CN108641741B - Coal multistage composite catalytic hydrogenation liquefaction process method - Google Patents
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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
- C10G1/002—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
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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
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The invention relates to a coal multi-stage composite catalytic hydrogenation liquefaction method, namely, a coal liquefaction reaction is carried out step by step under two or three reactors connected in series, and the method mainly comprises the following steps: the preheated coal slurry sequentially passes through a three-stage or two-stage series reactor to fully contact and react with reaction atmosphere and a catalyst, wherein the reaction atmosphere and the catalyst in the reactors 1, 2 and 3 are respectively as follows: the reactor 1 is mainly a synthesis gas/alkaline catalyst, the reactor 2 is mainly a hydrogen/iron catalyst, and the reactor 3 is a hydrogen/nickel-molybdenum-cobalt catalyst; water and light oil generated by liquefaction of the materials after reaction in the reactor 1 are discharged and separated along with reaction gas after passing through a separator, solid residues are separated out by high-temperature hydraulic cyclone after the liquid-solid slurry entering the reactor 2 reacts, and the low-solid-content materials rich in asphaltenes enter the reactor 3 for hydrogenation liquefaction. The invention does not need excessive dehydration and drying of the raw material coal, can improve the conversion rate and the oil yield of the coal, and is particularly suitable for low-rank coal.
Description
Technical Field
The invention relates to a coal multistage composite catalytic hydrogenation liquefaction process method, in particular to a multistage composite catalytic hydrogenation liquefaction technology suitable for direct liquefaction of low-rank coal, and belongs to the technical field of coal chemical industry and clean energy.
Background
China has abundant coal resources, and the liquefaction of coal for oil production is a practical and feasible way for reducing the external dependence of crude oil. Coal, especially low rank coal, has a high oxygen content and consumes a large amount of hydrogen and produces water during liquefaction. The high oxygen-containing coal generally has more internal water, the drying dehydration difficulty is higher, the energy consumption is higher, the excessive dehydration can also cause the collapse of the microporous structure of the lignite to prevent the contact of a hydrogen source and an active site in an inner hole of the coal through a solvent, so that the unfavorable liquefaction reaction is avoided, however, the condition that the high water-containing atmosphere is generated if the water in the raw material is superposed with the pyrolysis water of the high oxygen-containing raw material is not removed, and the deep hydrogenation liquefaction of the main body structure of the coal and the asphaltene in the same reactor is damaged; the typical asphaltene chemical structure shows that the single use of iron catalyst has insufficient high cracking hydrogenation efficiency on bonds between aromatic carbon oxygen bonds with higher bond energy and aromatic carbon aliphatic carbons, so that the content of asphaltene in the liquefied product is generally higher; the hydrogenation activity of the nickel-molybdenum-cobalt catalyst is obviously higher than that of an iron-based catalyst, and the nickel-molybdenum-cobalt catalyst needs to be regenerated and repeatedly used due to high price, so that the deep hydrogenation liquefaction of asphaltene can be completely realized by using the high-activity catalyst, the oil yield is directly improved, but the technical problems such as catalyst coking prevention, separation regeneration, service life prolonging and the like are faced in the high-solid-content material such as direct coal liquefaction, and the process is the main reason for realizing industrial application in the direction of direct coal liquefaction.
At present, Chinese patents CN107163974A, CN103555357A and CN1438294A disclose three coal liquefaction processes, which have advantages, but can not better solve the following problems in the coal liquefaction process: the high oxygen content in the low-rank coal causes the limitation of the hydrogenation of coal main bodies and asphaltenes by a high-water-content environment generated by liquefaction; insufficient activity of the iron catalyst, and difficulty in separating the nickel-molybdenum-cobalt catalyst from the liquefied residue. Based on the method, the multistage composite catalytic hydrogenation process method more suitable for direct liquefaction of low-rank coal can reduce the harm of pyrolysis water to liquefaction reaction, can further carry out hydro-conversion on asphaltene with lower activity, and has the characteristics of high oil yield and coal conversion rate, harmonious process conditions and liquefaction process, low system energy consumption, good economy and the like.
