CN103992823A - Method and system for synthesizing methane, gasoline and diesel oil by using low-rank coal and biomass as raw materials - Google Patents

Method and system for synthesizing methane, gasoline and diesel oil by using low-rank coal and biomass as raw materials Download PDF

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CN103992823A
CN103992823A CN201410213373.7A CN201410213373A CN103992823A CN 103992823 A CN103992823 A CN 103992823A CN 201410213373 A CN201410213373 A CN 201410213373A CN 103992823 A CN103992823 A CN 103992823A
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gas
oil
unit
biomass
low
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CN103992823B (en
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冯霄
何畅
王彧斐
邓春
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China University of Petroleum Beijing
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China University of Petroleum Beijing
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

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Abstract

The invention provides a method and a system for synthesizing methane, gasoline and diesel oil by using low-rank coal and biomass as raw materials. The method comprises: coking the low-rank coal to obtain a solid semicoke product and a gaseous product, and separating pyrolysis gas and tar from the gaseous product; gasifying the solid semicoke product to obtain semicoke gasified synthesis gas; gasifying the biomass to obtain biomass gasified synthesis gas; mixing the pyrolysis gas, the semicoke gasified synthesis gas and the biomass gasified synthesis gas, performing Fischer-Tropsch reaction, and then separating the obtained oil and gas to obtain synthetic oil and unconverted gas; mixing the obtained synthetic oil and tar, distilling to obtain fractions of which the temperatures are less than 180 DEG C, 180-320 DEG C and more than 320 DEG C, hydrotreating the fractions and separating out light hydrocarbons of which the carbon atom numbers are within 4; and mixing the light hydrocarbons of which the carbon atom numbers are within 4 and the unconverted gas to synthesize the methane. The method is favorable for developing the low-rank coal on large scale, and the economic benefits of the system are improved.

Description

Low-rank coal and biomass are the method and system of raw material synthesizing methane and petrol and diesel oil
Technical field
The present invention relates to the method and system that a kind of low-rank coal and biomass are raw material synthesizing methane and petrol and diesel oil, belong to energy fuel and chemical production technical field.
Background technology
Utilize the clean coal technology of coal synthetic oil fuel processed certainly will be in petroleum replacing production share in the highest flight.The direct liquid technology of comparing, indirect preparing liquid fuel technology in coal preparing liquid fuel technological line, take synthesis gas from coal gasification as raw material carries out Fischer-Tropsch synthesis process, can more easily realize the qualified discharge of sulfide, oxynitride, heavy hydrocarbons and heavy metal content.But the large-scale application of Fischer-Tropsch synthetic technology also exists many restraining factors.For example, be that current most study still utilizes the qualities such as hard coal, bituminous coal better, the coal that energy density is higher gasifies and synthesizes, and in coal geology storage, the highest low-rank coal (being often referred to brown coal and sub-bituminous coal) of ratio is carried out also rarely found report of the synthetic low-rank coal indirect coal liquefaction route of the synthetic system of Fischer-Tropsch.This is mainly owing to containing higher volatile part, sulfur, wet part and ash in most low-rank coal, and the lower unfavorable factors such as calorific value approximately the commercial applications of its directly extensive gasification technology.
New road has been opened up in the mass-producing utilization that the systematic study of coal decoupling zero thermal transition technology is low-rank coal.Decoupling zero thermal transition technology can or be peeled off certain in coal gasification course/some specific son and (for example react by process intensification, coking, cracking, reformation, gasification and burning) and the coupling of releasing reaction network, and then to being recombinated with integrated again by the reaction of decoupling zero.At present, the pyrolysis RMD fing mode decoupling of coal can form diversified New type coal conversion process, and this mainly comprises that double bed gasification, double bed coking/gasification, coal pull out a technology, two-part gasification, chemical cycle gasification etc.The Successful Practice of decoupling zero thermal transition technology means, the feature high according to low-rank coal fugitive constituent, oil length is high, can peel off the coking in coal conversion reaction network, utilize in coal independently separating out of light hydrocarbons in low temperature coking (pyrolysis) technique coal, hydrogen, product liquid (coal tar or coal synthetic oil), obtain the high-quality semicoke solid of upgrading simultaneously.Generally, although coal tar accounts for the mass ratio of coking product, only have 9.0%～15.0%, its energy density and economy are far above other semicoke and pyrolysis coal gas.Coal tar product liquid can be produced the transport fuels such as gasoline, diesel oil and kerosene through the refining refinement in downstream; And solid product the semicoke not still metallurgical fuel of high added value and industrial chemicals, also be good gasified raw material, can build and take the derived energy chemical platform that synthetic gas is core by char Gasification, produce the derived product of the high added values such as liquid fuel, electric power, chemicals, thereby realize the step coproduction of the high-level efficiency of low-rank coal thermochemistry conversion process, low pollution, high product quality and multi-product.
In addition on the one hand, for the ICL for Indirect Coal Liquefaction technology of directly utilizing coal based synthetic gas to be raw material production synthetic liquid fuel, if do not carry out reduction of greenhouse gas discharge processing, the greenhouse gas quantity discharged of its broad sense Fuel cycle process will be the twice left and right of traditional crude refining liquid fuel line, thereby environment is caused to larger negative impact.If application Technology of Reducing Greenhouse Gas Emissions, energy and economy cost have weakened again the competitive power of it and traditional oil preparing liquid fuel route greatly.It should be noted that, the reasons such as significant greenhouse gas emission due to exploitation of coal resources process, even adopt up-to-date carbon dioxide capture and storing technology in coal preparing liquid fuel process, total its greenhouse gas emissions are still high more than 25% than crude oil route.The feasible ground replacement scheme that reduces the greenhouse gas emissions in Fischer-Tropsch synthesis oil production process is by coal preparing liquid fuel and two PROCESS COUPLING of biomass-making liquid fuel, and this has comprised that biomass and coal gasify altogether and distinguish gasification two schemes separately.Biomass-making synthetic oil technology can obviously reduce the greenhouse gas emissions of Fischer-Tropsch synthetic route.Reason is, biomass energy realizes CO from the photosynthesis in growing process 2naturally catch, biofuel can reach lower CO in essence to the clean impact of weather (harvesting, transportation, storage and transform) 2discharge, its processing treatment process is also to the gentleer close friend of environment.For example, have result of study to show to compare traditional fossil energy route, the production process of corn ethanol can realize more than 50% effect of Life cycle reduction of greenhouse gas discharge.
