CN111718761A - Method for preparing synthesis gas by co-gasification of hydrothermal carbon and pulverized coal in livestock and poultry waste - Google Patents

Method for preparing synthesis gas by co-gasification of hydrothermal carbon and pulverized coal in livestock and poultry waste Download PDF

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Publication number
CN111718761A
CN111718761A CN202010541870.5A CN202010541870A CN111718761A CN 111718761 A CN111718761 A CN 111718761A CN 202010541870 A CN202010541870 A CN 202010541870A CN 111718761 A CN111718761 A CN 111718761A
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slurry
hydrothermal carbon
hydrothermal
coal water
oxidant
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白永辉
宋旭东
王焦飞
马萌
路广华
于广锁
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Ningxia University
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Ningxia University
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/46Gasification of granular or pulverulent flues in suspension
    • C10J3/48Apparatus; Plants
    • C10J3/485Entrained flow gasifiers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/093Coal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0913Carbonaceous raw material
    • C10J2300/0946Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10JPRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00Details of gasification processes
    • C10J2300/09Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0953Gasifying agents
    • C10J2300/0959Oxygen
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency

Abstract

The invention discloses a method for preparing synthesis gas by co-gasifying hydrothermal carbon and pulverized coal of livestock and poultry wastes, which comprises the following steps: (1) drying the livestock and poultry waste in the air; (2) hydrothermal carbonization to obtain hydrothermal carbon; (3) adding water into the hydrothermal carbon for pulping to obtain hydrothermal carbon pulp; (4) and (4) respectively feeding the hydrothermal carbon slurry, the coal water slurry, the hydrothermal carbon slurry oxidant and the coal water slurry oxidant obtained in the step (3) into a gasification furnace through respective flow channels of a multi-channel nozzle to obtain synthesis gas. The invention can kill pathogenic bacteria, and can recycle and recycle the energy of the organic matters in the waste, and the invention has large scale of raw material treatment, high reaction conversion rate and environmental protection, and provides technical possibility for the large-scale treatment of livestock and poultry waste. The invention carries out resource treatment on the poultry waste from the source, not only solves the great problem of environmental management, but also saves coal resources, promotes clean breeding of livestock and poultry, and realizes resource and clean utilization of the poultry waste.

Description

Method for preparing synthesis gas by co-gasification of hydrothermal carbon and pulverized coal in livestock and poultry waste
Technical Field
The invention belongs to the technical field of carbon-containing matrix resource utilization, and particularly relates to a method for cleaning and resource utilization of livestock and poultry wastes.
Background
The sustainable and stable development of the animal husbandry in China effectively guarantees the supply of agricultural and sideline products, but the untreated livestock and poultry waste becomes a great problem for environmental management. The waste contains nitrogen, sulfur, phosphorus and pathogenic bacteria, and the pollutant amount is large and concentrated.
The method has the advantages that the livestock and poultry clean breeding is greatly promoted, the source reduction of wastes is promoted, and the promotion of the resource utilization of the livestock and poultry wastes is a hard task with clear time limit requirements.
At present, livestock and poultry wastes are mainly treated by composting, but the composting technology is greatly influenced by the timeliness of land, climate and crop production, and has the problems of corresponding process wastewater treatment and relatively poor environmental and economic benefits.
The high water content, low carbon content, low energy density and irregular shape of the livestock and poultry waste limit the direct industrial application of the livestock and poultry waste as a gasification raw material.
Therefore, how to realize the resource utilization and the clean utilization of the livestock and poultry wastes is of great significance and is an important subject of technicians in the field.
Disclosure of Invention
The invention aims to provide a method for preparing synthesis gas by co-gasifying hydrothermal carbon and pulverized coal of livestock and poultry wastes so as to meet the requirements of related fields.