Disclosure of Invention
According to the process method for coal multistage composite catalytic hydrogenation liquefaction, preheated coal slurry is separated and liquefied through a reaction device formed by connecting three-stage or two-stage reactors in series, different requirements of different reaction stages on coal catalytic hydrogenation can be met according to the sequence characteristics of pyrolysis hydrogenation reaction, the coal multistage catalytic hydrogenation liquefaction is realized, the catalytic conversion of low-order coal can be particularly promoted, and the process method has the characteristics of high oil yield and coal conversion rate, harmonious process conditions and liquefaction process, low system energy consumption, good economy and the like.
The invention is realized by the following technologies:
a coal multistage composite catalytic hydrogenation liquefaction process method is characterized in that the method is a coal three-stage catalytic hydrogenation liquefaction method, and comprises the following steps: the preheated coal slurry passes through a reactor 1, a separator 1, a reactor 2, a separator 2, a high-temperature hydrocyclone separator, a reactor 3 and a separator 3 which are connected in series with one another in sequence, and liquefied oil is finally obtained after reaction and separation;
the method comprises the following steps:
introducing the preheated coal slurry into a reactor 1, and keeping the materials at 350-450 ℃ and 4-20MPa to fully contact with the synthesis gas and the catalyst containing alkali metal, wherein the retention time is 10-120 min; separating the reacted material after discharging the water and light oil generated by liquefaction along with the reaction gas through a separator 1, and allowing the liquid-solid material to enter a reactor 2 to be in full contact with hydrogen and the iron-containing catalyst at the temperature of 400-; the material flowing out of the reactor 2 enters a high-temperature hydrocyclone after passing through a separator 2 to separate low solid content liquid material rich in asphaltene; heating or boosting the pressure of the materials as required, then putting the materials into a reactor 3, allowing the materials to be catalyzed and deeply hydrogenated and converted with hydrogen and a catalyst containing nickel, molybdenum and cobalt under the conditions of 420-480 ℃ and 4-30MPa, staying for 10-120min, allowing the reacted materials to pass through a separator 3 to obtain liquefied oil, wherein part of heavy oil is hydrogenated and then used as a circulating solvent to prepare slurry with coal;
wherein the mass of the catalyst added in each reactor accounts for 0.5-5% of the mass of the raw coal; preferably 1 to 3%.
The catalyst containing alkali metal added into the reactor 1 is one of an alkaline catalyst, an alkaline catalyst and an iron catalyst, or an alkaline catalyst and a disposable catalyst;
the iron-containing catalyst added into the reactor 2 is one of an iron catalyst, an iron catalyst plus alkali catalyst or an iron catalyst plus a disposable catalyst;
the catalyst containing nickel, molybdenum and cobalt added in the reactor 3 is one or more of nickel, molybdenum and cobalt catalysts;
the synthesis gas in the reactor 1 is rich in CO and H with the CO concentration of more than 10 percent2The balance being hydrogen and other gases; the concentration of CO in the synthetic gas is preferably 30-70%.
In the reactor 2 and the reactor 3The hydrogen of (A) is pure hydrogen or hydrogen-rich gas (H)2Concentration 60-100%).
The coal slurry can be prepared by adopting dry coal, undried coal or partially dried coal.
The coal multistage composite catalytic hydrogenation liquefaction process method can also be a coal two-stage catalytic hydrogenation liquefaction method, namely, preheated coal slurry sequentially passes through a two-stage reactor and a separator thereof which are connected in series with each other and/or a high-temperature hydrocyclone separator, and light liquefied oil is finally obtained after reaction and separation; the method comprises the following steps: under the temperature, pressure and reaction time, the preheated coal slurry sequentially passes through the reactor 1, the separator 1, the reactor 2 and the separator 2 which are connected in series, fully contacts with the reaction atmosphere and the catalyst, and is reacted and separated to obtain liquefied oil; or:
the preheated coal slurry sequentially passes through a reactor 1, a separator 1, a high-temperature hydrocyclone separator, a reactor 3 and a separator 3 which are connected in series, fully contacts with the reaction atmosphere and the catalyst, and is reacted and separated to obtain liquefied oil; or:
and (3) enabling the preheated coal slurry to sequentially pass through the reactor 2, the separator 2, the high-temperature hydrocyclone separator, the reactor 3 and the separator 3 which are connected in series, fully contacting with the reaction atmosphere and the catalyst, and reacting and separating to obtain liquefied oil.
