CN110467943A - A kind of natural gas from coal, alkene and coal tar method - Google Patents

A kind of natural gas from coal, alkene and coal tar method Download PDF

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Publication number
CN110467943A
CN110467943A CN201810445891.XA CN201810445891A CN110467943A CN 110467943 A CN110467943 A CN 110467943A CN 201810445891 A CN201810445891 A CN 201810445891A CN 110467943 A CN110467943 A CN 110467943A
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gas
coal
hydrogen
water
steam
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CN110467943B (en
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李宁
李开建
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Chengdu Poly Energy Saving Technology Co Ltd
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Chengdu Poly Energy Saving Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46—Gasification of granular or pulverulent flues in suspension
    • C10J3/48—Apparatus; Plants
    • C10J3/485—Entrained flow gasifiers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/82—Gas withdrawal means
    • C10J3/84—Gas withdrawal means with means for removing dust or tar from the gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/103—Sulfur containing contaminants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • C10L3/104—Carbon dioxide
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913—Carbonaceous raw material
    • C10J2300/093—Coal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0973—Water
    • C10J2300/0976—Water as steam
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Industrial Gases (AREA)

Abstract

A kind of natural gas from coal, alkene and coal tar method, with temperature appropriate and gas phase media condition, directly by the protium in feed coal, the form for generating gaseous hydrocarbon is separated from coal；With protium by the carbon in coal, directly reaction is at hydrocarbon gas；At high temperature using oxygen-enriched water vapour, it by the carbon in residual coke remaining after production gaseous hydrocarbon, carries out water gas reaction and is converted into CO and H2, to greatly improve its efficient energy conversion, water resources consumption be greatly reduced, CO is greatly decreased2Discharge and environmental pollution, and plant investment is greatly decreased, reduce production cost.

Description

A kind of natural gas from coal, alkene and coal tar method
Technical field
The invention belongs to coal chemical technology, in particular to natural gas from coal, alkene, fuel oil energy technology with set It is standby.
Background technique
Existing coal oil and natural gas from coal, synthetic oil, the two-step method of gas or coal are direct again either after coal gasification Add the one-step method of hydrogen production oil, gas, because process route is complicated, technical process efficient energy conversion is low, coal oil only 40%, Consumption mark 3.6 ton/ton oil of coal, natural gas from coal only 50%, consumption mark 2.5 tons/km of coal3；Equipment investment is high, and 160,000,000,000 yuan of coal oil/ 10000000 tons, 28,000,000,000 yuan/4,000,000,000 m of natural gas from coal3；Water resources consumption is high, 7 ton/ton oil of coal oil water consumption, natural gas from coal 7 Ton/km3；Environmental pollution weight, cost of sewage disposal is high, CO2It discharges more.
Study carefully its main technical reason, synthesizes C again after coal gasificationnH2n+2(n=1 CH4, n=8 is gasoline, and n=16 is Diesel oil) it is known as two-step method, chemically react nCO+2nH2+H2=CnH2n+2+nH2Oxygen in O, CO has to use H2It goes to take out, and Tradition produces H2Energy consumption and cost it is all very high, so the coal gasification process of two-step method, the Lurgi gasifier generallyd use, Matter is that normal pressure gas furnace is exactly changed to pressurized-gasification furnace, adds hydrogen to directly generate hydrocarbon product because not can be carried out, therefore there are above-mentioned Shortcomings.
100 type gasification furnace of Rule is that traditional normal pressure two-stage gas-fired furnace is changed to 10MPa operating pressure, except first in coal gas Alkane increases outside 70% or so, and coal gas waste, steam decomposition rate etc. do not improve, and more carbon hydrocarbon are also reduced compared with 3MPa lurgi gasifier 25%, not too many advantage is not suitable for coal oil because voluminous methane consumes excessive hydrogen, since operation pressure is too high, if Standby investment is significantly increased, be also for natural gas from coal it is uneconomic, develop more than 50 so far years in the past, Lucci corporation does not have always There is subsequent further exploitation, there is no commercialized running achievement more.