The method comprises the following steps:
(1) naturally airing the livestock and poultry waste until the mass content of water in the livestock and poultry waste is below 20%;
(2) carrying out hydrothermal carbonization on the product obtained in the step (1) for 2-3 hours under the anaerobic condition of 180-250 ℃ and 1.5-3.5 MPa to obtain hydrothermal carbon with the particle size of 50-75 micrometers and the water content of 5-10%, and detecting by adopting an oxygen bomb combustion method, wherein the low-grade heat value of the hydrothermal carbon is 18-25 MJ/Kg and is equivalent to that of industrial gasification coal;
(3) adding water into the hydrothermal carbon obtained in the step (2) for pulping to obtain hydrothermal carbon pulp with the carbon matrix weight concentration of 60-65%;
(4) and (3) feeding the hydrothermal carbon slurry, the coal water slurry with the carbon matrix weight concentration of 60-65%, the hydrothermal carbon slurry oxidant and the coal water slurry oxidant which are obtained in the step (3) into a gasification furnace through respective flow channels of a multi-channel nozzle respectively, performing gasification reaction at the pressure of 3-4 MPa and the temperature of 1350-1500 ℃, and allowing the hydrothermal carbon slurry to stay for 6-8 s to obtain synthesis gas, wherein the dry-based synthesis gas comprises the following components in percentage by weight:
preferably, in the dry-based synthesis gas, the percentage contents of each component are as follows:
the weight ratio of the hydrothermal carbon slurry to the coal water slurry is as follows:
the ratio of the hydrothermal carbon slurry to the coal water slurry is 0.1-0.5: 1;
the ratio of the hydrothermal carbon slurry oxidant to the hydrothermal carbon slurry is 0.85-0.9: 1;
the ratio of the coal water slurry oxidant to the coal water slurry is 0.85-0.9: 1;
at the outlet of the multi-channel nozzle, the linear speed of each material is as follows:
1.5-2 m/s of hydrothermal carbon slurry, 1.5-2 m/s of coal water slurry, 100-120 m/s of hydrothermal carbon slurry oxidant and 100-120 m/s of coal water slurry oxidant;
the hydrothermal carbon slurry oxidant is selected from pure O2
The coal water slurry oxidant is selected from pure O2
The structure of the entrained flow gasifier is well known and can be referred to the technology disclosed in the patent CN 100366710C.
The term "residence time of the hydrothermal carbon slurry" refers to the time between the hydrothermal carbon slurry sprayed from the nozzle and reacting in the gasifier to obtain synthesis gas from the outlet at the top of the gasifier;
the invention has the beneficial effects that:
the heat value of the hydrothermal carbon prepared by hydrothermal treatment is equivalent to that of typical coal for gasification, so that the foundation is laid for the economy of the hydrothermal carbon for entrained flow bed gasification, and meanwhile, pathogenic bacteria in the hydrothermal carbon can be thoroughly killed from the source at the high temperature of 1500 ℃ in the gasification process of the high-temperature entrained flow bed.
The invention is a thermochemical method, can kill pathogenic bacteria, and can recycle and recycle the energy of organic matters in the waste, and the entrained flow bed gasification technology has the advantages of large scale of raw material treatment, high reaction conversion rate, environmental protection and the like, and provides technical possibility for large-scale treatment of livestock and poultry waste.
The invention can carry out resource treatment on the poultry waste from the source to the greatest extent, not only solves the great problem of environmental management, but also saves coal resources, greatly promotes the clean breeding of livestock and poultry, and achieves the resource and clean utilization of the poultry waste.
Drawings
FIG. 1 is a schematic view of an entrained flow gasifier with a multi-channel nozzle.
FIG. 2 is a schematic view of a multi-channel nozzle configuration.
Detailed Description
Referring to fig. 1 and 2, the entrained-flow gasifier with the multi-channel nozzle comprises a multi-channel nozzle 1 and an entrained-flow gasifier 2, wherein the multi-channel nozzle 1 is arranged at the upper part of the entrained-flow gasifier 2, and an outlet 101 of the multi-channel nozzle is communicated with an inner cavity of the entrained-flow gasifier 2;
the multi-channel nozzle 1 sequentially comprises from the center to the outer side:
the multichannel nozzle from the centre to the outside in proper order include: a coal water slurry passage pipe 102, a coal water slurry oxidant passage pipe 103 sleeved outside the coal water slurry passage pipe 102, a hydrothermal carbon slurry passage pipe 104 sleeved outside the coal slurry oxidant passage pipe 103, a hydrothermal carbon slurry oxidant passage pipe 105 sleeved outside the hydrothermal carbon slurry passage pipe 104 and an outlet (101).
In the multi-channel nozzle 1, a third channel for conveying the livestock and poultry waste hydrothermal carbon slurry is arranged between two channels for conveying a gasifying agent oxygen, the high-speed gasifying agent is in full contact with and collides with the livestock and poultry waste hydrothermal carbon slurry, the hydrothermal carbon slurry is fully atomized and then is uniformly dispersed under the action of the outer ring gasifying agent, and the gasification efficiency and the carbon conversion rate of the gasification furnace can be effectively improved.