The unreacted gas separated by the separator 1 is recycled into the reactor 1.
The unreacted gas separated by the separator 2 is recycled into the reactor 2.
The unreacted gas separated by the separator 3 is recycled into the reactor 3.
And the water and light oil at the outlet of the reactor 1 are separated after being discharged along with the reaction gas through a separator.
The liquid-solid separation technology is high-temperature hydrocyclone liquid-solid separation technology.
The main processing object of the reactor 3 is a low solid content liquid material rich in asphaltene.
The alkaline catalyst includes but is not limited to one or more of alkali-containing minerals, alkali metal sodium or potassium hydroxide, carbonate, meta-aluminate or silicate.
The iron catalyst includes but is not limited to one or more of iron-containing minerals, iron oxides, iron sulfides and iron hydroxides.
The disposable catalyst comprises, but is not limited to, red mud, natural pyrite, metallurgical fly ash, high-iron coal gangue and the like.
The nickel-molybdenum-cobalt catalyst comprises but is not limited to one or more of nickel-containing ore, molybdenum-containing ore, cobalt-containing ore, oxides of nickel, molybdenum and cobalt and sulfides of nickel, molybdenum and cobalt.
The main advantages of the invention are: the different requirements of different reaction stages on catalytic hydrogenation can be met according to the sequence characteristics of the coal pyrolysis hydrogenation reaction, active hydrogen can be generated by pyrolysis water by adopting synthesis gas/alkali catalysis, the hydrogenation liquefaction is facilitated, excessive dehydration and drying of raw materials are not needed, the energy consumption of a system is effectively reduced, and the conversion rate is improved; a large amount of moisture generated by coal pyrolysis in the first-stage reactor is separated by a separator at an outlet, so that adverse effects on subsequent hydrogenation are reduced, and the effect of a subsequent iron catalyst can be fully exerted; the high-temperature hydraulic cyclone liquid-solid separation technology is adopted, so that the temperature and pressure reduction is small, and the energy consumption is reduced; the third stage reactor is used for treating the low solid content liquid material rich in the asphaltene, so that the nickel-molybdenum-cobalt catalyst can be conveniently separated and recovered, and the conversion process of the asphaltene to the oil can be effectively promoted. In conclusion, the process conditions of the method are consistent with the liquefaction process, the raw coal does not need to be dehydrated excessively, the energy consumption is low, the coal conversion rate and the oil yield are high, the cost is low, the economical efficiency is good, and the method is particularly suitable for catalytic conversion of low-rank coal.
Drawings
Fig. 1 and fig. 2 are flow charts of coal multi-stage composite catalytic hydrogenation liquefaction, and are schematic diagrams of an embodiment of the invention.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to the drawings, but the present invention is not limited to the embodiments.
A coal multistage composite catalytic hydrogenation liquefaction process method comprises the following specific steps:
introducing the preheated coal slurry into a reactor 1 to ensure that the materials are maintained at 350-450 ℃ and 4-20MPa to be mixed with the synthesis gas (or other materials rich in CO and H)2Wherein the concentration of CO is 10-100%, the balance is hydrogen and other gases) and an alkaline catalyst (or an alkaline catalyst and an iron catalyst or an alkaline catalyst and a disposable catalyst) are fully contacted (the mass ratio of the catalyst to the raw coal is 0.5-5%), and the retention time is 10-120 min. After the reaction, the materials are separated after the moisture and light oil generated by liquefaction are discharged along with the reaction gas through a separator 1, the liquid-solid materials enter a reactor 2, the materials are kept at 470 ℃ of 400-. The material flowing out of the reactor 2 enters a high-temperature hydrocyclone separator after passing through the separator 2, the separated low-solid-content liquid material rich in asphaltene is heated or boosted as required and then enters a reactor 3, the material is subjected to deep hydrogenation conversion (the mass ratio of the catalyst to the raw coal is 0.5-5%) with the catalysis of hydrogen and nickel-molybdenum-cobalt catalysts (or other recyclable catalysts) under the conditions of 420-480 ℃ and 4-30MPa, and the retention time is 10-120 min. The reacted material is passed through separator 3 to obtain liquefied oil, in which part of heavy oil is hydrogenated and then used as circulating solvent to make slurry with coal.