Meanwhile, the synthetic Fischer-Tropsch synthesis oil producing of the coal tar that low-rank coal coking produces and Fischer-Tropsch need to upgrade to gasoline, diesel oil and the by product pitch that meets transport fuel standard at hydro carbons refined unit.Although these two kinds of raw material oil propertiess and composition be some differences slightly.But both surpass the drawback that technical uncertainty is brought at common refining advantage, for example, refine and can greatly save facility investment altogether, reduce the complicacy of harmonic process, different properties oil product is complementary to be utilized, etc.Above viewpoint is facts have proved by gyp Fischer-Tropsch synthesis oil factory.At present, for the common refining of high temperature fischer-tropsch synthetic oil and low temperature Fischer-Tropsch synthesis oil, produce diesel oil process, South Africa Sasol company has set up commercial plants in South Africa.In lot of documents, particularly for the liquid refinery of biomass, Sweet natural gas and coal, all related to and utilized Fischer-Tropsch synthesis oil to produce the process of motor spirit, diesel oil, aviation kerosene and liquefied petroleum gas (LPG).But most models still utilize experience productive rate or produce middle thick product (as petroleum naphtha and cut wet goods).And for synthetic oil refining detailed process model and layout strategy, in past 30 years, the document of this respect was also quite few.Be necessary to make the end product of oil product refining scheme to reach the preliminary every primary standard of fuel oil for vehicles, in the octane value that improves product gasoline, reduction aromatic hydrocarbon content is wherein to reach No. four oil product standard EU-4 in Europe.
On the one hand, once the Fischer-Tropsch synthesis process by type can produce a large amount of lighter hydrocarbons, is mainly from C in addition 1to C 4alkane and alkene, and unreacted CO and the H of approximately 50% left and right 2.Notice in above component, lighter hydrocarbons are main ingredients of synthetic natural gas, CO and H 2it is the main raw material of production synthetic natural gas.Have in view of that, can change traditional fuel power generation function or pump around circuit method, with the gas of this part high added value, produce synthetic Sweet natural gas, thereby greatly improve energy efficiency and the economy of whole multifunctional energy resource system.By coal liquefaction and this two intermediate item organic coupling of coal preparing natural gas, be to be also based on the feature of domestic energy structure, the efficient utilization and the clean low-carbon (LC) that are conducive to development of coal transform, produce clean energy, the energy development strategy that meets " the low carbonization utilization of high-carbon energy " is significant to realizing the sustainable use of coal resources.
Summary of the invention
It is the method for raw material synthesizing methane and petrol and diesel oil that one object of the present invention is to provide a kind of low-rank coal and biomass;
Another object of the present invention is to provide a kind of low-rank coal and biomass is the system of raw material synthesizing methane and petrol and diesel oil.
For reaching above-mentioned purpose, on the one hand, the invention provides a kind of method that low-rank coal and biomass are raw material synthesizing methane and petrol and diesel oil of take, described method comprises:
(1) low-rank coal coking is processed, obtained solid product semicoke and gas-phase product, wherein gas-phase product is isolated to pyrolysis gas and tar;
(2) the solid product semicoke of step (1) is gasified and obtains char Gasification synthetic gas;
(3) biomass gasified synthesis gas will be obtained after gasifying biomass;
(4) by carrying out fischer-tropsch reaction after the biomass gasified synthesis gas mixing of the char Gasification synthetic gas of the pyrolysis gas of step (1), step (2) and step (3), then the gas-oil separation obtaining is obtained respectively to synthetic oil and unconverted gas;
(5) synthetic oil step (4) being obtained mixes with the tar that step (1) obtains, and enters hydro carbons recovery tower distillation and obtain respectively temperature and be less than 180 ℃, 180-320 ℃ and be greater than the cut of 320 ℃, and above-mentioned cut is carried out respectively to hydrotreatment;
(6) by the carbonatoms of step (5) after the 4 unconverted gases with interior lighter hydrocarbons and step (4) mix for the synthesis of methane.
According to method of the present invention, preferred steps of the present invention (1) is after low-rank coal pre-treatment, to carry out coking processing again;
According to method of the present invention, wherein further preferred described pre-treatment, for low-rank coal is ground and is sized to the particle that particle diameter is 80-400mm, then is dried to humidity and is less than 8%.
According to method of the present invention, it is to carry out under the existence of air and middle pressure steam that the coking of step (1) is processed; Wherein preferred described middle pressure steam is that pressure is at the steam of 25atm;
According to method of the present invention, wherein preferred described coking processing is to carry out under ferrous oxide exists;
Wherein more preferably described ferrous oxide is FeO x, FeO and Fe 2o 3in one or more mixing;
According to method of the present invention, the temperature of reaction that wherein also preferred described coking is processed is 400 ℃～600 ℃, pressure 25atm.
According to method of the present invention, preferred steps of the present invention (1) obtains after solid product semicoke and gas-phase product, wherein by gas-phase product process solid impurity separating treatment, then isolates pyrolysis gas and tar.Gas-phase product, after solid impurity separating treatment, can be removed ash content and the semicoke particle in gas-phase product, carried secretly.
According to method of the present invention, preferred steps of the present invention (2) is that the solid product semicoke of step (1) is gasified and obtains char Gasification synthetic gas under oxygen, water and high pressure steam exist.
Wherein preferred described high pressure steam is the steam of pressure 40atm.
The further preferably oxygen carbon mass ratio 0.5-0.8 of the present invention wherein, water carbon mass ratio is 0.8-1.2.
According to method of the present invention, the gasification of step of the present invention (2) is this area routine operation, such as the gasification reaction conditions that the present invention preferably adopts is that temperature is 1400 ℃-1700 ℃, the about 40atm of pressure.
According to method of the present invention, wherein preferably described in step of the present invention (3), biomass and low-rank coal weight ratio are 0.50～1.5.
According to method of the present invention, the further preferred steps of the present invention (3) is that biomass are first carried out to pre-treatment, then gasifies and obtain biomass gasified synthesis gas;
Wherein said pre-treatment can be the pretreatment operation of this area routine, and the preferred described pre-treatment of the present invention is for biomass are ground and to be sized to the particle that particle diameter is 200-400mm, then is dried to humidity and is less than 8%;
According to method of the present invention, the described gasification of step of the present invention (3) is the gasifying biomass operation of this area routine, and preferred for this invention is 1200 ℃-1500 ℃ of temperature, the about 30atm of pressure;
According to method of the present invention, described fischer-tropsch reaction can be with reference to art methods, and the condition of the preferred described fischer-tropsch reaction of the present invention is: temperature 310-370 ℃, and catalyzer is Co or Ru series catalysts;
Wherein further preferred described catalyzer is Ru, TiO 2, Co, Zr, SiO 2with one or more the combination in MgO;
Ru/TiO more preferably wherein 2, Co/Zr/SiO 2or Co/MgO/SiO 2; Be understandable that, here/mixture of material before and after it represented;
According to method of the present invention, preferred steps of the present invention (4) is, after the biomass gasified synthesis gas of the char Gasification synthetic gas of the pyrolysis gas of step (1), step (2) and step (3) is mixed, first process CO transformationreation of gas mixture is carried out to fischer-tropsch reaction again;
According to method of the present invention, the preferred H of gas mixture after CO transformationreation wherein 2the mol ratio of/CO is 1.3-2.4; Wherein more preferably 1.5.