Example 1
The entrained-flow gasifier device shown in figure 1 and the multi-channel nozzle shown in figure 2 are adopted to prepare the synthesis gas by taking livestock and poultry waste and coal water slurry as raw materials.
(1) Collecting fresh livestock and poultry waste, and naturally airing until the water content is 16%;
(2) hydrothermally carbonizing the product obtained in the step (1) for 2.5 hours at 200 ℃ and 2MPa to obtain hydrothermal carbon with the particle size of 60 micrometers, the water content of 8 percent (by weight) and the heat value of about 20 MJ/kg;
(3) adding water into the hydrothermal carbon obtained in the step (2) for pulping to obtain hydrothermal carbon pulp with the carbon matrix weight concentration of 60%;
(4) and (3) respectively feeding the hydrothermal carbon slurry, the coal water slurry with the carbon matrix weight concentration of 60%, the hydrothermal carbon slurry oxidant and the coal water slurry oxidant which are obtained in the step (3) into a gasification furnace through respective flow channels of a multi-channel nozzle, performing gasification reaction under the pressure of 3MPa and the temperature of 1350 ℃, and obtaining synthesis gas with the retention time of the hydrothermal carbon slurry of 6s, wherein the dry-basis synthesis gas comprises the following components in percentage by weight:
the weight ratio of the hydrothermal carbon slurry to the coal water slurry is as follows:
the ratio of the hydrothermal carbon slurry to the coal water slurry is 0.2: 1;
the ratio of the hydrothermal carbon slurry oxidant to the hydrothermal carbon slurry is 0.85: 1,
the ratio of the coal water slurry oxidant to the coal water slurry is 0.85: 1,
at the outlet of the multi-channel nozzle, the linear speed of each material is as follows:
1.5 m/s of hydrothermal carbon slurry, 1.5 m/s of coal water slurry, 100 m/s of hydrothermal carbon slurry oxidant and 100 m/s of coal water slurry oxidant;
the hydrothermal carbon slurry oxidant is selected from pure O2
The coal water slurry oxidant is selected from pure O2
The coal water slurry prepared from 1 ton of coal dust is used as a raw material, and the weight ratio of the hydrothermal carbon slurry to the coal water slurry is as follows: the reference of hydrothermal carbon slurry and coal water slurry is 0.2: 1, in the above-mentioned process 2500Nm of synthetic gas can be obtained3(ii) a Carbon dioxide removal 500Nm3However, the hydrothermal carbon slurry of the livestock and poultry waste belongs to a biomass resource and is a carbon neutral substance (the biomass needs to fix CO in the atmosphere through photosynthesis in the growth process2) Actual emission of CO2CO generated by hydrothermal carbon slurry gasification should be deducted2Actual CO removal2420Nm3
Comparative example 1
The entrained-flow gasifier device shown in figure 1 and the multi-channel nozzle shown in figure 2 are adopted, only coal water slurry prepared from 1 ton of coal powder is used as a raw material, the same process conditions as those of the embodiment 1 are adopted, and synthesis gas and dry-based synthesis gas are prepared, wherein the percentage contents of all components are as follows:
in the above process, about 2200Nm of the synthesis gas can be obtained3(ii) a Exhaust of carbon dioxide 440Nm3
Therefore, the annual coal saving amount of the multi-nozzle coal water slurry industrial gasification device for co-burning 1 ten thousand tons of livestock and poultry waste hydrothermal carbon slurry can reach about 0.7 ten thousand tons, the raw material cost is saved by about 420 ten thousand yuan, and the carbon dioxide emission is reduced by about 200 ten thousand Nm3
Example 2
The entrained-flow gasifier device shown in figure 1 and the multi-channel nozzle shown in figure 2 are adopted to prepare the synthesis gas by taking livestock and poultry waste and coal water slurry as raw materials.