The reason of one-step method liquefaction low efficiency of existing coal direct hydrogenation, first is that operation pressure is up to 20MPa, equipment investment Greatly；Second is that carbon conversion ratio is low, residue carbon containing up to 40%, need to reheat in special gasification furnace could be secondary again At CO；Third is that using air-flow bed coal-gasification hydrogen manufacturing, since in air-current bed gasification process, hydrogen content of coal element is with hydrocarbon Form, 700 DEG C or less just first pyrolysis be gaseous hydrocarbon, immediately with the O in air-flow2Solid/liquid/gas reactions generate CO2And H2O releases heat, makes Furnace temperature reaches 1300~1700 DEG C of height, so it is protium burning contribution that the high furnace temperature of air flow bed, which has a large portion, Low so as to cause hydrogen mole fraction in coal gas, CO ingredient is especially high, and CO have to pass through transformation can just be converted into hydrogen, i.e., this Kind process for making hydrogen substantially burns up the H in coal first2, CO then is produced with the C element in coal again, CO is transformed again to be turned Turn to H2, so existing coal direct hydrogenation one-step method CnH2n+2There is also shortcomings above-mentioned.
Existing coal-to-olefin by the oxygen-enriched water vapour pressurized gasification of feed coal, heavy-oxygen-enriched water gas washing and coal tar separation, Oxygen-enriched water-gas CO transformation is CO/H2Proportion adjustment, the removing of gas with enriched oxygen acid gas, methanol-fueled CLC, separating methanol, methane separation, Process for preparing olefins by methanol dehydration process composition and technical process are tediously long, and energy consumption, water consume, environmental protection, investment have vast improvement Space.
Summary of the invention
The purpose of the present invention, first is that being generated with temperature appropriate and gas phase media condition directly by the H element in feed coal The form of gaseous hydrocarbon is separated from coal；Second is that directly reacted the carbon in coal into hydrocarbon gas with H element, Third is that at high temperature using oxygen-enriched water vapour, converting CO and H for the carbon in residual coke remaining after production gaseous hydrocarbon2, with Its efficient energy conversion is greatly improved, water resources consumption is greatly reduced, CO is greatly decreased2Discharge and environmental pollution, and substantially subtract Few plant investment, reduces production cost.
Specific summary of the invention is as follows:
1. a kind of natural gas from coal, alkene and coal tar method, by the oxygen-enriched water vapour pressurized gasification of feed coal, heavy-oxygen-enriched water coal Gas washing and coal tar separation, oxygen-enriched water-gas CO transformation are CO/H2Proportion adjustment, the removing of gas with enriched oxygen acid gas, methanol-fueled CLC, Separating methanol, methanol-fueled exhaust separation of methane, process for preparing olefins by methanol dehydration process composition, it is characterised in that:
Feed coal in the same pressurized gasification bed continuously moved down successively successively: by hydrocarbon-rich hydrogen heated by gas, dry It is dry, that is, remove moisture；By the pyrolysis of methane rich hydrogen coal gas, destructive distillation, i.e. hydrocarbon-rich hydrogen coal gas of the system rich in coal tar；Gasified by hydrogen, Obtain the methane rich hydrogen coal gas rich in methane；By H2O+CO2Gasification, i.e. water gas；By the O in Steam oxygen gasifying agent2Oxygen Change residues of combustion carbon.
2. according to the present invention, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that hydrogen follows Ring machine will produce the hydrogen of hydrocarbon-rich hydrogen coal gas, through driving heating device, be sent into the hydrogen dispenser being located in gasification bed top Afterwards, the downlink in restraining enters coke hydrogasification layer from the outlet of tube bank lower end after heat-exchanging tube bundle heats；Into coke plus Baffling is upward again for the hydrogen of hydrogen agent layer, directly reacts C+2H with the carbon in coke2=CH4, generate the methane containing methane Hydrogen coal gas, the heat of releasing directly heat layer of charcoal and generate high-temperature methane hydrogen coal gas through the hydrogen in heat-exchanging tube bundle heating tube； Semicoke hydrogasification layer is advanced on high-temperature methane hydrogen coal gas, active carbon abundant in hydrogen and semicoke carries out quick Gasification reaction C+2H2=CH4, methane content in methane hydrogen coal gas is increased significantly, becomes methane rich hydrogen coal gas, and release heat Increase bed temperature；It is advanced into pyrogenation and carbonization layer on high temperature methane rich hydrogen coal gas, provides heat for the pyrogenation and carbonization of coal, due to Methane partial pressure content is high in methane rich hydrogen coal gas, effectively inhibits the generation of methane in coal, is precipitated, forces the protium in coal, It is more to combine in hydrogen carbon than in lower coal tar, to be effectively increased yield and the carbon gasification of coal tar Rate also adds the coal tar content of methane rich hydrogen coal gas, makes methane rich hydrogen while improving the pyrogenation and carbonization rate of gasification of coal Coal gas becomes hydrocarbon-rich hydrogen coal gas；Hydrocarbon-rich hydrogen coal gas is advanced into feed coal drying layer on continuing, dry while heating feed coal Moisture in coal makes absorption water and chemical water in feed coal, is converted into water vapour and enters hydrocarbon-rich hydrogen coal gas, hydrocarbon-rich hydrogen coal gas warp Its furnace wall upper outlet is come out of the stove.
