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WO2013159662A1 - 基于生物质气化与甲烷化的燃气-蒸汽高效联产工艺及系统 - Google Patents

基于生物质气化与甲烷化的燃气-蒸汽高效联产工艺及系统 Download PDF

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Publication number
WO2013159662A1
WO2013159662A1 PCT/CN2013/074232 CN2013074232W WO2013159662A1 WO 2013159662 A1 WO2013159662 A1 WO 2013159662A1 CN 2013074232 W CN2013074232 W CN 2013074232W WO 2013159662 A1 WO2013159662 A1 WO 2013159662A1
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WIPO (PCT)
Prior art keywords
methanation
gas
gasification
steam
reactor
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Ceased
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PCT/CN2013/074232
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English (en)
French (fr)
Inventor
杨伟光
龚焱
詹晓东
宋德臣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sunshine Kaidi New Energy Group Co Ltd
Original Assignee
Sunshine Kaidi New Energy Group Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Priority to KR1020147032038A priority Critical patent/KR101739494B1/ko
Priority to JP2015507350A priority patent/JP5959721B2/ja
Priority to BR112014026705A priority patent/BR112014026705A2/pt
Priority to MX2014012990A priority patent/MX362684B/es
Priority to AP2014008078A priority patent/AP2014008078A0/xx
Priority to IN2282MUN2014 priority patent/IN2014MN02282A/en
Priority to SG11201406918UA priority patent/SG11201406918UA/en
Priority to CA2871701A priority patent/CA2871701A1/en
Priority to EP13781061.0A priority patent/EP2843031A4/en
Application filed by Sunshine Kaidi New Energy Group Co Ltd filed Critical Sunshine Kaidi New Energy Group Co Ltd
Priority to AU2013252316A priority patent/AU2013252316B2/en
Priority to RU2014147727/04A priority patent/RU2583785C1/ru
Publication of WO2013159662A1 publication Critical patent/WO2013159662A1/zh
Priority to US14/522,630 priority patent/US9593286B2/en
Anticipated expiration legal-status Critical
Priority to ZA2014/08643A priority patent/ZA201408643B/en
Priority to US15/429,129 priority patent/US10113125B2/en
Ceased legal-status Critical Current

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    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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
    • 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
    • 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
    • C10J3/86—Other features combined with waste-heat boilers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B1/00—Methods of steam generation characterised by form of heating method
    • F22B1/02—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
    • F22B1/18—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B27/00—Instantaneous or flash steam boilers
    • F22B27/14—Instantaneous or flash steam boilers built-up from heat-exchange elements arranged within a confined chamber having heat-retaining walls
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22G—SUPERHEATING OF STEAM
    • F22G1/00—Steam superheating characterised by heating method
    • F22G1/02—Steam superheating characterised by heating method with heat supply by hot flue gases from the furnace of the steam boiler
    • 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
    • C10J2300/0916—Biomass
    • 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
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
    • C10J2300/1656—Conversion of synthesis gas to chemicals
    • C10J2300/1662—Conversion of synthesis gas to chemicals to methane
    • 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
    • C10J2300/16—Integration of gasification processes with another plant or parts within the plant
    • C10J2300/1687—Integration of gasification processes with another plant or parts within the plant with steam generation
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/04—Gasification
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/06—Heat exchange, direct or indirect
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/10—Recycling of a stream within the process or apparatus to reuse elsewhere therein
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/42—Fischer-Tropsch steps
    • 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
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • 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
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
    • Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
    • 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
    • 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

Definitions

  • the invention relates to the field of biomass energy technology, in particular to a gas-steam efficient co-production process and system based on biomass gasification and methanation, which is composed of biomass such as rice husk, straw and wood chips.
  • the crude syngas produced by biomass gasification contains a large amount of CO, H 2 , C0 2 , etc., because of its low calorific value and CO toxicity, it is not suitable for direct use as fuel for city gas and combined cycle power plants; High calorific value and non-toxic, suitable as fuel for city gas and combined cycle power plants; in the presence of catalyst, both CO and CO 2 can be converted to methane, which is synthetic synthetic natural gas (SNG).
  • SNG synthetic synthetic natural gas
  • the design of methanation process mainly considers the control of heat of reaction and its recovery.
  • the heat of reaction can reach about 20% of the calorific value of syngas.
  • the efficient recovery of these heat is very good for any methanation technology. The essential.
  • Patent No.: CN 101245262 the patent entitled “Gas-Steam Combined Cycle System and Process Based on Coal Gasification and Methanation"
  • the raw material source is medium-low calorific value and non-renewable coal; and methanation reaction is used Sulfur
  • the molybdenum catalyst leads to low conversion efficiency of synthesis gas, and the treatment capacity is greatly limited, which is difficult to be practically applied.
  • the reason why it is more difficult to be applied on a large scale is that the design of the isothermal reactor is complicated, complicated in structure, high in manufacturing cost, and difficult to enlarge on the machine. Large, the catalyst is difficult to handle, and the like, and since the reaction is carried out in an isothermal reactor at 210 to 280 ° C, it is difficult to produce high-quality steam to efficiently recover the heat of reaction.
  • Patent No.: CN 100582201C the patent of the name "Electrical-Substituted Natural Gas Cogeneration System and Process Based on Coal Gasification and Methanation", the raw material source is medium-low calorific value and non-renewable coal; The methanation reaction is carried out in a high temperature reactor and a low temperature reactor. This process has a severe demand for the catalyst. The heat exchange efficiency of the product gas and the steam circulation system in the process is low, and the heat recovery rate of the methanation reaction heat is not high. Summary of the invention
  • the invention aims to comprehensively utilize biomass high temperature and high pressure gasification and circulating adiabatic fixed bed methanation technology, and proposes a gas-steam efficient cogeneration production process and system based on biomass gasification and methanation, and efficiently produces a large amount of superheated steam. And substitute natural gas.