Wherein said CO transformationreation can be the high temperature CO transformationreation of prior art routine, such as the preferred reaction conditions of the present invention is temperature 500-700 ℃, and pressure is 25atm, and catalyzer is Fe or Cu series catalysts;
Wherein also preferably by gas mixture after CO transformationreation, gas mixture is absorbed through Polyethylene glycol dimethyl ether (NHD), then carries out fischer-tropsch reaction;
Can also be preferably after NHD absorb according to the present invention, the CO in gas mixture 2and H 2s content is removed to respectively 500ppm and below 25ppm.
According to method of the present invention, preferred steps of the present invention (5) is described carries out respectively hydrotreatment operation and comprises that the cut that boiling temperature is less than to 180 ℃ (petroleum naphthas) and 180-320 ℃ (distillate) carries out hydrofining;
Wherein after the preferred hydrofining of the present invention, by cut, cut and collect respectively carbonatoms and take interior lighter hydrocarbons, the component that carbonatoms is 5-6, the component that carbonatoms is 7-12, the component that carbonatoms is 13-20 4;
Wherein said hydrofining can be the hydrofining of this area routine, and the present invention institute further preferably reaction conditions is that catalyzer is SiO 2-Al 2o 3type catalyzer, pressure 35-65atm, temperature 350-500 ℃, hydrogen/oil mol ratio 5-10:1;
According to method of the present invention, the carbonatoms of wherein separating 4 with interior lighter hydrocarbons can and the unconverted gas of step (4) mix after for the synthesis of methane;
The component that wherein carbonatoms is 5-6 can carry out isomerization as auxiliary agent to improve the octane value of gasoline;
Described isomerization can be the isomerization of this area routine, and wherein the further preferred isomerized reaction conditions of the present invention is that catalyzer is B 2o 3-Al 2o 3type catalyzer, pressure 30-40atm, temperature 320-450 ℃, hydrogen/oil mol ratio 5-10:1;
The component that wherein carbonatoms is 7-12 can carry out hydrogenation type catalytic reforming reaction as auxiliary agent to improve the octane value of gasoline;
Wherein said hydrogenation type catalytic reforming reaction can be the hydrogenation type catalytic reforming operation of this area routine, the further preferred hydrogenation type catalytic reforming reaction condition of the present invention is that catalyzer is Pt/L-type zeolite, pressure 30-40atm, temperature 350-500 ℃, hydrogen/oil mol ratio 5-10:1;
The component that wherein carbonatoms is 13-20 is as diesel oil head product;
According to method of the present invention, the present invention can also preferred steps (5) described hydrotreatment also comprise that boiling point is greater than to the cut of 320 ℃ carries out hydrocracking; Isocrackate is divided into four strands: 1) carbonatoms be take interior lighter hydrocarbons gas, 2 4) the carbonatoms component, 3 that is 5-6) the carbonatoms component and 4 that is 13-20) all the other components;
Wherein said hydrocracking can be the hydrocracking operation of this area routine, and the preferred hydrocracking reaction condition of the present invention is for take Magnesium Silicate q-agent molecular sieve as catalyzer, pressure 35-65atm, temperature 400-600 ℃, hydrogen/oil mol ratio 8-15:1;
According to method of the present invention, wherein carbonatoms 4 with interior lighter hydrocarbons gas can and the unconverted gas of step (4) mix after for the synthesis of methane;
Carbonatoms be the component of 5-6 can carry out isomerization as auxiliary agent to improve the octane value of gasoline;
Wherein said isomerisation conditions can be consistent with above-mentioned isomerisation conditions (catalyzer is B 2o 3-Al 2o 3type catalyzer, pressure 30-40atm, temperature 320-450 ℃);
Wherein said carbonatoms is that the component of 5-6 can be less than after component that carbonatoms that the cut fraction hydrogenation of 180 ℃ process to produce is 5-6 is mixed and carry out in the lump isomerization with temperature;
The component that wherein carbonatoms is 13-20 can be directly as diesel oil head product;
Wherein all the other components can carry out non-hydrogenation catalyst reformation as auxiliary agent to improve the octane value of gasoline;
Wherein said non-hydrogenation catalyst the condition of reorganization is ZSM-5 catalyzer, pressure 25-45atm, temperature 300-500 ℃);
Preferably in above-mentioned all the other components, only have 60%～80% component to participate in this reforming reaction production reformation body, remaining 20%-40% component is directly mixed as gasoline head product with reformation after product;
According to method of the present invention, step (5) is described is separated into this area routine operation altogether, is that the hydrogenation of tar of step (1) is processed in preferred steps of the present invention (5), then and the synthetic oil that obtains of step (4) be divided into from;
According to method of the present invention, after the preferred hydrotreatment of the present invention, the H/C mol ratio of tar is 0.7-1.2; Wherein more preferably 0.85;
According to method of the present invention, wherein said hydrotreatment is this area routine operation, such as the reaction conditions of the preferred hydrotreatment of the present invention is that catalyzer is FeS-Fe 2o 3type catalyzer, pressure 30-40atm, temperature 250-350 ℃.
According to method of the present invention, the carbonatoms of preferred steps of the present invention (5) 4 using interior lighter hydrocarbons and step (4) unconverted gas pressurization to after 25atm as methanation reaction gas;
According to method of the present invention, in the further preferred steps of the present invention (6), control the carbonatoms of step (5) after the 4 unconverted gases with interior lighter hydrocarbons and step (4) mix, gas mixture comprises following volume percent composition: CO:15～25%, H 2: 20～30%, CO 2: 30～40%, CH 4: 7.0～15%, C 2h 6: 5.0～10%, C 2h 4: 3.0～5.0%, C 3h 8: 2.0～4.0%, C 3h 10: 1.0～3.0%, C 4h 10: 0.5～2%, C 4h 8: 0.5～2%.
According to method of the present invention, in preferred steps of the present invention (6), the carbonatoms of step (5) after mixing, the 4 unconverted gases with interior lighter hydrocarbons and step (4) is first carried out to pre-methanation resynthesis methane;
Described pre-methane turns to this area routine operation, and for example reaction conditions preferred for this invention is that catalyzer is SiO 2type catalyzer, pressure 20-30atm, temperature 400-500 ℃.Wherein further preferably the carbonatoms of step (5) after mixing, the 4 unconverted gases with interior lighter hydrocarbons and step (4) is first carried out to CO 2membrane sepn, more pre-methanation, then synthesizing methane;
Wherein said membrane sepn is this area routine operation, such as the present invention preferably carries out CO 2after membrane sepn, the CO in gas 2volume percent is less than 2.0%.
