oil ratio is 300~800.It will Xun Huan
Each process regulation within the above range, is conducive to catalytic hydrogenation reaction and more fully carries out in solvent catalysis hydrogenation process,
The hetero atom in liquefied coal coil is removed, realizes that aromatic hydrocarbons obtains fractional saturation in liquefied coal coil, increases reactive hydrogen quantity in solvent, carries
The hydrogen supply capacity of high circulation solvent produces qualified coal liquefaction Xun Huan solvent, is conducive to DCL/Direct coal liquefaction reaction, promotes coal
Liquefaction conversion can relatively be fully converted into the oil of small molecule.
In coal direct liquefaction method provided by the present invention, using hydrogenation catalyst to the second liquid of part after including distillation
The liquefied coal coil of phase product carries out catalytic hydrogenation treatment, and above-mentioned hydrogenation catalyst can be loaded catalyst.Add to improve
Hydrogen catalyst prepares high liquefying activity Xun Huan solvent, it is preferable that carrier is aluminium oxide, load to the catalytic performance of liquefied coal coil
The active metal component of type catalyst is any one of group vib or VIII group or a variety of, it is further preferable that the metal of group vib
Component is Mo and W, and the metal component of VIII group is Ni and Co.
In coal direct liquefaction method provided by the present invention, to including coal liquefaction obtained by the second liquid phase product distillation of part
Oil carries out also obtaining Xun Huan solvent in the step of catalytic hydrogenation treatment, and during repeating, the first raw material includes part
Solvent is cycled, the solvent in the second raw material cycles solvent for another part, that is, directly adds when configuring coal using solvent catalysis
Liquid be fractionated in hydrogen liquid product, in addition to liquid fuel is as Xun Huan solvent.By liquefying at second
Hydrogen and Xun Huan hydrogen supply dissolvent are injected in reaction, improves the hydrogen partial pressure and active amt in reaction process, promotion is difficult to turn
The coal of change and the conversion of pitch metallic substance are favourable.
In a preferred embodiment, coal liquefaction Xun Huan solvent is above-mentioned catalytic hydrogenation liquid product>220 DEG C evaporate
Divide oil, density is 0.92~0.99g/cm3.Fractional saturation arene content is higher in the distillate, and hydrogen supply capacity is strong, is made with it
To cycle solvent, the effect of liquefaction reaction can be further improved, and then improves the yield of liquid fuel.It is it is highly preferred that above-mentioned
The density of distillate is 0.95~0.97g/cm3, total arene content>70wt%, monocyclic and two ring aromatic content>55wt%.With
It is as Xun Huan solvent, and hydrogen supply capacity is stronger, the yield higher of liquid fuel.
In coal direct liquefaction method provided by the present invention, in the step of carrying out Oil-gas Separation to the first liquefaction products
To the first gas-phase product, and the second gas-phase product is obtained in the step of carrying out Oil-gas Separation to the second liquefaction products, this time step
Rapid S3 can also include procedure below：Oil-gas Separation is carried out to the mixture of the first gas-phase product and the second gas-phase product, is obtained
3rd liquid product；3rd liquid product is distilled and catalytic hydrogenation treatment, preferably to the 3rd liquid product and the second liquid
The mixture of phase product is distilled and catalytic hydrogenation treatment.3rd liquid product and second liquid phase product are mixed and distilled
To liquefied coal coil, catalytic hydrogenation treatment is carried out to it, removes the hetero atom in liquefied coal coil, realizes that aromatic hydrocarbons obtains in liquefied coal coil
Fractional saturation increases reactive hydrogen quantity in solvent, and make cycling solvent has hydrogen supply capacity, is conducive to DCL/Direct coal liquefaction reaction,
Promote lique faction of coal conversion, can more fully convert the oil of small molecule.
