CN113801700A - Process method and equipment for upgrading combustible carbon substrate waste gasified synthesis gas - Google Patents

Process method and equipment for upgrading combustible carbon substrate waste gasified synthesis gas Download PDF

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Publication number
CN113801700A
CN113801700A CN202111105656.6A CN202111105656A CN113801700A CN 113801700 A CN113801700 A CN 113801700A CN 202111105656 A CN202111105656 A CN 202111105656A CN 113801700 A CN113801700 A CN 113801700A
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gasifying agent
preheating
communicated
raw material
upgrading
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李晓伟
刘建坤
沙丽佳
李明洋
蒋景沛
闫昌国
张大雷
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Liaoning Institute Of Energy Research Co ltd
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Liaoning Institute Of Energy Research Co ltd
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    • 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
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • C10J3/56—Apparatus; Plants
    • 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
    • C10J3/54—Gasification of granular or pulverulent fuels by the Winkler technique, i.e. by fluidisation
    • 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
    • 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
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2200/00—Details of gasification apparatus
    • C10J2200/15—Details of feeding means
    • C10J2200/158—Screws
    • 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
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953—Gasifying agents
    • C10J2300/0956—Air or oxygen enriched air
    • 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
    • C10J2300/0959—Oxygen
    • 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
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1807—Recycle loops, e.g. gas, solids, heating medium, water
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a process method and equipment for upgrading combustible carbon substrate waste gasified synthesis gas, wherein a built-in preheating pipeline is arranged in a bubbling fluidized bed, a heating cavity is formed between the bubbling fluidized bed and the built-in preheating pipeline, the top end of the heating cavity is communicated with a first gasifying agent conveying pipe, an inlet of the first gasifying agent conveying pipe is communicated with a steam generator and a gasifying agent mixing box, a feeding mechanism is communicated between a dilute phase area and a dense phase area, and a raw material preheating box for preheating raw materials in the feeding mechanism is sleeved on the outer side of the feeding mechanism. The raw material is preheated by the energy in the crude fuel gas, and the steam generated by heat supply and drying directly participates in the chemical reaction, so that the quality of combustible gas is improved, the contents of hydrogen and carbon monoxide are increased, the quality of synthesis gas is obviously improved, the steam amount required in the traditional oxygen enrichment-steam gasification process is reduced, and the heat loss in the furnace generated by the traditional oxygen enrichment-steam gasification process is reduced.

Description

Process method and equipment for upgrading combustible carbon substrate waste gasified synthesis gas
Technical Field
The invention relates to the technical field of biomass energy recycling, in particular to a process method and equipment for improving the quality of combustible carbon substrate waste gasified synthesis gas.
Background
The biomass energy is widely distributed, has the characteristics of reproducibility, low pollution and the like, so that the research on the development and utilization of the biomass energy is one of the important contents of sustainable development technologies in China. The biomass is the only carbon-containing renewable resource in the nature, can be directly converted into green liquid fuel, and occupies an important position in future energy structure and carbon emission reduction. The biomass gasification synthesis of the low-carbon mixed alcohol liquid fuel can realize the full-component utilization of biomass, and is one of the most promising high-efficiency conversion approaches. However, the low-quality biomass represented by agricultural and forestry wastes has low hydrogen-carbon ratio and high water content, and the problems of low yield of low-carbon mixed alcohol, difficult separation and purification of target products and the like exist in the gasification synthesis process, so that the problems need to be solved urgently.
At present, the biomass gasification synthesis gas is mainly prepared by gasifying air or oxygen and then carrying out chemical reaction with high-pressure steam when passing through a high-temperature heating device, so that the synthesis gas with higher hydrogen-carbon ratio is obtained. Experiments show that the temperature is an important influence factor for judging whether the gasification process is smooth, the supply of energy is necessary for the gasification process to be smoothly carried out, the gasification reaction is generally an endothermic reaction, and sufficient heat and sufficient retention time in the device are required for the reduction reaction to be completely carried out. The temperature in the furnace plays a decisive role, and has important influence on combustible components in the gas, the gas yield, the gasification intensity and the like, the gasification rate is accelerated along with the rise of the reaction temperature, and CO2Content (wt.)Decrease, increase in the value of combustible components in the gas; when carbon element is gasified and converted into combustible gas, the residual heat is not enough to provide sufficient heat for the reaction formula, so that the reduction reaction is difficult to carry out, the residual heat in the experiment is mainly consumed in the temperature rising process of air and raw materials, and a large amount of heat is also brought out by the generated crude combustible gas. The insufficient heat in the furnace and the low temperature can also cause the production of tar and reduce the generation of hydrogen and carbon monoxide.
