CN112143525A - Method for producing hydrogen by converting municipal solid waste - Google Patents
Method for producing hydrogen by converting municipal solid waste Download PDFInfo
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- CN112143525A CN112143525A CN201910578510.XA CN201910578510A CN112143525A CN 112143525 A CN112143525 A CN 112143525A CN 201910578510 A CN201910578510 A CN 201910578510A CN 112143525 A CN112143525 A CN 112143525A
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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
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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
- C10J3/58—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels combined with pre-distillation of the fuel
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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
- 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
- C10J2300/0946—Waste, e.g. MSW, tires, glass, tar sand, peat, paper, lignite, oil shale
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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
- 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
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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
- C10J2300/00—Details of gasification processes
- C10J2300/16—Integration of gasification processes with another plant or parts within the plant
- C10J2300/164—Integration of gasification processes with another plant or parts within the plant with conversion of synthesis gas
- C10J2300/1643—Conversion of synthesis gas to energy
- C10J2300/1653—Conversion of synthesis gas to energy integrated in a gasification combined cycle [IGCC]
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E20/00—Combustion technologies with mitigation potential
- Y02E20/16—Combined cycle power plant [CCPP], or combined cycle gas turbine [CCGT]
- Y02E20/18—Integrated gasification combined cycle [IGCC], e.g. combined with carbon capture and storage [CCS]
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Abstract
The invention relates to the field of municipal solid waste treatment, and discloses a method for producing hydrogen by converting municipal solid waste. The method comprises the following steps: (1) after non-combustible substances are removed from the municipal domestic waste by screening, draining water to obtain waste liquid and a waste raw material; (2) feeding the garbage raw material into a pyrolysis reactor for drying and pyrolysis reaction to obtain garbage semicoke and pyrolysis gas; (3) mixing the garbage semicoke and the garbage waste liquid with the coal powder and the dispersing agent to prepare the coal water slurry; (4) feeding the coal water slurry and the pyrolysis gas into a gasification furnace for gasification reaction to obtain crude synthesis gas and ash; (5) and indirectly exchanging heat between part of the crude synthesis gas and the pyrolysis reactor to provide heat, mixing the heat with the rest of the crude synthesis gas, and sequentially carrying out purification and shift reaction. The method provided by the invention can reduce the difference of different municipal wastes, solve the problem of secondary pollution caused by waste incineration, realize harmless and full resource treatment of municipal domestic wastes, and simultaneously realize large-scale rapid low-cost hydrogen preparation.
Description
Technical Field
The invention relates to the field of municipal solid waste treatment, in particular to a method for producing hydrogen by converting municipal solid waste.
Background
The hydrogen energy is used as green and efficient energy and becomes a key aspect in future energy development in China. The hydrogen consumption market is huge, 31 hydrogenation stations are built in China and under construction by 2018 and 2 months, and by 2030, application of millions of fuel cell vehicles is realized nationwide to build 1000 hydrogenation stations, so that the hydrogen demand of China in the future is huge.
The existing hydrogen production technology comprises a fossil fuel hydrogen production technology, a water electrolysis hydrogen production technology, a biological hydrogen production technology and a solar hydrogen production technology. The technology of the hydrogen production technology by the fossil fuel is mature, but the fossil fuel belongs to non-renewable resources and has high energy consumption; the water electrolysis hydrogen production technology has simple process, high product hydrogen purity, low efficiency and high production cost.
China is the world with the highest garbage load at present, the total emission amount of municipal garbage reaches 2.5 hundred million tons in 2015, and about 2/3 cities in China face the pressure of 'garbage enclosing city'. The total quantity of domestic garbage in China is estimated to reach 3.23 hundred million tons in 2020. The existing municipal refuse treatment modes have certain defects, such as large occupied area of a landfill method and difficult control of secondary pollution; the incineration method has the advantages of small occupied area, good volume reduction and decrement effects, wide application range, huge treatment capacity, relatively low cost, high treatment efficiency, capability of recovering heat energy for heating or power generation and the like, but the waste incineration is easy to generate secondary pollution, and particularly dioxin, incineration fly ash, heavy metals and compound components thereof have great harm to human bodies; the biochemical treatment method occupies a large area, and harmful substances in the fertilizer easily exceed the standard.
The gasification of domestic garbage refers to the process of heating organic matters in the garbage under the condition of oxygen deficiency, and carrying out thermochemical reaction on organic components and a gasifying agent to generate small molecular substances (gaseous state) and solid ash. The synthesis gas generated by gasifying the garbage can be used for generating power or preparing chemical products such as natural gas and the like, so that the abundant energy contained in the garbage can be effectively recycled while the garbage is reduced, and the synthesis gas is considered to be an important means for recycling the solid waste garbage at present.