According to further aspect of the application, a kind of Direct coal liquefaction device is provided, as shown in Figure 1, DCL/Direct coal liquefaction
Device includes：First liquefying reactor 130 has the first feed(raw material)inlet, first circulation material inlet and the first product exit；In
Between separator 140, there is the first product inlet and the first liquid-phase outlet, the first product inlet connects with the first product exit；The
Two liquefying reactors 150 have the second feed(raw material)inlet, second circulation material inlet and the second product exit, the second feed(raw material)inlet
It is connected with the first liquid-phase outlet；There is first high pressure hot separator 160 second product inlet and second liquid phase to export, the second production
Object entrance is connected with the second product exit, and second liquid phase outlet connects with first circulation material inlet and second circulation material inlet
It is logical；Vacuum distillation tower 180 has destilling tower entrance, the outlet of destilling tower oil phase and destilling tower solid-phase outlet, destilling tower entrance and institute
State second liquid phase outlet；And solvent catalysis hydrogenation unit, with destilling tower oil phase outlet.
In above-mentioned Direct coal liquefaction device provided by the present invention, due to anti-in the first liquefying reactor and the second liquefaction
It answers and adds an intermediate separator between device, when being stopped so as to not only significantly reduce light oil using the intermediate separator
Between, it avoids secondary cracking problem, reduces gas yield and hydrogen consumption, also help and reduce the stagnant of gas in second of liquefaction reaction
It stays, and then improves the residence time of more difficult transformation substance in the reaction, add the hydrogen partial pressure in reaction process；Also, by
In the second liquid phase outlet of the first high pressure hot separator and the first circulation material inlet and the second liquid of the first liquefying reactor
Change the second circulation material inlet connection of reactor, it is achieved thereby that cycling of the high score material in direct coal liquefaction process, carries
Catalyst content in high liquefaction reaction and the reaction time for being relatively difficult to convert coal and bitumen, and then improve
Lique faction of coal conversion ratio, finally improves the oil yield of the Coal Liquefaction Products obtained through catalytic hydrogenation treatment, improves resource
Utilization ratio enhances the competitiveness of direct coal liquefaction technology..
In above-mentioned Direct coal liquefaction device provided by the present invention, make to include the first raw material of coal slurry and hydrogen into the
First time liquefaction reaction is carried out in one liquefying reactor 130, obtains the first liquefaction products, and using intermediate separator 140 to the
One liquefaction products carry out Oil-gas Separation, obtain the first gas-phase product and the first liquid product, the operation temperature of intermediate separator 140
Need access to 130 temperature of the first liquefying reactor.In a preferred embodiment, the operation temperature of intermediate separator 140
For 410~440 DEG C, the liquid phase residence time is less than 5 minutes, is preferably less than 3 minutes, while note disturbance hydrogen or cooling oil can be used
The measures such as solvent are cycled, it can effectively there is a situation where cokings in intermediate separator for control material.
In above-mentioned Direct coal liquefaction device provided by the present invention, the second raw material including the first liquid product and hydrogen
Second of liquefaction reaction is carried out in the second liquefying reactor 150, obtains the second liquefaction products, the first high pressure hot separator 160
Oil-gas Separation is carried out to above-mentioned second liquefaction products, obtains the second gas-phase product gas phase portion and second liquid phase product liquid-solid phase portion
Point, a second liquid phase product part is recycled in the first liquefying reactor 130 or/and the second liquefying reactor 150, another part
Liquefied coal coil and residue are obtained after the distillation of vacuum distillation tower 180；In a preferred embodiment, the first thermal high separates
The temperature control of device 160 is 380~430 DEG C, the ratio between liquid-solid phase solid circulating rate and coal liquefaction feedstock amount 0.1~1.
