CN107267186B - The method that coal mild hydrogenation pyrolysis prepares liquid hydrocarbon - Google Patents
The method that coal mild hydrogenation pyrolysis prepares liquid hydrocarbon Download PDFInfo
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- CN107267186B CN107267186B CN201610207796.7A CN201610207796A CN107267186B CN 107267186 B CN107267186 B CN 107267186B CN 201610207796 A CN201610207796 A CN 201610207796A CN 107267186 B CN107267186 B CN 107267186B
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- 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
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
- C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
-
- 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
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- 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
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
-
- 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
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
Abstract
The present invention relates to the methods that coal mild hydrogenation pyrolysis prepares liquid hydrocarbon.This method includes that coal and solvent naphtha and catalyst and auxiliary agent mixed pulp, preheating, hydropyrolysis liquefy and separate obtained product；The gas-phase product isolated is enriched with after purification, it is returned obtained hydrogen-rich gas as circulating hydrogen in the preparation system, obtained hydrocarbon-rich gas as fuel is used；Separated liquid product out can produce the liquid hydrocarbon of different purposes directly as product or through further hydrofinishing；Separated solid product such as semicoke out can be by gasification production hydrogen or directly as product.Compared with existing coal directly produces the method for liquid form product, method of the invention can realize high oil yield under mild reaction conditions, and have many advantages, such as simple process and at low cost.
Description
Technical field
The invention belongs to the technical fields of Coal dressing production liquid hydrocarbon.Specifically, the present invention relates to coal mild hydrogenations
The method that pyrolysis prepares liquid hydrocarbon.
Background technique
It is well known that the reserves of coal are huge in non-renewable energy, and reserves is relatively fewer.But due to petroleum
It is easy to transport and process, so that countries in the world are thirsted for meeting industry, life, national defence etc. by obtaining a large amount of petroleum resources
Demand.With the economic development in China, the demand of oil product (such as gasoline, diesel oil) is also increasingly increased in recent years.
But due to China's endowment of resources rich in coal and poor in oil, so that oil selfsufficiency rate declines year by year, external dependence degree is continuously increased, therefore stone
The supply of stablizing of oil product becomes one of an important factor for restricting China's economic development.Lack the feature of oil based on the more coals in China, with
Coal is that raw material produces the coal conversion technology of liquid hydrocarbon as the effective way to solve the above problems.
Coal liquefaction is the coal solid state by a series of physical, chiral process, converts it into liquid
The coal conversion technology of hydrocarbon.According to different processing routes, the technology that can convert coal into liquid hydrocarbon is divided into the dry distillation of coal (heat
Solution), DCL/Direct coal liquefaction and ICL for Indirect Coal Liquefaction three categories.The dry distillation of coal (pyrolysis) is to heat coal in the case where completely cutting off air conditions, makes it
It decomposes, generates the process of the products such as coke (or semicoke), coal tar, crude benzol, coal gas.By the difference of heating final temperature, height can be divided into
The three classes distillation process such as warm destructive distillation (900-1100 DEG C), medium temperature carbonization (700-900 DEG C) and low temperature distillation (500-600 DEG C).Coal
Charcoal direct liquefaction is the technology that the coal of macromolecular is converted to the liquid hydrocarbon of small molecule under certain temperature, hydrogen and pressure.
Indirect coal liquefaction is to convert coal into synthesis gas (CO+H by gasification2), catalyzed conversion (F- T synthesis) technology is then used,
By CO and H2It is converted into liquid hydrocarbon.
The dry distillation of coal (pyrolysis) obtained liquid is commonly referred to as coal tar.Energy consumption is high for this production process, liquid yield is low,
And product component distribution is wide, and separation costs are high, and coal tar constituent is complicated.Coal tar aromatization degree is high, production
There is serious problem of environmental pollution with separation process.Indirect coal liquefaction technology relative maturity, produced oil product is without miscellaneous
Atom, arene content is extremely low, and successful comercial operation case occur in the states such as South Africa after World War II.Compared with indirect coal liquefaction, coal
Charcoal direct liquefaction has the advantages that overall process energy efficiency is high.The existing very long developing history of Technology of direct coal liquefaction.The
Before World War II, just there are DCL/Direct coal liquefaction comercial operation device, but the extremely harshness (about 470 of operating condition at that time in Germany
DEG C, about 70MPa).After World War II, due to the rapid development of petroleum industry, DCL/Direct coal liquefaction factory is closed successively.By nearly one
The effort of a century related researcher, the especially liquefaction of Shenhua DCL/Direct coal liquefaction in recent years technology (ShenHua) Commercial Demonstration
The successful operation of device is practiced, and the severe of DCL/Direct coal liquefaction operating condition is made to have a reduction by a relatively large margin, but from objective
For upper still more harsh (about 455 DEG C, about 20MPa).Typical direct coal liquefaction process and operating condition such as the following table 1 institute
Show.
Table 1: typical direct coal liquefaction process and operating condition
The harsh reaction condition of existing direct coal liquefaction technology correspond to a high investment cost and high operation at
This.Therefore, related researcher has been working hard the method for seeking coal hydro-conversion under mild reaction conditions.
Chinese invention patent ZL200480035693.2, Chinese invention patent ZL200610070581.1, Chinese invention are special
Coal hydrogenation disclosed in sharp ZL201010192050.6, China ZL96102808.4 and Chinese invention patent ZL200910075453.X
The method of conversion all has reaction condition opposite the characteristics of mitigating.
Wherein, the temperature and pressure of hydrogenation reaction disclosed in Chinese invention patent ZL200480035693.2 is respectively 360
DEG C -440 DEG C and 3-30MPa, however, the hydrogenation reaction also needs to realize that product separates using solvent-extracted method, therefore,
In need to include solvent deliming unit and Solvent deasphalting unit.
Chinese invention patent ZL96102808.4 is mainly for the production of solvent refined coal, and wherein oil product is byproduct.The party
Method because do not pursue high oil yield, the hydrogenation conditions used more mitigates (temperature of hydrogenation reaction for 350 DEG C-
480 DEG C, pressure 2-20MPa), this is not obviously able to satisfy the needs commercially produced.
Chinese invention patent ZL200610070581.1 discloses a kind of using hydrogen source material, under normal pressure directly adds coal
The method of hydrogen.The detailed process of this method includes: after mixing coal base preasphaltene with metal material, through at 600-1200 DEG C
Carbonisation be made hydrogen storage material；By this hydrogen storage material and metallic compound, one is made by ball milling in a hydrogen atmosphere
Kind hydrogen source material；Then this hydrogen source material is mixed to the direct hydrogenation liquid for realizing coal under normal pressure with coal-based pitch alkene and coal
Change.Although hydrogenation reaction temperature range used in this method is 380 DEG C -450 DEG C, must be in 600-1200 in this method
It is carbonized under DEG C this harsh reaction condition.