  • a gas-steam efficient co-production process based on biomass gasification and methanation of the present invention comprises the following steps:
  • Biomass gasification The oxygen and water vapor mixed biomass produced by the air separation plant is gasified in a high temperature and high pressure biomass by a nozzle at a pressure of 1 to 3 MPa in the furnace, and the temperature in the gasification furnace is controlled at 1500 to 1800 ° C. Obtaining coarse gasification gas, and generating 5 ⁇ 6MPa medium pressure superheated steam to the steam turbine through sensible heat recovery;
  • step 2) Conversion and purification: According to the methanation reaction requirement, the crude gasification gas produced in step 1) is adjusted by a shift reaction, and the hydrogen-carbon ratio of the gasification gas is 3:1, and then the purified synthesis gas is obtained by desulfurization of sulfur by low-temperature methanol elution;
  • Step 2) Purify the synthesis gas from the hydrogen to carbon ratio into the methanation unit.
  • the methanation process of the synthesis gas is divided into a large number of methanation stages and a supplementary methanation stage.
  • the large number of methanation stages are series two-stage reactors. The stage has two parallel reactors. After a large amount of methanation in the second stage, part of the process gas is recycled back to the inlet of the first stage of the large number of methanation reactors, mixed with the fresh feed gas and then passed to the first large amount of methanation reactor.
  • the circulating process gas is used as an inert medium to take heat to control the catalyst bed temperature.
  • the replenishing methanation stage consists of two replenishing methanation reactors in series, converting a small amount of unreacted CO and most of the CO 2 to CH 4 ; the methanation stage produces medium pressure superheated steam to the steam turbine; 4) Methane concentration: Step 3)
  • the high molar concentration of synthetic natural gas doped with a small amount of nitrogen and water vapor is concentrated by pressure swing adsorption, methane molar concentration reaches 96%, and the calorific value of synthetic natural gas can reach 8256kcal/Nm 3 , in line with current national standards.
  • the steps described above 1) The oxygen produced by the air separation plant is mixed with superheated steam and treated biomass, and passed through a nozzle at a speed of 100 to 120 m/s into an entrained flow gasifier for cocurrent gasification.
  • the step 1) is to control the temperature of the crude gasification gas taken from the upper side of the gasifier to 1200 ⁇ 1500 °C, and the crude gasification gas of the gasifier enters the waste heat boiler to recover waste heat, and generates medium pressure superheated steam, part of which is oxygen.
  • Mixing as a gasifying agent the rest is sent to the steam turbine; the temperature of the gasification gas after the heat is recovered is lowered to 220 ⁇ 280 °C, and then the two parts of the cyclone separation and washing tower are used to purify most of the dust and water vapor in the gasification gas.
  • the temperature of the gasification gas is lowered to 50 to 55 ° C, and the dust content is reduced to 50 mg/m 3 or less to form a gasification gas mainly containing CO, H 2 and N 2 .
  • the step 3) is to adjust the hydrogen-carbon ratio of the purified synthesis gas into two equal feeds into the first large-scale methanation reactor and the second large-scale methanation reactor, and enter the raw materials of the first-stage large-scale methanation reactor.
  • the gas is first mixed with the recycle gas, and the mixed gas is controlled to enter the reactor catalytic bed at 300-330 ° C, and an exothermic methanation reaction occurs; the temperature of the mixed gas at the outlet is 600 to 630 ° C, and the first methanation waste heat boiler is passed.
  • the steam superheater produces medium pressure steam;
  • the process gas leaving the steam superheater is mixed with another fresh raw material gas and then enters the second large methanation reactor at 300 to 330 ° C for further methanation reaction;
  • the second large amount of methane The outlet gas temperature of the reactor is 600 to 630 ° C, and the hot process gas leaving the second large amount of methanation reactor passes through the second methanation waste heat boiler and the steam superheater to produce medium pressure steam and preheats the circulating gas;
  • the hot process gas leaving the methanation reactor is divided into two strands, one strand accounts for 30 ⁇ 40%, and is recycled by the recycle compressor to the first large amount of methanation reactor, and the other strand accounts for 60 ⁇ 70%.
  • the process gas temperature is 270 ⁇ 290 ° C into the first supplementary methanation reactor for further methanation reaction
  • the first supplementary methanation reactor outlet mixed gas temperature is 440 ⁇ 460 ° C
  • the second supplemental methanation reactor inlet feed gas temperature is 270 ⁇ 290 ° C, and further methanation reaction occurs in the second supplementary methanation reactor to achieve the SNG product gas specification; medium pressure steam produced by the methanation process Send steam turbines.
  • the medium pressure superheated steam produced by the waste heat boiler and the steam superheater recovering the reaction heat in the large amount of methanation reaction stage is 4.5 to 5 MPa.
  • the hot process gas exiting from the second bulk methanation reactor passes through the second methanation waste heat boiler and steam After the superheater is cooled, the first portion of the gas is recycled from the recycle compressor to the first large amount of methanation reactor, which accounts for 60 to 70%; the second feed enters the first supplementary methanation reactor, which accounts for 30 to 40%.
  • the system for biomass-gasification and methanation-based gas-steam efficient co-production process of the present invention comprises: biomass gasification unit, conversion unit, purification unit, methanation unit, methane concentration unit, biomass gasification unit
  • the upper part of the gasification furnace is provided with a waste heat boiler, and the crude gasification gas of the gasification furnace is recovered by the waste heat boiler to generate the medium pressure superheated steam to be sent to the steam turbine; and the localized constant high temperature heating is set in the gasification gas extraction section of the biomass gasification furnace.
  • the gasification temperature in the gasifier is maintained at 1500 ⁇ 1800 °C, and the temperature of the crude gasification gas extracted by the gasification gas is controlled at 1200 ⁇ 1500 °C.
  • the methanation unit comprises a plurality of methanation units and a supplementary methanation unit, the plurality of methanation units are two-stage reactors in series, two parallel reactors in each stage, and two large-scale methanation reactor outlets in the second stage.