CN105001915B describes a method for converting waste organic matters into clean fuel gas, which comprises sorting, crushing and homogenizing waste organic matters such as domestic garbage, etc., then spraying the sorted, crushed and homogenized waste organic matters, coal powder (or coal water slurry), oxygen and water into a decomposing furnace through a multifunctional nozzle to complete the decomposition processes such as combustion, heat release, gasification, etc., and generating a large amount of combustible gas, wherein the combustible gas is conveyed to a fuel gas purification system and then conveyed to a fuel gas storage system, and the gas storage system provides fuel gas supply for downstream civil or industrial use, and also can provide raw material gas for methanol production. However, this method also has the following drawbacks: 1) the municipal waste in China has the characteristics of high kitchen waste content, high water content, low heat value and large variation wave of production amount and composition, so that the municipal waste in China has low thermal efficiency during combustion and gasification; 2) the composition of the urban garbage is complex, and the garbage is difficult to directly crush or the energy consumption is high; 3) the urban garbage particles easily cause the blockage of the multifunctional nozzle.
CN106244239A provides a process for producing synthetic natural gas by gasifying garbage. The method comprises the steps of feeding raw material garbage into a gasification furnace through a feeding system for high-temperature gasification to obtain crude synthesis gas and high-temperature molten slag, feeding the crude synthesis gas into a gasification purification system for purification after dust removal and washing, and obtaining refined synthesis gas after CO conversion and acid gas removal, wherein the refined synthesis gas passes through a methanation section and a natural gas purification section to obtain qualified natural gas. The method directly gasifies the garbage, the process application is limited due to different garbage properties, the direct gasification temperature is lower, the gasification efficiency is poor, the tar yield is high, and the operation stability of the gasification process is poor.
CN106479534A describesA method and a system for preparing hydrogen fuel by garbage pyrolysis plasma gasification. The method comprises the following steps: feeding the garbage into a heat accumulating type rotating bed for drying and pyrolyzing to obtain pyrolysis water, a pyrolysis oil-gas mixture and pyrolysis carbon; introducing the pyrolysis oil-gas mixture into a plasma gasification reaction chamber to obtain synthesis gas; introducing the synthesis gas into a purification device for purification treatment to obtain pure CO and H2Synthesis gas; introducing the pure synthesis gas into a pressure swing adsorption device to prepare H2And (3) fuel. The method for gasifying the garbage by the plasma gasification technology has higher requirements on devices and higher operation cost, only utilizes partial products of garbage pyrolysis, and other pyrolysis products are not recycled, thereby causing waste.
The municipal solid waste in China has the characteristics of high kitchen waste content, high water content, low heat value and large variation wave of production amount and composition, and the heat value is 4000-6000kJ/kg, so that the municipal solid waste is limited to be directly gasified, the single gasification temperature is low, the gasification efficiency is poor, the tar yield is high, and the operation stability of the gasification process is poor. Therefore, it is necessary to select a proper garbage pretreatment and gasification technology according to the characteristics of domestic garbage in China.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to a method for producing hydrogen by converting municipal solid waste. The method provided by the invention can reduce the difference of different municipal wastes, improve the gasification efficiency, realize harmless and sufficient resource treatment of the municipal domestic wastes, and simultaneously realize large-scale rapid low-cost hydrogen preparation.
In order to achieve the above object, the present invention provides a method for producing hydrogen by converting municipal solid waste, comprising:
(1) after non-combustible substances are removed from the municipal domestic waste by screening, draining the water in the municipal domestic waste to respectively obtain waste liquid and a waste raw material;
(2) feeding the garbage raw material into a pyrolysis reactor, and performing drying and pyrolysis reaction under the indirect heating of the pyrolysis reactor to obtain garbage semicoke and pyrolysis gas; the final pyrolysis temperature in the pyrolysis reactor is 350-650 ℃, and the retention time of the garbage raw materials is 10-120 min;
(3) mixing and grinding the garbage semicoke and the garbage waste liquid with coal powder and a dispersing agent to prepare coal water slurry;
(4) feeding the coal water slurry and the pyrolysis gas into a gasification furnace, so that the coal water slurry is subjected to gasification reaction in the presence of a gasification agent, and the pyrolysis gas is further cracked to obtain crude synthesis gas and ash;
(5) indirectly exchanging heat between part of the crude synthesis gas and the pyrolysis reactor to be used as a heat source for drying and pyrolyzing the garbage raw material; then mixing with the rest part of the crude synthesis gas, sequentially purifying and converting to convert CO in the gas into H2。
The scheme provided by the invention effectively couples the pyrolysis technology and the coal water slurry gasification technology to be applied to the hydrogen production process by treating and converting municipal domestic garbage, utilizes the waste liquid in the garbage to prepare the slurry (as the coal water slurry gasification raw material), reasonably utilizes the garbage waste liquid, and reduces the pollution of the waste liquid to the environment and the waste liquid treatment cost. Garbage pyrolysis and coal water slurry gasification are both carried out in an oxygen-deficient atmosphere, so that generation of dioxin is avoided, and pollution of the dioxin to the environment is reduced. In addition, in the high-temperature gasification process, toxic and harmful substances such as heavy metals in the garbage are fixed in the glassy state slag with stable properties, so that the risk of secondary pollution to the environment is avoided. The method of the invention simultaneously realizes the treatment of the solid waste and the liquid waste of the garbage, and develops a new idea of reducing, harmless treatment and resource utilization of the municipal garbage.