Traditional gasification technology adopts oxygen boosting-vapor gasification to improve the hydrogen-carbon ratio, the temperature of guaranteeing vapor is preheated at the pre-heater after gasification agent and vapor mix, then in being sent to the furnace body gas chamber, advance to the stove through the air distribution plate and carry out gasification reaction, the gasification agent temperature is lower, can absorb partly heat, make incomplete that reduction reaction goes on, and vapor belongs to the gasification agent of extra interpolation, advance in the stove after because the heat in the heat conductivity can earlier absorption stove reacts again, can reduce gasification efficiency like this. The traditional gasification process can produce a certain amount of tar, the tar has adhesion and is easily adsorbed on the surface of a pipe wall to cause pipeline blockage, and the coke washing wastewater easily pollutes the environment. With the continuous research of the directional synthesis of alcohol liquid fuel from biomass gasification synthesis gas, the requirement on gasification produced gas is higher and higher, and the produced gas has higher hydrogen-carbon ratio and tar and ash content lower than 10mg/Nm3Or less, the gasification of the traditional process needs additional steam, the production cost is increased, and the temperature in the furnace is reduced to be not beneficial to the gasification reaction; the amount of tar produced also increases, resulting in energy loss.
Disclosure of Invention
The invention aims to provide a process method and equipment for improving the quality of combustible carbon substrate waste gasified synthesis gas, so as to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following scheme: the invention provides a process device for upgrading combustible carbon substrate waste gasified synthesis gas, which comprises a bubbling fluidized bed, wherein a built-in preheating pipeline is arranged in the bubbling fluidized bed, a heating cavity is formed between the bubbling fluidized bed and the built-in preheating pipeline, and a dilute phase area and a dense phase area are sequentially arranged in the built-in preheating pipeline from top to bottom; a second gasifying agent conveying pipe is communicated between the bottom end of the heating cavity and the bottom end of the dense-phase area; the top end of the heating cavity is communicated with a first gasifying agent conveying pipe, an inlet of the first gasifying agent conveying pipe is communicated with a water vapor generator and a gasifying agent mixing box, and the gasifying agent mixing box is communicated with a blower and an oxygen bottle;
a feeding mechanism is communicated between the dilute phase area and the dense phase area, and a raw material preheating box for preheating raw materials in the feeding mechanism is sleeved on the outer side of the feeding mechanism; the top end of the dilute phase zone is communicated with a cyclone dust collector, the cyclone dust collector is communicated with the air inlet end of the raw material preheating box, and the air outlet end of the raw material preheating box is communicated with a purifying device.
Preferably, a first flowmeter is arranged between the gasifying agent mixing box and the air blower, a second flowmeter is arranged between the gasifying agent mixing box and the oxygen cylinder, and a third flowmeter is arranged between the first gasifying agent conveying pipe and the water vapor generator.
Preferably, the outlet of the first gasifying agent conveying pipe is communicated with a plurality of groups of gasifying agent branch pipelines, the gasifying agent branch pipelines are communicated with the heating cavity, and the distances between any two adjacent groups of gasifying agent branch pipelines are the same; the second gasifying agent conveying pipes are provided with at least two groups and the distance between any two adjacent groups of second gasifying agent conveying pipes is the same.
Preferably, the bubbling fluidized bed is fixedly connected with an air distribution plate in the dense-phase zone, and the air distribution plate is arranged between the air inlet and the air outlet of the second gasifying agent conveying pipe.
Preferably, the feeding mechanism comprises a feeding pipe, a helical blade is arranged inside the feeding pipe, and the helical blade is driven by a motor; a discharge hole is formed in one end, close to the bubbling fluidized bed, of the feeding pipe, and a feeding hopper is communicated with one end, far away from the bubbling fluidized bed, of the feeding pipe; the raw material preheating box is of a tubular structure and is sleeved outside the feeding pipe, a preheating cavity is formed between the feeding pipe and the raw material preheating box, and the cyclone dust collector and the purifying device are respectively connected to the air inlet end and the air outlet end of the preheating cavity.
Preferably, a refractory cement heat-insulating layer is arranged on the side wall of the bubbling fluidized bed, and rock wool heat-insulating layers are arranged on the side walls of the cyclone dust collector and the raw material preheating box.
A process method for upgrading combustible carbon substrate waste gasified synthesis gas comprises the following steps:
mixing air and oxygen in proportion to form a primary mixed gasifying agent;
step two, the gasifying agent obtained by preliminary mixing in the step one and water vapor are formed into a gasifying agent according to the proportion, and the gasifying agent is conveyed into a heating cavity in the bubbling fluidized bed for preheating;
step three, the preheated gasifying agent in the step two is heated to 590-615 ℃ and then conveyed into a dense-phase region, and is subjected to gasification reaction with the preheated raw material to generate crude fuel gas;
and step four, performing dust removal treatment on the crude fuel gas obtained in the step three, and performing purification treatment after preheating the raw materials in the step three by the crude fuel gas after dust removal treatment.