The invention is further illustrated by the following comparative examples and examples, without being limited thereto.
Comparative example 1
The traditional two-stage process of lignite liquefaction is adopted, wherein the first stage is under hydrogen atmosphere and reaction temperature of 450 ℃, materials and iron catalyst act, and the second stage is under hydrogen atmosphere and reaction temperature of 455 ℃, and hydrogenation catalyst acts. The oil yield was 51.6%, the water yield was 22.7%, and the gas yield was 22.4%.
Comparative example 2
Preheating coal slurry prepared from victory lignite, introducing the preheated coal slurry into a reactor 1, and reacting the preheated coal slurry with a mixed catalyst (the addition amount of the mixed catalyst is 1 percent of the mass of raw coal) of sodium metaaluminate and red mud for 10min under the conditions that the temperature of the materials is 350 ℃, the atmosphere of pure carbon monoxide and the pressure is 4 MPa; the reacted materials are directly fed into a reactor 2, the temperature of the materials is maintained at 400 ℃, and the materials react with a pyrite catalyst (the addition amount of the materials accounts for 1 percent of the mass of the raw coal respectively) for 10min under the hydrogen pressure of 4 MPa; the product flows out of the reactor 2 and is distilled under reduced pressure, the liquid material enters the reactor 3, the temperature of the material is maintained at 420 ℃, and the material reacts with a cobalt ore catalyst (the addition amount accounts for 0.5 percent of the mass of the raw coal) for 10min under the hydrogen pressure of 4 MPa. The material after reaction is passed through separator 3 to obtain liquefied oil. Product yield (on a dry ashless basis): the water yield was 14.3%, the gas yield was 10.3%, the oil yield was 52.1%, the asphaltene yield was 13.4%, and the residue yield was 11.9% (conversion was 90.1%).
Example 1
Preheating coal slurry prepared from victory lignite, introducing into a reactor 1, maintaining the temperature of the material at 450 ℃, and introducing synthetic gas (CO: H)21:1) and a sodium carbonate catalyst (the addition amount accounts for 5 percent of the raw coal mass) under the pressure of 20MPa for 120 min; separating the reacted material after discharging water and light oil along with the reaction gas through a separator 1, introducing the rest materials into a reactor 2, and reacting the materials with an iron trioxide catalyst (the addition amount accounts for 5 percent of the raw coal mass) for 120min under the condition that the temperature of the materials is 470 ℃ and the hydrogen pressure is 25 MPa; the material flowing out of the reactor 2 enters a high-temperature hydrocyclone after passing through a separator 2, the separated low solid content liquid material rich in asphaltene enters a reactor 3, the temperature of the material is maintained at 480 ℃, and the material reacts with a molybdenum sulfide catalyst (the addition amount of the molybdenum sulfide catalyst accounts for 5 percent of the raw coal mass) under the hydrogen pressure of 30MPa for 120 min. The material after reaction is passed through separator 3 to obtain liquefied oil. Product yield (on a dry ashless basis): the water yield was 10.1%, the gas yield was 15.3%, the oil yield was 55.8%, the asphaltene yield was 12.4%, and the residue yield was 6.4% (93.6% conversion).
Example 2
Preheating coal slurry prepared from red willow sub-bituminous coal, introducing into reactor 1, maintaining the temperature at 430 deg.C, and introducing into synthesis gas (CO: H)2Reacting with a mixed catalyst of sodium bicarbonate and ferric oxide (the addition amounts of the mixed catalyst respectively account for 1.5 percent and 0.5 percent of the mass of the raw coal) for 40min under the pressure of 15MPa, wherein the ratio of the sodium bicarbonate to the ferric oxide is 1: 9; the reacted material is separated after the water and light oil are discharged with the reaction gas by a separator 1, and the rest isIntroducing the materials into a reactor 2, keeping the temperature of the materials at 430 ℃, and reacting the materials with a ferric oxide mixed catalyst and a sodium bicarbonate mixed catalyst (the addition amounts of the materials respectively account for 1.5 percent and 0.5 percent of the mass of the raw coal) for 40min under the hydrogen pressure of 15 MPa; the material flowing out of the reactor 2 enters a high-temperature hydrocyclone separator after passing through a separator 2, the separated low solid content liquid material rich in asphaltene enters a reactor 3, the temperature of the material is maintained at 430 ℃, and the material reacts with the nickel oxide and cobalt oxide mixed catalyst (the addition amounts of the nickel oxide and the cobalt oxide respectively account for 0.5 percent and 0.5 percent of the raw coal mass) under the hydrogen pressure of 15MPa for 40 min. The material after reaction is passed through separator 3 to obtain liquefied oil. Product yield (on a dry ashless basis): the water yield was 12.9%, the gas yield was 13.2%, the oil yield was 53.5%, the asphaltene yield was 12.2%, and the residue yield was 8.2% (conversion was 91.8%).
