WO2014194812A1 - Procédé et dispositif de refroidissement et de purification de gaz de synthèse de biomasse à haute pression et à haute température - Google Patents

Procédé et dispositif de refroidissement et de purification de gaz de synthèse de biomasse à haute pression et à haute température Download PDF

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Publication number
WO2014194812A1
WO2014194812A1 PCT/CN2014/079101 CN2014079101W WO2014194812A1 WO 2014194812 A1 WO2014194812 A1 WO 2014194812A1 CN 2014079101 W CN2014079101 W CN 2014079101W WO 2014194812 A1 WO2014194812 A1 WO 2014194812A1
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Prior art keywords
synthesis gas
pressure
biomass synthesis
temperature
waste heat
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PCT/CN2014/079101
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English (en)
Chinese (zh)
Inventor
张岩丰
聂洪涛
夏明贵
刘文焱
张亮
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武汉凯迪工程技术研究总院有限公司
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Publication of WO2014194812A1 publication Critical patent/WO2014194812A1/fr

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    • 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
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/02—Dust removal
    • C10K1/028—Dust removal by electrostatic precipitation
    • 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
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
    • 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

Definitions

  • the invention relates to a synthesis gas purification technology, in particular to a high temperature and high pressure biomass synthesis gas cooling purification process and a device thereof. Background technique
  • biomass gas Like coal-based gas, biomass gas also undergoes purification processes such as cooling and dust removal.
  • purification processes such as cooling and dust removal.
  • the traditional gas primary cooling method is divided into indirect primary cooling, direct primary cooling, and combined primary cooling.
  • Initial cooling mainly refers to the gas coming out of the carbonization chamber and cooling it to 22 ⁇ 35 °C before entering the electric tar catcher.
  • indirect primary cooling the gas and the cooling medium are not in direct contact, and the two phases only indirectly transfer heat, and the mass transfer process is not carried out, and the cooling and purifying effect of the gas is good.
  • the gas is directly in contact with the sprayed ammonia during direct initial cooling for mass transfer and heat transfer.
  • direct primary cooling has the characteristics of high gas cooling efficiency, low resistance, low equipment cost, and high power consumption.
  • the combined initial cooling is a process in which the gas is first indirectly cooled and then directly cooled, and its characteristics are to exert the advantages of both.
  • there are many methods for dust removal from gas including sedimentation, filtration, cyclone dust removal, electric dust removal, water washing or venturi dust removal. Different methods of dust removal and resistance consumption are also different.
  • Gas tar removal equipment is mainly an electric tar catcher.
  • the temperature of the crude gas coming out of the carbonization chamber is about 650 °C, and the temperature of the synthesis gas at the outlet of the biomass gasifier is higher than the temperature of the gas at the outlet of the carbonization chamber. If the biomass gas outlet is neglected, the smoke temperature is higher than that of the coal gas. The specific situation of the high temperature of the export smoke, the photo-cooling of the set of gas The art method obviously cannot achieve the cooling effect and purification index of the biomass synthesis gas.
  • the object of the present invention is to provide a high temperature and high pressure biomass syngas cooling and purification process and a device thereof, which have good cooling effect on syngas, high sensible heat recovery rate, and can effectively reduce biomass syngas. Dust and tar content.
  • a high temperature and high pressure biomass syngas cooling and purifying process comprising the following steps:
  • Staged cooling First, the first indirect heat exchange is carried out by using process water, and the high temperature and high pressure biomass synthesis gas output from the gasifier is cooled to 350 to 550 ° C, and the intermediate pressure steam generated by the waste heat recovery is externally supplied; The second indirect heat exchange is carried out by using the process water, and the biomass synthesis gas is continuously cooled to 100 to 300 ° C, and the low pressure steam generated by the waste heat recovery is externally supplied;
  • the generated medium pressure steam is returned to the gasification furnace as a gasifying agent for the biomass fuel.
  • the steam generated by the waste heat recovery is used as a gasifying agent to supply pressure to the purification equipment, that is, the equipment is operated under a positive pressure state, preventing external air from leaking into the cooling and purifying equipment, thereby reducing the possibility of gas explosion, and Significantly reduced the overall energy consumption of the section.