Preferably, in the fourth step, the dried raw material and the water vapor generated after the raw material is preheated by the crude fuel gas are all conveyed into the dilute phase region and the dense phase region; the temperature of the crude fuel gas entering the preheating cavity is not lower than 550 ℃, and the water content of the dried raw material is not higher than 15%.
The invention discloses the following technical effects: the invention preheats the raw material by the energy in the crude fuel gas, reduces the yield of macromolecular condensable liquid products in the pyrolysis gasification process of the treated raw material, improves the quality of the combustible gas because the heat supply and the dried water vapor directly participate in the chemical reaction, increases the content of hydrogen and carbon monoxide, and measures H2The ratio of/CO reaches 1.65, the quality of the synthesis gas is obviously improved, and the subsequent synthesis gas modulation and the synthesis of liquid fuel are facilitated; meanwhile, the invention reduces the amount of water vapor required in the traditional oxygen enrichment-water vapor gasification process, reduces the heat loss in the furnace generated by the traditional oxygen enrichment-water vapor gasification, and reduces the electric energy consumption generated by generating water vapor.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
FIG. 1 is a schematic diagram of the apparatus of the present invention;
the system comprises a blower 1, an oxygen bottle 2, a gasifying agent mixing box 3, a bubbling fluidized bed 4, a built-in preheating pipeline 5, a dense-phase zone 6, an air chamber 7, a second gasifying agent delivery pipe 8, a dilute-phase zone 9, a gasifying agent branch pipeline 10, a cyclone dust collector 11, a feeding mechanism 12, a raw material preheating box 13, a water vapor generator 14, a heating chamber 15, a first gasifying agent delivery pipe 16, a first flowmeter 17, a second flowmeter 18, a third flowmeter 19, a preheating chamber 20, an air distribution plate 21, a feeding pipe 121, a helical blade 122 and a feeding hopper 123.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Referring to fig. 1, the invention provides a process equipment for upgrading combustible carbon substrate waste gasified synthesis gas, which comprises a bubbling fluidized bed 4, wherein a built-in preheating pipeline 5 is arranged in the bubbling fluidized bed 4, a heating cavity 15 is formed between the bubbling fluidized bed 4 and the built-in preheating pipeline 5, and a dilute phase region 9 and a dense phase region 6 are sequentially arranged in the built-in preheating pipeline 5 from top to bottom; a second gasifying agent conveying pipe 8 is communicated between the bottom end of the heating cavity 15 and the bottom end of the dense-phase zone 6; the top end of the heating cavity 15 is communicated with a first gasifying agent delivery pipe 16, the inlet of the first gasifying agent delivery pipe 16 is communicated with a water vapor generator 14 and a gasifying agent mixing box 3, and the gasifying agent mixing box 3 is communicated with a blower 1 and an oxygen bottle 2.
A feeding mechanism 12 is communicated between the dilute phase zone 9 and the dense phase zone 6, and a raw material preheating box 13 for preheating raw materials in the feeding mechanism 12 is sleeved outside the feeding mechanism 12; the top end of the dilute phase zone 9 is communicated with a cyclone dust collector 11, the cyclone dust collector 11 is communicated with the air inlet end of a raw material preheating box 13, and the air outlet end of the raw material preheating box 13 is communicated with a purifying device.
In a further optimized scheme, a first flow meter 17 is arranged between the gasifying agent mixing box 3 and the air blower 1, a second flow meter 18 is arranged between the gasifying agent mixing box 3 and the oxygen cylinder 2, and a third flow meter 19 is arranged between the first gasifying agent conveying pipe 16 and the water vapor generator 14. The amount of air, oxygen and water vapor in the gasifying agent is respectively measured by a first flow meter 17, a second flow meter 18 and a third flow meter 19.
In a further optimization scheme, a plurality of groups of gasification agent branch pipelines 10 are communicated with the outlet of the first gasification agent delivery pipe 16, the gasification agent branch pipelines 10 are communicated with the heating cavity 15, and the distances between any two adjacent groups of gasification agent branch pipelines 10 are the same; the gasifying agent branch pipeline 10 is provided with five paths, a small-sized orifice plate flowmeter is arranged on each path of gasifying agent branch pipeline 10, the gas flow in the five paths of gasifying agent branch pipelines 10 is tested, and the gasifying agent is guaranteed to be uniformly conveyed to the heating cavity 15. The second gasifying agent conveying pipes 8 are provided with at least two groups and the distance between any two adjacent groups of the second gasifying agent conveying pipes 8 is the same.