Example 3
Preheating coal slurry prepared from lignite of Haoyote, introducing into reactor 1, maintaining the temperature of the material at 410 deg.C, and introducing into synthesis gas (CO: H)23:2) reacting with sodium carbonate and potassium carbonate catalysts (the addition amounts of the catalysts respectively account for 0.75 percent of the mass of the raw coal) for 60min under the pressure of 13 MPa; separating the reacted material after discharging water and light oil along with the reaction gas through a separator 1, introducing the rest materials into a reactor 2, and reacting the materials with an iron hydroxide catalyst (the addition amount is 2.0 percent of the raw coal mass) for 60min under the condition that the temperature of the materials is 440 ℃ and the hydrogen pressure is 18 MPa; the material flowing out of the reactor 2 enters a high-temperature hydrocyclone after passing through a separator 2, the separated low solid content liquid material rich in asphaltene enters a reactor 3, the temperature of the material is kept at 470 ℃, and the material reacts with molybdenum sulfide and nickel sulfide catalysts (the addition amounts respectively account for 0.5 percent of the raw coal mass) under the hydrogen pressure of 25MPa for 60 min. The material after reaction is passed through separator 3 to obtain liquefied oil. Product yield (on a dry ashless basis): the water yield was 9.5%, the gas yield was 15.9%, the oil yield was 57.8%, the asphaltene yield was 11.6%, and the residue yield was 5.2% (94.8% conversion).
Example 4
Preheating coal slurry prepared from brown coal of Haoyote, introducing into reactor 1, maintaining the temperature of the material at 350 deg.C, and introducing into synthesis gas (CO: H)24:1) catalysis with sodium bicarbonate at a pressure of 10MPaReacting for 45min by using a reagent (the addition amount of the reagent accounts for 3 percent of the mass of the raw coal); the reacted material is separated after the water and light oil are discharged along with the reaction gas through a separator 1, solid residue is separated from the rest materials through high-temperature hydraulic cyclone, the liquid material with low solid content and rich in asphaltene enters a reactor 3, the temperature of the material is maintained at 460 ℃, and the material reacts with a nickel sulfide catalyst (the addition amount accounts for 3 percent of the raw coal mass) for 30min under the hydrogen pressure of 25 MPa. The material after reaction is passed through separator 3 to obtain liquefied oil. Product yield (on a dry ashless basis): the water yield was 11.2%, the gas yield was 12.3%, the oil yield was 52.8%, the asphaltene yield was 14.1%, and the residue yield was 9.6% (90.4% conversion).
Through the comparative example 1 and the examples 1 to 4, the oil yield obtained by the traditional coal two-stage liquefaction is 51.6 percent, which is 53.5 to 57.8 percent lower than the oil yield obtained by the multistage composite catalytic hydrogenation process, and the process has obvious effect on the staged hydrogenation liquefaction of low-rank coal. Through the comparative example 2 and the examples 1 to 4, it can be found that the oil yield can be effectively improved by 1.4 to 5.7 percent through separating water generated by the reaction from the material through the separator 1 and then separating the liquid and solid materials through the hydrocyclone technology. The process can effectively utilize pyrolysis water and self-contained moisture in coal to generate active hydrogen under the action of alkali catalysis through a synthesis gas shift reaction in a first reaction stage, so that the liquefaction and conversion of low-rank coal are promoted, and the moisture is discharged in a first-stage reactor, so that the adverse effect on the subsequent hydrogenation of an iron catalyst is small; through the high-temperature hydraulic cyclone liquid-solid separation technology, the material rich in asphaltene is effectively hydrogenated in the third stage, and the nickel-molybdenum-cobalt catalyst is favorably separated and recovered.