3. according to the present invention, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that after coming out of the stove Hydrocarbon-rich hydrogen coal gas, through tar dust separator remove tar removing dust, reduce temperature through heat exchanger, then be cooled to often through cooler Temperature is simultaneously separated off grease and isolates H into acid gas Hydrogen Separation process2S、COS、CO2, after CO sour gas and hydrogen, at For the coal synthetic natural gas for meeting GB/T 33445-2016 standard, a portion enters methane anaerobic alkene/aromatic hydrocarbons dress It sets, while obtained alkene/aromatic hydrocarbons, a large amount of hydrogen of generation are directly entered hydrogen manifold, with acid gas Hydrogen Separation process point The hydrogen come is separated out, water-gas acid gas removes the hydrogen that process is come, and together after the boosting of hydrogen circulator, enters furnace production again Hydrocarbon-rich hydrogen coal gas.
4. according to the present invention, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that by oxygen After entering furnace from furnace bottom with the gasifying agent of water vapour mixing composition, fire grate is passed through to lower and upper and passes through ash bed, absorbs its carrying Heat, temperature are increased to 600 DEG C or so and enter oxygen gasified burning zone, and the oxygen in gasifying agent makes carbon remaining in residual coke Rapid combustion gasification generates CO2And release a large amount of heat, make water vapour and bed temperature in gasifying agent reach 1000 DEG C with On, below ash fusion point；Contain CO2High-temperature water vapor from bottom to top, it is residual that heat is transmitted to the hydrogasification from hydrogen coal gas section While burnt, the steam gasification to absorb heat with the carbon in residual coke reacts C+H2O=CO+H2, make the major part in residual coke 30~40% water molecule reactions in carbon and water vapour, the CO and H being converted into raw gas2, become temperature at 700 DEG C or so Damp and hot raw gas, be advanced into the coal gas gas collector on raw gas conversion zone top on raw gas, then pass through the raw gas on furnace wall It comes out of the stove outlet.
5. according to the present invention, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that come out of the stove Raw gas is after dedusting, steam superheater heating steam in the boiler, into steam needed for waste heat steam boiler production section coal gasification Afterwards, waste-heat recovery device is washed into water-gas, is invented using No. 2011100943882 recycling process of coal gas waste heat special 30~75% Steam Reforming in coal gas is recovered as gasification water vapour by benefit, and coal gas enters CO shift conversion step, by 95% Above CO carries out CO+H by catalyst2O=CO+H2Conversion reaction；Transformed coal gas is known as conversion gas, main component For H2And CO2；CO in conversion gas2Acid gas and a small amount of H2S acid gas is removed using pressure-variable adsorption PSA separating technology, and Combustible component calorific value 400kJ/Nm will be contained3Above part CO2Stripping gas is sent into gas turbine exhaust gas boiler or low heat value combustion Gas boiler wherein will be converted into steam energy recycling by combustible component.
6. according to the present invention, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that normal raw When production, enter the steam in the Steam oxygen gasifying agent of furnace, by water leg drum, coal gas waste heat boiler, the CO being connected with water leg Reaction heat and water-gas washing waste-heat recovery device provide jointly；The wherein steaming of water-gas washing waste-heat recovery device production Vapour is already higher than condensation temperature, while the recovered steam contains a small amount of O2And corrosive impurity and dissolved salt, to improve steam mistake Hot device service life, water-gas wash waste-heat recovery device production recovered steam not into steam superheater, and its outlet with Superheated steam mixing, then adds appropriate O2, after so that the steam oxygen ratio of gasifying agent is reached technique requirement, through Steam oxygen gasifying agent Import enters furnace.