Specifically, the method for producing hydrogen by converting municipal solid waste provided by the invention has the advantages that:
1) the method of the invention not only can solve the problem of municipal waste treatment, change the domestic waste into valuable, realize the harmless and resource treatment of the municipal waste, but also can produce hydrogen, compared with other existing hydrogen production technologies, the method can provide hydrogen for the hydrogen consumption market rapidly and conveniently, and avoid the high cost caused by the long-distance transportation of hydrogen production raw materials and hydrogen;
2) the method of the invention firstly adopts the pyrolysis reaction to pre-treat the municipal refuse, thus improving the heat value of the municipal refuse, reducing the difference of different municipal refuse, improving the grindability of the refuse, reducing the grinding energy consumption in the refuse crushing project, enhancing the combustion characteristic of the refuse and improving the gasification efficiency;
3) according to the method, before the gasification of the municipal domestic garbage, the municipal solid garbage is pyrolyzed and converted to obtain garbage semicoke, the garbage semicoke and garbage wastewater are mixed with coal to prepare coal water slurry, so that the coal water slurry becomes a high-energy-density and stable gasification raw material for hydrogen production, and the influence of the garbage amount and composition fluctuation on the gasification process can be reduced by adjusting the addition amount of the coal, so that the progress of the co-gasification process and the composition of a gas product are influenced; thus, the gasification temperature can be increased, the carbon conversion rate is promoted, the defects of low heat value and large composition change fluctuation of the municipal refuse are overcome, and the stability of the gasification process is improved;
4) the invention can fully utilize water resources in the garbage; along with the gasification process, harmful substances, pathogenic microorganisms and viruses in the waste water can be subjected to harmless treatment, so that the reduction and resource utilization of the waste water are achieved;
5) because the garbage pyrolysis and gasification processes are both in an oxygen-deficient reducing atmosphere (namely the pyrolysis and gasification are carried out under the oxygen-deficient condition to generate the gas containing CH4、CO、H2Reducing gas) is eliminated, condition factors for generating dioxin are eliminated, the production of dioxin is avoided, and the environment is prevented from being polluted;
6) in the high-temperature gasification process, the fly ash or the gasification furnace slag is melted into vitreous ash slag which can be used as a raw material for preparing building materials, and heavy metals can be stabilized in a crystal phase and cannot be leached out, so that the risk of secondary pollution of the heavy metals to the environment is avoided.
Drawings
FIG. 1 is a schematic flow chart of a method for producing hydrogen by converting municipal solid waste according to an embodiment of the present invention.
Description of the reference numerals
1: storing the urban garbage in a warehouse; 2: a pyrolysis reactor; 3: a mixing pulping device; 4: a gasification furnace;
5: a dust removal device; 6: a gas purification device; 7: a shift reaction device; 8: a gas drying device;
9: a hydrogen separation device.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a method for producing hydrogen by converting municipal solid waste, which comprises the following steps:
(1) after non-combustible substances are removed from the municipal domestic waste by screening, draining the water in the municipal domestic waste to respectively obtain waste liquid and a waste raw material;
(2) feeding the garbage raw material into a pyrolysis reactor, and performing drying and pyrolysis reaction under the indirect heating of the pyrolysis reactor to obtain garbage semicoke and pyrolysis gas; the final pyrolysis temperature in the pyrolysis reactor is 350-650 ℃, and the retention time of the garbage raw materials is 20-120 min;
(3) mixing and grinding the garbage semicoke and the garbage waste liquid with coal powder and a dispersing agent to prepare coal water slurry;
(4) feeding the coal water slurry and the pyrolysis gas into a gasification furnace, so that the coal water slurry is subjected to gasification reaction in the presence of a gasification agent, and the pyrolysis gas is further cracked to obtain crude synthesis gas and ash;
(5) indirectly exchanging heat between part of the crude synthesis gas and the pyrolysis reactor to be used as a heat source for drying and pyrolyzing the garbage raw material; then mixing with the rest part of the crude synthesis gas, sequentially purifying and converting to convert CO in the gas into H2。
The method of the present invention is suitable for treating any municipal solid waste, and thus the municipal solid waste is not particularly limited. Generally, the main components of the municipal solid waste include non-combustibles such as glass, metal, stone and the like, and combustibles such as kitchen waste, plastics, textiles, paper and wood and bamboo, and the total moisture content of the municipal solid waste is generally 30 to 65 wt%.
According to the method of the invention, in the step (1), the screening is performed for removing glass, metal, stone and other incombustibles from the garbage and crushing the garbage. The screening typically includes sorting and crushing processes, and the specific operations are well known in the art and will not be described further herein.