In Direct coal liquefaction device provided by the present invention, intermediate separator 140 also has the first gaseous phase outlet, the first heat
High-pressure separator 160 also has the second gaseous phase outlet, and Direct coal liquefaction device further includes the first cold high pressure separator 170, and the
One cold high pressure separator 170 connects respectively with the first gaseous phase outlet, the second gaseous phase outlet and vacuum distillation tower entrance.Using above-mentioned
First cold high pressure separator 170 can be by the light components in the first liquefaction products and the second liquefaction products and the first thermal high point
It is distilled to obtain liquefied coal coil and liquefied residue after mixing from 160 Partial Liquid Phase product of device, catalysis is carried out to liquefied coal coil and is added
Hydrogen processing, provides the cycling solvent with stronger hydrogen supply capacity, so as to improve lique faction of coal conversion ratio and oil yield.
In Direct coal liquefaction device provided by the present invention, catalytic hydrogenation unit can include sequential communication surge tank 210
With catalytic hydrogenation reaction device 220, and the destilling tower oil phase outlet of surge tank 210 and vacuum distillation tower 180.It is urged by above-mentioned
Change the catalytic hydrogenation treatment for the liquefied coal coil that hydrogenation unit can be realized to including second liquid phase product, so as to obtain coal liquefaction production
Product and the coal liquefaction solvent with stronger hydrogen supply performance；Preferably, above-mentioned catalytic hydrogenation reaction device 220 for fixed bed reactors or
Fluidized bed reactor；More preferably fluidized bed reactor, strong to adaptability to raw material, catalyst can be replaced online, ensure catalysis
Agent bed is activity stabilized, so as to ensure that Xun Huan solvent property is stablized.
In Direct coal liquefaction device provided by the present invention, the exit of catalytic hydrogenation reaction device 220 can be cycled
Solvent, i.e., Direct coal liquefaction device using the present invention directly can be hydrogenated with liquid phase during coal using solvent catalysis
Liquid be fractionated in product, in addition to liquid fuel is as Xun Huan solvent.By being noted in the second liquefying reactor 150
Enter hydrogen and cycle hydrogen supply dissolvent, improve the hydrogen partial pressure and active amt in reaction process, to promotion be difficult to the coal converted and
The conversion of pitch metallic substance is favourable, ensures that the reaction process in second reactor has higher hydrogen partial pressure and active amt, so as to carry
High lique faction of coal conversion ratio and oil yield.
In preparation method provided by the present invention, liquefaction reaction uses the common reactor of those skilled in the art.
In a preferred embodiment, the first liquefying reactor 130 and the second liquefying reactor 150 are independently selected from forced circulation
Suspended-bed reactor, bubbling bed reactor, paste state bed reactor or the circulation flow reactor with guide shell are more preferably forced to follow
Ring suspended-bed reactor, it is ensured that the flow rate of liquid in reactor reduces deposition of solids, and realization device long period is steady
Fixed operating.
Above-mentioned introduction according to the present invention, those skilled in the art can select specific operating system, to coal is straight
Connect liquefaction liquid fuel was prepared.Specific operating process can be as follows：
Become coal dust after coal is crushed, and after drying with Xun Huan solvent, catalyst for coal liquefaction in coal preparing tank 110
In be hybridly prepared into pump conveying coal slurry.Coal slurry is mixed after high-pressure coal pulp pump 101 boosts with hydrogen, into heating furnace
120, heat temperature raising.120 outlet temperature of heating furnace is controlled at 350 DEG C or more.