7. according to the present invention, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that normal raw When production, enter the oxygen in the Steam oxygen gasifying agent of furnace, according to the vapour content in water-gas and needs the water vapour of air lift Number, amount of oxygen 30~80% as water-gas washing waste-heat recovery device in stripping medium be added gasifying agent in, 20~70% are added in gasifying agent as the magnitude of recruitment for meeting steam-to-gas ratio requirement.
8. according to the present invention, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that same company The continuous pressurized gasification bed moved down is set as, the two stage pressurization moving bed gas burner of upper-lower section different function structure, Lower part is designed as, and produces hydrogen with the residual coke from hydrocarbon-rich hydrogen coal gas section for raw material using oxygen and water vapor mixture agent With the water-gas section of carbon monoxide, residual coke gasification bed ratio of height to diameter 0.5~1.5；Upper part is designed as, using methane≤ 15%, hydrogen 80~95%, CO+CO2+H2O+N2≤ 5%, H2S≤0.5%, O2≤ 0.1%, i.e., it is as main component with hydrogen Hydrogen gasifying agent is directly produced with feed coal using natural gas, alkene and coal tar as major product, more carbon hydrocarbon hydrogen coal gas sections, Its gasified raw material coal bed layer ratio of height to diameter is 2~6.8.
9. according to the present invention, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that water-gas Section maximum temperature is the slag gasification mode of ash fusion point temperature dry deslagging gasification mode below or ash fusion point temperature or more.
10. according to the present invention, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that pressurization coal Gasifier bed layer process pressure is 1~3MPa or 3~6MPa, 6~10MPa, and methane anaerobic olefin process pressure is hydrocarbon-rich hydrogen coal 0.95~0.6 times of gas outlet pressure or 0.6~0.3 times or 0.3~0.1 times or 0.1~0.05 times.
Natural gas from coal, alkene and coal tar, are had the positive effect that using the present invention:
1. during normal production, coal gasification steam is realized self-supporting, that is, it is not required to boiler and gasification process steam is provided, both saved throwing Money energy conservation again, also reduces environmental pollution, reduces water resources consumption and CO2Discharge.
2. significantly simplifying coal-to-olefin process, with entrained flow gasification, compare, throws through methanol-fueled CLC, preparing olefin by methyl alcohol dewatering Money and process energy consumption, oxygen consumption, water resources consumption, CO2Discharge, environmental pollution are greatly decreased；Methane anaerobic alkene point Solve a large amount of H2It is directly becoming the raw hydrogen of coal hydrogenation hydrocarbon-rich hydrogen coal gas, greatly reduces the demand of coal hydrogen manufacturing；
3. carrying out pyrolysis of coal destructive distillation using methane rich hydrogen coal gas, not only coal tar oil yield is significantly increased, since temperature is mild, Tar quality is good, and added value is high, for adding hydrogen liquefaction, can reduce production cost.
4. natural gas from coal feed coal, water resource, oxygen consumption is greatly decreased, with fischer-tropsch synthesis process first than eliminating first Alkane catalyzes and synthesizes process, methane dehydration procedure, has saved investment.
5. the direct C+2H of coal hydrogenation2=CH4Generate methane reaction heat, both for feed coal pyrogenation and carbonization, drying and dehydrating, Raw coal is heated, the water vapour that heating jacket recirculated water production water gas reaction needs is also used to, heat is utilized by abundant coupling, Effectively increase the natural gas from coal thermal efficiency.
Detailed description of the invention
Fig. 1 is the method and process general flow chart of a kind of natural gas from coal described in this case, alkene and coal tar.