A kind of utilization hydrogen supply dissolvent and catalyst for preparing hydrogen low pressure are disclosed in Chinese invention patent ZL2010101922050.6
Hydrogen supply in situ makes the method that coal directly converts, and the detailed process of this method includes: by coal, naphthane, methanol or ethyl alcohol, calcium oxide
Or sodium carbonate and FeS are mixed in proportion, are slurried mixture, then heating is reacted in a nitrogen atmosphere, wherein is added
The temperature of hydrogen reaction is 350 DEG C -450 DEG C, pressure 1MPa.
The characteristics of Chinese invention patent ZL200910075453.X be by coal and heavy oil coprocessing with and meanwhile produce liquid and fire
Material and pitch class paveio(u)r, because not pursuing high liquid yield, the reaction condition used, which also more mitigates, (adds hydrogen anti-
The temperature answered is 300 DEG C -450 DEG C, pressure 5-20MPa).
As it can be seen that in the previous disclosed method for converting coal direct hydrogenation, if chased after for the purpose of producing liquid fuel
Higher liquid hydrocarbon yield is sought, then is undoubtedly needed using harsh reaction condition (such as Chinese invention patent
Need to be carbonized at 600-1200 DEG C in ZL200610070581.1 etc.) or need to be using the catalysis of cumbersome technical process and valuableness
Agent come improve liquid hydrocarbon yield (for example, Chinese invention patent ZL200480035693.2 report under harsh reaction condition
Maximum conversion is 81%；Chinese invention patent ZL201010192050.6 report the conversion ratio under harsh reaction condition be
50.5%-81.8%, oil+gas yield are 31.5%-62.0%)；Meanwhile through research, the inventor has found that, if by above-mentioned
When technique is implemented under relatively mild reaction conditions, then exist above-mentioned technique can not carry out operation or liquid hydrocarbon yield (that is,
Oil yield) too low problem.Moreover, the method for the presently disclosed mild direct hydrogenation conversion of major part coal is ground also in laboratory
Study carefully the stage, and can not be applied at industrial scale.
Summary of the invention
The present invention is intended to provide a kind of reaction condition is mild, investment is low with operating cost, the simple coal of technical process adds
The method that hydrogen pyrolysis prepares liquid hydrocarbon.The present invention by catalysts and solvents oil effective cooperation, thus opposite in technical process
It still is able in the case that simpler, reaction condition is more mild (of the invention with high coal conversion ratio and liquid hydrocarbon yield
Conversion ratio is between 82.01%-95.95%, and liquid hydrocarbon yield is between 57.08%-73.09%) obtain liquid hydrocarbon.
In one aspect, the present invention provides the method that coal mild hydrogenation pyrolysis prepares liquid hydrocarbon, this method includes following
Step:
(1) coal dust is made in feed coal crushing；
(2) coal dust obtained in step (1) is mixed with solvent naphtha, catalyst, auxiliary agent, to obtain coal；
(3) coal obtained in step (2) and fresh hydrogen and/or hydrogen-rich gas are sent into preheater and are carried out in advance
Heat, to obtain preheated coal and preheated fresh hydrogen and/or hydrogen-rich gas；
(4) coal preheated obtained in step (3) and preheated hydrogen-rich gas are sent into hydropyrolysis liquid
Change and reacted in reactor, to generate gas-phase product and liquid consolidates mix products；
(5) gas-phase product generated in hydropyrolysis liquefying reactor is sent into thermal high gas-liquid separator and is divided
From；Gas-phase product and liquid product are generated in thermal high gas-liquid separator, wherein the liquid generated in thermal high gas-liquid separator
Phase product is hot high score oil；
(6) gas-phase product generated in thermal high gas-liquid separator is sent into cold anticyclone gas-liquid separator and is separated；
Liquid product and gas-phase product are generated in cold anticyclone gas-liquid separator, wherein the liquid phase generated in cold anticyclone gas-liquid separator
Product obtains cold high score oil and water after water-oil separating, and the gas-phase product generated in cold anticyclone gas-liquid separator is separated, is enriched with
After purification, hydrogen-rich gas, hydrocarbon-rich gas and tail gas are obtained；
(7) by the liquid generated in the hydropyrolysis liquefying reactor of step (4) consolidate mix products be sent into medium pressure flash tank into
Row separation；Gas-phase product and liquid-solid mixture are generated in medium pressure flash tank, wherein produce the gas phase generated in medium pressure flash tank
Object is separated through gas-liquid separator, to generate liquid product and gas-phase product in gas-liquid separator, wherein gas-liquid separation
The liquid product generated in device is flash oil；
(8) hot high score oil obtained in step (5) is merged to obtain with flash oil obtained in step (7) in crude oil tank
Mixing crude oil；
(9) by liquid-solid mixture obtained in medium pressure flash tank and the (mixing of remainder of part or all of mixing crude oil
Crude oil can be used as final products collection) it carries out being mixed and fed into atmospheric distillation tower and is separated；Go out from the top of atmospheric distillation tower
Mouth generates often top oil and water；Normal side oil is generated from the outlet of the side line of atmospheric distillation tower；It is generated in the bottom of the atmospheric distillation tower
Liquid-solid mixture；
(10) liquid-solid mixture generated in the bottom of atmospheric distillation tower feeding vacuum distillation tower is separated；From decompression
The side line outlet of destilling tower, which generates, subtracts side oil；Liquid-solid mixture is generated in the bottom of the vacuum distillation tower；
(11) some or all of liquid-solid mixture of tower bottom will be evaporated under reduced pressure and be sent into extraction tower or delayed coking unit；
Extract oil is obtained from the outlet of the side line of extraction tower, obtains extracting residue in the bottom of extraction tower；Delayed coking unit generation LPG,
Coking light oil, coking mink cell focus and semicoke.
In certain embodiments of the present invention, the feed coal in step (1) is lignite, bituminous coal, mud coal or theirs is mixed
Close object.
In certain embodiments of the present invention, in step (2), the solvent naphtha is that boiling range is in 220 DEG C -550 DEG C
Oil in range.
In certain embodiments of the present invention, the solvent naphtha in step (2) is the mixing rich in aromatic hydrocarbons and hydrogenation of aromatics
Oil, for example, the miscella rich in aromatic hydrocarbons and hydrogenation of aromatics is selected from: hot high score oil obtained in step (5)；The step
(6) cold high score oil obtained in；Flash oil obtained in step (7)；Mixing crude oil obtained in step (8)；In step (9)
The normal side oil and normal top oil arrived；Subtract side oil obtained in step (10)；Coking mink cell focus obtained in step (11), coking lightweight
Oil and extract oil；Catalytic cracked oil pulp；Catalytic cracking recycle oil；Aromatics Extractive Project oil；Reduced crude；Decompression residuum；Visbreaker tar；
Coal tar；Shale oil；Or their mixture or reprocessing product.