  • a routing line connected to the first stage of the large number of methanation reactor inlets, mixed with fresh feed gas to enter the first bulk methanation reactor; another routing line connected to the supplemental methanation reactor, supplementing the methanation reactor
  • the first supplemental methanation reactor and the second supplemental methanation reactor are connected in series; the second supplemental methanation reactor is sent to the methane concentration unit.
  • the mixed gas of the first stage large amount of methanation reactor outlet is recovered by the first methanation waste heat boiler and the steam superheater, and the mixed gas of the second stage large amount of methanation reactor outlet passes through the second methanation waste heat boiler and The steam superheater recovers the heat of reaction, and the generated medium pressure superheated steam is sent to the steam turbine.
  • the invention has the following advantages and outstanding effects.
  • the local external constant high temperature heat source used in the gasification device can significantly improve the effective gas composition of CO and H 2 , and improve the biomass gasification efficiency; 2 usually biomass gas
  • the chemical will generate a large amount of tar.
  • the high temperature of the gasification unit can greatly reduce the amount of tar produced, increase the carbon conversion rate, and save the investment of the tar removal unit.
  • the methanation process has a CO conversion rate of 100%, and the conversion rate is 13 ⁇ 4.
  • the biggest advantage of the invention is that it can convert biomass energy into clean, high calorific value and convenient Natural gas is utilized, and a large amount of heat released from biomass gasification and methanation is efficiently recovered by producing high-grade superheated steam.
  • FIG. 1 is a flow chart of a gas-steam efficient co-production process based on biomass gasification methanation according to the present invention.
  • FIG. 2 is a schematic view of a biomass gasification unit of the present invention.
  • FIG. 3 is a schematic illustration of a high efficiency methanation unit of the present invention. detailed description
  • Step 1) The biomass such as rice straw and straw is pre-dried, crushed and sorted.
  • the biomass material with diameter or maximum length less than 2mm is directly sent to the high-temperature entrained gasifier through the screw feeder.
  • the pressure in the furnace is l ⁇ 3MPa.
  • the gasifier is provided with a local external constant high temperature heater in the gasification gas extraction section to maintain the gasification temperature in the gasifier at 1500 ⁇ 1800 °C, while ensuring gasification intensity, gasification gas quality and heat transfer enhancement process. .
  • the superheated steam and oxygen are premixed as a gasifying agent, and then uniformly mixed with the treated biomass, and sprayed through a special nozzle into the gasifier at a speed of 100 to 120 m/s to carry out cocurrent gasification.
  • the feedstock is heated to the furnace temperature at the instant of the furnace, and the evaporation of moisture, the decomposition of volatiles, the cracking of tar, the combustion of carbon and the gasification process are carried out almost simultaneously.
  • the alkali metal ash is discharged into the liquid slag and discharged directly.
  • the small particles of biomass stay in the reaction zone for less than 3 s, can not be melted and quickly vaporized, and can be separated by high-speed gas flow without sticking and cohesion.
  • the temperature of the crude gasification gas from the upper side of the gasification furnace is controlled at 1200 ⁇ 1500 °C.
  • the waste gas boiler is arranged in the upper part of the gasification furnace, and the crude gasification gas from the gasification furnace enters the waste heat boiler to recover waste heat, which generates a large amount of steam and is recovered.
  • the temperature of the gasification gas will be 220 ⁇ 280°C, and then through the two-stage cyclone separation and washing tower, most of the dust and water vapor in the gasification gas will be purified and cooled, and the temperature of the gasification gas will be reduced to 50 ⁇ 55.
  • the dust content will be below 50mg/m 3 .
  • a gasification gas mainly containing CO and H 2 is produced.
  • Step 2 Washing the dust-removed crude gas into the sulfur-tolerant conversion process to adjust the H 2 and CO in the gas.
  • the ratio of 0 2 , the ratio of hydrogen to carbon is 3: 1, and at the same time, the majority of organic sulfur in the gas is converted into inorganic sulfur; and then purified, the low temperature methanol washing section uses methanol to remove the C0 2 which is not required for the methanation reaction in the process gas. All the sulfides make the process gas components meet the requirements of methane production.
  • the methanol-rich absorbing CO 2 and H 2 S and COS is regenerated by decompression, flash evaporation, nitrogen stripping, etc., and the refrigeration is recovered and reused.
  • Step 3) Methanation Step 2) Purifying the hydrogen-to-carbon ratio of the purified synthesis gas into two equal groups into the first large amount of methanation reactor and the second large amount of methanation reactor, into the first large amount of methanation
  • the feed gas is first mixed with the recycle gas, and the mixed gas is introduced into the adiabatic reactor catalytic bed at 300 to 330 ° C, and an exothermic methanation reaction occurs here.
  • the hot gas temperature at the outlet is approximately 600 to 630 ° C for the production and superheating of medium pressure steam in the first methanation waste heat boiler and the first superheater.
  • the process gas leaving the first superheater is mixed with another fresh feed gas and then subjected to a further methanation reaction at 300 to 330 ° C in a second bulk methanation reactor.
  • the second large amount of methanation reactor outlet gas has a temperature of about 600 to 630 ° C for producing steam in the second methanation waste heat boiler and the fourth superheater and preheating the circulating gas.
  • the hot process gas leaving the second methanation waste heat boiler is divided into two parts, one share 30 ⁇ 40% recycled from the recycle compressor to the first large methanation reactor, and the other share 60 ⁇ 70% into the first supplement Methanation reactor.
  • the second supplemental methanation reactor inlet feed gas temperature is 270 ⁇ 290 ° C, and further methanation reaction occurs in the second supplemental methanation reactor to achieve SNG product gas specification; medium pressure steam feed produced by methanation process Steam turbine.
  • the medium pressure superheated vapor pressure produced by the waste heat boiler and the steam superheater recovers the reaction heat is 4.5 to 5 MPa.