In figure
1. Steam oxygen gasifying agent import；
2. the cooling water inlet of gas burner collet shell；
3. raw gas exports；
4. hydrogen gasifying agent import；
5. hydrocarbon-rich hydrogen gas exit；
6. the cooling water outlet of gas burner collet shell；
7. feed coal；
8. coal is locked；
9. coal feeder；
10. drying layer；
11. destructive distillation layer；
12. blender；
13. sieve plate；
14. hydrogen dispenser；
15. semicoke hydrogasification layer；
16. heat-exchanging tube bundle；
17. coke hydrogasification layer；
18. manhole；
19. coal gas gas collector；
20. water gas reaction layer；
21. oxidizing fire layer；
22. ash bed；
23. gas burner pressure-bearing collet shell；
23A. gas burner collet recirculated cooling water gas-liquid separator, i.e. collet drum；
23B. jacket steam and pipeline；
24. ash lock；
25. clinker；
26. driving steam and pipeline；
27. gasification oxygen and pipeline；
27A. air lift water vapour is with oxygen (recycling water vapour process requirement in water-gas)；
27B. adjusts steam oxygen ratio oxygen；
28. the steam and pipeline that are recycled from water-gas；
29. coal gas dust removal and steam superheating combination unit, i.e. dedusting superheater；
30. coal gas waste heat boiler；
31. water-gas washing and gas waste heat recovery device；
32. coal gas CO shift conversion step；
33.CO2、H2S acid gas removes process；
33A. sulfur recovery process；
34. acid gas, which removes the calorific value that process excludes, has recovery value exhaust gas, main component is CO2, remove exhaust combustion pot Furnace；
35. hydrogen manifold；
35A. hydrogen circulator；
Enter furnace hydrogen heating device when 36. driving；
37. tar dust separator；
Coal tar, the dust, water of 37A. tar dust separator arduously out；
38. hydrocarbon-rich hydrogen coal gas waste heat reclaiming process device；
39. the cooling of hydrocarbon-rich hydrogen coal gas and water-oil separating process unit
The You Heshui that 39A. is separated；
40.H2S, COS acid gas and Hydrogen Separation process unit；
40A. sulfur recovery process；
41. methane anaerobic alkene/aromatic hydrocarbons or so device；
41A. alkene/aromatic hydrocarbon product；
42. coal tar, oil, gas sewage Separation process arrangements；
42A. coal tar, oil product；
H2--- hydrogen and molecular formula；
CH4--- methane and molecular formula；
CO2--- carbon dioxide and molecular formula；
A --- hydrogen coal gas section；
B --- water-gas section.
Specific embodiment
About gasification furnace:
The pressing gas furnace containing water-gas section and hydrogen coal gas section, the design of each technique unit equipment, manufacture are completed first, Then erecting bed installation in place, the installation of craft piping, electric meter, corrosion-resistant thermal insulation, system leak test, pressure testing, debugging conjunction are transported to Lattice make it have the structure and function of design requirement.
Then the coal gas boiler ash sediment of 300mm thickness is successively spread on the fire grate of water-gas section, needed for steam gasification layer 20~80mm of granularity, the coke of thickness 2000mm；20~80mm of granularity is added in the coke hydrogasification layer of oil gas section, it is thick 3000mm coke is spent, the semicoke of 3000mm thickness is added in semicoke hydrogasification layer, 20~80mm of granularity is added in destructive distillation layer, 20~80mm of granularity, the weakly caking coal of thickness 1000mm is added in drying layer in the weakly caking coal of 2000mm thickness.
1. by air with 5000~10000Nm per hour3Flow, be sent into furnace with the temperature rise rate of 50 DEG C/h, in richness The emptying of hydrocarbon hydrogen gas exit；About at 6 hours or so, since the burning point of coke is about at 350 DEG C, the oxygen combustion of water-gas section Layer will start the phenomenon that temperature is more than into stove air temperature occur, reaches 700 DEG C or so when oxygen combustion layer increases rapidly, will put Sky is vented after changing into the water-gas outlet of water-gas section；Nitrogen can be added in right amount in entering stove air, reduce its O2Content, with Oxygen combustion layer heating rate is controlled in 100 DEG C/h or so, after oxygen combustion layer temperature reaches 900~1000 DEG C, gradually will Atmosphere temperature rising is changed to oxygen water vapor mixture agent, and controls its temperature and no longer go up, and scabs to prevent water-gas section overtemperature.
2. by the hot nitrogen with water-gas exiting flue gas isothermal, with every 5000~10000Nm3The flow of/h passes through hydrogen coal Hydrogen coal gas section is added in the hydrogen inlet of gas section, and is vented in hydrogen gas exit, for coke, the semicoke of further heating hydrogen coal gas section And feed coal, appropriate air can be filled into hot nitrogen and (actually fill into oxygen, it is to note that coke hydrogasification layer and semicoke add Hydrogen gasification layer maximum temperature must not exceed 700 on DEG C) to accelerate heating rate using the combustion heat of oxygen and coke；
3. being that can start blender low-speed running in real time when hydrogen coal gas section destructive distillation layer temperature is greater than 400 DEG C, coal supply apparatus is opened Dynamic automatic control circuit, to be automatically added to feed coal in due course.