  • the generated low-pressure steam is applied to the step 4) to purify the dust and the tar in the biomass synthesis gas as a wet gas stream.
  • the steam generated by the waste heat recovery is reused for the purification system, further reducing the energy consumption of the purification section.
  • the biomass synthesis gas first performs the first indirect heat exchange, the middle performs the dry dust removal process, and then the second indirect heat exchange.
  • a preliminary dust removal step is provided between the first stage cooling and the second stage cooling, which saves a lot of washing water and water treatment energy in the subsequent wet dust removal step, and also saves the sewage treatment equipment.
  • the first stage indirect heat exchange is cooled from the biomass synthesis gas to 400 to 500 ° C; in the second indirect heat exchange, the biomass synthesis gas is cooled to 150 to 250 °C.
  • the initial temperature of the high-temperature and high-pressure biomass synthesis gas outputted from the gasifier is controlled to be 700 to 1500 ° C, the dust content is ⁇ 20 ⁇ /?1 ⁇ 21 3 , and the tar content is ⁇ 3 ⁇ /? 1 ⁇ 21 3 .
  • the high-temperature biomass syngas is cooled by the built-in water-cooled wall in the upper part of the gasifier, and the temperature is lowered to about 700 ⁇ 1500 °C.
  • the condensed slag is discharged from the bottom of the furnace to avoid slag pollution on the heating surface of the subsequent waste heat boiler to ensure waste heat.
  • the heat transfer performance of the boiler is stable.
  • the generated medium pressure steam pressure is 1.6 to 2.0 MPa
  • the generated low pressure steam pressure is 0.5 to 0.8 MPa.
  • High-temperature and high-pressure biomass syngas cooling and purification equipment designed to achieve the above processes, including a shell-and-tube waste heat boiler for cooling biomass synthesis gas, a vertical flue gas waste heat boiler, and a venturi for purifying biomass syngas a washing tower and a wet electrostatic precipitator, wherein an inlet of the shell-and-tube waste heat boiler is connected to a synthesis gas outlet of the biomass gasification furnace, and an outlet of the shell-and-tube waste heat boiler and a vertical heat exchanger of the vertical smoke tube a gas port is connected, an air outlet of the vertical smoke tube waste heat boiler is connected to an air inlet of a venturi scrubber, and an air outlet of the venturi scrubber is connected to an input end of the wet electrostatic precipitator, the wet electric dust removal
  • the output of the device is connected to the air inlet of the air tank.
  • the steam outlet of the shell-and-tube waste heat boiler is connected to the gasification agent inlet of the biomass gasifier through an intermediate pressure steam delivery pipe.
  • the steam outlet of the vertical flue waste heat boiler is connected to the wet air inlet of the wet electrostatic precipitator through a low pressure steam delivery pipe.
  • a dry gas filter is disposed between the shell-and-tube waste heat boiler and the vertical pipe waste heat boiler, and the air inlet of the lower end of the dry gas filter is connected to the air outlet of the shell-and-tube waste heat boiler
  • the air outlet of the top of the dry gas filter is connected to the air inlet of the vertical heat pipe boiler, and the dust outlet of the bottom end of the dry gas filter is connected with the feed port of the warehouse pump.
  • the discharge port is connected to the ash store.
  • the dry gas filter is installed as a preliminary dust removal filter between the two-stage waste heat boilers. After initial dust removal, it saves a lot of washing water and water treatment energy consumption, and also saves water treatment equipment; the filtered dust is collected by the warehouse pump.
  • the output of the wet electrostatic precipitator is also connected to the air inlet of the exhaust gas incinerator.
  • the exhaust gas incineration boiler fully utilizes the heat energy after combustion of the exhaust gas generated by the gasification and synthesis sections to improve the thermal efficiency of the device; the gas storage tank parallel exhaust gas incinerator burns the exhaust gas and generates low pressure steam to be externally supplied.
  • the invention combines the high-temperature gasification process of biomass and the physical and chemical properties of the synthesis gas, and has done a lot of experimental research on its cooling and purifying method. Compared with the prior art, the advantages are mainly reflected in the following aspects:
  • the cooling and purifying process of the present invention is cooled in two stages, and the first stage cooling temperature is 350 to 550 ° C, and the temperature is controlled above the condensation point of the heavy tar to avoid condensation of the tar therein, and the second stage cooling temperature Up to 100 ⁇ 300 °C, so that the heavy tar is coagulated and collected in this section, thus achieving centralized collection and treatment of heavy tar, and performing step-by-step dust removal and decoking depth treatment, and finally making dust in the treated biomass synthesis gas.
  • the content is ⁇ 10mg/Nm 3
  • the tar content is ⁇ lOmg/Nm 3