In the step (1), the household garbage after being screened can be fermented for several days in a garbage storage pool (i.e. an urban garbage storage), and then the moisture in the household garbage is drained, so that garbage waste liquid and garbage raw materials are respectively obtained. The water content of the waste material may be determined by the water content of the municipal solid waste being processed. Preferably, the water content in the garbage raw material is reduced by 20-60% compared with the water content of the municipal solid waste.
According to the method, in the step (2), the garbage raw materials are dried and pyrolyzed in the pyrolysis reactor in sequence to obtain the garbage semicoke and pyrolysis gas. And (3) the heat required by the drying and pyrolysis reaction is provided by indirect heat exchange between part of the raw synthesis gas prepared in the step (4) and the pyrolysis reactor. The main components of the pyrolysis gas comprise CO and CO2、CH4、C2H4And the like.
Preferably, the final pyrolysis reaction temperature in the pyrolysis reactor is 450-.
According to the method, in the step (3), the mixing and grinding can be carried out by referring to the existing gasified coal water slurry preparation technology, and the invention has no special requirement for the method. Generally, based on the total weight of the prepared coal water slurry, the amount of the garbage semicoke is 30-50 wt%, the amount of the garbage waste liquid is 35-44 wt%, the amount of the coal dust is 10-30 wt%, and the amount of the dispersing agent is 0.8-1.5 wt%.
It should be noted that, under the condition that the final pyrolysis reaction temperature in the pyrolysis reactor is 450-600 ℃, the utilization rate of the prepared garbage semicoke for preparing the coal water slurry is higher, and specifically, the coal water slurry can introduce more garbage semicoke and reduce the addition amount of coal powder while meeting the requirement of higher gasification efficiency.
In a preferred embodiment, the amount of the garbage semicoke is 35-45 wt%, the amount of the garbage waste liquid is 35-44 wt%, the amount of the coal dust is 15-25 wt%, and the amount of the dispersant is 1-1.5 wt%, based on the total weight of the prepared coal-water slurry.
According to the method of the present invention, preferably, the dispersant is selected from at least one of naphthalene-based dispersants, sodium methylenedinaphthalene sulfonate, sodium lignin sulfonate and a methyl naphthalene sulfonate formaldehyde condensate. The dispersants are all commercially available.
According to the method of the present invention, in the step (4), the gasifying agent may be selected with reference to the prior art, and may be selected from at least one of oxygen, air and oxygen-enriched air, for example, and is preferably oxygen. The oxygen content in the oxygen-enriched air is preferably greater than 35% by volume.
In a preferred manner, the conditions of the gasification reaction include: oxygen-to-carbon ratio (O/C) of 0.8-1.05m3The gasification pressure is 3-6MPa, under the condition, the gasification temperature in the gasification furnace can reach the higher gasification reaction temperature of the existing coal water slurry (the coal water slurry prepared by water, coal powder and additives), thereby not only improving the gasification efficiency of the coal water slurry, but also ensuring that the pyrolysis gas is cracked into CO and H2Thereby increasing the hydrogen yield. Specifically, the temperature of the gasification reaction is 1300-1600 ℃, and more preferably 1400-1600 ℃.
The raw synthesis gas obtained in the step (4) contains CO and H2O、CO2、CH4、H2S and H2O and the like. The temperature of the raw synthesis gas is typically 1000 ℃ to 1200 ℃, and the raw synthesis gas can be extracted from the pyrolysis reactorThe heat required for drying and pyrolyzing the garbage raw material is supplied.
Therefore, according to the method of the present invention, in the step (5), the raw synthesis gas is divided into two streams, one stream is sent to the pyrolysis reactor as a heat source for the drying and pyrolysis reaction, and then is purified together with the other stream to perform a shift reaction. The ratio of the amount of raw synthesis gas returned to the pyrolysis reactor for indirect heat exchange to the remaining portion of raw synthesis gas may be 1: 0.5 to 3, preferably 1: 1-2.5.
In step (5), the purpose of said purification is to remove dust and acid gases of the raw synthesis gas.
According to a preferred embodiment, the purification treatment comprises:
s1: dedusting the crude synthesis gas to obtain dedusted gas, dust and fly ash;
s2: purifying and deacidifying the dedusted gas to obtain synthesis gas;
s3: and returning the dust and the fly ash to the gasification furnace for high-temperature slag treatment.
In the step (5), the shift reaction is not particularly limited, and the shift reaction can be performed by referring to the coal water slurry gasification hydrogen production technology, and the specific operation is well known in the art and is not described herein again.
According to the method of the present invention, in order to separate the product hydrogen gas with high purity, it is preferable that the method further comprises: (6) and (5) drying and separating the product obtained in the step (5) to obtain hydrogen and purge gas, and returning the purge gas to the gasification furnace for gasification reaction.
The present invention is not particularly limited to the above separation method, and can be carried out by referring to the prior art. For example, pressure swing adsorption, temperature swing adsorption or membrane separation can be selected to obtain a high purity hydrogen product gas.