  • a system for a gas-steam efficient co-production process based on biomass gasification and methanation comprises: a biomass gasification unit, a conversion unit, a purification unit, a methanation unit, and a methane concentration unit. .
  • the upper part of the gasification furnace of the biomass gasification unit is provided with a waste heat boiler, and the crude gasification gas of the gasification furnace is recovered by the waste heat boiler to generate the medium pressure superheated steam to the steam turbine; in the biomass gasification furnace
  • the gasification gas extraction section is provided with a local external constant high temperature heater, and the gasification temperature in the gasification furnace is maintained at 1500 ⁇ 1800 °C, and the temperature of the crude gasification gas extracted by the gasification gas is controlled at 1200 ⁇ 1500 °C.
  • the methanation unit comprises a large number of methanation units and a supplementary methanation unit, a large number of methanation units are two-stage reactors in series, two parallel reactors in each stage, and a large number of methanation reactors in the second stage.
  • the reactor comprises a first supplemental methanation reactor and a second supplemental methanation reactor in series; and a second supplemental methanation reactor is sent to the methane concentration unit.
  • part of the process gas is recycled back to the first stage of the large number of methanation reactor inlets, mixed with fresh feed gas and then passed to the first large amount of methanation reactor to reduce the amount of methanation inlet reactants.
  • concentration recycles the process gas as an inert medium to take heat to control the catalyst bed temperature.
  • Most methanation reactions are A large number of methanation stages are completed. The methanation reaction temperature is relatively high and the methanation is low. This stage consists of two supplementary methanation reactors in series, converting a small amount of unreacted CO and most of the CO 2 to CH 4 . After methanation, the product gas is cooled and sent to the methane concentration step.
  • the mixed gas of the first stage large amount of methanation reactor outlet is recovered by the first methanation waste heat boiler and the steam superheater, and the mixed gas of the second stage large amount of methanation reactor outlet passes through the second methanation waste heat boiler and The steam superheater recovers the heat of reaction, and the generated medium pressure superheated steam is sent to the steam turbine.