The first liquid that coal slurry after heated is exported with hydrogen into the first liquefying reactor 130, the first liquefying reactor 130
Change product and enter intermediate separator 140, temperature control is at 410~440 DEG C, and the residence time is less than 3 minutes, intermediate separator 140
The first liquid product (liquid phase material) of outlet is conveyed through coal liquefaction second reactor feed pump 102, and molten with hydrogen and Xun Huan
Agent enters the second liquefying reactor 150 after mixing.In two liquefying reactors, controlling reaction temperature is 420~470 DEG C, pressure
It is 800~1200L/Kg for 15~20MPa, hydrogen and coal slurry ratio, under the effect of the catalyst, liquefaction reaction generation occurs for coal dust
Gas-phase product and liquid product mixture.Second liquefaction products of the second liquefying reactor 150 outlet divide into the first thermal high
Oil-gas Separation is carried out from device 160, separation temperature is controlled at 400~420 DEG C；The of first high pressure hot separator, 160 top output
It is separated after the first gas-phase product mixing that two gas-phase products are isolated with intermediate separator 140 after cooling into the first cold anticyclone
Device 170；First cold high pressure separator 170 is controlled below 45 DEG C, and the discharge of top gas phase part returns to heating furnace as recycle hydrogen
120 entrances, are partly discharged, and the second liquid phase product section that 160 bottom of the first high pressure hot separator is isolated is recycled back to
One liquefying reactor 130 and/or the second liquefying reactor 150；First cold high pressure separator, 170 bottom generate liquid product with
Enter vacuum distillation tower 180 after another part liquid product mixing of first high pressure hot separator, 160 bottom.In vacuum distillation tower
Separation of solid and liquid is carried out in 180, in order to ensure that coal liquefaction solvent fully recycles, while residue has good transportation performance, control
The solid concentration being evaporated under reduced pressure in bottom of towe residue is 50~55%.
The liquefied coal coil of 180 output of vacuum distillation tower enters surge tank 210, after 103 boosting of hydrogenating materials pump, with hydrogen
Into catalytic hydrogenation reaction device 220 after gas mixing preheating, catalytic hydrogenation reaction is carried out, realizes aromatic moiety hydrogenation saturation, simultaneously
Generation work desulfurization, denitrogenation and deoxygenation.During catalytic hydrogenation reaction, control pressure be 8~20MPa, reaction temperature 320
~390 DEG C, 0.5~2.0h of volume space velocity-1.The material that catalytic hydrogenation reaction device 220 exports output is separated into the second thermal high
Device 230.The gas phase of second high pressure hot separator, 230 output is after supercooling into the second cold high pressure separator 240, temperature control
System is below 45 DEG C.The discharge of second cold high pressure separator, 240 top gas phase part returns to hydrogenation catalyst reactant as recycle hydrogen
System, is partly discharged；Second high pressure hot separator, 230 bottom liquid phases material flows into fractionating column 250 after decompression, is produced
Product separate, and obtain liquid fuel and Xun Huan solvent, and the liquid fuel of formation includes naphtha and diesel oil.
The present invention is described in further detail below in conjunction with specific embodiment, these embodiments are it is not intended that limit this
Invent scope claimed.
Embodiment 1
Coal direct liquefaction method provided in this embodiment carries out coal liquefaction experiment using DCL/Direct coal liquefaction long run test device,
Device uses the suspended-bed reactor of two forced circulations, and intermediate separator is set between reactor, the second liquefying reactor
Outlets products liquid-solid phase material parts after separation are recycled back to the first liquefying reactor entrance.Using refreshing eastern coal as test raw material coal,
Feed coal is placed in coal slurry tank and mixed with catalyst, coal liquefaction Xun Huan solvent, obtains coal slurry, feed coal fundamental property is shown in Table 1,
Above-mentioned coal direct liquefaction method comprises the following steps：
First, above-mentioned coal slurry liquefies with hydrogen into the first liquefying reactor (forced circulation suspended-bed reactor), first
First liquefaction products of reactor outlet enter intermediate separator, and temperature is controlled at 430 DEG C, residence time 5min, centre point
The first liquid product from device outlet convey through the second liquefying reactor feed pump, and with hydrogen and cycling after solvent mixes and entering the
Two liquefying reactors (forced circulation suspended-bed reactor), in two liquefying reactors, controlling reaction temperature is 455 DEG C, instead
Pressure 19.0MPa, hydrogen and coal ratio are answered as 1000L/Kg, and catalyst for coal liquefaction is artificial synthesized 863 catalyst, coal liquid
Change catalyst loading is 1.0wt%, and auxiliary agent is sulphur, control n (S)/n (Fe)=2；The second of second liquefying reactor outlet
Liquefaction products carry out Oil-gas Separation into the first high pressure hot separator, and separation temperature is controlled at 410 DEG C；First high pressure hot separator
The first gas-phase product that the second gas-phase product and the intermediate separator of top output are isolated enters first after mixing after cooling
Cold high pressure separator；First cold high pressure separator is controlled below 45 DEG C, and the discharge of top gas phase part is returned as recycle hydrogen to be added
Hot stove entrance, is partly discharged, and the second liquid phase product section that the first high pressure hot separator bottom is isolated is recycled back to first
Liquefying reactor 130, and part second liquid phase product and the first material quantity are than 0.3；What the first cold high pressure separator bottom generated
Liquid product enters vacuum distillation tower after being mixed with another part liquid product of the first high pressure hot separator bottom, is steamed in decompression
It evaporates and separation of solid and liquid is carried out in tower 180, it is 50% to control the solid concentration in vacuum distillation bottom of towe residue.