(1) Collecting fresh livestock and poultry waste, and naturally airing until the water content is 12%;
(2) performing hydrothermal carbonization on the product obtained in the step (1) for 2 hours at 250 ℃ under the anaerobic condition of 2.5MPa to obtain hydrothermal carbon with the particle size of 50 microns, the water content of 5 percent (by weight) and the low calorific value of about 25 MJ/kg;
(3) adding water into the hydrothermal carbon obtained in the step (2) for pulping to obtain hydrothermal carbon pulp with the carbon matrix weight concentration of 65%;
(4) and (3) respectively feeding the hydrothermal carbon slurry, the coal water slurry with the carbon matrix weight concentration of 65%, the hydrothermal carbon slurry oxidant and the coal water slurry oxidant which are obtained in the step (3) into a gasification furnace through respective flow channels of a multi-channel nozzle, performing gasification reaction under the pressure of 4MPa and the temperature of 1400 ℃, and obtaining synthesis gas with the retention time of the hydrothermal carbon slurry of 8s, wherein the percentage contents of all components in dry-base raw gas are as follows:
the weight ratio of the hydrothermal carbon slurry to the coal water slurry is as follows:
the ratio of the hydrothermal carbon slurry to the coal water slurry is 0.4: 1;
the ratio of the hydrothermal carbon slurry oxidant to the hydrothermal carbon slurry is 0.9: 1;
the ratio of the coal water slurry oxidant to the coal water slurry is 0.9: 1;
at the outlet of the multi-channel nozzle, the linear speed of each material is as follows:
2 m/s of hydrothermal carbon slurry, 2 m/s of coal water slurry, 120 m/s of hydrothermal carbon slurry oxidant and 120 m/s of coal water slurry oxidant;
the hydrothermal carbon slurry oxidant is selected from pure O2
The coal water slurry oxidant is selected from pure O2
The coal water slurry prepared from 1 ton of coal dust is used as a raw material, and the weight ratio of the hydrothermal carbon slurry to the coal water slurry is as follows: the synthesis gas 2800Nm can be obtained in the above process based on the ratio of hydrothermal carbon slurry to coal water slurry of 0.4: 13(ii) a Carbon dioxide removal about 550Nm3(ii) a However, the livestock and poultry waste hydrothermal carbon slurry belongs to biomass resources and is a carbon neutral substance, and CO is actually discharged2CO generated by hydrothermal carbon slurry gasification should be deducted2Actual reduction of CO2380Nm3
Comparative example 2
The entrained-flow gasifier device shown in figure 1 and the multi-channel nozzle shown in figure 2 are adopted, only coal water slurry prepared from 1 ton of coal powder is used as a raw material, the same process conditions as those of the embodiment 2 are adopted, and synthesis gas and dry-base synthesis gas are prepared, wherein the percentage contents of all components are as follows:
CO 45.1%
H236.2%
CH40.10%
CO218.6%
in the above process, about 2300Nm of the synthesis gas can be obtained3(ii) a Carbon dioxide removal 400Nm3
Therefore, the annual coal saving amount of the multi-nozzle coal water slurry industrial gasification device for co-burning 1 ten thousand tons of livestock and poultry waste hydrothermal carbon slurry can reach about 1 ten thousand tons, the raw material cost is saved by about 600 ten thousand yuan, and the carbon dioxide emission is reduced by about 200 ten thousand Nm3
Comparative example 3
The method of example 1 is adopted, wherein the multi-channel nozzle is the technology disclosed in the patent CN100366710C, and the hydrothermal carbon slurry and the coal water slurry are mixed first and then are fed into the gasification furnace through the multi-channel nozzle together.
The obtained synthesis gas comprises the following components in percentage by weight in the dry-basis synthesis gas:
in the above process, the synthesis gas may be obtained in 2200Nm3(ii) a Carbon dioxide removal of 430Nm3
Therefore, the annual coal saving amount of the multi-nozzle coal water slurry industrial gasification device for co-burning 1 ten thousand tons of livestock and poultry waste hydrothermal carbon slurry can reach about 0.6 ten thousand tons, the raw material cost is saved by about 360 ten thousand yuan, and the reduction is realizedAbout 230 ten thousand Nm for carbon dioxide emission3Left and right.
The embodiment and the comparative example show that the invention can carry out resource treatment on the poultry waste from the source to the greatest extent, not only solves the great problem of environmental management, but also saves coal resources, greatly promotes the clean breeding of livestock and poultry, and achieves the resource and clean utilization of the poultry waste.