According to the method of the invention, the method for producing hydrogen by converting municipal solid waste can be carried out by adopting a system for producing hydrogen by converting municipal solid waste, which comprises the following steps:
the system comprises an urban garbage storage bin, a pyrolysis reactor, a mixed pulping device, a gasification furnace, a purification unit and a shift reaction device; wherein the content of the first and second substances,
in the municipal refuse storage bin, the refuse after non-combustible materials are removed by screening is leached out of water, and refuse waste liquid and refuse raw materials are respectively obtained;
in the pyrolysis reactor, the garbage raw materials from the municipal garbage storage bin are dried and pyrolyzed under the heat provided by part of the crude synthesis gas from the gasification furnace to obtain garbage semicoke and pyrolysis gas;
in the mixing and pulping device, waste liquid from the municipal waste storage bin, waste semicoke from the pyrolysis reactor, coal powder and a dispersing agent are mixed to prepare coal water slurry;
in the gasification furnace, coal water slurry from the mixed pulping device is subjected to gasification reaction in the presence of a gasification agent, pyrolysis gas from the pyrolysis reactor is further cracked to obtain crude synthesis gas and ash, and part of the crude synthesis gas returns to the pyrolysis reactor to perform indirect heat exchange with the pyrolysis reactor to be used as a heat source for drying and pyrolysis reaction of the garbage raw material;
mixing the part of the crude synthesis gas after indirect heat exchange with the rest part of the crude synthesis gas, and respectively performing purification and shift reaction sequentially by the purification unit and the shift reaction device to convert CO in the gas into H2。
Preferably, the purification unit comprises a dust removal device and a gas purification device; in the dust removal device, the crude synthesis gas is subjected to dust removal treatment to obtain dust-removed gas, dust and fly ash, and the dust and the fly ash are returned to the gasification furnace; in the gas purification device, the dedusted gas from the dedusting device is purified and deacidified to obtain the synthesis gas.
Preferably, the system further comprises: a gas drying device and a hydrogen separation device; in the gas drying device, drying the product from the shift reaction device to obtain dried gas; in the hydrogen separation device, the dried gas from the gas drying device is separated to obtain a hydrogen product and purge gas, and the purge gas returns to the gasification furnace.
The mixing and pulping device is not particularly limited, as long as the components in the raw materials can be mixed and ground to obtain the coal water slurry capable of running in the gasification furnace.
According to a preferred embodiment, the method for producing hydrogen by converting municipal solid waste specifically comprises the following steps:
(1) after the municipal solid waste is screened to remove incombustibles such as glass, metal, stone and the like, the municipal solid waste is placed in a municipal waste storage bin 1 for 3 to 7 days, and the water in the municipal solid waste is drained, namely, the waste liquid of the municipal solid waste is separated out, and a waste raw material is obtained;
(2) feeding the garbage raw material into a pyrolysis reactor 2, and carrying out drying and pyrolysis reaction under the indirect heating of part of the crude synthesis gas from a gasification furnace 4 to obtain garbage semicoke and pyrolysis gas;
(3) grinding and stirring the garbage semicoke, the garbage waste liquid, the coal powder and the dispersant in a mixing and pulping device 3 to prepare coal water slurry;
(4) feeding the coal water slurry into a gasification furnace 4, carrying out gasification reaction in the presence of a gasification agent, and simultaneously feeding pyrolysis gas from a pyrolysis reactor 2 into the gasification furnace 4 for further pyrolysis to obtain crude synthesis gas;
(5-1) dividing the raw synthesis gas into two parts, returning one part of the raw synthesis gas to the pyrolysis reactor 2 to indirectly heat the garbage raw material, combining the two parts of the raw synthesis gas with the other part of the raw synthesis gas, and entering a dust removal device 5 for dust removal treatment to obtain a dust-removed gas, dust and fly ash;
(5-2) introducing the dedusted gas into a gas purification device 6 for purification and deacidification, and introducing the obtained synthesis gas into a shift reaction device 7 for shift reaction;
(5-3) returning the dust and the fly ash to the gasification furnace 4 for high-temperature molten slag treatment;
(6) and (5) drying the product obtained in the step (5-2) by a gas drying device 8, and then separating the product in a hydrogen separation device 9 to obtain the product hydrogen and purge gas, wherein the purge gas returns to the gasification furnace 4 for gasification reaction.
The present invention will be described in detail below by way of examples.
In the examples and the comparative examples,
measurement of carbon content in slag-volumetric method of combustion gas (CSM 08000601-2005).
The following examples will all illustrate the method for producing hydrogen by converting municipal solid waste according to the present invention with reference to FIG. 1. The specific operations of the schemes are as described above unless otherwise indicated.