On the other hand, it is the system of raw material synthesizing methane and petrol and diesel oil that the present invention also provides a kind of low-rank coal and biomass, and described system comprises: low-rank coal coking unit 2, coal tar recovering equipment 4, char Gasification unit 6, gasifying biomass unit 8, synthetic gas mixing tank 9, Fischer-Tropsch synthesis device 12, oil gas splitter 13, oil product are refined unit 14, unstripped gas mixing tank 15, methanator 18 altogether, wherein low-rank coal enters low-rank coal coking unit 2, obtains gas-phase product and solid product semicoke, and wherein gas-phase product is transported to coal tar recovering equipment 4, isolates tar and pyrolysis gas, and its coal-tar middle oil oil product that is transported to is refined unit 14 altogether, the solid product semicoke obtaining in low-rank coal coking unit 2 is transported to char Gasification unit 6, obtains char Gasification synthetic gas, biomass obtain biomass gasified synthesis gas in gasifying biomass unit 8, pyrolysis gas wherein, char Gasification synthetic gas and biomass gasified synthesis gas are transported to synthetic gas mixing tank 9 to be mixed, gas mixture is transported to Fischer-Tropsch synthesis device 12 to carry out fischer-tropsch reaction and obtains oil gas, oil gas is transported to oil gas splitter 13, isolate synthetic oil and unconverted gas, wherein synthetic oil be transported to oil product refine altogether unit 14 and tar be divided into from, the carbonatoms that separation obtains is transported to respectively in unstripped gas mixing tank 15 with interior lighter hydrocarbons and the isolated unconverted gas of oil gas splitter 13 4, then be transported to methanator 18 synthesizing methanes.
According to system of the present invention, described system comprises: low-rank coal pretreatment unit 1, low-rank coal coking unit 2, solid impurity separator 3, coal tar recovering equipment 4, air separation plant 5, char Gasification unit 6, biomass pretreatment unit 7, gasifying biomass unit 8, synthetic gas mixing tank 9, synthetic gas CO shift-converter 10, purified synthesis gas unit 11, Fischer-Tropsch synthesis device 12, oil gas splitter 13, oil product are refined unit 14, unstripped gas mixing tank 15, CO altogether 2membrane separation plant 16, pre-methanator 17, methanator 18; Wherein low-rank coal pretreatment unit 1 is connected with low-rank coal coking unit 2, the gas-phase product obtaining in low-rank coal coking unit 2 is successively by solid impurity separator 3 and coal tar recovering equipment 4, coal tar recovering equipment 4 is refined altogether unit 14 with oil product and is connected, and the solid product semicoke obtaining in low-rank coal coking unit 2 is transported to char Gasification unit 6; Biomass are transported to gasifying biomass unit 8 through biomass pretreatment unit 7; Air passes into char Gasification unit 6 through the isolated oxygen of air separation plant 5, char Gasification unit 6, gasifying biomass unit 8 and coal tar recovering equipment 4 are connected with synthetic gas mixing tank 9 respectively, make pyrolysis gas from coal tar recovering equipment 4, from the char Gasification synthetic gas of char Gasification unit 6 with from the biomass gasified synthesis gas of gasifying biomass unit 8, in synthetic gas mixing tank 9, mix, synthetic gas mixing tank 9 downstreams are connected with CO shift-converter 10, purified synthesis gas unit 11, Fischer-Tropsch synthesis device 12 and oil gas splitter 13 successively; Two outlets of oil gas splitter 13 are refined altogether unit 14 with oil product respectively and are connected with unstripped gas mixing tank 15; The outlet that oil product is refined unit 14 is altogether connected with unstripped gas mixing tank 15, and the carbonatoms that makes oil gas splitter 13 unconverted gas out and oil product refine altogether unit 14 passes through successively CO after unstripped gas mixing tank 15 mixes again with interior lighter hydrocarbons 4 2membrane separation plant 16, pre-methanator 17 enter into methanator 18;
According to system of the present invention, wherein said low-rank coal coking unit 2 can adopt prior art conventional equipment, and the present invention is preferably fixed-bed reactor;
According to system of the present invention, wherein said char Gasification unit 6 can adopt prior art conventional equipment, and the present invention is preferably slurry fluidized gas producer;
According to system of the present invention, wherein said gasifying biomass unit 8 can adopt prior art conventional equipment, and the present invention is preferably as fluidized-bed gasification furnace;
According to system of the present invention, wherein said oil product is refined unit 14 altogether can be total to refining plant for the oil product of prior art routine, the oil product that wherein the present invention further preferably adopts is refined altogether unit and is comprised, the coal tar hydrogenating treatment unit being connected with coal tar recovering equipment 4, coal tar hydrogenating enters hydro carbons recovery tower with oil gas splitter 13 synthetic oil out after processing and carries out separated;
According to system of the present invention, wherein the outlet of the further preferred hydro carbons recovery tower of the present invention connects respectively naphtha hydrotreater, distillate hydrogenation treatment unit and wax hydrofining cracking unit, makes petroleum naphtha, distillate and the paraffin oil separated be admitted to respectively naphtha hydrotreater, distillate hydrogenation treatment unit and wax hydrofining cracking unit;
According to system of the present invention, wherein oil product of the present invention is refined altogether unit 14 and is further comprised Pt-zeolite reformer, is greater than 6 component carries out dehydrogenation processing for the carbonatoms that the petroleum naphtha after hydrotreatment is separated;
According to system of the present invention, wherein oil product of the present invention is refined altogether unit 14 and is further comprised isomerization unit, for the component that is 5-6 by the carbonatoms of the paraffin oil of separating, carries out isomerization;
According to system of the present invention, wherein oil product of the present invention is refined altogether unit 14 and is further comprised non-hydrogenation type ZSM-5 catalytic reforming unit, for other components except carbonatoms is 2-4,5-6 and 13-20 that paraffin oil is separated, carries out isomerization.
In sum, the invention provides the method and system that a kind of low-rank coal and biomass are raw material synthesizing methane and petrol and diesel oil.Method and system tool of the present invention has the following advantages:
1, the multifunctional energy resource system of low-rank coal of the present invention and biomass alliance, the tar of high added value wherein is first provided by cascade utilization low-rank coal, rationally utilize again solid semicoke product wherein, not only be conducive to develop on a large scale exploitation and the conversion of low-rank coal, greatly improved the economic benefit of system simultaneously.
2, the multifunctional energy resource system of low-rank coal of the present invention and biomass alliance, by adding parallel biomass gasification device, by coal preparing liquid fuel and two PROCESS COUPLING of biomass-making liquid fuel, reduce flexibly and easily the Life cycle greenhouse gas emissions in coal liquefaction production process.