4. when coke hydrogasification layer and semicoke hydrogasification layer maximum temperature reach 600 on DEG C, with 1MPa's per hour Rate starts system boosting, to note as far as possible in boost process: reducing water-gas outlet and the pressure difference of hydrogen inlet levels off to Zero, it is advanced into water-gas gas collector under the gas to prevent hydrogen coal gas section and is exported from water-gas and flows out.
5. after the oxygen being added in hot nitrogen is turned off 30 minutes when pressure is raised to 2MPa, or turning off oxygen, hot spot temperature After 100 DEG C of degree decline, hot nitrogen is entered into furnace and is changed to hot hydrogen with 5000~10000Nm3The flow of/h enters furnace, turns hydrogen coal gas section Enter hydrocarbon-rich hydrogen gas process processed, and gradually increased with the rate of 1MPa per hour, finally stablizes pressure in Process Planning level pressure Power.
Control for Kiln Temperature: water-gas section by entering furnace steam oxygen ratio, control its oxygen combustion layer temperature 30 below ash fusion point~ 80℃；Hydrogen coal gas section adds maximum temperature≤1000 of hydrogen section by methane content in control hydrogen temperature and hydrogen, control semicoke ℃；
Hydrocarbon-rich hydrogen gas composition control: in hydrocarbon-rich hydrogen coal gas methane content according to coal activity, volatile matter, by control into Furnace hydrogen flowing quantity, temperature, methane content, the final methane content that controls in hydrocarbon-rich hydrogen coal gas is 50~60%, other gaseous hydrocarbons 100 ~200g/Nm3Oil gas.
About the recuperation of heat of hydrocarbon-rich hydrogen coal gas, purification, separation and anaerobic alkene:
Since the steam contained in hydrocarbon-rich hydrogen coal gas all is from feed coal, i.e. the moisture content of as-fired coal is hydrocarbon-rich hydrogen coal The key factor of gas tapping temperature key determinant and coal gas waste amount, so the moisture reduced in feed coal can be effective Reduce coal gas waste.
Since steam largely reduces in hydrocarbon-rich hydrogen coal gas, the reduction for also bringing its cost of equipment is also greatly decreased in waste heat.
Due to CO, CO in hydrocarbon-rich hydrogen coal gas2Content is low, after cooling, oil-water separation, is designed according to methane purposes different Separating technology: if methane is mainly liquefied natural gas LNG, hydrogen is mentioned using cryogenic separation, if methane is mainly used as using methane Anaerobic olefin process then should mention hydrogen using pressure-variable adsorption PSA technique, with substantially because methane anaerobic olefin process pressure is low Reduce process energy consumption.
About the recycling of water-gas waste heat, purification separation, hydrogen manufacturing:
Since this case water-gas feed coal is the residual coke of hydrogasification, so there is no tar in coal gas, methane content also compared with It is few, temperature at 700 DEG C or so, out furnace water gas can be used common dry method cyclone dust collectors remove 98% or more dust, then Cool down 100 DEG C or so through steam superheater, into waste heat steam boiler, heat is switched into process steam thermal energy, temperature is down to 250 DEG C or so, into No. 2011100943882 patent water-gas washings and waste-heat recovery device, due to moisture content mistake in coal gas Height will lead to CO transformation catalyst overtemperature inactivation, and steam extra in coal gas is switched to can be back into the recovered steam of furnace, both CO transformation catalyst is protected to obtain gasification water vapour again, also reduce gas sewage discharge capacity.
Since the final purpose of water gas two-stage gasifier is exactly to produce hydrogen, so CO transformation uses the depth of 95% or more change rate Degree transformation, to obtain hydrogen more as far as possible, transformed coal gas is known as conversion gas, and ingredient is mainly H2And CO, due to transformation The dry method decarburization of PSA system is adsorbed, not water consumption, simple process, high degree of automation.Hydrogen yield is separated up to 98% CO2, wherein containing a small amount of CO, CH4Combustible should recycle, and heat is greater than the CO of 400kJ/Nm32, it is sent into Combustion engine tail gas Boiler for producing steam, realization are made the best use of everything, and the hydrogen separated is sent into hydrogen manifold as hydrocarbon-rich hydrogen coal gas raw hydrogen.