The total water content of the second quarter domestic waste in a certain region of a city treated in the following examples 1-3 was 55% by weight, and the physical composition is shown in table 1:
TABLE 1
| Species of | Kitchen waste | Paper products | Plastic material | Fabric | Lime soil | Metal | Glass |
| Content/weight% | 61.39 | 17.40 | 18.84 | 0.36 | 0.9 | 0.07 | 1.04 |
Example 1
(1) Sorting and crushing municipal solid waste, removing glass, metal and other incombustibles, placing the municipal solid waste in a municipal waste storage bin 1 for 4 days, draining water in the municipal solid waste to reduce the total water content of the municipal solid waste to 43 weight percent, and taking the drained waste liquid of the municipal solid waste as water for subsequent pulping;
(2) the garbage raw materials enter a pyrolysis reactor 2, are dried under the indirect heating of the crude synthesis gas from a gasification furnace 4 and are subjected to pyrolysis reaction to obtain garbage semicoke and pyrolysis gas, the final pyrolysis temperature in the reactor is 450 ℃, and the retention time of the garbage raw materials is 40 minutes;
(3) grinding and stirring the garbage semicoke, the garbage waste liquid, the coal powder and the sodium methylene dinaphthalene sulfonate according to the mass percentage of 40%, 38.5%, 20% and 1.5% to prepare coal water slurry;
(4) the coal water slurry and the pyrolysis gas enter a gasification furnace 4, gasification reaction and cracking reaction are carried out under the action of oxygen to obtain crude synthesis gas, and the oxygen-carbon ratio is controlled to be 0.92m3Kg, gasification pressure is 4 MPa;
(5) after the raw synthesis gas is purified, CO in the raw synthesis gas is converted into H through a shift reaction2And drying and pressure swing adsorption are carried out on the transformation product to obtain the product hydrogen.
In the whole process, the ratio of the usage amount of the raw synthesis gas which enters the pyrolysis reactor 2 as a heat source to the usage amount of the raw synthesis gas which is directly subjected to the purification treatment is 1: 2.
the gasification reaction temperature in the gasification furnace 4 is up to 1490 ℃, the carbon content in the slag is 3%, and the carbon conversion rate is 99.2%, which shows that the coal water slurry prepared by the method in the embodiment 1 achieves the gasification effect equivalent to that of the existing coal water slurry.
Example 2
(1) Treating municipal solid waste according to the method of example 1 to obtain a waste material and waste effluent;
(2) the garbage raw materials enter a pyrolysis reactor 2, are dried under the indirect heating of the crude synthesis gas from a gasification furnace 4 and are subjected to pyrolysis reaction to obtain garbage semicoke and pyrolysis gas, the final pyrolysis temperature in the reactor is 550 ℃, and the retention time of the garbage raw materials is 60 minutes;
(3) grinding and stirring the garbage semicoke, the garbage waste liquid, the coal powder and the sodium methylene dinaphthalene sulfonate according to the mass percentage of 44%, 39.5%, 15% and 1.5% to prepare coal water slurry;
(4) the coal water slurry and the pyrolysis gas enter a gasification furnace 4, gasification reaction and cracking reaction are carried out under the action of oxygen to obtain crude synthesis gas, and the oxygen-carbon ratio is controlled to be 0.95m3Kg, gasification pressure is 5 MPa;
(5) after the raw synthesis gas is purified, CO in the raw synthesis gas is converted into H through a shift reaction2And drying and pressure swing adsorption are carried out on the transformation product to obtain the product hydrogen.
In the whole process, the ratio of the usage amount of the raw synthesis gas which enters the pyrolysis reactor 2 as a heat source to the usage amount of the raw synthesis gas which is directly subjected to the purification treatment is 1: 1.8.
the gasification reaction temperature in the gasification furnace 4 is up to 1540 ℃, the carbon content in the slag is 2%, and the carbon conversion rate is 99.7%, which shows that the coal water slurry prepared by the method in the embodiment 2 achieves the gasification effect equivalent to that of the existing coal water slurry.
Example 3
Municipal solid waste was treated in the same manner as in example 1, except that the final pyrolysis temperature in the pyrolysis reactor 2 was controlled to 350 ℃ and the retention time of the waste material was controlled to 40 minutes;
in the whole process, the ratio of the usage amount of the raw synthesis gas which enters the pyrolysis reactor 2 as a heat source to the usage amount of the raw synthesis gas which is directly subjected to the purification treatment is 1: 2.2.
the gasification reaction temperature in the gasification furnace 4 reaches up to 1320 ℃, the carbon content in the slag is 5%, and the carbon conversion rate is 97.1%, which shows that the coal water slurry prepared by the method in the embodiment 3 achieves the gasification effect equivalent to that of the existing coal water slurry.
In addition, the vaporization efficiency of example 3 was lower than that of example 1. In order to achieve the same gasification temperature as in example 1, the amounts of the pyrolysis semicoke and the pulverized coal were adjusted to 34% and 26%, respectively.
Comparative example 1
Municipal solid waste was treated in the same manner as in example 1, except that the final pyrolysis temperature in the pyrolysis reactor 2 was controlled to 300 ℃ and the retention time of the waste material was controlled to 50 minutes;
in the whole process, the ratio of the usage amount of the raw synthesis gas which enters the pyrolysis reactor 2 as a heat source to the usage amount of the raw synthesis gas which is directly subjected to the purification treatment is 1: 3.
the gasification reaction temperature in the gasification furnace 4 reaches 1100 ℃ at most, the carbon content in the slag is 12%, and the carbon conversion rate is 86%.