In certain embodiments of the present invention, the catalyst in step (2) be ferrum-based catalyst (such as magnetic iron ore),
Nickel-base catalyst, catalyst with base of molybdenum, cobalt-base catalyst, tungsten-based catalyst；And/or based in iron, nickel, molybdenum, cobalt and tungsten
The catalyst of any two or various metals.In further preferred embodiment of the present invention, the catalyst in step (2) is preferred
For ferrum-based catalyst and/or Ni/Mo base catalyst.
In certain embodiments of the present invention, the auxiliary agent in step (2) is elemental sulfur, hydrogen sulfide, thioether and/or anti-
Decomposable other sulfur-containing compounds under the conditions of answering.
In certain embodiments of the present invention, in step (2), coal dust: solvent naphtha: catalyst: the mass ratio of auxiliary agent
For 100:(70-1200): (0.1-5.0): (0-5.0), wherein catalyst is in terms of metallic element quality.
In certain embodiments of the present invention, the outlet temperature of the preheater in step (3) is 300 DEG C -400 DEG C.
In certain embodiments of the present invention, the hydropyrolysis liquefying reactor in step (4) be suspended-bed reactor,
Any one of reactors such as fluidized bed reactor, expanded bed reactor, any two or three kinds.
In certain embodiments of the present invention, the operating condition of the hydropyrolysis liquefying reactor in step (4) is as follows:
Temperature is 350 DEG C -450 DEG C；Pressure is 2-10MPa；The average response residence time is 15-120min；
In certain embodiments of the present invention, the operating condition of the thermal high gas-liquid separator in step (5) is as follows: temperature
Degree is 300 DEG C -430 DEG C, pressure 2-10MPa.
In certain embodiments of the present invention, the operating condition of the cold anticyclone gas-liquid separator in step (6) is as follows: temperature
Degree is 0-30 DEG C, pressure 2-10MPa.
In certain embodiments of the present invention, the separation of the gas-phase product of the cold anticyclone gas-liquid separator in step (6)
It include pressure-variable adsorption, UF membrane or cryogenic separation with enrichment process.
In certain embodiments of the present invention, in step (6), the purification of gas-phase product is using conventional gas purification
Method, for example, alcohol amine absorption process, liquid phase oxidation reduction method, copper wash method or crystallization sulphur method.
In certain embodiments of the present invention, in step (6), hydrogen-rich recycle gas is back to for coal mild hydrogenation
The system that pyrolysis prepares liquid hydrocarbon, to recycle to economize on resources and reduce production cost.
In certain embodiments of the present invention, it in step (6), is used using hydrocarbon-rich gas as fuel.
In certain embodiments of the present invention, in step (6), tail gas is discharged.
In certain embodiments of the present invention, the outlet pressure of the medium pressure flash tank in step (7) is that about 1 standard is big
Air pressure is to about 8MPa.
In certain embodiments of the present invention, in step (7), by the gas-phase product generated in gas-liquid separator through net
It is discharged after change as tail gas.
In certain embodiments of the present invention, the column bottom temperature of the atmospheric distillation tower in step (9) is 300 DEG C -350
℃。
In certain embodiments of the present invention, the column bottom temperature of the vacuum distillation tower in step (10) is 300 DEG C -350
℃。
In certain embodiments of the present invention, it in step (11), is handled in extraction tower using extraction solvent.
In further preferred embodiment, in step (11), used extraction solvent is C3-C10Alkane solvent is (for example, third
Alkane, butane, pentane, hexane and/or heptane) or mixing light oil (for example, cold high score oil obtained in step (6)).
In certain embodiments of the present invention, in step (11), according to inlet amount 3wt%-100wt% to prolong
Water is injected in slow coking plant, the outlet temperature of the heating furnace in delayed coking unit is 495 DEG C -520 DEG C.
In certain embodiments of the present invention, in step (11), semicoke is passed through into gasification production hydrogen.
In certain embodiments of the present invention, following substance directly or after mixing is used as product or solvent naphtha: step (5)
Obtained in hot high score oil, cold high score oil obtained in step (6), flash oil obtained in step (7), step obtains in (8)
Mixing crude oil, often side oil and often top oil obtained in step (9) subtract in side oil or step (11) obtained in step (10)
Obtained coking mink cell focus, coking light oil and extract oil；Or direct after the hydrogenated upgrading of above-mentioned substance or mixing can be made
For product or solvent naphtha；Or product or solvent are used as after can mixing after the hydrogenated upgrading of above-mentioned substance and with non-hydrogenated oil
Oil.
The present invention have the advantages that reaction condition is mild, oil yield is high, simple process, investment and operating cost it is low etc..
Detailed description of the invention
Fig. 1 is the process flow for the embodiment that coal mild hydrogenation pyrolysis of the present invention prepares liquid hydrocarbon method
Figure, wherein respectively label respectively indicates following content in attached drawing:
1 coal blending device, 2 gas preheaters, 3 coal preheaters, 4 hydropyrolysis liquefying reactors, 5 thermal highs
Gas-liquid separator, 6 cold anticyclone gas-liquid separators, 7 medium pressure flash tanks, 8 gas-liquid separators, 9 crude oil tanks, 10 atmospheric distillation towers, 11
Vacuum distillation tower, 12 extraction towers, 13 delayed coking units.
Specific embodiment
In the present invention, unless otherwise indicated, term " liquid hydrocarbon " refers to cold high score oil, mixing crude oil, often top oil, normal side
Oil subtracts side oil, LPG, coking light oil and/or coking mink cell focus.
In the present invention, unless otherwise indicated, term " coal conversion ratio ", which refers to, prepares liquid hydrocarbon in coal mild hydrogenation pyrolysis
Percentage between the weight of the coal converted in the process and the coal dust weight for preparing coal.
In the present invention, unless otherwise indicated, term " liquid hydrocarbon yield " refers to is prepared by the method for the invention
Percentage between the weight of liquid hydrocarbon and the coal dust weight for preparing coal.
In the present invention, unless otherwise indicated, it is regarded as being modified by term " about " before each specific value occurred,
Indicate the error range that there is the numerical value this field to be generally understood and receive.