In a further optimized scheme, the bubbling fluidized bed 4 is fixedly connected with an air distribution plate 21 in the dense-phase zone 6, and the air distribution plate 21 is arranged between the air inlet and the air outlet of the second gasifying agent conveying pipe 8.
In a further optimized scheme, the feeding mechanism 12 comprises a feeding pipe 121, a helical blade 122 is arranged inside the feeding pipe 121, and the helical blade 122 is driven by a motor; a discharge hole is formed in one end, close to the bubbling fluidized bed 4, of the feeding pipe 121, and a feeding hopper 123 is communicated with one end, far away from the bubbling fluidized bed 4, of the feeding pipe 121; the raw material preheating box 13 is of a tubular structure, the raw material preheating box 13 is sleeved on the outer side of the feeding pipe 121, a preheating cavity 20 is formed between the feeding pipe 121 and the raw material preheating box 13, and the cyclone dust collector 11 and the purifying device are respectively connected to the air inlet end and the air outlet end of the preheating cavity 20.
In a further optimized scheme, a fireproof cement heat-insulating layer is arranged on the side wall of the bubbling fluidized bed 4, and rock wool heat-insulating layers are arranged on the side walls of the cyclone dust collector 11 and the raw material preheating box 13.
A process method for upgrading combustible carbon substrate waste gasified synthesis gas comprises the following steps:
mixing air and oxygen in proportion to form a primary mixed gasifying agent; namely, the blower 1 and the oxygen cylinder 2 respectively supply air and oxygen to the gasifying agent mixing box 3, and the air and the oxygen are metered by the first flow meter 17 and the second flow meter 18 to form a preliminarily mixed gasifying agent.
Step two, the gasifying agent obtained by preliminary mixing in the step one and water vapor are formed into the gasifying agent according to the proportion, and the gasifying agent is conveyed into a heating cavity 15 in the bubbling fluidized bed 4 for preheating; the gasifying agent is quickly diffused and filled after entering the heating cavity 15, the flow rate of the gasifying agent is reduced, the preheating is carried out in the heating cavity 15, the built-in preheating pipeline 5 is arranged in the furnace body, the heights of the built-in preheating pipeline 5 and the bubbling fluidized bed 4 are the same, and the sum of the heights of the dense phase zone 6 and the dilute phase zone 9 is 7.5m, so that the sufficient retention time of the gasifying agent is ensured, and the temperature T of the gasifying agent is enabled to be T1Over 600 deg.c.
And step three, the preheated gasifying agent in the step two is heated to 590-615 ℃ and then conveyed into the dense-phase region 6, a second gasifying agent conveying pipe 8 is communicated between the bottom end of the heating cavity 15 and the bottom end of the dense-phase region 6, the gasifying agent is conveyed into the air chamber 7 through the second gasifying agent conveying pipe 8, so that the gasifying agent is diffused and uniformly mixed, preferably, the gasifying agent is heated to 600 ℃, and the gasifying agent at 600 ℃ enters the dense-phase region 6 through the air distribution plate 21 for gasification reaction. The gasifying agent and the preheated raw material are subjected to gasification reaction to generate crude fuel gas.
And step four, performing dust removal treatment on the crude fuel gas obtained in the step three, and performing purification treatment after preheating the raw materials in the step three by the crude fuel gas after dust removal treatment. Conveying the crude fuel gas to a preheating cavity 20 by conveying, wherein the preheating cavity 20 preheats the raw material in the feeding pipe 121, and the generated dried raw material and water vapor are all conveyed into a dilute phase zone 9 and a dense phase zone 6; the temperature of the crude fuel gas entering the preheating cavity 20 is not lower than 550 ℃, and the water content of the dried raw material is not higher than 15%. The raw materials are conveyed into the dilute phase zone 9 and the dense phase zone 6 through the helical blades 122 in the feeding mechanism 12, the length of the feeding pipe 121 is not less than 2000mm, the sufficient preheating time of the raw materials is ensured, the water content of the raw materials is reduced below the requirement, and the raw materials and the high-temperature gasifying agent in the furnace are subjected to gasification reaction. The produced crude fuel gas is conveyed to a cyclone dust collector 11 from the top of the furnace body, large-particle impurities and the like in the crude fuel gas are removed through the cyclone dust collector 11, and then the crude fuel gas is conveyed into a preheating cavity 20 through a pipeline to preheat raw materials. After the gasification reaction in the furnace reaches the balance, the temperature T of the furnace body outlet3At 600 ℃ and after passing through the cyclone 11, the temperature T4、T5Measured as 550 ℃, the temperature T of the gas produced after preheating the raw material6The temperature is 350 ℃, and then the combustible gas produced under the blowing and drawing matching is purified in a device.