Compared with example 1, the coal water slurry prepared by the comparative example has very low gasification efficiency, which can result in H after the shift of the raw synthesis gas2The content is low, the application value of the coal water slurry gasification hydrogen production is low, and the hydrogen production cost is high.
The following examples 4-6 treated domestic waste in the first quarter of a city in a certain region had a total moisture content of 42 wt%, and the physical composition is shown in table 2:
TABLE 2
Example 4
(1) Sorting and crushing municipal solid waste, removing incombustibles such as glass, metal, stone and the like, placing the municipal solid waste in a municipal waste storage bin 1 for 7 days, draining water in the municipal solid waste to reduce the total water content of the municipal solid waste to 40 wt%, and taking the drained waste liquid of the municipal solid waste as water for subsequent pulping;
(2) the garbage raw materials enter a pyrolysis reactor 2, are dried under the indirect heating of the crude synthesis gas from a gasification furnace 4 and are subjected to pyrolysis reaction to obtain garbage semicoke and pyrolysis gas, the final pyrolysis temperature is 600 ℃, and the retention time of the garbage raw materials is 60 minutes;
(3) grinding and stirring the garbage semicoke, the garbage waste liquid, the coal powder and the sodium lignosulfonate according to the mass percentage of 43%, 38%, 18% and 1% to prepare coal water slurry;
(4) the coal water slurry and the pyrolysis gas enter a gasification furnace 4, gasification reaction and cracking reaction are carried out under the action of oxygen to obtain crude synthesis gas, and the oxygen-carbon ratio is controlled to be 1.02m3Kg, gasification pressure 6 MPa.
(5) After the raw synthesis gas is purified, CO in the raw synthesis gas is converted into H through a shift reaction2And drying and pressure swing adsorption are carried out on the transformation product to obtain the product hydrogen.
In the whole process, the ratio of the usage amount of the raw synthesis gas which enters the pyrolysis reactor 2 as a heat source to the usage amount of the raw synthesis gas which is directly subjected to the purification treatment is 1: 1.8.
the gasification reaction temperature in the gasification furnace 4 is up to 1560 ℃, the carbon content in the slag is 2%, and the carbon conversion rate is 99.4%, which shows that the coal water slurry prepared by the method of the embodiment 4 achieves the gasification effect equivalent to that of the existing coal water slurry.
Example 5
(1) Treating municipal solid waste according to the method of example 4 to obtain a waste material and waste effluent;
(2) the garbage raw materials enter a pyrolysis reactor 2, are dried under the indirect heating of the crude synthesis gas from a gasification furnace 4 and are subjected to pyrolysis reaction to obtain garbage semicoke and pyrolysis gas, the final pyrolysis temperature is 480 ℃, and the retention time of the garbage raw materials is 50 minutes;
(3) grinding and stirring the garbage semicoke, the garbage waste liquid, the coal powder and the sodium lignosulfonate according to the mass percentage of 45%, 38%, 16% and 1% to prepare coal water slurry;
(4) the coal water slurry and the pyrolysis gas enter a gasification furnace 4, gasification reaction and cracking reaction are carried out under the action of oxygen to obtain crude synthesis gas, and the oxygen-carbon ratio is controlled to be 0.97m3Kg, gasification pressure 4 MPa.
(5) After the raw synthesis gas is purified, CO in the raw synthesis gas is shifted through shift reactionTo H2And drying and pressure swing adsorption are carried out on the transformation product to obtain the product hydrogen.
In the whole process, the ratio of the usage amount of the raw synthesis gas which enters the pyrolysis reactor 2 as a heat source to the usage amount of the raw synthesis gas which is directly subjected to the purification treatment is 1: 1.2.
the gasification reaction temperature in the gasification furnace 4 is up to 1470 ℃, the carbon content in the slag is 3%, and the carbon conversion rate is 99.1%, which shows that the coal water slurry prepared by the method in the embodiment 5 achieves the gasification effect equivalent to that of the existing coal water slurry.
Example 6
Municipal solid waste was treated in accordance with the method of example 4, except that the final pyrolysis temperature in the pyrolysis reactor 2 was controlled to 650 ℃ and the retention time of the waste material was controlled to 40 minutes;
in the whole process, the ratio of the usage amount of the raw synthesis gas which enters the pyrolysis reactor 2 as a heat source to the usage amount of the raw synthesis gas which is directly subjected to the purification treatment is 1: 0.9.
the gasification reaction temperature in the gasification furnace 4 is up to 1360 ℃, the carbon content in the slag is 4.6%, and the carbon conversion rate is 97.8%, which shows that the coal water slurry prepared by the method of the embodiment 6 achieves the gasification effect equivalent to that of the existing coal water slurry.