Illustrative technical solution of the invention can be by content described in following paragraph [1] to paragraph [29] to being subject to
Illustrate:
[1] a kind of method that the pyrolysis of coal mild hydrogenation prepares liquid hydrocarbon of, the described method comprises the following steps:
(1) coal dust is made in feed coal crushing；
(2) coal dust obtained in the step (1) is mixed with solvent naphtha, catalyst, auxiliary agent, to obtain coal；
(3) coal obtained in the step (2) is sent into preheater with fresh hydrogen and/or hydrogen-rich gas and is carried out
Preheating, to obtain preheated coal and preheated fresh hydrogen and/or hydrogen-rich gas；
(4) coal preheated obtained in the step (3) and preheated hydrogen-rich gas are sent into heat from hydrogenation
It is reacted in solution liquefying reactor, to generate gas-phase product and liquid consolidates mix products；
(5) gas-phase product generated in the hydropyrolysis liquefying reactor is sent into thermal high gas-liquid separator and is carried out
Separation；Gas-phase product and liquid product are generated in the thermal high gas-liquid separator, wherein the thermal high gas-liquid separator
The liquid product of middle generation is hot high score oil；
(6) gas-phase product generated in the thermal high gas-liquid separator is sent into cold anticyclone gas-liquid separator and is divided
From；Liquid product and gas-phase product are generated in the cold anticyclone gas-liquid separator, are generated in the cold anticyclone gas-liquid separator
Liquid product cold high score oil and water are obtained after water-oil separating, the gas-phase product warp generated in the cold anticyclone gas-liquid separator
After separation, enrichment and purification, hydrogen-rich recycle gas, hydrocarbon-rich gas and tail gas are obtained；
(7) liquid generated in the hydropyrolysis liquefying reactor of the step (4) is consolidated in mix products feeding to press and flashes
Tank is separated；Gas-phase product and liquid-solid mixture are generated in medium pressure flash tank, wherein will be in medium pressure flash tank
The gas-phase product of generation is separated through gas-liquid separator, so that liquid product and gas-phase product are generated in gas-liquid separator,
Wherein, the liquid product generated in the gas-liquid separator is flash oil；
(8) by flash oil obtained in hot high score oil obtained in the step (5) and the step (7) in crude oil tank
Merging obtains mixing crude oil；
(9) liquid-solid mixture obtained in medium pressure flash tank is mixed with the part or all of mixing crude oil
And it is sent into atmospheric distillation tower and is separated；Often top oil and water are generated from the top exit of the atmospheric distillation tower；From the normal pressure
The side line outlet of destilling tower generates normal side oil；Liquid-solid mixture is generated in the bottom of the atmospheric distillation tower；
(10) liquid-solid mixture generated in the bottom of the atmospheric distillation tower feeding vacuum distillation tower is separated；From
The side line outlet of the vacuum distillation tower, which generates, subtracts side oil；Liquid-solid mixture is generated in the bottom of the vacuum distillation tower；
(11) by some or all of liquid-solid mixture generated in the bottom of the vacuum distillation tower be sent into extraction tower or
Person's delayed coking unit；It is exported from the side line of the extraction tower and generates extract oil, it is residual to generate extracting in the bottom of the extraction tower
Slag；The delayed coking unit generates LPG, coking light oil, coking mink cell focus and semicoke.
[2] method of the as described in paragraph [1], which is characterized in that in the step (1), the feed coal be lignite,
Bituminous coal, mud coal or their mixture.
[3] method of the as described in paragraph [1] or [2], which is characterized in that in the step (2), the solvent naphtha is
Boiling range is in the oil within the scope of 220 DEG C -550 DEG C.
[4] method of the as described in either segment in paragraph [1]-[3], which is characterized in that described molten in the step (2)
Agent oil is the miscella rich in aromatic hydrocarbons and hydrogenation of aromatics.
[5] method of the as described in paragraph [4], which is characterized in that described to be rich in aromatic hydrocarbons and hydrogenation in the step (2)
The miscella of aromatic hydrocarbons is selected from: hot high score oil obtained in the step (5)；Cold high score oil obtained in the step (6)；It is described
Flash oil obtained in step (7)；Mixing crude oil obtained in the step (8)；Normal side oil obtained in the step (9) and
Often top oil；Subtract side oil obtained in the step (10)；Coking mink cell focus obtained in the step (11), coking light oil and
Extract oil；Catalytic cracked oil pulp；Catalytic cracking recycle oil；Aromatics Extractive Project oil；Reduced crude；Decompression residuum；Visbreaker tar；Coal tar
Oil；Shale oil；Or their mixture or reprocessing product.
[6] method of the as described in either segment in paragraph [1]-[5], which is characterized in that described to urge in the step (2)
Agent is ferrum-based catalyst, nickel-base catalyst, catalyst with base of molybdenum, cobalt-base catalyst, tungsten-based catalyst；And/or based on selected from iron,
The catalyst of any two or various metals in nickel, molybdenum, cobalt and tungsten.
[7] method of the as described in either segment in paragraph [1]-[6], which is characterized in that described to help in the step (2)
Agent is selected from elemental sulfur, hydrogen sulfide and/or thioether.
[8] method of the as described in either segment in paragraph [1]-[7], which is characterized in that in the step (2), coal dust:
Solvent naphtha: catalyst: the mass ratio of auxiliary agent be 100:(70-1200): (0.1-5.0): (0-5.0), wherein the catalyst with
Metallic element quality meter.
[9] method of the as described in either segment in paragraph [1]-[8], which is characterized in that described pre- in the step (3)
The outlet temperature of hot device is 220 DEG C -400 DEG C.
[10] method of the as described in either segment in paragraph [1]-[9], which is characterized in that described in the step (4)
Hydropyrolysis liquefying reactor is that suspended-bed reactor, fluidized bed reactor, expanded bed reactor are any one or more of.
[11] method of the as described in either segment in paragraph [1]-[10], which is characterized in that described in the step (4)
The operating condition of hydropyrolysis liquefying reactor is as follows: temperature is 350 DEG C -450 DEG C；Pressure is 2-10MPa；Average response stops
Time is 15-120min.
[12] method of the as described in either segment in paragraph [1]-[11], which is characterized in that described in the step (5)
The operating condition of thermal high gas-liquid separator is as follows: temperature is 300 DEG C -430 DEG C, pressure 2-10MPa.
[13] method of the as described in either segment in paragraph [1]-[12], which is characterized in that described in the step (6)
The operating condition of cold anticyclone gas-liquid separator is as follows: temperature is 0-30 DEG C, pressure 2-10MPa.
[14] method of the as described in either segment in paragraph [1]-[13], which is characterized in that described in the step (6)
The separation of the gas-phase product generated in cold anticyclone gas-liquid separator and enrichment process include pressure-variable adsorption, UF membrane or deep cooling point
From.