Then, the liquefied coal coil of output enters stabilized hydrogenation raw material surge tank in the middle part of vacuum distillation tower, by hydrogenating materials
After pump boosting, enter catalytic hydrogenation reaction device (forced-circulation boiling bed hydroprocessing reactor) after preheating is mixed with hydrogen, urged
Change hydrogenation reaction, realize aromatic moiety hydrogenation saturation, while desulfurization, denitrogenation and deoxygenation occurs；Catalytic hydrogenation reaction process
In, control pressure 19MPa, reaction temperature is 380 DEG C, volume space velocity 1.0h-1, hydrogen-oil ratio 300, the outlet of catalytic hydrogenation reaction device
The material of output enters the second high pressure hot separator；The gas phase of second high pressure hot separator output is cold into second after supercooling
High-pressure separator, temperature are controlled below 45 DEG C；The discharge of second cold high pressure separator top gas phase part is returned as recycle hydrogen
Hydrogenation catalyst reaction system is returned, is partly discharged；Second high pressure hot separator bottom liquid phases material flows into after decompression to be divided
Tower is evaporated, carries out product separation, obtains the liquid fuel for including naphtha and diesel oil and Xun Huan solvent, and the temperature for cycling solvent is
220 DEG C of distillate.
Embodiment 2
Coal direct liquefaction method provided in this embodiment and embodiment 1 difference lies in：
The inlet amount of part second liquid phase product and the first raw material is than 0.1.
Embodiment 3
Coal direct liquefaction method provided in this embodiment and embodiment 1 difference lies in：
The inlet amount of part second liquid phase product and the first raw material is than 1.
Embodiment 4
Coal direct liquefaction method provided in this embodiment and embodiment 1 difference lies in：
The inlet amount of part second liquid phase product and the second raw material is than 0.1.
Embodiment 5
Coal direct liquefaction method provided in this embodiment and embodiment 1 difference lies in：
The inlet amount of part second liquid phase product and the second raw material is than 1.0.
Embodiment 6
Coal direct liquefaction method provided in this embodiment and embodiment 1 difference lies in：
Part second liquid phase product and the first raw material/inlet amount than 0.2, part second liquid phase product and the first raw material
Inlet amount is than 0.3.
Embodiment 7
Coal direct liquefaction method provided in this embodiment and embodiment 1 difference lies in：
The temperature of Coal liquefaction is 430 DEG C, and reaction pressure 15.0MPa, hydrogen and coal ratio are 750L/Kg.
Embodiment 8
Coal direct liquefaction method provided in this embodiment and embodiment 1 difference lies in：
The temperature of Coal liquefaction is 460 DEG C, and reaction pressure 20.0MPa, hydrogen and coal ratio are 1200L/Kg.