Claims (5)
1. A coal multistage composite catalytic hydrogenation liquefaction process method is characterized in that the method is a coal three-stage catalytic hydrogenation liquefaction method, and comprises the following steps: the preheated coal slurry passes through a reactor 1, a separator 1, a reactor 2, a separator 2, a high-temperature hydrocyclone separator, a reactor 3 and a separator 3 which are connected in series with one another in sequence, and liquefied oil is finally obtained after reaction and separation;
the method comprises the following steps:
introducing the preheated coal slurry into a reactor 1, and keeping the materials at 350-450 ℃ and 4-20MPa to fully contact with the synthesis gas and the catalyst containing alkali metal, wherein the retention time is 10-120 min; separating the reacted material after discharging the water and light oil generated by liquefaction along with the reaction gas through a separator 1, and allowing the liquid-solid material to enter a reactor 2 to be in full contact with hydrogen and the iron-containing catalyst at the temperature of 400-; the material flowing out of the reactor 2 enters a high-temperature hydrocyclone after passing through a separator 2 to separate low solid content liquid material rich in asphaltene; heating or boosting the pressure of the heavy oil as required, then putting the heavy oil into a reactor 3, catalyzing the material with hydrogen and a catalyst containing nickel, molybdenum and cobalt at the temperature of 420-480 ℃ and under the pressure of 4-30MPa, deeply performing hydro-conversion, staying for 10-120min, allowing the reacted material to pass through a separator 3 to obtain liquefied oil, wherein part of the heavy oil is hydrogenated and then used as a circulating solvent to prepare slurry with coal;
wherein the mass of the catalyst added in each reactor accounts for 0.5-5% of the mass of the raw coal;
the catalyst containing alkali metal added in the reactor 1 is one of alkali metal catalyst, or alkali metal catalyst and iron catalyst, or alkali metal catalyst and disposable catalyst;
the iron-containing catalyst added into the reactor 2 is one of an iron catalyst, an iron catalyst plus a basic catalyst, or an iron catalyst plus a disposable catalyst;
the catalyst containing nickel, molybdenum and cobalt added in the reactor 3 is one or more of nickel, molybdenum and cobalt catalysts;
the synthesis gas in the reactor 1 is rich in CO and H with the CO concentration of more than 10 percent2The gas of (4);
the hydrogen in the reactor 2 and the reactor 3 is pure hydrogen or H2Hydrogen-rich gas with concentration of 60-100%;
the coal slurry can be prepared by adopting dry coal, undried coal or partially dried coal.
2. The coal multistage composite catalytic hydrogenation liquefaction process method as claimed in claim 1, characterized in that unreacted gas separated by the separator 1 is recycled into the reactor 1; unreacted gas separated by the separator 2 is recycled into the reactor 2; the unreacted gas separated by the separator 3 is recycled into the reactor 3.
3. The coal multistage composite catalytic hydrogenation liquefaction process method of claim 1, wherein the basic catalyst comprises alkali-containing minerals, one or more of hydroxides, carbonates, meta-aluminates or silicates of sodium or potassium alkali metals;
the iron catalyst comprises one or more of iron-containing minerals, iron oxides, iron sulfides and iron hydroxides;
the disposable catalyst comprises one or more of red mud, natural pyrite, metallurgical fly ash and high-iron coal gangue;
the nickel, molybdenum and cobalt catalyst comprises one or more of nickel-containing ore, molybdenum-containing ore, cobalt-containing ore, oxides of nickel, molybdenum and cobalt and sulfides of nickel, molybdenum and cobalt.
4. The coal multistage composite catalytic hydrogenation liquefaction process method of claim 1, wherein the concentration of CO in the synthesis gas is 30-70%.
5. The coal multistage composite catalytic hydrogenation liquefaction process method of claim 1, wherein the mass of the catalyst added in each reactor accounts for 1-3% of the mass of raw coal.
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