[15] method of the as described in either segment in paragraph [1]-[14], which is characterized in that described in the step (6)
The purification of the gas-phase product generated in cold anticyclone gas-liquid separator uses method chosen from the followings: alcohol amine absorption process, liquid phase oxidation
Reduction method, copper wash method or crystallization sulphur method.
[16] method of the as described in either segment in paragraph [1]-[15], which is characterized in that described in the step (6)
Hydrogen-rich recycle gas is back to the system for preparing liquid hydrocarbon for coal mild hydrogenation pyrolysis.
[17] method of the as described in either segment in paragraph [1]-[16], which is characterized in that in the step (6), by institute
Hydrocarbon-rich gas is stated to use as fuel.
[18] method of the as described in either segment in paragraph [1]-[17], which is characterized in that in the step (6), by institute
State tail gas discharge.
[19] method of the as described in either segment in paragraph [1]-[18], which is characterized in that described in the step (7)
The outlet pressure of medium pressure flash tank is that 1 normal atmosphere is depressed into 8MPa.
[20] method of the as described in either segment in paragraph [1]-[19], which is characterized in that in the step (7), by institute
It is purified rear as tail gas discharge to state the gas-phase product generated in gas-liquid separator.
[21] method of the as described in either segment in paragraph [1]-[20], which is characterized in that described in the step (9)
The column bottom temperature of atmospheric distillation tower is 300 DEG C -350 DEG C.
[22] method of the as described in either segment in paragraph [1]-[21], which is characterized in that in the step (10), institute
The column bottom temperature for stating vacuum distillation tower is 300 DEG C -350 DEG C.
[23] method of the as described in either segment in paragraph [1]-[22], which is characterized in that in the step (11),
It is handled in the extraction tower using extraction solvent.
[24] method of the as described in paragraph [23], which is characterized in that in the step (11), the extraction solvent is
C3-C10Alkane solvent or mixing light oil.
[25] method of the as described in paragraph [24], which is characterized in that the extraction solvent be propane, butane, pentane, oneself
Alkane and/or heptane.
[26] method of the as described in paragraph [24], which is characterized in that the extraction solvent is to obtain in the step (6)
Cold high score oil.
[27] method of the as described in either segment in paragraph [1]-[26], which is characterized in that in the step (11), press
The 3wt%-100wt% for shining into doses injects water, the heating furnace in the delayed coking unit into the delayed coking unit
Outlet temperature be 495 DEG C -520 DEG C.
[28] method of the as described in either segment in paragraph [1]-[27], which is characterized in that, will in the step (11)
The semicoke passes through gasification production hydrogen.
[29] method of the as described in either segment in paragraph [1]-[28], which is characterized in that by following substance directly or mixing
Be used as product or solvent naphtha afterwards: hot high score obtained in the step (5) is oily, cold high score oil, institute obtained in the step (6)
State flash oil obtained in step (7), mixing crude oil obtained in the step (8), normal side oil obtained in the step (9)
It is oily with normal top, subtract coking mink cell focus, coking lightweight obtained in side oil or the step (11) obtained in the step (10)
Oil and extract oil；
Or it regard direct after the hydrogenated upgrading of above-mentioned substance or mixing as product or solvent naphtha；
Or product or solvent naphtha are used as after mixing after the hydrogenated upgrading of above-mentioned substance and with non-hydrogenated oil.
In an exemplary embodiment of the present invention, Fig. 1 of the present invention is related to following process flow:
Feed coal is crushed manufactured coal dust to mix in coal blending device 1 with catalyst, auxiliary agent and solvent naphtha, from
And it is configured to coal.Coal is mixed with the hydrogen-rich gaseous mixture (fresh hydrogen+hydrogen-rich recycle gas) of a part, through oily coal
It starches after preheater 3 preheats and is sent into hydropyrolysis liquefying reactor 4.Meanwhile the hydrogen-rich gaseous mixture of remainder being preheated through gas
After device 2 preheats, it is also fed into hydropyrolysis liquefying reactor 4.
The gas-phase product generated in hydropyrolysis liquefying reactor 4 is sent into thermal high gas-liquid separator 5.In thermal high gas
Hot high score oil is isolated in liquid/gas separator 5, and the gas-phase product generated in thermal high gas-liquid separator 5 is sent into cold anticyclone gas-liquid
Separator 6.Cold high score oil and water are isolated in cold anticyclone gas-liquid separator 6, and the gas phase in cold anticyclone gas-liquid separator 6 produces
Object obtains hydrogen-rich recycle gas, hydrocarbon-rich gas and tail gas after separation, enrichment and purification；Wherein, hydrogen-rich recycle gas is back to
For the system that coal mild hydrogenation pyrolysis prepares liquid hydrocarbon, hydrocarbon-rich gas is used as fuel, and tail gas is discharged.
The liquid that hydropyrolysis liquefying reactor 4 generates is consolidated mix products feeding medium pressure flash tank 7 to separate.It will be in
The gas-phase product generated in pressure flash tank 7 is separated into flash oil and gas-phase product in gas-liquid separator 8, by the gas-phase product
It is discharged after purified as tail gas.By the flash oil that gas-liquid separator 8 is isolated and the heat that thermal high gas-liquid separator 5 is isolated
High score oil is mixed to get mixing crude oil in crude oil tank 9.By liquid-solid phase mixture obtained in medium pressure flash tank 7 and part or entirely
Portion's mixing crude oil (wherein, the mixing crude oil of remainder is collected as final products) carries out being mixed and fed into atmospheric distillation tower 10
It is separated.Air-distillation through atmospheric distillation tower 10 isolates often top oil and water from the top exit of atmospheric distillation tower 10, from
Normal side oil is isolated in the side line outlet of atmospheric distillation tower 10, and generates normal base oil slurry (in normal pressure in the bottom of atmospheric distillation tower 10
The liquid-solid mixture that the bottom of destilling tower generates).By normal base oil starch be sent into vacuum distillation tower 11 separate, be evaporated under reduced pressure from
The side line outlet of vacuum distillation tower 11, which is isolated, subtracts side oil, and subtracts base oil slurry in the generation of the bottom of vacuum distillation tower 11 and (depressurizing
The liquid-solid mixture that the bottom of destilling tower generates).
Base oil slurry will be subtracted and be sent into extraction tower 12, isolate extract oil from the outlet of the side line of extraction tower 12, and in extraction tower 12
Bottom generate extracting residue.It is handled alternatively, base oil will be subtracted and starch delayed coking plant 13, obtains LPG, coking lightweight
Oil, coking mink cell focus and semicoke.Preferably further obtained semicoke is used to produce hydrogen by gasification.