Embodiment 9
Coal direct liquefaction method provided in this embodiment and embodiment 1 difference lies in：
The additive amount of catalyst for coal liquefaction is 0.4wt%.
Embodiment 10
Coal direct liquefaction method provided in this embodiment and embodiment 1 difference lies in：
The additive amount of catalyst for coal liquefaction is 2.0wt%.
Embodiment 11
Coal direct liquefaction method provided in this embodiment and embodiment 1 difference lies in：
The pressure of solvent catalysis hydrotreating is 8MPa, and reaction temperature is 320 DEG C, volume space velocity 0.8h-1, hydrogen-oil ratio is
800。
Embodiment 12
Coal direct liquefaction method provided in this embodiment and embodiment 1 difference lies in：
The pressure of solvent catalysis hydrotreating is 19MPa, and reaction temperature is 390 DEG C, volume space velocity 2.0h-1, hydrogen-oil ratio
For 800.
Embodiment 13
Coal direct liquefaction method provided in this embodiment and embodiment 1 difference lies in：
Liquefaction second reactor entrance is not injected into the solvent for cycling.
Comparative example 1
This comparative example and embodiment 1 difference lies in：
Coal liquefaction experiment is carried out using DCL/Direct coal liquefaction long run test device, which uses the suspension of two forced circulations
Bed reactor, but intermediate separator is not provided between reactor, high score material does not cycle.
Comparative example 2
This comparative example and embodiment 1 difference lies in：
Coal liquefaction experiment is carried out using DCL/Direct coal liquefaction long run test device, which uses the suspension of two forced circulations
Bed reactor, sets intermediate separator between reactor, second liquid phase product is not recycled to the first liquefying reactor and the second liquid
Change reactor.
God east lique faction of coal reaction result is shown in Table 2 in above-described embodiment 1-13 and comparative example 1-2.
Table 1
Table 2
By table 2 as it can be seen that separation among setting under identical reaction conditions, between two tandem reactors of DCL/Direct coal liquefaction
After device and high score material parts Xun Huan, gas yield has to be declined by a relatively large margin, is minimized 12.60% by 15.42%, is reduced by 3
More than percentage point, hydrogen consumption slightly decreases, and minimum 5.53% is reduced to by 5.79%；Simultaneously it is also found that the liquid of the eastern coal of god
Change conversion ratio and increase to highest 92.21% by 88.89%, increase by 2 percentage points or more, while pitch yield also has apparent drop
It is low, 7.21% is minimized by 10.49%, reduces by 3 percentage points or more；Distillation oil yield has and increases by a relatively large margin, by
53.79% increases to highest 59.92%, increases by 6 percentage points or more.
It is also known by table 2, intermediate separator is set between two tandem reactors of DCL/Direct coal liquefaction but high score material does not follow
In the case of ring, gas yield is also decreased obviously, and 13.98% is minimized by 15.42%, reduces about 1.5 percentage points, hydrogen consumption
Variation is little；Refreshing east lique faction of coal conversion ratio increases to highest 91.10% by 88.89%, increases by 1 percentage point or more, drips simultaneously
Blue or green yield is also substantially reduced, and is minimized 8.77% by 10.49%, is reduced about 1.8 percentage points.
It is also known by table 2, sets intermediate point under identical reaction conditions, between two tandem reactors of DCL/Direct coal liquefaction
From device, after high score material parts cycle, but the second liquefying reactor entrance is not injected into cycling solvent, and gas yield substantially rises, by
12.60% rises to 14.37%；Hydrogen consumes also more apparent increase, and 6.07% is increased to by 5.53%；The conversion ratio of coal is by 92.21% drop
To 90.63%, 1.5 percentage points or more are reduced；Oil yield is down to 54.66% by 59.92%, reduce 5 percentage points with
On, asphalitine yield increases to 9.98% by 7.21%, adds about 2.7 percentage points.