Claims (10)

1. The method for preparing the synthesis gas by co-gasifying the hydrothermal carbon and the pulverized coal in the livestock and poultry waste is characterized by comprising the following steps of:
(1) drying the livestock and poultry waste in the sun until the mass content of water in the livestock and poultry waste is below 20%;
(2) then carrying out hydrothermal carbonization to obtain hydrothermal carbon;
(3) adding water into the hydrothermal carbon obtained in the step (2) for pulping to obtain hydrothermal carbon pulp with the carbon matrix weight concentration of 60-65%;
(4) and (4) feeding the hydrothermal carbon slurry, the coal water slurry with the carbon matrix weight concentration of 60-65%, the hydrothermal carbon slurry oxidant and the coal water slurry oxidant obtained in the step (3) into a gasification furnace through respective flow channels of a multi-channel nozzle to obtain synthesis gas.
2. The method according to claim 1, wherein in the step (2), hydrothermal carbonization is carried out for 2-3 hours under the oxygen-free condition of 180-250 ℃ and 1.5-3.5 MPa, so as to obtain the hydrothermal carbon with the particle size of 50-75 micrometers and the moisture content of 5-10% by weight.
3. The method according to claim 2, wherein the hydrothermal carbon has a lower calorific value of 18 to 25MJ/Kg, which is equivalent to that of industrial gasification coal.
4. The method according to claim 1, wherein in the step (4), the hydrothermal carbon slurry, the coal water slurry with the carbon matrix weight concentration of 60-65%, the hydrothermal carbon slurry oxidant and the coal water slurry oxidant in the step (3) are respectively fed into a gasification furnace through respective flow channels of a multi-channel nozzle, gasification reaction is carried out under the pressure of 3-4 MPa and the temperature of 1350-1500 ℃, and the retention time of the hydrothermal carbon slurry is 6-8 s.
5. The method according to claim 1, wherein the dry-based synthesis gas comprises the following components in percentage by weight:
6. the method according to claim 4, wherein the dry-based synthesis gas comprises the following components in percentage by weight:
7. the method according to claim 1, wherein the weight ratio of the hydrothermal carbon slurry to the coal water slurry is as follows:
the ratio of the hydrothermal carbon slurry to the coal water slurry is 0.1-0.5: 1;
the ratio of the hydrothermal carbon slurry oxidant to the hydrothermal carbon slurry is 0.85-0.9: 1;
the ratio of the coal water slurry oxidant to the coal water slurry is 0.85-0.9: 1.
8. The method of claim 7, wherein at the outlet of the multi-channel nozzle, the linear velocity of each material is: 1.5-2 m/s of hydrothermal carbon slurry, 1.5-2 m/s of coal water slurry, 100-120 m/s of hydrothermal carbon slurry oxidant and 100-120 m/s of coal water slurry oxidant;
the hydrothermal carbon slurry oxidant is selected from pure O2
The coal water slurry oxidant is selected from pure O2
9. The method according to any one of claims 1 to 8, wherein the entrained-flow gasifier with the multi-channel nozzle comprises a multi-channel nozzle and an entrained-flow gasifier, the multi-channel nozzle is arranged at the upper part of the entrained-flow gasifier, and the outlet of the multi-channel nozzle is communicated with the inner cavity of the entrained-flow gasifier.
10. The method of claim 9, wherein the multi-channel nozzle comprises, in order from the center to the outside: the coal water slurry oxidation device comprises a coal water slurry passage pipe (102), a coal water slurry oxidant passage pipe (103) sleeved outside the coal water slurry passage pipe (102), a hydrothermal carbon slurry passage pipe (104) sleeved outside the coal slurry oxidant passage pipe (103), a hydrothermal carbon slurry oxidant passage pipe (105) sleeved outside the hydrothermal carbon slurry passage pipe (104) and an outlet (101).
CN202010541870.5A 2020-06-15 2020-06-15 Method for preparing synthesis gas by co-gasification of hydrothermal carbon and pulverized coal in livestock and poultry waste Pending CN111718761A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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JP2015017197A (en) * 2013-07-11 2015-01-29 日曹エンジニアリング株式会社 Method for gasifying organic waste
CN108728168A (en) * 2017-04-14 2018-11-02 航天长征化学工程股份有限公司 A kind of gasification burner tip
CN108726833A (en) * 2018-06-04 2018-11-02 中国科学院生态环境研究中心 A kind of municipal sludge situ catalytic vaporizing system for high-purity hydrogen new process
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