Embodiment
Technical solution of the present invention is further described in detail hereinafter with reference to following embodiments.However, this hair
Bright protection scope is not limited to these examples.
Embodiment 1
Lignite is worn into powdery using ball mill, crossing 200 mesh screens and obtaining granularity is 200 mesh coal dust below.In device
Before operating, by mixing crude oil obtained in following embodiments 5, normal side oil, often top is oily, subtract side oil and coking mink cell focus mixes
Oil product of the boiling range within the scope of 220 DEG C -550 DEG C obtained from adding hydrogen upgrading is closed as solvent naphtha；It, will in device operation process
Mixing crude oil that the present embodiment obtains, normal side oil, often top oil, subtract side oil and coking mink cell focus carries out mixed hydrogenation upgrading and obtains
Oil product of the boiling range within the scope of 220 DEG C -550 DEG C as solvent naphtha；Using magnetic iron ore as catalyst；Using thioether conduct
Auxiliary agent.
Above-mentioned coal dust is uniformly mixed with solvent naphtha, catalyst and auxiliary agent according to the mass ratio of 100:600:1:5, height is obtained
Spend the coal of dispersion.By obtained coal (flow velocity 2t/h), fresh hydrogen (flow velocity 350Nm3/ h) and hydrogen-rich follow
Ring gas (flow velocity 850Nm3/ h) be sent into preheater in preheat.
The hydrogen-rich gaseous mixture (fresh hydrogen+hydrogen-rich recycle gas, 220 DEG C) for passing through preheating and coal (400 DEG C) are sent
Enter and reacted in suspension bed reactor, reaction temperature is 450 DEG C and reaction pressure is 10MPa, and material is put down in the reactor
Equal time residence time is 15min.
The gas-phase product that will be generated in suspended-bed reactor, feeding operation temperature is 430 DEG C and operating pressure is 10MPa's
It is separated in thermal high gas-liquid separator, to obtain hot high score oil.The gas phase generated in thermal high gas-liquid separator is produced
Object is sent into the cold anticyclone gas-liquid separator that operation temperature is 0 DEG C and operating pressure is 10MPa and is separated, to obtain cold height
Divide oil and water, meanwhile, the gas-phase product generated in cold anticyclone gas-liquid separator obtains hydrogen-rich recycle after separation, enrichment and purification
Body, hydrocarbon-rich gas and tail gas.
The liquid generated in suspended-bed reactor is consolidated in the medium pressure flash tank that mix products feeding pressure is 8MPa and is divided
From.The gas-phase product generated in medium pressure flash tank is further separated into flash oil and tail gas in gas-liquid separator.It will flash distillation
Oily and hot high score oil mixes in crude oil tank, to obtain mixing crude oil.
By mixing crude oil (flash oil and the hot high score oil in liquid-solid phase mixture obtained in medium pressure flash tank and crude oil tank
Mixture) carry out being mixed and fed into atmospheric distillation tower (330 DEG C of column bottom temperature) and separated, to obtain often pushing up oil, water, often
Side oil and normal base oil slurry (in the liquid-solid mixture that the bottom of atmospheric distillation tower generates).Normal base oil is starched and is sent into vacuum distillation tower
It is separated in (330 DEG C of column bottom temperature), to obtain subtracting side oil and subtract base oil slurry (in the liquid that the bottom of vacuum distillation tower generates
Solid mixture).
Base oil slurry feeding delayed coking unit will be subtracted to handle, obtain LPG, coking light oil, coking mink cell focus and half
It is burnt.In delayed coker operation, water is injected thereto according to the 100wt% of inlet amount, and the heating furnace in the device goes out
Mouth temperature is 520 DEG C.
According to calculation method generally in the art, it is calculated the coal conversion ratio and liquid hydrocarbon yield of embodiment 1, and by phase
The result answered is shown in the following table 2.
Embodiment 2
In addition to carrying out following adjustment, other reaction process and condition are with embodiment 1: catalyst being adjusted to Ni/Mo base and is urged
Agent, hydropyrolysis liquefying reactor are adjusted to fluidized bed reactor, by the temperature of the fluidized bed reactor be adjusted to 430 DEG C and
Pressure is adjusted to 4MPa, and mean residence time is adjusted to 60min, coal dust: solvent naphtha: catalyst: the mass ratio of auxiliary agent is adjusted to
100:70:0.5:3, the pressure of medium pressure flash tank are adjusted to 2MPa, and the outlet temperature of coal preheater is adjusted to 380 DEG C, heat
The operation temperature and pressure of high-pressure gas-liquid separator adjust separately as 400 DEG C and 4MPa, the operation temperature of cold anticyclone gas-liquid separator
Degree and pressure adjust separately as 10 DEG C and 4MPa, and the column bottom temperature of atmospheric distillation tower and vacuum distillation tower is adjusted to 350 DEG C.
In the same manner as shown in Example 1, the coal conversion ratio and liquid hydrocarbon yield of embodiment 2 are calculated, and by phase
The result answered is shown in the following table 2.
Embodiment 3
In addition to carrying out following adjustment, other reaction process and condition are with embodiment 1: hydropyrolysis liquefying reactor is adjusted
For expanded bed reactor, the temperature of the expanded bed reactor is adjusted to 390 DEG C and reaction pressure is adjusted to 3MPa, it is average to stop
Time is adjusted to 30min, coal dust: solvent naphtha: catalyst: the mass ratio of auxiliary agent is adjusted to 100:110:3:0.1, medium pressure flash tank
Pressure be adjusted to 1MPa, the outlet temperature of coal preheater is adjusted to 330 DEG C, the operation temperature of thermal high gas-liquid separator
Adjust separately with pressure as 350 DEG C and 3MPa, the operation temperature and pressure of cold anticyclone gas-liquid separator adjust separately as 30 DEG C and
3MPa。
In the same manner as shown in Example 1, the coal conversion ratio and liquid hydrocarbon yield of embodiment 3 are calculated, and by phase
The result answered is shown in the following table 2.
Embodiment 4
In addition to carrying out following adjustment, other reaction process and condition are with embodiment 1: the temperature of suspended-bed reactor is adjusted
For 380 DEG C and pressure is adjusted to 5MPa, and mean residence time is adjusted to 30min, and auxiliary agent is adjusted to hydrogen sulfide, coal dust: solvent naphtha:
Catalyst: the mass ratio of auxiliary agent is adjusted to 100:110:5:0.1, and the pressure of medium pressure flash tank is adjusted to 3MPa, coal preheating
The outlet temperature of device is adjusted to 330 DEG C, the operation temperature and pressure of thermal high gas-liquid separator adjust separately as 350 DEG C and
5MPa, the operation temperature and pressure of cold anticyclone gas-liquid separator adjust separately as 20 DEG C and 5MPa.