It can be seen from the above description that the above embodiments of the present invention realize following technique effect：
1st, added between first time liquefaction reaction and second of liquefaction reaction and oil gas point is carried out to the first liquefaction products
From the step of, Coal liquefaction is divided into two relatively independent systems by a system, not only significantly reduces light oil
Residence time avoids secondary cracking problem, reduces gas yield and hydrogen consumption, also helps and reduce gas in second of liquefaction reaction
The delay of body, and then the residence time of more difficult transformation substance in the reaction is improved, the hydrogen partial pressure in reaction process is added, is had
Beneficial to raising lique faction of coal conversion ratio and oil yield；
2nd, the first raw material and/or the second raw material further include the second liquid phase production that the second liquefaction products obtain after Oil-gas Separation
Part second liquid phase product circulation is returned Coal liquefaction process by object, improve catalyst content in liquefaction reaction and compared with
It is difficult to convert the residence time of coal and bitumen, and then improves lique faction of coal conversion ratio, ultimately increase coal liquefaction
Oil yield improves resource utilization, enhances the competitiveness of direct coal liquefaction technology；
3rd, by injecting hydrogen and Xun Huan hydrogen supply dissolvent in second of liquefaction reaction, the hydrogen point in reaction process is improved
Pressure and active amt, promotion are difficult to the coal converted and the oil for being further converted to small molecule of pitch metallic substance, are also beneficial to carry
The conversion ratio and oil yield of high coal.
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should all be included in the protection scope of the present invention.
Claims (14)
1. a kind of coal direct liquefaction method, which is characterized in that comprise the following steps：
S1 makes the first raw material for including coal slurry and hydrogen carry out first time liquefaction reaction, obtains the first liquefaction products, and to described
First liquefaction products carry out Oil-gas Separation, obtain the first liquid product；
S2 makes the second raw material for including first liquid product, hydrogen and solvent carry out second of liquefaction reaction, obtains second
Liquefaction products, and Oil-gas Separation is carried out to second liquefaction products, obtain second liquid phase product；
S3, distills the part second liquid phase product and catalytic hydrogenation treatment, obtains Coal Liquefaction Products；And
S4 repeats above-mentioned steps S1 to S3, and first raw material and/or described during described repeat
Two raw materials further include second liquid phase product described in remainder.
2. coal direct liquefaction method according to claim 1, which is characterized in that the remainder second liquid phase product with
The inlet amount of first raw material is than 0.1~1, the inlet amount ratio of the remainder second liquid phase product and second raw material
0.1~1.
3. coal direct liquefaction method according to claim 1, which is characterized in that the first time liquefaction reaction and/or institute
The pressure for stating second of liquefaction reaction is each independently 15~20MPa, and reaction temperature is each independently 440~460 DEG C, hydrogen
The volume of gas and the weight ratio of coal slurry are each independently 800~1200L/Kg.
4. coal direct liquefaction method according to claim 1, which is characterized in that the coal slurry includes coal dust and coal liquefaction is urged
Agent, preferably described catalyst for coal liquefaction include nanoscale hydrated ferric oxide, natural crystal, the compound of pure state iron and nanoscale
Any one of ferrous sulfide is a variety of, and the more preferable catalyst for coal liquefaction is nanoscale hydrated ferric oxide；It is preferred that the coal
The dosage of deliquescence accelerant accounts for 0.5~1.5wt% of the coal slurry.
5. coal direct liquefaction method according to claim 1, which is characterized in that in the step S1, to described first
Liquefaction products carry out the temperature of Oil-gas Separation as 410~440 DEG C, and the time is less than 5min, and the preferably time is less than 3min.
6. coal direct liquefaction method according to claim 1, which is characterized in that in the step S2, to described second
The temperature that liquefaction products carry out Oil-gas Separation is 380~430 DEG C.