3, the multifunctional energy resource system of low-rank coal of the present invention and biomass alliance, by adding parallel biomass gasification device, by coal preparing liquid fuel and two PROCESS COUPLING of biomass-making liquid fuel, reduce flexibly and easily the Life cycle greenhouse gas emissions in coal liquefaction production process.
4, the multifunctional energy resource system of low-rank coal of the present invention and biomass alliance, by changing traditional fuel power generation function or pump around circuit method, can produce a large amount of lighter hydrocarbons (C by the Fischer-Tropsch synthesis process by type once 1～C 4) the unreacted synthetic gas of peace treaty is as the raw material of productive manpower synthetic natural gas, thereby greatly improve whole multifunctional energy resource system energy efficiency and economy.
5, refining of the present invention meets the vapour of automobile-use standard, the method for diesel oil, by common refining coal tar and high temperature fischer-tropsch synthetic oil, can greatly save facility investment, reduce the complicacy of harmonic process, make full use of the complementary utilization of two kinds of different properties oil products, make the product of final oil product refining scheme reach the preliminary every primary standard of fuel oil for vehicles, in the octane value that improves product gasoline, reduction aromatic hydrocarbon content is wherein to reach No. four oil product standard EU-4 in Europe.
Accompanying drawing explanation
Fig. 1 is that low-rank coal provided by the invention and biomass are the multifunctional energy resource system schematic diagram of raw material production vapour, diesel oil and synthetic natural gas.
Embodiment
By specific embodiment, describe below the beneficial effect of implementation process of the present invention and generation in detail, be intended to help reader to understand better essence of the present invention and feature, not as restriction that can practical range to this case.
Embodiment 1
Fig. 1 is the multifunctional energy resource system schematic diagram that the low-rank coal that provides of invention and biomass are raw material production vapour, diesel oil and synthetic natural gas.Wherein, S1 represents each burst of trunk gas/liquid logistics of system to S37, and V1 represents each strand of steam of system to V9.Wherein S1 is low-rank coal, S2 and S11 are air, S3 is biomass, S6 and S8 are oxygen, S4 and S10 are the water removing, wherein S7 is gasification water, S12 is the gas-phase product that low-rank coal coking is processed, S14 is solid product semicoke, S15 is char Gasification synthetic gas, S20 is pyrolysis gas, S21 is pyrolysis gas, the gas mixture of char Gasification synthetic gas and biomass gasified synthesis gas, S22 is biomass gasified synthesis gas, S24 is tar, S26 is hydrogen, S27 is synthetic oil, S29 is the oil gas that fischer-tropsch reaction obtains, S30 is unconverted gas, S31 is lighter hydrocarbons, S32, S33 is diesel oil and hydrocarbon product, S34 is the methanation unstripped gas that lighter hydrocarbons and unconverted gas mix, S5, S9, S19, S25, S28, S35, S36, S37 is the material through respective handling, S13, S16, S17, S18, the refuse matter of S23 for discharging.
Major equipment has low-rank coal pretreatment unit 1, low-rank coal coking unit 2, solid impurity separator 3, coal tar recovering equipment 4, air separation plant 5, char Gasification unit 6, biomass pretreatment unit 7, gasifying biomass unit 8, synthetic gas mixing tank 9, synthetic gas CO shift-converter 10, purified synthesis gas unit 11, Fischer-Tropsch synthesis device 12, oil gas splitter 13, oil product to refine altogether unit 14, unstripped gas mixing tank 15, CO 2membrane separation plant 16, pre-methanator 17, methanator 18.Wherein low-rank coal pretreatment unit 1 is connected with low-rank coal coking unit 2, and it exports one synthetic gas and refines altogether unit 14 with solid impurity separator 3 coal tar recovering equipment 4 with oil product successively and be connected, and exports another strand of synthetic gas and is connected with char Gasification unit 6; Biomass pretreatment unit 7 is connected with gasifying biomass unit 8; Synthetic gas from coal tar recovering equipment 4 and pyrolysis gas, char Gasification unit 6 and synthetic gas and gasifying biomass unit 8 is connected with CO shift-converter 10, purified synthesis gas unit 11 successively jointly after synthetic gas mixing tank 9 mixes, Fischer-Tropsch synthesis device 12 is connected with oil gas splitter 13; The Fischer-Tropsch synthesis oil that goes out oil gas splitter 13 is refined altogether unit 14 with oil product and is connected; After mixing in unstripped gas mixing tank 15, the lighter hydrocarbons that the unconverted gas that goes out oil gas splitter 13 and oil product are refined unit 14 altogether pass through successively again CO 2membrane separation plant 16, pre-methanator 17 and methanator 18.
Idiographic flow is: it forms low-rank coal S1(in Table 1) first after low-rank coal pretreatment unit 1 dewaters and pulverizes, (low-rank coal is ground and is sized to the particle that particle diameter is 80-400mm, be dried to again humidity and be less than 8%), enter low-rank coal coking unit 2 together with air S4 and middle pressure (25atm) steam V1, in warp, low temperature pyrogenation reacts to obtain solid product semicoke S14, gas-phase product S12 and ash S13 and a small amount of low-pressure steam V4 of by-product, reaction conditions is under excess air and middle pressure steam (25atm) atmosphere, temperature of reaction is 500 ℃, pressure 25atm.After the refuse S18 such as the ash content that gas-phase product S12 wherein carries secretly through 3 removals of solid impurity separator and a small amount of semicoke particle, entering coal tar recovering equipment 4(oil gas splitter) condensation, quiet putting with layering reclaim tar S24 and pyrolysis gas S20, produces a small amount of waste water S23 simultaneously.Pyrolysis chemical reaction is shown in formula 1, and main products mass distribution is in Table 2:
Table 1
Table 2
Solid product semicoke S14 after entering char Gasification unit 6 to make coal water slurry together with S7 with feedwater again and the reaction of the high-purity oxygen S6 generating gasification of high pressure (40atm) steam V2 and air separation plant 5 (temperature is 1500 ℃, the about 40atm of pressure), after cooling, obtain synthetic gas S15 and by-product middle pressure steam V5.Meanwhile, it forms biomass S3(in Table 1) through biomass pretreatment unit 7, pulverize and grind that (grinding is sized to the particle that particle diameter is 200-400mm, be dried to again humidity and be less than 8%) enter gasifying biomass list 8, carry out equally gasification reaction (1200 ℃ of temperature, the about 30atm of pressure) and obtain synthetic gas S22 and middle pressure steam V6.Synthetic gas S15, the S22 more than obtaining mixes at synthetic gas mixing tank 9 with pyrolysis gas S20, then enters 550 ℃ of CO shift-converter 10(temperature, pressure 25atm, catalyzer is Fe series catalysts) by the H of Fischer-Tropsch synthetic raw gas active principle 2/ CO is increased to 1.5(mol ratio).Concrete Fischer-Tropsch synthetic raw gas is composed as follows:
Table 3
Go out the Fischer-Tropsch synthetic raw gas S25 of CO shift-converter 10 first through synthetic gas clean unit 11, utilize NHD solvent for absorption agent, remove most H in gas 2s, SO 2with part CO 2(the CO in gas mixture 2and H 2s content is removed to respectively 500ppm and 25ppm is following).It is synthetic to there is high temperature fischer-tropsch in the mode that is once circulated and refluxed by nothing through Fischer-Tropsch synthesis device 12(in clean unstripped gas, temperature of reaction is 320 ℃, catalyzer is Ru series catalysts), and reclaim after its byproduct middle pressure steam V8 separating high-temp Fischer-Tropsch synthesis oil S27 and unconverted gas S30 in oil gas splitter 13.