In the same manner as shown in Example 1, the coal conversion ratio and liquid hydrocarbon yield of embodiment 4 are calculated, and by phase
The result answered is shown in the following table 2.
Embodiment 5
In addition to carrying out following adjustment, other reaction process and condition are with embodiment 1: coal class being adjusted to bituminous coal, is suspended
The temperature of bed reactor is adjusted to 430 DEG C and pressure is adjusted to 2MPa, and mean residence time is adjusted to 90min, solvent naphtha adjustment
For coal tar, coal dust: solvent naphtha: catalyst: the ratio of auxiliary agent is adjusted to 100:600:0.1:0, the pressure tune of medium pressure flash tank
Whole is 0.1MPa, and the outlet temperature of coal preheater is adjusted to 380 DEG C, the operation temperature and pressure of thermal high gas-liquid separator
It adjusts separately as 390 DEG C and 2MPa, the operation temperature and pressure of cold anticyclone gas-liquid separator adjust separately as 15 DEG C and 2MPa, will
Subtract base oil slurry and is sent into extraction tower extracting.
In the same manner as shown in Example 1, the coal conversion ratio and liquid hydrocarbon yield of embodiment 5 are calculated, and by phase
The result answered is shown in the following table 2.
Embodiment 6
In addition to carrying out following adjustment, other reaction process and condition are with embodiment 1: the temperature of suspended-bed reactor is adjusted
For 350 DEG C and pressure is adjusted to 10MPa, and mean residence time is adjusted to 120min, and auxiliary agent is adjusted to elemental sulfur, coal dust: solvent
Oil: catalyst: the mass ratio of auxiliary agent is adjusted to 100:1200:3:1, and the pressure of medium pressure flash tank is adjusted to 6MPa, and coal is pre-
The outlet temperature of hot device is adjusted to 300 DEG C, the operation temperature and pressure of thermal high gas-liquid separator adjust separately as 300 DEG C and
10MPa, the operation temperature and pressure of cold anticyclone gas-liquid separator adjust separately as 10 DEG C and 10MPa, atmospheric distillation tower and decompression
The column bottom temperature of destilling tower is adjusted to 300 DEG C.
In the same manner as shown in Example 1, the coal conversion ratio and liquid hydrocarbon yield of embodiment 6 are calculated, and by phase
The result answered is shown in the following table 2.
Table 2: the reaction result of embodiment 1-6
Claims (26)
1. a kind of method that the pyrolysis of coal mild hydrogenation prepares liquid hydrocarbon, the described method comprises the following steps:
(1) coal dust is made in feed coal crushing；
(2) coal dust obtained in the step (1) is mixed with solvent naphtha, catalyst, auxiliary agent, to obtain coal；
(3) coal obtained in the step (2) and fresh hydrogen and/or hydrogen-rich gas are sent into preheater and are carried out in advance
Heat, to obtain preheated coal and preheated fresh hydrogen and/or hydrogen-rich gas；
(4) preheated coal and preheated fresh hydrogen and/or hydrogen-rich gas obtained in the step (3) are sent
Enter and reacted in hydropyrolysis liquefying reactor, to generate gas-phase product and liquid consolidates mix products；
(5) gas-phase product generated in the hydropyrolysis liquefying reactor is sent into thermal high gas-liquid separator and is divided
From；Gas-phase product and liquid product are generated in the thermal high gas-liquid separator, wherein in the thermal high gas-liquid separator
The liquid product of generation is hot high score oil；
(6) gas-phase product generated in the thermal high gas-liquid separator is sent into cold anticyclone gas-liquid separator and is separated；
Liquid product and gas-phase product, the liquid generated in the cold anticyclone gas-liquid separator are generated in the cold anticyclone gas-liquid separator
Phase product obtains cold high score oil and water after water-oil separating, and the gas-phase product generated in the cold anticyclone gas-liquid separator is through dividing
From, enrichment and purification after, obtain hydrogen-rich recycle gas, hydrocarbon-rich gas and tail gas；
(7) by the liquid generated in the hydropyrolysis liquefying reactor of the step (4) consolidate mix products be sent into medium pressure flash tank into
Row separation；Gas-phase product and liquid-solid mixture are generated in medium pressure flash tank, wherein will generate in medium pressure flash tank
Gas-phase product separated through gas-liquid separator, to generate liquid product and gas-phase product in gas-liquid separator, wherein
The liquid product generated in the gas-liquid separator is flash oil；
(8) hot high score oil obtained in the step (5) is merged in crude oil tank with flash oil obtained in the step (7)
Obtain mixing crude oil；
(9) liquid-solid mixture obtained in medium pressure flash tank is mixed and is sent with the part or all of mixing crude oil
Enter atmospheric distillation tower to be separated；Often top oil and water are generated from the top exit of the atmospheric distillation tower；From the air-distillation
The side line outlet of tower generates normal side oil；Liquid-solid mixture is generated in the bottom of the atmospheric distillation tower；
(10) liquid-solid mixture generated in the bottom of the atmospheric distillation tower feeding vacuum distillation tower is separated；From described
The side line outlet of vacuum distillation tower, which generates, subtracts side oil；Liquid-solid mixture is generated in the bottom of the vacuum distillation tower；
(11) some or all of liquid-solid mixture generated in the bottom of the vacuum distillation tower is sent into extraction tower or prolonged
Slow coking plant；It is exported from the side line of the extraction tower and generates extract oil, generate extracting residue in the bottom of the extraction tower；Institute
It states delayed coking unit and generates LPG, coking light oil, coking mink cell focus and semicoke；
In the step (2), the solvent naphtha is the oil that boiling range is within the scope of 220 DEG C -550 DEG C；
In the step (2), the catalyst be ferrum-based catalyst, nickel-base catalyst, catalyst with base of molybdenum, cobalt-base catalyst,
Tungsten-based catalyst；And/or the catalyst based on any two or various metals in iron, nickel, molybdenum, cobalt and tungsten；
In the step (2), the auxiliary agent is selected from elemental sulfur, hydrogen sulfide and/or thioether.
2. the method as described in claim 1, which is characterized in that in the step (1), the feed coal be lignite, bituminous coal,
Mud coal or their mixture.
3. method according to claim 1 or 2, which is characterized in that in the step (2), the solvent naphtha is rich in virtue
The miscella of hydrocarbon and hydrogenation of aromatics.