  • the temperature is ⁇ 55°C
  • the sensible heat recovery rate is greater than 80%.
  • the invention inputs the steam generated by the waste heat boiler into the biomass gasification furnace, and serves as a gasifying agent to provide pressure for the purification equipment.
  • the pressure head of the outlet of the biomass gasification furnace can be overcome to overcome the cooling and purifying equipment.
  • the positive pressure of 0.1 ⁇ lMPa (G) can be guaranteed, which ensures that the equipment is working under positive pressure, preventing external air from leaking into the cooling and purifying equipment, reducing the possibility of gas explosion.
  • the air blower of the gas chemical section and the air compressor of the synthetic section are omitted, which greatly reduces the overall energy consumption of the gasification and synthetic oil section, and solves the complicated system, long process, high energy consumption and low efficiency in the traditional gas purification process. , stability and economics are not good, and the problem is not targeted.
  • the device of the invention adopts a two-stage tube-and-tube waste heat boiler and a vertical smoke tube waste heat boiler, double pressure waste heat recovery, and sectional cooling, thereby realizing centralized collection and processing of heavy tar, and reusing the residual heat step to improve the equipment.
  • Thermal efficiency At the same time, the use of non-filled venturi scrubber scrubbing dedusting, wet electrostatic precipitator decoking and dust removal after the high pressure process, the realization of biomass syngas dedusting, deodorization purification target.
  • the device of the invention is adapted to the biomass gasification furnace without the outer cylinder, and solves the technical problem that the structure of the gasification furnace is complicated when the outer cylinder is water-cooled, the size of the furnace body is large, the wall surface is easy to hang the slag, and the water side is easy to scale. While improving the gasification stability, the cost of the gasification main equipment is also saved; in addition, the purification device of the invention has the advantages of simple structure, smooth process, low energy consumption, high efficiency, good safety and stability, and high economic benefit.
  • FIG. 1 is a schematic structural view of a high temperature and high pressure biomass syngas cooling and purifying apparatus. detailed description
  • the high temperature and high pressure biomass syngas cooling purification apparatus shown in Fig. 1 comprises a shell-and-tube waste heat boiler 2 for cooling biomass synthesis gas, a vertical flue gas waste heat boiler 4, and a venturi for purifying biomass syngas.
  • the washing tower 5 and the wet electrostatic precipitator 6, the tube-type waste heat boiler 2 and the vertical flue gas waste heat boiler 4 are provided with a dry gas filter 3, the inlet 8 of the shell-and-tube waste heat boiler 2 and the biomass
  • the syngas outlet 7 of the gasification furnace 1 is connected, the gas outlet 10 of the shell-and-tube waste heat boiler 2 is connected to the inlet 18 of the lower end of the dry gas filter 3, and the steam outlet of the shell-and-tube waste heat boiler 2 is conveyed by medium pressure steam.
  • the tube 9 is connected to the gasification agent inlet of the biomass gasification furnace 1, and the gas outlet 19 at the top end of the dry gas filter 3 is connected to the inlet port 11 of the vertical smoke tube waste heat boiler 4, and the bottom end of the dry gas filter 3
  • the dust outlet 20 is connected to the feed port of the silo pump 21, the discharge port 22 of the silo pump 21 is connected to the ash silo 23, and the air outlet 12 of the vertical flue gas waste heat boiler 4 is connected to the air inlet 13 of the venturi scrubber 5 , steam of the vertical pipe waste heat boiler 4
  • the outlet is connected to the wet gas inlet of the wet electrostatic precipitator 6 via a low pressure steam delivery pipe 27, and the gas outlet 14 of the venturi scrubber 5 is connected to the input 15 of the wet electrostatic precipitator 6, the output 16 of the wet electrostatic precipitator 6
  • the air inlets 26 of the air reservoirs 17 are connected, and the output 16 of the wet electrostatic precipitator 6 is also connected to the air inlet 25 of the exhaust gas
  • the gas storage tank 17 is a high-pressure spherical gas storage tank; the dry gas filter 3 is a ceramic dry filter, and the ceramic dry filter can ensure that the dust removal efficiency reaches 99.9% or more in the range of 350 to 550 °C.
  • the subsequent configuration of the wet electrostatic precipitator 6 ensures that the control indicators for dust removal and tar removal are finally achieved.
  • the process of the above equipment is as follows:
  • the temperature from the biomass synthesis gas outlet 7 of the biomass gasification furnace 1 is 700 to 1500 ° C, the dust content is ⁇ 20 ⁇ /?1 ⁇ 2 3 , and the tar content is ⁇ 3 ⁇ /?1 ⁇ 2 3
  • the biomass synthesis gas first enters the shell-and-tube waste heat boiler 2 from the inlet 8 of the shell-and-tube waste heat boiler 2, and uses the process water for the first indirect heat exchange cooling, and the shell-and-shell waste heat boiler 2 recovers the medium temperature waste heat from the tube.