Oil-feed product refine altogether the high temperature fischer-tropsch synthetic oil S27 of unit and mole composition of tar S20 is as shown in table 4.At oil product, refine altogether in unit, also have in addition the high-quality refinery hydrogen S26 of one outsourcing.First (reaction conditions is that catalyzer is FeS-Fe coal tar to be carried out to hydrofining processing 2o 3type catalyzer, pressure 40atm, 400 ℃ of temperature), the H/C that tentatively departs from sulphur wherein and improve tar molecule than (mole) to 0.85.Tar after processing mixes with Fischer-Tropsch synthesis oil, and enter the wherein each active principle of a hydro carbons recovery tower initial gross separation: temperature is less than the cut (distillate) of cut (petroleum naphtha), temperature 180-320 ℃ of 180 ℃ and the cut (paraffin oil) that temperature is greater than 320 ℃, and they are admitted to respectively, and petroleum naphtha hydrogenation is refining, fraction oil hydrogenation refining wax hydrofining cracking unit.(reaction conditions is that catalyzer is SiO for petroleum naphtha hydrogenation and fraction oil hydrogenation refining 2-Al 2o 3type catalyzer, pressure 40atm, 350 ℃ of temperature, hydrogen/oil mol ratio 10:1) after carbonatoms 4 with interior lighter hydrocarbons can and the unconverted gas of step (4) mix after for the synthesis of methane; C 5/ C 6component is sent to C 5/ C 6in isomerization unit by the C of positive structure body 5/ C 6(reaction conditions is that catalyzer is B in isomerization 2o 3-Al 2o 3type catalyzer, pressure 30atm, 400 ℃ of temperature, hydrogen/oil mol ratio 10:1) to improve the octane value of product gasoline; Other carbonatoms is that the component of 7-12 is sent to and in reformer, carries out hydrogenation type catalytic reforming (reaction conditions is that catalyzer is Pt/L type-zeolite, pressure 30atm, 450 ℃ of temperature, hydrogen/oil mol ratio 10:1) by 100% naphthenic hydrocarbon wherein with approximately 60% alkane carries out respectively isomery dehydrogenation and the octane value that aromatic hydrocarbons improves gasoline S33 is produced in dehydrocyclization; Carbonatoms is that the component of 13-20 is as diesel oil head product S33.The temperature that goes out hydro carbons recovery tower is greater than the cut (paraffin oil) of 320 ℃ and is divided into four strands through hydrocracked, treated (reaction conditions for take Magnesium Silicate q-agent molecular sieve as catalyzer, pressure 50atm, 500 ℃ of temperature, hydrogen/oil mol ratio 15:1): 1) C 2/ C 3/ C 4lighter hydrocarbons gas S31 pressurization (25atm) after deliver to unstripped gas mixing tank 15 and the carbonatoms obtaining above after the 4 unconverted gases of usining interior lighter hydrocarbons and step (4) mix as methanation reaction gas; 2) containing C 5/ C 6the C that component logistics and hydrotreatment above produce 5/ C 6logistics mixes delivers to C 5/ C 6(catalyzer is B to isomerization unit 2o 3-Al 2o 3type catalyzer, pressure 30atm, 400 ℃ of temperature); 3) containing C 13～C 20component is directly as diesel oil head product S33; 4) remaining component is delivered to non-hydrogenation type ZSM-5 catalytic reforming unit (catalyzer is ZSM5 catalyzer, pressure 40atm, 400 ℃ of temperature), 60%～80% alkane renormalization production reformation body alkane wherein, to increase the octane value of gasoline S33, can effectively be controlled to gasoline aromaticity content simultaneously.
Table 4
Go out oil product and refine altogether the lighter hydrocarbons gas S31 of unit 14 and mix at unstripped gas mixing tank 15 with the unconverted gas S30 that goes out oil gas splitter 13, the concrete methanation unstripped gas S34 dry gas volumn concentration obtaining is as follows: CO:18.3%, H 2: 25.7%, CO 2: 31.2%, CH 4: 9.8%, C 2h 6: 5.6%, C 2h 4: 3.24%, C 3h 8: 2.50%, C 3h 10: 1.90%, C 4h 10: 0.95%, C 4h 8: 0.80%.Methanation unstripped gas S34 is first through a CO 2membrane separation plant 16, utilizes the mould material of hollow by CO wherein 2after volume percent is down to below 2.0%, enter pre-methanator 17, main reaction (2) side reaction (3) (4) occurs, by 98% C wherein 2, C 3and C 4lighter hydrocarbons be converted into synthetic gas.The unstripped gas that goes out pre-methanator enters methanator and produces final synthetic natural gas (reaction conditions is that catalyzer is SiO 2type catalyzer, pressure 25atm, 500 ℃ of temperature), the reaction of reaction is (5) (6), and a large amount of middle pressure steam V9 of by-product.Final methanation gas product and petrol and diesel oil form as shown in table 4.
C nH m+nH 2O→(n+0.5m)H 2+nCO,n>1 （2）
The final methanation product gas product of the present invention meets GB17820-1999 Natural gas standard, belongs to a class natural gas.Its dry gas volume percent is: CH 4: 95.3%, CO 2: 1.5%, H 2: 1.25% and C nh m: 1.95%(n>1), net calorific value 32.0MJ/m 3, gross calorific value 35.8MJ/m 3.
For the advantage of better explanation system of the present invention, a minute product system for native system and reference is carried out to Performance Ratio, be respectively coal liquefaction system, coal preparing natural gas system, biomass refinery and biomass-making natural gas system, be shown in Table 5.According to the definition of relative energy saving ratio (7) (8), the accumulative total greenhouse gas emission of the Life cycle requiring in design reaches under the prerequisite of traditional petroleum path, and the fractional energy savings of native system still can reach 19.8%.