  • Example 1 The calculation of the overall performance of the system at the time of the base load of the example based on the raw material biomass of 1000 ton / day.
  • the gasification biomass used in the first embodiment uses dry rice stem biomass, and its composition and low calorific value are shown in Table 1. Table 1 Analysis of raw material biomass and calorific value
  • Example 1 Biomass 1000 tons / day, using 93% (volume)
  • Example 2 biomass 1000 tons / day, using 98% (volume

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Description

基于生物质气化与甲烷化的燃气 -蒸汽高效联产工艺及系统 技术领域
本发明涉及生物质能源技术领域， 特别是涉及由稻壳、 秸秆、 木屑等生物质为原料 的一种基于生物质气化与甲烷化的燃气-蒸汽高效联产工艺及系统。 背景技术
近年来， 随着经济和社会的发展， 天然气的需求迅猛增长， 将成为 21世纪消费量增 长最快的能源。 但是我国天然气的供应能力相对滞后， 导致天然气供需矛盾突出， 因此 除了立足国内现有资源外， 还必须多渠道、 多方式扩大资源供给， 满足日益增长的市场 需求， 在开发国内和引进国外天然气资源的同时， 利用我国丰富的生物质资源， 积极发 展生物质制代用天然气以缓解天然气供应紧张局面， 对于实现对油气资源的逐步替代， 在能源安全、 节能减排等方面具有战略性意义。
生物质气化所产生的粗合成气中含有大量的 CO、 H2、 C02等， 因其低热值和 CO的 毒性， 不适于直接作为城市燃气和联合循环电站的燃料来使用； 天然气因其高热值及无 毒， 适宜作为城市燃气和联合循环电站燃料； 在催化剂存在条件下， 可将 CO和 C02全部 转化为甲烷， 这就是人工合成代用天然气 （SNG)。 甲烷化主反应如下：
CO+3H2-CH4+H20 Δ =-206KJ/mol
根据甲烷化反应强放热的特点， 甲烷化工艺路线设计主要考虑反应热的控制及其回 收， 该反应热可达合成气热值的 20%左右， 高效回收这些热量对任何甲烷化技术都十分 关键。
BIGCC作为一种新型清洁高效生物质发电技术， 凭借其较高的发电效率和 C02减排 优势， 受到越来越多的重视。
这样不仅能解决生物质不适于长距离运输问题， 促进生物质的高效、 清洁利用； 并 可利用已有的天然气管道， 以较低的经济代价， 有效缓解天然气的供需矛盾， 这是生物 质进行综合利用的有力措施。
专利号为： CN 101245262， 其名称"基于煤气化与甲烷化的燃气 -蒸汽联合循环系统 及工艺 "的专利中，所述的原料来源是中低热值且不可再生的煤； 并且甲烷化反应使用硫 化钼催化剂， 导致合成气转化效率不高， 处理能力受到极大限制， 难以实际应用； 更难 大规模应用的原因是该等温反应器设计繁琐、 结构复杂、 制造成本高， 在机械上放大难 度大， 催化剂的装卸困难等， 同时由于反应在在 210〜280°C的等温反应器中进行， 难以 产生高品质的蒸汽从而高效回收反应热。
专利号为： CN 100582201C, 其名称 "基于煤气化与甲烷化的电 -替代天然气联产系 统及工艺"的专利中，所述的原料来源是中低热值且不可再生的煤； 并且所述的甲烷化反 应在一个高温反应器和一个低温反应器中进行， 此工艺对催化剂有苛刻需求， 工艺中产 品气与蒸汽循环系统的热交换效率低， 甲烷化反应热的热回收率不高。 发明内容
本发明的目的在于综合利用生物质高温高压气化和循环绝热固定床甲烷化技术， 提 出一种基于生物质气化与甲烷化的燃气-蒸汽高效联产工艺及系统，同时高效生产大量过 热蒸汽和代用天然气。
本发明的技术方案：本发明的一种基于生物质气化与甲烷化的燃气-蒸汽高效联产工 艺， 包括如下步骤：
1 )生物质气化： 空分设备生产的氧气和水蒸气混合生物质经喷嘴在高温高压生物质 气化在炉内压力 l〜3MPa， 气化炉内温度控制在 1500〜1800°C， 制得粗气化气， 经过显 热回收产生 5〜6MPa的中压过热蒸汽送蒸汽轮机；
2)变换与净化： 根据甲烷化反应需求将步骤 1 )产生的粗气化气经过变换反应调整 气化气氢碳比为 3: 1， 之后通过低温甲醇洗脱硫脱碳得到净化合成气；
3 ) 甲烷化： 步骤 2)调整了氢碳比的净化合成气进入甲烷化单元， 合成气甲烷化过 程分大量甲烷化阶段及补充甲烷化阶段， 大量甲烷化阶段为串联两级反应器， 每级有两 个并联反应器， 在第二级大量甲烷化后， 有部分的工艺气循环回到第一级大量甲烷化反 应器入口， 与新鲜原料气混合后进入第一大量甲烷化反应器， 以降低大量甲烷化入口反 应物浓度， 另一方面循环工艺气作为惰性介质取热以控制催化剂床层温度， 绝大多数甲 烷化反应在大量甲烷化阶段完成； 大量甲烷化后的合成气进入补充甲烷化反应， 补充甲 烷化阶段由串联的两个补充甲烷化反应器组成， 将少量未反应的 CO及大多数的 C02转化 为 CH4; 甲烷化阶段产生中压过热蒸汽送蒸汽轮机； 4) 甲烷浓縮： 步骤 3 )得到的掺杂微量氮气和水蒸气的高摩尔浓度的合成天然气通 过变压吸附浓縮甲烷， 甲烷摩尔浓度达到 96%， 合成天然气热值可达 8256kcal/Nm3， 符 合现阶段国家标准。
所述的步骤 1 ) 空分设备生产出来的氧气混合过热蒸气及经过处理的生物质， 以 100〜120m/s的速度经过喷嘴进入气流床气化炉， 进行并流气化。