7. coal direct liquefaction method according to claim 1, which is characterized in that in the step S3, the catalysis adds
The pressure of hydrogen processing is 15~19MPa, and reaction temperature is 350~390 DEG C, and volume space velocity is 0.8~2.0h-1, hydrogen-oil ratio 300
~800.
8. coal direct liquefaction method according to claim 1, which is characterized in that in the step S3, urged using hydrogenation
Agent carries out the second liquid phase product after distillation catalytic hydrogenation treatment, and the hydrogenation catalyst is loaded catalyst,
Preferred vector is aluminium oxide, and the active metal component of the loaded catalyst is any one of group vib or VIII group or more
Kind, the metal component of more preferable group vib is Mo and W, and the metal component of VIII group is Ni and Co.
9. coal direct liquefaction method according to claim 4, which is characterized in that the part second liquid phase product into
Xun Huan solvent is also obtained in the step of row catalytic hydrogenation treatment, during described repeat, first raw material includes
Part the cycling solvent, the solvent in second raw material is cycles solvent described in another part, preferably described cycling
Solvent is more than 220 DEG C of distillate for temperature, and density is 0.92~0.99g/cm3。
10. coal direct liquefaction method according to claim 1, which is characterized in that carried out to first liquefaction products
The first gas-phase product is obtained in the step of Oil-gas Separation, and is obtained in the step of carrying out Oil-gas Separation to second liquefaction products
To the second gas-phase product, the step S3 further includes procedure below at this time：
Oil-gas Separation is carried out to the mixture of first gas-phase product and second gas-phase product, obtains the production of the 3rd liquid phase
Object；
3rd liquid product is distilled and catalytic hydrogenation treatment, preferably to the 3rd liquid product and described second
The mixture of liquid product carries out the distillation and the catalytic hydrogenation treatment.
11. a kind of Direct coal liquefaction device, which is characterized in that the Direct coal liquefaction device includes：
First liquefying reactor (130) has first circulation material inlet and the first product exit；
Intermediate separator (140) has the first product inlet and the first liquid-phase outlet, first product inlet and described first
Product exit connects；
Second liquefying reactor (150) has the second feed(raw material)inlet, second circulation material inlet and the second product exit, described
Second feed(raw material)inlet is connected with first liquid-phase outlet；
First high pressure hot separator (160) there is the second product inlet and second liquid phase to export, second product inlet and institute
The connection of the second product exit is stated, the second liquid phase outlet enters with the first circulation material inlet and the second circulation material
Mouth connection；
Vacuum distillation tower (180) has destilling tower entrance, the outlet of destilling tower oil phase and destilling tower solid-phase outlet, the destilling tower
Entrance and the second liquid phase outlet；And
Solvent catalysis hydrogenation unit, with the destilling tower oil phase outlet.
12. Direct coal liquefaction device according to claim 11, which is characterized in that the intermediate separator (140) also has
There is the first gaseous phase outlet, first high pressure hot separator (160) also has the second gaseous phase outlet, the Direct coal liquefaction device
The first cold high pressure separator (170) is further included, and first cold high pressure separator (170) goes out respectively with first gas phase
Mouth, second gaseous phase outlet are connected with the vacuum distillation tower entrance.
13. Direct coal liquefaction device according to claim 11, which is characterized in that first liquefying reactor (130)
It is anti-independently selected from forced circulation suspended-bed reactor, bubbling bed reactor, slurry bed system with second liquefying reactor (150)
Device and the circulation flow reactor with guide shell are answered, is preferably forced circulation suspended-bed reactor.
14. Direct coal liquefaction device according to claim 11, which is characterized in that the solvent catalysis hydrogenation unit includes
The surge tank (210) of sequential communication and catalytic hydrogenation reaction device (220), and the surge tank (210) and the vacuum distillation tower
(180) connect, preferably described catalytic hydrogenation reaction device (220) is fixed bed reactors or fluidized bed reactor, is more preferably boiled
Rise a reactor.
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