The raw material water content required by gasification is required to be below 15%, while the inherent in-situ water content obtained by industrial analysis of the biomass raw material is about 5%, that is, the raw material water content per unit mass is about 20%, the raw material is preheated, the water on the surface is released firstly along with the heat absorption of the raw material, the inherent in-situ water is also released gradually along with the rise of the temperature of the raw material, and then the dried raw material, the steam and the heat obtained by heat transfer enter the furnace together to participate in the reaction.
The gasification agent and the raw materials are subjected to gasification reaction to generate carbon dioxide, water vapor, carbon monoxide, hydrogen, methane, coke, tar and the like, a large amount of heat is generated, and the raw materials are subjected to complex oxidation-reduction reaction in the furnace to generate the required combustible gas components.
According to the Kerbelon equation PV-nRT, the volume of the gasifying agent is changed to be more than 3 times of the original volume when the temperature of the gasifying agent is increased to 600 ℃ from normal temperature, the amount of substances in the volume expansion unit volume is reduced, and the system adopts the blowing matching, so that the gasifying agent amount entering the furnace from the air distribution plate 21 is not reduced, and the gasification reaction parameter equivalence ratio ER is reduced. The above reaction formula shows that the residual heat after the oxidation reaction is not enough to support more reduction reaction, so that when the gasifying agent is preheated to 600 ℃, a large amount of heat is brought into the dense phase zone, thereby providing heat guarantee for the reduction reaction.
The second gasification agent delivery pipe 8 is provided with a T1A T is arranged at the temperature measuring point and the outlet of the gasification agent mixing box 32A T is arranged at the air outlet of the temperature measuring point and the dilute phase zone 93A T is arranged at the air outlet of the cyclone dust collector 11 of the temperature measuring point4The temperature measuring point, the air inlet end and the air outlet end of the preheating cavity 20 are respectively provided with a T5Temperature measurement point and T6And measuring the temperature.
At present, the biomass gasification synthesis gas is mainly prepared by gasifying air or oxygen and then carrying out chemical reaction with high-pressure steam when passing through a high-temperature heating device, so that the synthesis gas with higher hydrogen-carbon ratio is obtained. Therefore, the synthesis gas contains a part of inert gas-nitrogen, which does not participate in gasification reaction, but dilutes the content of combustible components in the produced gas and influences the quality of the synthetic alcohol liquid fuel. Meanwhile, tar in the synthesis gas is attached to the wall of the pipeline before entering the high-temperature device, the contained combustible substrate cannot be well utilized, most of the tar is benzene derivatives and polycyclic aromatic hydrocarbons, the tar is in a gaseous state at high temperature and is completely mixed with the combustible gas, the tar is condensed into a sticky liquid at low temperature (generally lower than 200 ℃), the separation and treatment are difficult, and the generation amount of the tar can be reduced through gasification high-temperature reaction in the furnace, so that the tar is cracked and converted into hydrogen and carbon monoxide.
The basic principle of biomass gasification is that biomass raw materials are incompletely combusted under the participation of gasification agents (air, oxygen, water vapor or the like) so that organic hydrocarbon chains with higher molecular weight are cracked and changed into CO and H with lower molecular weight2、CH4And the like. The biomass gasification method comprises two processes, namely thermochemical reactionA process; the second is the equipment required by the thermochemical reaction process conditions. From a chemical point of view, thermochemical processes are very complex, involving many chemical equations, mainly linked to the equations shown in equations (1) to (6):
C+O2←→CO2+408.8kJ (1)
2C+O2←→2CO+246.44kJ (2)
C+CO2←→2CO-162.41kJ (3)
H2O+CO←→CO2+H2-43.58kJ (4)
H2O+C←→CO+H2-118.82kJ (5)
2H2O+C←→CO2+2H2-75.24kJ (6)
among the above 6 chemical reaction formulas, it can be seen that formulas (1) and (2) are crucial, and the heat is released by the above two oxidation reactions, so that the temperature in the furnace is increased to provide the required heat for reduction reaction formulas (3) to (6). Experiments show that the temperature is an important influence factor for judging whether the gasification process is smooth, the supply of energy is necessary for the gasification process to be smoothly carried out, the gasification reaction is generally an endothermic reaction, and sufficient heat and sufficient retention time in the device are required for the reduction reaction to be completely carried out. The temperature in the furnace plays a decisive role, and has important influence on combustible components in the gas, the gas yield, the gasification intensity and the like, the gasification rate is accelerated along with the rise of the reaction temperature, and CO2The content is reduced, and the value of combustible components in the gas is increased; and adding the 6 chemical reaction formulas to obtain:
3C+O2+2H2O→CO2+2CO+2H2+127.6kJ (7)
formula (7) shows that when carbon element is gasified and converted into combustible gas, the residual heat (127.6kJ) is not enough to provide enough heat for reaction formulas (3) - (6), so that the reduction reaction is difficult to carry out, the residual heat in the experiment is mainly consumed in the temperature rise process of air and raw materials, and the generated crude combustible gas also carries out a large amount of heat. The insufficient heat in the furnace and the low temperature can also cause the production of tar and reduce the generation of hydrogen and carbon monoxide.