所述的步骤 1 ) 从气化炉侧上方引出的粗气化气温度控制在 1200〜1500°C， 出气化 炉的粗气化气进入废热锅炉回收余热， 产生中压过热蒸汽， 一部分与氧气混合作为气化 剂， 其余送蒸汽轮机； 回收热量后的气化气温度降至 220〜280°C， 然后经两级旋风分离 和洗涤塔， 将气化气中的大部分粉尘和水汽经过净化冷却， 气化气温度降至 50〜55°C， 含尘量将至 50mg/m3以下， 生成主要含有 CO、 H2和 N2的气化气。
所述的步骤 3 ) 调整了氢碳比的净化合成气分为相等的两股分别进第一大量甲烷化 反应器和第二大量甲烷化反应器， 进入第一级大量甲烷化反应器的原料气先与循环气混 合， 混合气体控制在 300〜330°C进反应器催化床层， 发生放热的甲烷化反应； 出口的混 合气体温度为 600〜630°C， 经过第一甲烷化废热锅炉和蒸汽过热器中生产中压蒸汽； 离 开蒸汽过热器的工艺气与另一股新鲜原料气混合后在 300〜330°C下进入第二大量甲烷 化反应器进一步甲烷化反应； 第二大量甲烷化反应器出口气体温度 600〜630°C， 从第二 大量甲烷化反应器离开的热工艺气体经过第二甲烷化废热锅炉和蒸汽过热器生产中压蒸 汽并预热循环气体； 从第二大量甲烷化反应器离开的热工艺气体分成两股， 一股占 30〜 40%, 由循环压縮机循环至第一大量甲烷化反应器， 另一股占 60〜70%， 进入第一补充 甲烷化反应器，冷却后工艺气体温度在 270〜290°C进第一补充甲烷化反应器进一步甲烷 化反应， 第一补充甲烷化反应器出口混合气体温度在 440〜460°C， 第二补充甲烷化反应 器入口原料气温度在 270〜290°C， 进一步的甲烷化反应发生在第二补充甲烷化反应器 中， 以达到 SNG产品气规格； 甲烷化过程生产的中压蒸汽送蒸汽轮机。
所述的大量甲烷化反应阶段由废热锅炉和蒸汽过热器回收反应热生产的中压过热蒸 气压力为 4.5〜5MPa。
所述的步骤 3 )甲烷化以高负载镍作为催化剂，反应温度为 270〜630°C，压力为 1〜 3MPa, 按照 CO+3H2=CH4+H20 AH =-206KJ/mol进行。
所述的从第二大量甲烷化反应器离开的热工艺气体经过第二甲烷化废热锅炉和蒸汽 过热器冷却后气体的第一股由循环压縮机循环至第一大量甲烷化反应器的占 60〜70% ; 第二股进第一补充甲烷化反应器的占 30〜40%。
本发明的基于生物质气化与甲烷化的燃气 -蒸汽高效联产工艺的系统包括：生物质气 化单元、 变换单元、 净化单元、 甲烷化单元、 甲烷浓縮单元， 生物质气化单元的气化炉 上部设有废热锅炉， 出气化炉的粗气化气经过废热锅炉回收余热， 产生中压过热蒸气送 蒸汽轮机； 在生物质气化炉气化气引出段设局部外置恒定高温加热器， 配合维持气化炉 内气化温度在 1500〜1800°C， 气化气引出的粗气化气温度控制在 1200〜1500°C。
所述的甲烷化单元包括分大量甲烷化单元及补充甲烷化单元， 大量甲烷化单元为串 联两级反应器， 每级有两个并联反应器， 在第二级大量甲烷化反应器出口两路， 一路由 管路连接到第一级大量甲烷化反应器入口， 与新鲜原料气混合后进入第一大量甲烷化反 应器； 另一路由管路连接到补充甲烷化反应器， 补充甲烷化反应器包括串联的第一补充 甲烷化反应器和第二补充甲烷化反应器； 第二补充甲烷化反应器送至甲烷浓縮单元。
所述的第一级大量甲烷化反应器出口的混合气体经过第一甲烷化废热锅炉和蒸汽过 热器回收反应热， 第二级大量甲烷化反应器出口的混合气体经过第二甲烷化废热锅炉和 蒸汽过热器回收反应热， 产生的中压过热蒸气送蒸汽轮机。
本发明具有以下优点及突出效果， ①本气化装置采用的局部外置恒定高温热源， 会 使得 CO和 H2的有效气成分得到显著提升， 生物质气化效率得到提高；②通常生物质气化 都会产生大量焦油， 本气化单元高温可以使焦油的产生量大大降低， 提高了碳转化率， 也省去了去除焦油的装置投资③甲烷化过程 CO转化率达 100%， 1¾转化率为 99% ; 同时 副产大量中压过热蒸汽， 并减小了传统甲烷化工艺中循环压縮机功耗； ④本发明最大的 优势在于， 既能将生物质能源转化为干净、 高热值、 方便利用的天然气， 并且能高效的 通过产生高品位过热蒸汽的方式回收生物质气化与甲烷化反应中放出的大量热量。 附图说明
图 1为本发明基于生物质气化甲烷化的燃气-蒸汽高效联产工艺流程图。
图 2为本发明生物质气化单元的示意图。
图 3为本发明高效甲烷化单元的示意图。 具体实施方式
通过附图和实施例对本发明可更详细的介绍，但并不是对本发明的保护范围的限定。 如附图 1、 图 2、 图 3所示：
步骤 1 ) 稻杆、 秸秆等生物质经过预干燥、 破碎、 分选， 直径或最大长度在 2mm以 下的生物质原料通过螺旋加料器直接送入高温气流床气化炉， 炉内压力 l〜3MPa， 气化 炉在气化气引出段设局部外置恒定高温加热器， 配合维持气化炉内气化温度在 1500〜 1800 °C , 同时保证气化强度、 气化气质量和强化传热过程。 过热水蒸气和氧气作为气化 剂经过预混合， 再与经过处理的生物质均匀混合， 以 100〜120m/s的速度喷射经过特殊 喷嘴进入气化炉， 进行并流气化， 由于粒度小， 加上气流床较强的传热能力， 因而原料 入炉的瞬间即被加热到炉内温度， 几乎同时进行着水分的蒸发、 挥发份的分解、 焦油的 裂化、 碳的燃烧与气化过程。 含碱金属灰渣变成液态渣直接排出。 生物质小颗粒在反应 区内停留不足 3s， 来不及熔化而迅速气化， 且能被高速气流各自分离开， 不会出现黏结 凝聚等现象。 从气化炉上侧方引出的粗气化气温度控制在 1200〜1500°C， 气化炉上部设 有废热锅炉， 出气化炉的粗气化气进入废热锅炉回收余热， 产生大量蒸汽， 回收热量后 的气化气温度将至 220〜280°C， 然后经两级旋风分离和洗涤塔， 将气化气中的大部分粉 尘和水汽等经过净化冷却， 气化气温度降至 50〜55°C左右， 含尘量将至 50mg/m3以下。 生成主要含有 CO和 H2的气化气。
步骤 2) 洗涤除尘后的粗气化气进入耐硫变换工序， 调节气体中的 H2、 CO和。02的 比例， 氢碳比为 3: 1， 同时将气体中的绝大部分有机硫转化为无机硫； 然后净化， 低温 甲醇洗工段利用甲醇脱出工艺气中甲烷化反应不需要的 C02和所有的硫化物， 使工艺气 成分达到甲烷生产要求， 吸收了 C02和 H2S及 COS的富甲醇通过减压、 闪蒸、 氮气汽提等 方法对其再生并回收冷量， 重复利用。