Compared with example 4, example 6 has higher pyrolysis temperature, higher energy consumption, more high-temperature raw synthesis gas is needed, but the gasification efficiency is lower.
Comparative example 2
Municipal solid waste was treated in the same manner as in example 4, except that the final pyrolysis temperature in the pyrolysis reactor 2 was controlled to 800 ℃ and the retention time of the waste material was controlled to 40 minutes;
in the whole process, the ratio of the usage amount of the raw synthesis gas which enters the pyrolysis reactor 2 as a heat source to the usage amount of the raw synthesis gas which is directly subjected to the purification treatment is 1: 0.8.
the gasification reaction temperature in the gasification furnace 4 reaches 1040 ℃ at most, the carbon content in the slag is 14%, and the carbon conversion rate is 82%.
As compared with example 4, the comparative example shows higher pyrolysis temperature and higher energy consumption, butThe gasification efficiency of coal water slurry is very low, which can result in H after conversion of raw synthesis gas2The content is low, the application value of the coal water slurry gasification hydrogen production is low, and the hydrogen production cost is high.
The embodiment and the comparative example show that the method for producing hydrogen by converting municipal solid waste can treat different municipal solid waste, and the water-coal-slurry is prepared by using the waste liquid and the pyrolysis product of the waste raw material under the specific pyrolysis condition, so that the treatment of liquid waste and solid waste in the waste can be realized, and the prepared water-coal-slurry can obtain higher gasification efficiency.
In addition, the slurry forming property of the garbage raw material is poor, the coal water slurry cannot be prepared, and if the garbage raw material is directly gasified with the coal powder, the coal powder dosage needs to be greatly increased to reach the gasification reaction temperature of the embodiment.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A method for producing hydrogen by converting municipal solid waste, which comprises the following steps:
(1) after non-combustible substances are removed from the municipal domestic waste by screening, draining the water in the municipal domestic waste to respectively obtain waste liquid and a waste raw material;
(2) feeding the garbage raw material into a pyrolysis reactor, and performing drying and pyrolysis reaction under the indirect heating of the pyrolysis reactor to obtain garbage semicoke and pyrolysis gas; the final pyrolysis temperature in the pyrolysis reactor is 350-650 ℃, and the retention time of the garbage raw materials is 20-120 min;
(3) mixing and grinding the garbage semicoke and the garbage waste liquid with coal powder and a dispersing agent to prepare coal water slurry;
(4) feeding the coal water slurry and the pyrolysis gas into a gasification furnace, so that the coal water slurry is subjected to gasification reaction in the presence of a gasification agent, and the pyrolysis gas is further cracked to obtain crude synthesis gas and ash;
(5) indirectly exchanging heat between part of the crude synthesis gas and the pyrolysis reactor to be used as a heat source for drying and pyrolyzing the garbage raw material; then mixing with the rest part of the crude synthesis gas, sequentially purifying and converting to convert CO in the gas into H2。
2. The process according to claim 1, wherein in step (1) the water content of the refuse material obtained is reduced by 20-60% compared to the water content of the municipal solid waste.
3. The method as claimed in claim 1, wherein, in the step (2), the final pyrolysis temperature in the pyrolysis reactor is 450-600 ℃.
4. The method according to any one of claims 1 to 3, wherein in the step (3), the dispersant is selected from at least one of naphthalene-based dispersants, sodium methylenedinaphthalene sulfonate, sodium lignin sulfonate and a methylnaphthalenesulfonate formaldehyde condensate.
5. The method according to any one of claims 1 to 4, wherein in the step (3), based on the total weight of the prepared coal-water slurry, the amount of the garbage semicoke is 30 to 50 wt%, the amount of the garbage waste liquid is 35 to 44 wt%, the amount of the coal dust is 10 to 30 wt%, and the amount of the dispersant is 0.8 to 1.5 wt%.
6. The process of any one of claims 1 to 5, wherein in step (4), the gasification reaction conditions comprise: the oxygen-carbon ratio is 0.8-1.05m3Kg, the gasification pressure is 3-6 MPa;
preferably, the temperature of the gasification reaction is 1300-.
7. The method according to any one of claims 1 to 6, wherein in step (4), the gasifying agent is at least one selected from the group consisting of oxygen, air and oxygen-enriched air, preferably oxygen.
8. The method according to any one of claims 1 to 7, wherein in step (5), the ratio of the amount of the raw synthesis gas returned to the pyrolysis reactor for indirect heat exchange to the remaining part of the raw synthesis gas is 1: 0.5-3.
9. The method of claim 1, wherein the purifying comprises:
s1: dedusting the crude synthesis gas to obtain dedusted gas, dust and fly ash;
s2: purifying and deacidifying the dedusted gas to obtain synthesis gas;
s3: and returning the dust and the fly ash to the gasification furnace for high-temperature slag treatment.
10. The method of any one of claims 1-9, wherein the method further comprises:
(6) and (5) drying and separating the product obtained in the step (5) to obtain hydrogen and purge gas, and returning the purge gas to the gasification furnace for gasification reaction.
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