The traditional gasification technology adopts oxygen enrichment-steam gasification to improve the hydrogen-carbon ratio, the temperature of the steam is guaranteed by preheating in a preheater after the gasification agent (oxygen) and the steam are mixed, then the steam is sent to a furnace body gas chamber, the gasification reaction is carried out in the furnace through an air distribution plate, the temperature of the gasification agent is lower, a part of heat can be absorbed, the reduction reaction is not thorough, the steam belongs to the gasification agent which is additionally added, the gasification agent reacts after entering the furnace because the heat in the furnace can be absorbed firstly by the heat conductivity, and the gasification efficiency can be reduced.
The traditional gasification process can produce a certain amount of tar, the tar can be removed by a subsequent physical method or other methods, the tar has adhesiveness, is easy to be adsorbed on the surface of a pipe wall to cause pipe blockage, and the coke washing wastewater is easy to pollute the environment. Tar is mainly aromatic compounds, and hydrogen and carbon monoxide are generated after cracking, and the formula is shown as the following formula (8):
CnHm+nH2O←→(n+m/2)H2+nCO (8)
with the continuous research of the directional synthesis of alcohol liquid fuel from biomass gasification synthesis gas, the requirement on gasification produced gas is higher and higher, and the produced gas has higher hydrogen-carbon ratio and tar and ash content lower than 10mg/Nm3Or less, the gasification of the traditional process needs additional steam, the production cost is increased, and the temperature in the furnace is reduced to be not beneficial to the gasification reaction; the amount of tar produced also increases, resulting in energy loss.
Comparative example 1
50kg/h self-heating bubbling fluidized bed is taken as a reaction device, and wood chips are taken as raw materials. According to the traditional oxygen enrichment-steam gasification experiment, air, oxygen and steam are fully mixed and preheated in a preheating mixing box, enter an air chamber of a furnace body through a heat-insulating pipeline and are mixed again, then enter a dense-phase area in the furnace through an air distribution plate and carry out gasification reaction with raw materials conveyed by a feeding device, produced gas is sent out from the top of the furnace body, passes through purifying equipment such as cyclone dust removal, water bath cooling decoking and the like, and finally is conveyed into a gas storage tank through a draught fan. Steam hairThe temperature of the raw material from the generator is 169 ℃, the temperature of the gasification agent is maintained at 160 ℃ after preheating and heat preservation, and T1Temperature measurement point and T5The temperatures at the temperature measurement points were 160 ℃ and 25 ℃, respectively. The process adopts the drum-guide matching, ensures that the pressure at the outlet of the furnace is micro negative pressure, and starts to test after the system is normal and stable.
Example 2
Firstly, air and oxygen are mixed according to the proportion, and a primarily mixed gasification agent is formed in a gasification agent mixing box 3.
And step two, the gasifying agent obtained by the preliminary mixing in the step one and water vapor are formed into the gasifying agent according to the proportion, and the gasifying agent is conveyed into a heating cavity 15 in the bubbling fluidized bed 4 for preheating.
Step three, the preheated gasifying agent in the step two is heated and then conveyed into a dense-phase zone 6, T1The temperature of the temperature measuring point is 595.0 ℃, and the gasifying agent and the preheated raw material are subjected to gasification reaction to generate crude fuel gas.
Step four, performing dust removal treatment on the crude fuel gas obtained in the step three, preheating the raw materials in the step three by the crude fuel gas after the dust removal treatment, and then performing purification treatment, T5The temperature at the temperature measurement point is 556.3 ℃.
The whole process adopts the drum-guide matching, ensures that the pressure at the outlet of the furnace is micro-negative pressure, and starts to test after the system is normal and stable.
Example 3
Firstly, air and oxygen are mixed according to the proportion, and a primarily mixed gasification agent is formed in a gasification agent mixing box 3.