步骤 3 )甲烷化： 步骤 2)调整了氢碳比的净化合成气分为大致相等的两股分别进第 一大量甲烷化反应器和第二大量甲烷化反应器， 进第一大量甲烷化的原料气先与循环气 混合， 混合气体在 300〜330°C进绝热反应器催化床层， 放热的甲烷化反应在此发生。 出 口的热气体温度大约为 600〜630°C，用来在第一甲烷化废热锅炉和第一过热器中生产及 过热中压蒸汽。离开第一过热器的工艺气与另一股新鲜原料气混合后在 300〜330°C下进 第二大量甲烷化反应器进一步甲烷化反应。 第二大量甲烷化反应器出口气体温度 600〜630°C左右，用于在第二甲烷化废热锅炉 和第而过热器中生产蒸汽并预热循环气体。 从第二甲烷化废热锅炉离开的热工艺气体分 成两股，一股占 30〜40%由循环压縮机循环至第一大量甲烷化反应器，另一股占 60〜70% 进入第一补充甲烷化反应器。
第二补充甲烷化反应器入口原料气温度在 270〜290°C，进一步的甲烷化反应发生在 第二补充甲烷化反应器中， 以达到 SNG产品气规格； 甲烷化过程生产的中压蒸汽送蒸汽 轮机。
大量甲烷化反应阶段由废热锅炉和蒸汽过热器回收反应热生产的中压过热蒸气压力 为 4.5〜5MPa。
甲烷化以高负载镍作为催化剂， 反应温度为 270〜630°C， 压力为 l〜3MPa， 按照 CO+3H2=CH4+H20 AH^ =-206KJ/mol进行。
步骤 4) 甲烷浓縮： 粗天然气通过变压吸附浓縮甲烷， 得到符合国家标准的代用天 然气。 在一般情况下， 天然气进入城市燃气管道作为居民燃气； 当电力紧缺时， 也可部 分进入燃气轮机发电。
如附图 1， 本发明的一种基于生物质气化与甲烷化的燃气 -蒸汽高效联产工艺的系统 包括： 生物质气化单元、 变换单元、 净化单元、 甲烷化单元、 甲烷浓縮单元。
如图 2所示， 生物质气化单元的气化炉上部设有废热锅炉， 出气化炉的粗气化气经 过废热锅炉回收余热， 产生中压过热蒸气送蒸汽轮机； 在生物质气化炉气化气引出段设 局部外置恒定高温加热器， 配合维持气化炉内气化温度在 1500〜1800°C， 气化气引出的 粗气化气温度控制在 1200〜1500°C。
如图 3所示， 甲烷化单元包括分大量甲烷化单元及补充甲烷化单元， 大量甲烷化单 元为串联两级反应器， 每级有两个并联反应器， 在第二级大量甲烷化反应器出口两路， 一路由管路连接到第一级大量甲烷化反应器入口， 与新鲜原料气混合后进入第一大量甲 烷化反应器； 另一路由管路连接到补充甲烷化反应器， 补充甲烷化反应器包括串联的第 一补充甲烷化反应器和第二补充甲烷化反应器； 第二补充甲烷化反应器送至甲烷浓縮单 元。 在第二级大量甲烷化后， 有部分的工艺气循环回到第一级大量甲烷化反应器入口， 与新鲜原料气混合后进入第一大量甲烷化反应器， 以降低大量甲烷化入口反应物浓度， 另一方面循环工艺气作为惰性介质取热以控制催化剂床层温度。 绝大多数甲烷化反应在 大量甲烷化阶段完成。 补充甲烷化反应温度较大量甲烷化为低， 此阶段由串联的两个补 充甲烷化反应器组成， 将少量的未反应的 CO及大多数的 C02转化为 CH4。 甲烷化后产品 气经冷却后送至甲烷浓縮步工序。
所述的第一级大量甲烷化反应器出口的混合气体经过第一甲烷化废热锅炉和蒸汽过 热器回收反应热， 第二级大量甲烷化反应器出口的混合气体经过第二甲烷化废热锅炉和 蒸汽过热器回收反应热， 产生的中压过热蒸气送蒸汽轮机。
实施例 1 :以原料生物质 1000吨 /天为基础来对实施例进行基本负荷时系统整体性能 的计算。
本实施例 1所用的气化生物质采用干的稻杆生物质， 其成分及低位热值见表 1。 表 1 原料生物质元素分析及热值
Figure imgf000009_0001
实施例 1: 生物质 1000吨 /天， 采用 93% (体积
表 2 实施例 1 物料平衡及产品气性能参数
实施例 1
气化气 变换气 合成气 广口口 流量 Nm3/h 43960 53320 29300 7350 组分 vol%
CO 43.41% 12.03% 20.36% 0.01
H2 16.42% 37.30% 67.53% 0.30
N2 5.77% 4.76% 8.04% 1.17
C02 21.19% 41.23% 1.88% 1.13
CH4 1.92% 1.59% 2.16% 96.13
H20 9.29% 1.45% 0.03% 1.26
C2-C4 1.92% 1.59% 0.00% 0.00 合成天然气热值 kcal/m3 2579 8227 合成天然气产量 m3/d 176400 生物质合成 SNG化学效率 (SNG化学能量 /生物质化学 47% 能量）
甲烷化产出蒸汽 450 °C、 4.7MPa (t/h) 21.45 实施例 2: 生物质 1000吨 /天， 采用 98% (体积
表 3 实施例 2物料平衡及产品气性能参数
实施例 2
气化气 变换气 合成气 广口口 流量 Nm3/h 51140 64640 39670 10190 组分 vol%
CO 52.10% 14.46% 21.91% 0.01%
H2 22.81% 44.81% 72.66% 0.20
N2 2.02% 1.60% 2.48% 2.00%
C02 12.55% 36.70% 1.79% 0.28%
CH4 1.17% 0.92% 1.13% 96.47%
H20 9.27% 1.45% 0.02% 1.03%
C2-C4 0.02% 0.01% 0.00% 0.00% 合成天然气热值 kcal/m3 2672 8256 合成天然气产量 m3/d 244560 生物质合成 SNG化学效率 (SNG化学能量 /生物质化学能量） 64% 甲烷化产出蒸汽 450 °C 、 4.7MPa (t/h) 30.90

Claims

权利要求书
1.一种基于生物质气化与甲烷化的燃气-蒸汽高效联产工艺， 包括如下步骤：