Table 5
PES = E ref - E mfe E ref = Σ i = 1 p ( E P i / η i ‾ ) - Σ j = 1 f E F j Σ i = 1 n ( E P i / η i ‾ ) = 1 - Σ j = 1 f E F j Σ i = 1 p ( E P i / η i ‾ ) - - - ( 7 )
η i ‾ = E P 1 , i + E P 2 , i . . . + E P j , i . . . + E P f , i E F 1 , i + E F 2 , i . . . + E F j , i . . . + E F f , i = E P 1 , i + E P 2 , i . . . + E P j , i . . . + E P f , i E P 1 , i / η 1 , i + E P 2 , i / η 2 , i . . . + E P j , i / η j , i . . . + E P f , i / η f , i = Σ j = 1 f E P j , i Σ j = 1 f ( E P j , i / η j , i ) - - - ( 8 )
In formula, E mfeand E refthe Lower heat value amount (MW) that represents respectively multifunctional energy resource system and reference system input thereof, wherein with the product i and Lower heat value amount (MW) corresponding to raw material j that represent respectively energy mix system, and the thermo-efficiency of reference system (%); with product, the Lower heat value amount (MW) of raw material and the thermo-efficiency (%) of process thereof representing respectively in sub-per unit area yield system from raw material j to product i process.

Claims (10)

1. take the method that low-rank coal and biomass are raw material synthesizing methane and petrol and diesel oil, it is characterized in that, described method comprises:
(1) low-rank coal coking is processed, obtained solid product semicoke and gas-phase product, wherein gas-phase product is isolated to pyrolysis gas and tar;
(2) the solid product semicoke of step (1) is gasified and obtains char Gasification synthetic gas;
(3) biomass gasified synthesis gas will be obtained after gasifying biomass; Wherein preferred described biomass and low-rank coal dry ash-free basis mass ratio are 0.50～1.5;
(4) by carrying out fischer-tropsch reaction after the biomass gasified synthesis gas mixing of the char Gasification synthetic gas of the pyrolysis gas of step (1), step (2) and step (3), then the gas-oil separation obtaining is obtained respectively to synthetic oil and unconverted gas; The condition of preferred described fischer-tropsch reaction is: temperature 310-370 ℃, and catalyzer is Co and/or Ru series catalysts; Be preferably Ru, TiO 2, Co, Zr, SiO 2with one or more the combination in MgO; Ru/TiO more preferably wherein 2, Co/Zr/SiO 2or Co/MgO/SiO 2;
(5) synthetic oil step (4) being obtained mixes with the tar that step (1) obtains, and enters hydro carbons recovery tower distillation and obtain respectively temperature and be less than 180 ℃, 180-320 ℃ and be greater than the cut of 320 ℃; Respectively above-mentioned cut is carried out to hydrotreatment;
Wherein preferably the temperature in above-mentioned cut is less than to 180 ℃ and carries out hydrofining with the cut of 180-320 ℃, preferred hydrorefined reaction conditions is that catalyzer is SiO 2-Al 2o 3type catalyzer, pressure 35-65atm, temperature 350-500 ℃, hydrogen/oil mol ratio 5-10:1; Then collect respectively carbonatoms that above-mentioned hydrofining obtains and take interior lighter hydrocarbons, the component that carbonatoms is 5-6, the component that carbonatoms is 7-12, the component that carbonatoms is 13-20 4; Wherein preferably by cut cutting, collect; The component that wherein also preferred carbonatoms is 5-6 carry out isomerization as auxiliary agent to improve the octane value of gasoline; Wherein preferred isomerized reaction conditions is that catalyzer is B 2o 3-Al 2o 3type catalyzer, pressure 30-40atm, temperature 320-450 ℃, hydrogen/oil mol ratio 5-10:1; Carbonatoms be the component of 7-12 carry out hydrogenation type catalytic reforming reaction as auxiliary agent to improve the octane value of gasoline; Wherein preferred catalytic reforming reaction condition is that catalyzer is Pt/L-type zeolite catalyst, pressure 30-40atm, temperature 350-500 ℃, hydrogen/oil mol ratio 5-10:1; Carbonatoms is that the component of 13-20 is as diesel oil head product;
The above-mentioned cut that is greater than 320 ℃ is carried out to hydrocracking; Preferred reaction conditions is for take Magnesium Silicate q-agent molecular sieve as catalyzer, pressure 35-65atm, temperature 400-600 ℃, hydrogen/oil mol ratio 8-15:1; Isocrackate is divided into four strands: 1) carbonatoms 4 with interior lighter hydrocarbons gas; 2) component that carbonatoms is 5-6 and temperature are less than after component that carbonatoms that the cut fraction hydrogenation of 180 ℃ process to produce is 5-6 is mixed carries out isomerization, and isomerization reaction condition is consistent with above-mentioned isomerization; 3) component that carbonatoms is 13-20 is directly as diesel oil head product; 4) remaining component is carried out non-hydrogenation catalyst reformation; In preferred non-hydrogenation catalyst reforming process, only have 60%～80% alkane isomerization production reformation body alkane in order to increase gasoline octane rating, catalytic reforming condition is ZSM-5 type catalyzer, pressure 25-45atm, temperature 300-500 ℃;
(6) by the carbonatoms of step (5) after the 4 unconverted gases with interior lighter hydrocarbons and step (4) mix for the synthesis of methane; Wherein the carbonatoms of preferred steps (5) 4 using interior lighter hydrocarbons and step (4) unconverted gas pressurization to after 25atm as methanation reaction gas; Wherein also preferably control the carbonatoms of step (5) after the 4 unconverted gases with interior lighter hydrocarbons and step (4) mix, gas mixture comprises following volume percent composition: CO:15～25%, H 2: 20～30%, CO 2: 30～40%, CH 4: 7.0～15%, C 2h 6: 5.0～10%, C 2h 4: 3.0～5.0%, C 3h 8: 2.0～4.0%, C 3h 10: 1.0～3.0%, C 4h 10: 0.5～2%, C 4h 8: 0.5～2%.
2. method according to claim 1, is characterized in that, step (1) is after low-rank coal pre-treatment, to carry out coking processing again; Preferred described pre-treatment is for low-rank coal is ground and to be sized to the particle that particle diameter is 80-400mm, then is dried to humidity and is less than 8%.
3. method according to claim 1, is characterized in that, it is to carry out under the existence of air and middle pressure steam that the coking of step (1) is processed; Wherein preferred described middle pressure steam is that pressure is at the steam of 25atm; Wherein preferred described coking processing is to carry out under ferrous oxide exists; More preferably the temperature of reaction that described coking is processed is 400 ℃～600 ℃, pressure 25atm; More preferably described ferrous oxide is FeO x, FeO and Fe 2o 3in one or more mixing.
4. method according to claim 1, is characterized in that, step (1) obtains after solid product semicoke and gas-phase product, wherein by gas-phase product process solid impurity separating treatment, then isolates pyrolysis gas and tar.