Claims (10)

1. a kind of natural gas from coal, alkene and coal tar method, by the oxygen-enriched water vapour pressurized gasification of feed coal, oxygen-enriched water-gas is washed Wash separated with coal tar, oxygen-enriched water-gas CO transformation i.e. CO/H2Proportion adjustment, the removing of gas with enriched oxygen acid gas, methanol-fueled CLC, methanol Separation, methanol-fueled exhaust separation of methane, process for preparing olefins by methanol dehydration process composition, it is characterised in that:
Feed coal in the same pressurized gasification bed continuously moved down successively successively: by hydrocarbon-rich hydrogen heated by gas, drying, i.e., Remove moisture；By the pyrolysis of methane rich hydrogen coal gas, destructive distillation, i.e. hydrocarbon-rich hydrogen coal gas of the system rich in coal tar；Gasified by hydrogen, obtains Methane rich hydrogen coal gas rich in methane；By H2O+CO2Gasification, i.e. water gas；By the O in Steam oxygen gasifying agent2Oxidizing fire Remaining carbon.
2. according to claim 1, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that hydrogen circulation Machine will produce the hydrogen of hydrocarbon-rich hydrogen coal gas, through driving heating device, after being sent into the hydrogen dispenser being located in gasification bed top, The downlink in restraining enters coke hydrogasification layer from the outlet of tube bank lower end after heat-exchanging tube bundle heats；Into coke hydrogenation Baffling is upward again for the hydrogen of agent layer, directly reacts C+2H with the carbon in coke2=CH4, generate the methane hydrogen coal containing methane Gas, the heat of releasing directly heat layer of charcoal and generate high-temperature methane hydrogen coal gas through the hydrogen in heat-exchanging tube bundle heating tube；High temperature Semicoke hydrogasification layer is advanced on methane hydrogen coal gas, active carbon abundant in hydrogen and semicoke is quickly gasified React C+2H2=CH4, methane content in methane hydrogen coal gas is increased significantly, becomes methane rich hydrogen coal gas, and release heat to make bed Layer temperature increases；It is advanced into pyrogenation and carbonization layer on high temperature methane rich hydrogen coal gas, heat is provided for the pyrogenation and carbonization of coal, due to being the richest in Methane partial pressure content is high in alkane hydrogen coal gas, effectively inhibits the generation of methane in coal, is precipitated, forces the protium in coal, more Combination in hydrogen carbon than in lower coal tar, to be effectively increased the yield and carbon rate of gasification of coal tar, While improving the pyrogenation and carbonization rate of gasification of coal, the coal tar content of methane rich hydrogen coal gas is also added, methane rich hydrogen coal is made Gas becomes hydrocarbon-rich hydrogen coal gas；Hydrocarbon-rich hydrogen coal gas is advanced into feed coal drying layer on continuing, while heating feed coal, moisture-free coal In moisture, make absorption water and the chemical water in feed coal, be converted into water vapour and enter hydrocarbon-rich hydrogen coal gas, hydrocarbon-rich hydrogen coal gas is through it Furnace wall upper outlet is come out of the stove.
3. according to claim 1, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that after coming out of the stove Hydrocarbon-rich hydrogen coal gas removes tar removing dust through tar dust separator, reduces temperature through heat exchanger, then be cooled to room temperature through cooler And it is separated off grease, into acid gas Hydrogen Separation process, isolate H2S、COS、CO2, after CO sour gas and hydrogen, become Meet the coal synthetic natural gas of GB/T 33445-2016 standard, a portion enters methane anaerobic alkene/aromatic hydrocarbons dress It sets, while obtained alkene/aromatic hydrocarbons, a large amount of hydrogen of generation are directly entered hydrogen manifold, with acid gas Hydrogen Separation process point The hydrogen come is separated out, water-gas acid gas removes the hydrogen that process is come, and together after the boosting of hydrogen circulator, enters furnace production again Hydrocarbon-rich hydrogen coal gas.