1 )生物质气化： 空分设备生产的氧气和水蒸气混合生物质经喷嘴在高温高压生物质 气化在炉内压力 l〜3MPa， 气化炉内温度控制在 1500〜1800°C， 制得粗气化气， 经过显 热回收产生 5〜6MPa的中压过热蒸汽送蒸汽轮机；
2) 变换与净化： 根据甲烷化反应需求将步骤 1 ) 产生的粗气化气经过变换反应调整 气化气氢碳比为 3: 1， 之后通过低温甲醇洗脱硫脱碳得到净化合成气；
3 ) 甲烷化： 步骤 2) 调整了氢碳比的净化合成气进入甲烷化单元， 合成气甲烷化过 程分大量甲烷化阶段及补充甲烷化阶段， 大量甲烷化阶段为串联两级反应器， 每级有两 个并联反应器， 在第二级大量甲烷化后， 有部分的工艺气循环回到第一级大量甲烷化反 应器入口， 与新鲜原料气混合后进入第一大量甲烷化反应器， 以降低大量甲烷化入口反 应物浓度， 另一方面循环工艺气作为惰性介质取热以控制催化剂床层温度， 绝大多数甲 烷化反应在大量甲烷化阶段完成； 大量甲烷化后的合成气进入补充甲烷化反应， 补充甲 烷化阶段由串联的两个补充甲烷化反应器组成， 将少量未反应的 CO及大多数的 C02转 化为 CH4; 甲烷化阶段产生中压过热蒸汽送蒸汽轮机；
4) 甲烷浓縮： 步骤 3 ) 得到的掺杂微量氮气和水蒸气的高摩尔浓度的合成天然气通 过变压吸附浓縮甲烷， 甲烷摩尔浓度达到 96%， 合成天然气热值可达 8256kcal/Nm3， 符 合现阶段国家标准。
2. 根据权利要求 1 所述的基于生物质气化与甲烷化的燃气-蒸汽高效联产工艺， 其 特征在于：步骤 1 )空分设备生产出来的氧气混合过热蒸气及经过处理的生物质，以 100〜 120m/s的速度经过喷嘴进入气流床气化炉， 进行并流气化。
3. 根据权利要求 1或 2所述的基于生物质气化与甲烷化的燃气-蒸汽高效联产工艺， 其特征在于： 步骤 1 ) 从气化炉侧上方引出的粗气化气温度控制在 1200〜1500°C， 出气 化炉的粗气化气进入废热锅炉回收余热， 产生中压过热蒸汽， 一部分与氧气混合作为气 化剂， 其余送蒸汽轮机； 回收热量后的气化气温度降至 220〜280°C， 然后经两级旋风分 离和洗涤塔，将气化气中的大部分粉尘和水汽经过净化冷却，气化气温度降至 50〜55°C， 含尘量将至 50mg/m3以下， 生成主要含有 CO、 ¾和 的气化气。
4. 根据权利要求 1或 2所述的基于生物质气化与甲烷化的燃气-蒸汽高效联产工艺， 其特征在于：步骤 3 )调整了氢碳比的净化合成气分为相等的两股分别进第一大量甲烷化 反应器和第二大量甲烷化反应器， 进入第一级大量甲烷化反应器的原料气先与循环气混 合， 混合气体控制在 300〜330°C进反应器催化床层， 发生放热的甲烷化反应； 出口的混 合气体温度为 600〜630°C， 经过第一甲烷化废热锅炉和蒸汽过热器中生产中压蒸汽； 离 开蒸汽过热器的工艺气与另一股新鲜原料气混合后在 300〜330°C下进入第二大量甲烷化 反应器进一步甲烷化反应； 第二大量甲烷化反应器出口气体温度 600〜630°C， 从第二大 量甲烷化反应器离开的热工艺气体经过第二甲烷化废热锅炉和蒸汽过热器生产中压蒸汽 并预热循环气体； 从第二大量甲烷化反应器离开的热工艺气体分成两股， 一股占 30〜 40% , 由循环压縮机循环至第一大量甲烷化反应器， 另一股占 60〜70%， 进入第一补充 甲烷化反应器， 冷却后工艺气体温度在 270〜290°C进第一补充甲烷化反应器进一步甲烷 化反应， 第一补充甲烷化反应器出口混合气体温度在 440〜460°C， 第二补充甲烷化反应 器入口原料气温度在 270〜290°C，进一步的甲烷化反应发生在第二补充甲烷化反应器中， 以达到 SNG产品气规格； 甲烷化过程生产的中压蒸汽送蒸汽轮机。
5. 根据权利要求 4所述的基于生物质气化与甲烷化的燃气-蒸汽高效联产工艺， 其 特征在于： 大量甲烷化反应阶段由废热锅炉和蒸汽过热器回收反应热生产的中压过热蒸 气压力为 4.5〜5MPa。
6. 根据权利要求 1或 2所述的基于生物质气化与甲烷化的燃气-蒸汽高效联产工艺， 其特征在于：步骤 3 )甲烷化以高负载镍作为催化剂，反应温度为 270〜630°C，压力为 1〜 3MPa, 按照 CO+3H2=CH4+H20 AH。e =-206KJ/mol进行。
7. 根据权利要求 4所述的基于生物质气化与甲烷化的燃气-蒸汽高效联产工艺， 其 特征在于： 从第二大量甲烷化反应器离开的热工艺气体经过第二甲烷化废热锅炉和蒸汽 过热器冷却后气体的第一股由循环压縮机循环至第一大量甲烷化反应器的占 60〜70%； 第二股进第一补充甲烷化反应器的占 30〜40%。
8. 一种用于权利要求 1〜7的基于生物质气化与甲烷化的燃气-蒸汽高效联产工艺的 系统， 包括： 生物质气化单元、 变换单元、 净化单元、 甲烷化单元、 甲烷浓縮单元， 其 特征在于： 生物质气化单元的气化炉上部设有废热锅炉， 出气化炉的粗气化气经过废热 锅炉回收余热， 产生中压过热蒸气送蒸汽轮机； 在生物质气化炉气化气引出段设局部外 置恒定高温加热器， 配合维持气化炉内气化温度在 1500〜1800°C， 气化气引出的粗气化 气温度控制在 1200〜1500°C。
9. 根据权利要求 8 所述的基于生物质气化与甲烷化的燃气-蒸汽高效联产工艺的系 统， 其特征在于： 甲烷化单元包括分大量甲烷化单元及补充甲烷化单元， 大量甲烷化单 元为串联两级反应器， 每级有两个并联反应器， 在第二级大量甲烷化反应器出口两路， 一路由管路连接到第一级大量甲烷化反应器入口， 与新鲜原料气混合后进入第一大量甲 烷化反应器； 另一路由管路连接到补充甲烷化反应器， 补充甲烷化反应器包括串联的第 一补充甲烷化反应器和第二补充甲烷化反应器； 第二补充甲烷化反应器送至甲烷浓縮单 元。
10. 根据权利要求 9所述的基于生物质气化与甲烷化的燃气-蒸汽高效联产工艺的系 统， 其特征在于： 第一级大量甲烷化反应器出口的混合气体经过第一甲烷化废热锅炉和 蒸汽过热器回收反应热， 第二级大量甲烷化反应器出口的混合气体经过第二甲烷化废热 锅炉和蒸汽过热器回收反应热， 产生的中压过热蒸气送蒸汽轮机。
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