5. method according to claim 1, is characterized in that, step (2) is that the solid product semicoke of step (1) is gasified and obtains char Gasification synthetic gas under oxygen, water and high pressure steam exist; Wherein preferred described high pressure steam is the steam of pressure 40atm.
6. method according to claim 1, it is characterized in that, step (4) is, after the biomass gasified synthesis gas of the char Gasification synthetic gas of the pyrolysis gas of step (1), step (2) and step (3) is mixed, first process CO transformationreation of gas mixture is carried out to fischer-tropsch reaction again; The preferred H of gas mixture after CO transformationreation wherein 2the mol ratio of/CO is 1.3-2.4, more preferably 1.5; Wherein also preferably by gas mixture after CO transformationreation, gas mixture, through Polyethylene glycol dimethyl ether solvent absorbing, then is carried out to fischer-tropsch reaction; Wherein preferably by the CO in gas mixture 2and H 2s content is removed to respectively 500ppm and below 25ppm, then carries out fischer-tropsch reaction.
7. method according to claim 1, is characterized in that, in step (5), be the hydrogenation of tar of step (1) is processed, then and the synthetic oil that obtains of step (4) carry out common refining; Wherein after preferred hydrotreatment, the H/C mol ratio of tar is increased to 0.7-1.2, and wherein more preferably the reaction conditions of hydrotreatment is that catalyzer is FeS-Fe 2o 3type catalyzer, pressure 30-40atm, temperature 250-350 ℃.
8. method according to claim 1, is characterized in that, in step (6), the carbonatoms of step (5) is first carried out to pre-methanation resynthesis methane after the 4 unconverted gases with interior lighter hydrocarbons and step (4) mix; Wherein preferably the carbonatoms of step (5) after mixing, the 4 unconverted gases with interior lighter hydrocarbons and step (4) is first carried out to CO 2membrane sepn, then more than 2 lighter hydrocarbons are converted into synthetic gas by carbonatoms by pre-methanation reaction, then synthesizing methane; Wherein preferably carry out CO 2cO in gas after membrane sepn 2volume percent is less than 2.0%, and wherein the reaction conditions of preferably pre-methanation is that catalyzer is SiO 2type catalyzer, pressure 20-30atm, temperature 400-500 ℃.
9. a low-rank coal and biomass are the system of raw material synthesizing methane and petrol and diesel oil, it is characterized in that, described system comprises: low-rank coal coking unit (2), coal tar recovering equipment (4), char Gasification unit (6), gasifying biomass unit (8), synthetic gas mixing tank (9), Fischer-Tropsch synthesis device (12), oil gas splitter (13), oil product are refined unit (14), unstripped gas mixing tank (15), methanator (18) altogether, wherein low-rank coal enters low-rank coal coking unit (2), obtains gas-phase product and solid product semicoke, and wherein gas-phase product is transported to coal tar recovering equipment (4), isolates tar and pyrolysis gas, and its coal-tar middle oil oil product that is transported to is refined unit (14) altogether, the solid product semicoke obtaining in low-rank coal coking unit (2) is transported to char Gasification unit (6), obtains char Gasification synthetic gas, biomass obtain biomass gasified synthesis gas in gasifying biomass unit (8), pyrolysis gas wherein, char Gasification synthetic gas and biomass gasified synthesis gas are transported to synthetic gas mixing tank (9) to be mixed, gas mixture is transported to Fischer-Tropsch synthesis device (12) to carry out fischer-tropsch reaction and obtains oil gas, oil gas is transported to oil gas splitter (13), isolate synthetic oil and unconverted gas, wherein synthetic oil be transported to oil product refine altogether unit (14) and tar be divided into from, the carbonatoms that separation obtains is transported to respectively in unstripped gas mixing tank (15) with interior lighter hydrocarbons and the isolated unconverted gas of oil gas splitter (13) 4, then be transported to methanator (18) synthesizing methane.
10. system according to claim 9, it is characterized in that, described system comprises: low-rank coal pretreatment unit (1), low-rank coal coking unit (2), solid impurity separator (3), coal tar recovering equipment (4), air separation plant (5), char Gasification unit (6), biomass pretreatment unit (7), gasifying biomass unit (8), synthetic gas mixing tank (9), synthetic gas CO shift-converter (10), purified synthesis gas unit (11), Fischer-Tropsch synthesis device (12), oil gas splitter (13), oil product is refined unit (14) altogether, unstripped gas mixing tank (15), CO 2membrane separation plant (16), pre-methanator (17), methanator (18), wherein low-rank coal pretreatment unit (1) is connected with low-rank coal coking unit (2), the gas-phase product obtaining in low-rank coal coking unit (2) is successively by solid impurity separator (3) and coal tar recovering equipment (4), coal tar recovering equipment (4) is refined altogether unit (14) with oil product and is connected, and the solid product semicoke obtaining in low-rank coal coking unit (2) is transported to char Gasification unit (6), biomass are transported to gasifying biomass unit (8) through biomass pretreatment units (7), air passes into char Gasification unit (6) through the isolated oxygen of air separation plant (5), char Gasification unit (6), gasifying biomass unit (8) is connected with synthetic gas mixing tank (9) respectively with coal tar recovering equipment (4), make the pyrolysis gas from coal tar recovering equipment (4), from the char Gasification synthetic gas of char Gasification unit (6) with from the biomass gasified synthesis gas of gasifying biomass unit (8), in synthetic gas mixing tank (9), mix, synthetic gas mixing tank (9) downstream successively with CO shift-converter (10), purified synthesis gas unit (11), Fischer-Tropsch synthesis device (12) is connected with oil gas splitter (13), two outlets of oil gas splitter (13) are refined altogether unit (14) with oil product respectively and are connected with unstripped gas mixing tank (15), the outlet that oil product is refined unit (14) is altogether connected with unstripped gas mixing tank (15), and the carbonatoms that makes oil gas splitter (13) unconverted gas out and oil product refine altogether unit (14) passes through successively CO after unstripped gas mixing tank (15) mixes again with interior lighter hydrocarbons 4 2membrane separation plant (16), pre-methanator (17) enter into methanator (18),
Wherein preferred described low-rank coal coking unit (2) is fixed-bed reactor;
Preferred described char Gasification unit (6) is slurry fluidized gas producer;
Preferably gasifying biomass unit (8) is fluidized-bed gasification furnace.
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CN105713686A (en) * 2016-04-22 2016-06-29 杨皓 Process for producing civil fuel gas by utilizing coke oven and methanation process
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CN109868159A (en) * 2019-01-30 2019-06-11 浙江天禄环境科技有限公司 A method of utilizing volatile matter ammonia in low-order coal
US11697779B2 (en) 2019-03-22 2023-07-11 King Fahd University Of Petroleum And Minerals Co-gasification of microalgae biomass and low-rank coal to produce syngas/hydrogen
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