4. according to claim 1, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that by oxygen and After the gasifying agent of water vapour mixing composition enters furnace from furnace bottom, fire grate is passed through to lower and upper and passes through ash bed, absorbs the heat of its carrying Amount, temperature are increased to 600 DEG C or so and enter oxygen gasified burning zone, and the oxygen in gasifying agent keeps carbon remaining in residual coke fast Fast combustion gasification generates CO2And release a large amount of heat, make water vapour and bed temperature in gasifying agent reach 1000 DEG C with On, below ash fusion point；Contain CO2High-temperature water vapor from bottom to top, it is residual that heat is transmitted to the hydrogasification from hydrogen coal gas section While burnt, the steam gasification to absorb heat with the carbon in residual coke reacts C+H2O=CO+H2, make the major part in residual coke 30~40% water molecule reactions in carbon and water vapour, the CO and H being converted into raw gas2, become temperature at 700 DEG C or so Damp and hot raw gas, be advanced into the coal gas gas collector on raw gas conversion zone top on raw gas, then pass through the raw gas on furnace wall It comes out of the stove outlet.
5. according to claim 1, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that comes out of the stove is thick Coal gas is after dedusting, steam superheater heating steam in the boiler, into after steam needed for waste heat steam boiler production section coal gasification, Waste-heat recovery device is washed into water-gas, it, will using No. 2011100943882 recycling process of coal gas waste heat patents of invention 30~75% Steam Reforming in coal gas is recovered as gasification water vapour, and coal gas enters CO shift conversion step, by 95% or more CO CO+H is carried out by catalyst2O=CO+H2Conversion reaction；Transformed coal gas is known as conversion gas, main component H2 And CO2；CO in conversion gas2Acid gas and a small amount of H2S acid gas is removed using pressure-variable adsorption PSA separating technology, and will be contained There is combustible component calorific value 400kJ/Nm3Above part CO2Stripping gas is sent into gas turbine exhaust gas boiler or fuel gas with low heat value pot Furnace wherein will be converted into steam energy recycling by combustible component.
6. according to claim 1, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that normal production When, enter the steam in the Steam oxygen gasifying agent of furnace, is become by the water leg drum, coal gas waste heat boiler, CO that are connected with water leg It changes reaction heat and water-gas washing waste-heat recovery device provides jointly；The wherein steaming of water-gas washing waste-heat recovery device production Vapour is already higher than condensation temperature, while the recovered steam contains a small amount of O2And corrosive impurity and dissolved salt, to improve steam mistake Hot device service life, water-gas wash waste-heat recovery device production recovered steam not into steam superheater, and its outlet with Superheated steam mixing, then adds appropriate O2, after so that the steam oxygen ratio of gasifying agent is reached technique requirement, through Steam oxygen gasifying agent Import enters furnace.
7. according to claim 1, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that normal production When, enter the oxygen in the Steam oxygen gasifying agent of furnace, according to the vapour content in water-gas and needs the water vapour of air lift Number, the 30~80% of amount of oxygen are added in gasifying agent as the stripping medium in water-gas washing waste-heat recovery device, and 20 ~70% is added in gasifying agent as the magnitude of recruitment for meeting steam-to-gas ratio requirement.
8. according to claim 1, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that same continuous The pressurized gasification bed moved down is set as, the two stage pressurization moving bed gas burner of upper-lower section different function structure, under Portion is designed as, using oxygen and water vapor mixture agent, with the residual coke from hydrocarbon-rich hydrogen coal gas section for raw material, production hydrogen and The water-gas section of carbon monoxide, residual coke gasification bed ratio of height to diameter 0.5~1.5；Upper part is designed as, using methane≤15%, Hydrogen 80~95%, CO+CO2+H2O+N2≤ 5%, H2S≤0.5%, O2≤ 0.1%, i.e., with hydrogen hydrogen gas as main component Agent is directly produced with feed coal using natural gas, alkene and coal tar as major product, more carbon hydrocarbon hydrogen coal gas sections, gasification Feed coal bed ratio of height to diameter is 2~6.8.
9. according to claim 1, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that water-gas section Maximum temperature is the slag gasification mode of ash fusion point temperature dry deslagging gasification mode below or ash fusion point temperature or more.
10. according to claim 1, a kind of natural gas from coal, alkene and coal tar method, which is characterized in that pressurization coal Gasifier bed layer process pressure is 1~3MPa or 3~6MPa, 6~10MPa, and methane anaerobic olefin process pressure is hydrocarbon-rich hydrogen coal 0.95~0.6 times of gas outlet pressure or 0.6~0.3 times or 0.3~0.1 times or 0.1~0.05 times.
CN201810445891.XA 2018-05-11 2018-05-11 Method for preparing natural gas, olefin and coal tar from coal Expired - Fee Related CN110467943B (en)

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