  • the biomass synthesis gas from the gas outlet 10 of the shell type waste heat boiler 2 is preferably cooled to 350 to 550 ° C, more preferably to 400 to 500 ° C, and medium pressure steam is generated in the shell-and-tube waste heat boiler 2, and the shell-and-shell type waste heat is generated.
  • the design pressure of the boiler 2 is ⁇ 1.6 MPa, preferably 1.6-2.0 MPa.
  • the medium-pressure steam is discharged from the steam outlet of the shell-and-tube waste heat boiler 2, and then returned to the biomass gasification furnace 1 through the medium-pressure steam delivery pipe 9 as a raw material.
  • the gasification agent of the material fuel, the size of the steam pressure can be adjusted by installing a pressure regulating valve on the steam delivery pipe; then the biomass synthesis gas is sent from the inlet 18 of the lower end of the dry gas filter 3 to the dry gas.
  • Filter 3 performs preliminary dust removal, after The highly efficient dust-removed biomass syngas exits the gas outlet 19 at the top of the dry gas filter 3;
  • the biomass synthesis gas from the gas outlet 12 of the waste heat boiler 4 is preferably cooled to 100 to 300 ° C, more preferably to 150 to 250 ° C, and the low pressure steam generated in the vertical pipe waste heat boiler 4 is supplied to the subsequent wet type electrostatic precipitator.
  • the design pressure of the vertical pipe waste heat boiler 4 is ⁇ 0.5MPa, preferably 0.5 ⁇ 0.8MPa.
  • the low pressure steam exits from the steam outlet of the vertical pipe waste heat boiler 4 and passes through the low pressure steam transmission pipe.
  • the biomass synthesis gas is sent from the inlet 13 of the lower end of the venturi scrubber 5 to the unfilled venturi scrubber 5 for washing and dust removal, and In one step of cooling, most of the dust, tar drops and water-soluble gas in the biomass synthesis gas are removed into the washing liquid.
  • the washing liquid is washing water, and circulating water or industrial water can be used.
  • the gas outlet 14 from the upper end of the venturi scrubber 5 The temperature of the biomass synthesis gas is reduced to 25 ⁇ 65 °C. Finally, the biomass synthesis gas is sent from the inlet 15 of the lower end of the wet electrostatic precipitator 6 to the wet electrostatic precipitator 6, and the waste heat of the vertical pipe is utilized.
  • the low-pressure steam generated in the boiler 4 is subjected to deep dust removal and decoking treatment, thereby purging and removing a small amount of dust and tar mist remaining in the biomass synthesis gas, and reducing the pressure of the biomass synthesis gas to 0.1 to 1 Mpa, and purifying by the above cooling.
  • the dust content of the biomass syngas from the gas outlet 16 at the top of the wet electrostatic precipitator 6 is ⁇ 10 mg/Nm3, the tar content is ⁇ 10 mg/Nm3, the temperature is ⁇ 55 °C, and the sensible heat recovery rate is greater than 80%.
  • the biomass synthesis gas is sent to the gas storage tank 17 for storage or output from the gas outlet port 28 of the gas storage tank for use in the downstream section, and in parallel with the gas storage tank 17, is an exhaust gas incineration boiler 24, which is in system startup, biomass bonding When the gas-forming components exceed the standard, it is an important equipment for burning the exhaust gas.
  • the dust filtered by the dry filter 3 enters the silo pump 21 through the dust outlet 20 at the bottom end of the dry filter 3, and the dust collected by the silo pump 21 is pneumatically transported to the ash silo 23 for storage through the discharge port 22 of the silo pump 21. And use it reasonably.
  • the invention inputs the medium pressure steam generated by the shell-and-tube waste heat boiler 2 into the biomass gasification furnace 1 as a gasifying agent to supply pressure to the purification system, saves the gas blower, and ensures the biomass gasification furnace by adjusting the pressure of the steam.
  • the pressure head of the outlet 1 overcomes the resistance of the cooling and purifying system and reaches the inlet 26 of the gas storage tank 17, the positive pressure of 0.1 ⁇ lMPa (G) can be ensured, that is, the biomass gasification furnace 1, the shell-and-tube waste heat boiler 2 is guaranteed.
  • Venturi scrubber 5 wet scrubber 6, and gas storage tank 17 are operated under positive pressure to prevent external air from leaking into the above purification equipment, reducing the possibility of gas explosion, and saving
  • the air compressor that pressurizes the biomass gas in the subsequent synthetic oil section is eliminated, which greatly reduces the overall energy consumption of the gasification and synthetic oil section.
  • the above is the main process flow and related equipment for high temperature and high pressure biomass synthesis gas cooling and purification. It can add some standard and non-standard equipment to auxiliary systems such as two-stage waste heat boiler feed water, Venturi scrubbing tower circulating water, wet electrostatic precipitator flushing water. They form their own subsystems through pipes and valves to service related equipment, thus completing the cooling and purification process of biomass synthesis gas.