And step two, the gasifying agent obtained by the preliminary mixing in the step one and water vapor are formed into the gasifying agent according to the proportion, and the gasifying agent is conveyed into a heating cavity 15 in the bubbling fluidized bed 4 for preheating.
Step three, the preheated gasifying agent in the step two is heated and then conveyed into a dense-phase zone 6, T1The temperature of the temperature measuring point is 602.7 ℃, and the gasifying agent and the preheated raw material are subjected to gasification reaction to generate crude fuel gas.
Step four, performing dust removal treatment on the crude fuel gas obtained in the step three, and performing dust removal treatment on the crude fuel gas in the step threePreheating the material and purifying the preheated material T5The temperature at the temperature measurement point is 548.9 ℃.
The whole process adopts the drum-guide matching, ensures that the pressure at the outlet of the furnace is micro-negative pressure, and starts to test after the system is normal and stable.
Example 4
Firstly, air and oxygen are mixed according to the proportion, and a primarily mixed gasification agent is formed in a gasification agent mixing box 3.
And step two, the gasifying agent obtained by the preliminary mixing in the step one and water vapor are formed into the gasifying agent according to the proportion, and the gasifying agent is conveyed into a heating cavity 15 in the bubbling fluidized bed 4 for preheating.
Step three, the preheated gasifying agent in the step two is heated and then conveyed into a dense-phase zone 6, T1The temperature of the temperature measuring point is 610.8 ℃, and the gasifying agent and the preheated raw material are subjected to gasification reaction to generate crude fuel gas.
Step four, performing dust removal treatment on the crude fuel gas obtained in the step three, preheating the raw materials in the step three by the crude fuel gas after the dust removal treatment, and then performing purification treatment, T5The temperature at the temperature measurement point is 552.9 ℃.
The whole process adopts the drum-guide matching, ensures that the pressure at the outlet of the furnace is micro-negative pressure, and starts to test after the system is normal and stable.
Comparative example 1, example 2, example 3 and example 4 the gas was collected and the gas composition was measured by means of a hue spectrum, the test results being shown in the following table:
gas component table measured by gas chromatography
Figure BDA0003272203690000151
In the above table, No. 1 is a combustible gas component obtained in the conventional oxygen-rich-steam gasification experiment of comparative example 1; 2. 3 and 4 are combustible gas components obtained from examples 2, 3 and 4 using the protocol of the invention. As can be seen from the table, H is obtained after the gasification agent and the raw material are preheated at high temperature2The ratio of/CO is obviously improved to reach the level of 1.65, and CO is reduced2And the macromolecular chain gas component is obviously reduced, the gas heat value is also obviously increased, and the subsequent synthesis gas modulation and the synthesis of liquid fuel are facilitated.
In the description of the present invention, it is to be understood that the terms "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, are merely for convenience of description of the present invention, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.

Claims (8)

1. A process equipment for upgrading combustible carbon substrate waste gasification synthesis gas is characterized in that: the device comprises a bubbling fluidized bed (4), wherein a built-in preheating pipeline (5) is arranged in the bubbling fluidized bed (4), a heating cavity (15) is formed between the bubbling fluidized bed (4) and the built-in preheating pipeline (5), and a dilute phase region (9) and a dense phase region (6) are sequentially arranged in the built-in preheating pipeline (5) from top to bottom; a second gasification agent conveying pipe (8) is communicated between the bottom end of the heating cavity (15) and the bottom end of the dense-phase zone (6); the top end of the heating cavity (15) is communicated with a first gasifying agent conveying pipe (16), the inlet of the first gasifying agent conveying pipe (16) is communicated with a water vapor generator (14) and a gasifying agent mixing box (3), and the gasifying agent mixing box (3) is communicated with a blower (1) and an oxygen bottle (2);
a feeding mechanism (12) is communicated between the dilute phase zone (9) and the dense phase zone (6), and a raw material preheating box (13) for preheating raw materials in the feeding mechanism (12) is sleeved on the outer side of the feeding mechanism (12); the top end of the dilute phase zone (9) is communicated with a cyclone dust collector (11), the cyclone dust collector (11) is communicated with the air inlet end of the raw material preheating box (13), and the air outlet end of the raw material preheating box (13) is communicated with a purification device.
2. The process equipment for upgrading combustible carbon substrate waste gasification syngas according to claim 1, characterized in that: a first flowmeter (17) is arranged between the gasifying agent mixing box (3) and the air blower (1), a second flowmeter (18) is arranged between the gasifying agent mixing box (3) and the oxygen cylinder (2), and a third flowmeter (19) is arranged between the first gasifying agent conveying pipe (16) and the water vapor generator (14).