4. method as claimed in claim 3, which is characterized in that described to be rich in aromatic hydrocarbons and hydrogenation of aromatics in the step (2)
Miscella be selected from: the oil of hot high score obtained in the step (5)；Cold high score oil obtained in the step (6)；The step
(7) flash oil obtained in；Mixing crude oil obtained in the step (8)；Normal side oil obtained in the step (9) and often top
Oil；Subtract side oil obtained in the step (10)；Coking mink cell focus, coking light oil and extracting obtained in the step (11)
Oil；Catalytic cracked oil pulp；Catalytic cracking recycle oil；Aromatics Extractive Project oil；Reduced crude；Decompression residuum；Visbreaker tar；Coal tar；
Shale oil；Or their mixture or reprocessing product.
5. method according to claim 1 or 2, which is characterized in that in the step (2), coal dust: solvent naphtha: catalyst:
The mass ratio of auxiliary agent is 100:(70-1200): (0.1-5.0): (0-5.0), wherein the catalyst is with metallic element quality
Meter.
6. method according to claim 1 or 2, which is characterized in that in the step (3), the outlet temperature of the preheater
Degree is 220 DEG C -400 DEG C.
7. method according to claim 1 or 2, which is characterized in that in the step (4), the hydropyrolysis liquefaction is anti-
Answer device any one or more of for suspended-bed reactor, fluidized bed reactor, expanded bed reactor.
8. method according to claim 1 or 2, which is characterized in that in the step (4), the hydropyrolysis liquefaction is anti-
Answer the operating condition of device as follows: temperature is 350 DEG C -450 DEG C；Pressure is 2-10MPa；The average response residence time is 15-
120min。
9. method according to claim 1 or 2, which is characterized in that in the step (5), the thermal high gas-liquid separation
The operating condition of device is as follows: temperature is 300 DEG C -430 DEG C, pressure 2-10MPa.
10. method according to claim 1 or 2, which is characterized in that in the step (6), the cold anticyclone gas-liquid separation
The operating condition of device is as follows: temperature is 0-30 DEG C, pressure 2-10MPa.
11. method according to claim 1 or 2, which is characterized in that in the step (6), the cold anticyclone gas-liquid separation
The separation of the gas-phase product generated in device and enrichment process include pressure-variable adsorption, UF membrane or cryogenic separation.
12. method according to claim 1 or 2, which is characterized in that in the step (6), the cold anticyclone gas-liquid separation
The purification of the gas-phase product generated in device use method chosen from the followings: alcohol amine absorption process, liquid phase oxidation reduction method, copper wash method or
Crystallize sulphur method.
13. method according to claim 1 or 2, which is characterized in that in the step (6), the hydrogen-rich recycle gas is returned
It is back to the system for preparing liquid hydrocarbon for coal mild hydrogenation pyrolysis.
14. method according to claim 1 or 2, which is characterized in that in the step (6), using the hydrocarbon-rich gas as
Fuel uses.
15. method according to claim 1 or 2, which is characterized in that in the step (6), the tail gas is discharged.
16. method according to claim 1 or 2, which is characterized in that in the step (7), medium pressure flash tank goes out
Mouth pressure is that 1 normal atmosphere is depressed into 8MPa.
17. method according to claim 1 or 2, which is characterized in that, will be in the gas-liquid separator in the step (7)
It is discharged after the gas-phase product of generation is purified as tail gas.
18. method according to claim 1 or 2, which is characterized in that in the step (9), the tower of the atmospheric distillation tower
Bottom temperature is 300 DEG C -350 DEG C.
19. method according to claim 1 or 2, which is characterized in that in the step (10), the vacuum distillation tower
Column bottom temperature is 300 DEG C -350 DEG C.
20. method according to claim 1 or 2, which is characterized in that in the step (11), adopted in the extraction tower
It is handled with extraction solvent.
21. method as claimed in claim 20, which is characterized in that in the step (11), the extraction solvent is C3-C10
Alkane solvent or mixing light oil.
22. method as claimed in claim 21, which is characterized in that the extraction solvent be propane, butane, pentane, hexane and/
Or heptane.
23. method as claimed in claim 21, which is characterized in that the extraction solvent is cold obtained in the step (6)
High score oil.
24. method according to claim 1 or 2, which is characterized in that in the step (11), according to inlet amount
3wt%-100wt% injects water, the outlet temperature of the heating furnace in the delayed coking unit into the delayed coking unit
It is 495 DEG C -520 DEG C.
25. method according to claim 1 or 2, which is characterized in that in the step (11), the semicoke is passed through gas
Metaplasia hydrogen producing.
26. method according to claim 1 or 2, which is characterized in that following substance directly or after mixing is used as to product or molten
Agent oil: hot high score obtained in the step (5) is oily, cold high score oil obtained in the step (6), in the step (7)
The flash oil arrived, mixing crude oil obtained in the step (8), often side oil and often top oil obtained in the step (9) are described
Subtract coking mink cell focus, coking light oil and extract oil obtained in side oil or the step (11) obtained in step (10)；
Or it regard direct after the hydrogenated upgrading of above-mentioned substance or mixing as product or solvent naphtha；
Or product or solvent naphtha are used as after mixing after the hydrogenated upgrading of above-mentioned substance and with non-hydrogenated oil.
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| CN110643380B (en) * | 2019-08-22 | 2020-10-13 | 中科合成油工程有限公司 | Method for converting coal pyrolysis product into gasoline, diesel oil and hydrogen |
| CN111234855A (en) * | 2020-01-17 | 2020-06-05 | 广东润丰实业有限公司 | Method for replacing petroleum crude oil by clean coal self-hydrogenation liquefied coalification oil |
| CN113214874A (en) * | 2021-05-26 | 2021-08-06 | 西京学院 | Method for kerosene co-catalytic pyrolysis-semicoke catalytic gasification |
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| CN102391886A (en) * | 2011-09-27 | 2012-03-28 | 长安大学 | Dry distillation and liquefying method for coal |
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| CN103265971A (en) * | 2013-05-15 | 2013-08-28 | 煤炭科学研究总院 | Heterogeneous coal tar suspension bed hydrogenation method |
| CN103555357A (en) * | 2013-11-04 | 2014-02-05 | 华东理工大学 | Method for liquifying coal mildly |
| CN104893751A (en) * | 2015-06-29 | 2015-09-09 | 神华集团有限责任公司 | Coal liquefaction system and coal liquefaction method |
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Address after: 101407 No.1, south 2nd Yueyuan street, C District, Yanqi Economic Development Zone, Huairou District, Beijing Patentee after: Zhongke synthetic oil Technology Co.,Ltd. Address before: 101407 No.1, south 2nd Yueyuan street, C District, Yanqi Economic Development Zone, Huairou District, Beijing Patentee before: SYNFUELS CHINA TECHNOLOGY Co.,Ltd. |