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

Abstract

L'invention concerne un procédé de purification et de refroidissement de gaz de synthèse de biomasse à haute pression et à haute température comprenant : 1) le refroidissement par sous-sections; 2) la collecte et l'élimination d'huile empyreumatique; 3) le lavage et la purification; et 4) un traitement de précipitation électrostatique de type humide. L'invention concerne également un dispositif de refroidissement et de purification de gaz de synthèse de biomasse à haute pression et à haute température, comprenant principalement une chaudière à récupération de chaleur (2) à calandre, un filtre de gaz sec (3), une chaudière à récupération de chaleur (4) à tubes de fumée verticaux, une tour de lavage (5) et un dispositif de précipitation électrostatique de type humide (6). Le dispositif de la présente invention est simple, sûr et stable; présente une consommation d'énergie basse et une efficacité élevée et atteint de bons bénéfices économiques.
PCT/CN2014/079101 2013-06-03 2014-06-03 Procédé et dispositif de refroidissement et de purification de gaz de synthèse de biomasse à haute pression et à haute température WO2014194812A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310218735.7 2013-06-03
CN201310218735.7A CN103265979B (zh) 2013-06-03 2013-06-03 高温高压生物质合成气冷却净化工艺及其设备

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CN103265979B (zh) * 2013-06-03 2015-04-08 武汉凯迪工程技术研究总院有限公司 高温高压生物质合成气冷却净化工艺及其设备
CN104927925B (zh) * 2015-06-24 2017-11-14 武汉凯迪工程技术研究总院有限公司 用于制油的生物质合成气超高压冷却净化工艺及其设备
CN106479521B (zh) * 2016-12-10 2023-03-17 葛霖 焦炉上升管防结焦高效余热回收装置及其防结焦方法
CN107456848B (zh) * 2017-07-20 2023-12-12 云威能源科技（上海）有限公司 一种气体干燥装置及干燥工艺

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CN102604685A (zh) * 2011-12-29 2012-07-25 武汉凯迪工程技术研究总院有限公司 用于制油的生物质合成气正压净化工艺方法和***配置
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