3. The process equipment for upgrading combustible carbon substrate waste gasification syngas according to claim 1, characterized in that: the outlet of the first gasifying agent conveying pipe (16) is communicated with a plurality of groups of gasifying agent branch pipelines (10), the gasifying agent branch pipelines (10) are communicated with the heating cavity (15), and the distances between any two adjacent groups of gasifying agent branch pipelines (10) are the same; the second gasifying agent conveying pipes (8) are provided with at least two groups and the distance between any two adjacent groups of the second gasifying agent conveying pipes (8) is the same.
4. The process equipment for upgrading combustible carbon substrate waste gasification syngas according to claim 3, characterized in that: and the bubbling fluidized bed (4) is fixedly connected with an air distribution plate (21) in the dense-phase zone (6), and the air distribution plate (21) is arranged between the air inlet and the air outlet of the second gasifying agent conveying pipe (8).
5. The process equipment for upgrading combustible carbon substrate waste gasification syngas according to claim 1, characterized in that: the feeding mechanism (12) comprises a feeding pipe (121), a spiral blade (122) is arranged inside the feeding pipe (121), and the spiral blade (122) is driven by a motor; a discharge hole is formed in one end, close to the bubbling fluidized bed (4), of the feeding pipe (121), and a feed hopper (123) is communicated with one end, far away from the bubbling fluidized bed (4), of the feeding pipe (121); the raw material preheating box (13) is of a tubular structure, the raw material preheating box (13) is sleeved on the outer side of the feeding pipe (121), a preheating cavity (20) is formed between the feeding pipe (121) and the raw material preheating box (13), and the cyclone dust collector (11) and the purifying device are respectively connected to the air inlet end and the air outlet end of the preheating cavity (20).
6. The process equipment for upgrading combustible carbon substrate waste gasification syngas according to claim 1, characterized in that: and a refractory cement heat-insulating layer is arranged on the side wall of the bubbling fluidized bed (4), and rock wool heat-insulating layers are arranged on the side walls of the cyclone dust collector (11) and the raw material preheating box (13).
7. A process method for upgrading combustible carbon substrate waste gasification synthesis gas, which is based on the process equipment for upgrading combustible carbon substrate waste gasification synthesis gas as claimed in any one of claims 1-6, and is characterized in that: the method comprises the following steps:
mixing air and oxygen in proportion to form a primary mixed gasifying agent;
step two, the gasifying agent obtained by preliminary mixing in the step one and water vapor are formed into the gasifying agent according to the proportion, and the gasifying agent is conveyed into a heating cavity (15) in the bubbling fluidized bed (4) for preheating;
step three, the preheated gasifying agent in the step two is heated to 590-615 ℃ and then conveyed into a dense-phase zone (6) to be subjected to gasification reaction with the preheated raw material to generate crude fuel gas;
and step four, performing dust removal treatment on the crude fuel gas obtained in the step three, and performing purification treatment after preheating the raw materials in the step three by the crude fuel gas after dust removal treatment.
8. The process of upgrading combustible carbon substrate waste gasification syngas according to claim 7, characterized in that: in the fourth step, the dried raw material and the water vapor generated after the raw material is preheated by the crude fuel gas are all conveyed into the dilute phase region (9) and the dense phase region (6); the temperature of the crude fuel gas entering the preheating cavity (20) is not lower than 550 ℃, and the water content of the dried raw material is not higher than 15%.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1673317A (en) * 2004-03-23 2005-09-28 财团法人电力中央研究所 Carbonization and gasification of biomass and power generation system
DE102008037318A1 (en) * 2008-08-06 2010-02-11 Technische Universität Bergakademie Freiberg Method for flow gasification of solid fuels e.g. dusty fuels, involves bounding mixing of water vapor with post-gasification raw gases in internally circulating flow, and compensating water loss by water supply
CN106047421A (en) * 2016-06-30 2016-10-26 昆明理工大学 Method for preparing synthetic gas from molten-state copper slag
RU2662440C1 (en) * 2017-09-25 2018-07-26 Федеральное государственное унитарное предприятие "Центр эксплуатации объектов наземной космической инфраструктуры" (ФГУП "ЦЭНКИ") Method of gasification of solid fuel and device for its implementation

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1673317A (en) * 2004-03-23 2005-09-28 财团法人电力中央研究所 Carbonization and gasification of biomass and power generation system
DE102008037318A1 (en) * 2008-08-06 2010-02-11 Technische Universität Bergakademie Freiberg Method for flow gasification of solid fuels e.g. dusty fuels, involves bounding mixing of water vapor with post-gasification raw gases in internally circulating flow, and compensating water loss by water supply
CN106047421A (en) * 2016-06-30 2016-10-26 昆明理工大学 Method for preparing synthetic gas from molten-state copper slag
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