CN111547678A - Method and system for preparing methanol by full-component thermal catalysis of marsh gas - Google Patents
Method and system for preparing methanol by full-component thermal catalysis of marsh gas Download PDFInfo
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Abstract
The invention provides a method for preparing methanol by full-component thermal catalysis of methane, which comprises the following steps: providing dried and desulfurized biogas, mixing the biogas with steam to obtain mixed gas, carrying out dry-wet double reforming in the presence of a catalyst, reacting to obtain synthesis gas, and preparing to obtain methanol. The invention provides a novel method for deep utilization of biogas, which utilizes the reaction of methane, carbon dioxide and water vapor in the biogas to produce biological methanol. The invention directly prepares the environment-friendly chemical product methanol by using renewable biogas as a raw material, and the components such as methane, carbon dioxide and the like in the biogas participate in the reaction, thereby having obvious carbon emission reduction effect; the energy utilization efficiency is high; the steam is introduced to react with the methane, so that the incomplete methane reaction can be avoided, the environment is polluted, the energy utilization rate is reduced, and the generation of carbon deposition in the reaction can be inhibited; the method avoids the environmental pollution caused by reaction wastes while obtaining the methanol with high energy efficiency.
Description
Technical Field
The invention relates to the technical field of methanol preparation, in particular to a method and a system for preparing methanol by full-component thermal catalysis of methane.
Background
The energy supply in the world is mainly based on three non-renewable fossil resources, namely coal, petroleum and natural gas. At present, globalization is carried out in the new century, the number of people is rapidly increased, the total amount of economy is rapidly increased, the earth resources are utilized widely, although various resources such as deep sea oil gas, combustible ice, coal bed gas and shale gas can be developed and utilized at present, people also pay attention to the potential shortage problem of non-renewable fossil fuels, and non-renewable natural resources such as petroleum and natural gas are exhausted before 2050, so that the view is consistent and agreed in the whole society. Meanwhile, the imbalance problem of energy distribution also causes and aggravates practical social linkage contradiction such as petroleum crisis and the like. The energy is the foundation of human civilization survival and development, and is also an important index for measuring comprehensive national strength and restricting national economy, thereby having a key role in national safety. China is seriously deficient in oil reserves and yield, and the current oil consumption activities mainly depend on import and seriously depend on foreign supply, so that China faces great energy safety threat. Therefore, the petroleum resources are inseparable from the national security, and become the core content of the energy safety strategy in China. CO 22Is the main component of greenhouse gases, and more than 90% of artificial CO2The emission is considered to be generated when fossil energy is used, and the emission of a large amount of greenhouse gas increases the concentration of greenhouse gas in the atmosphere and the greenhouse effect, thereby causing problems of global warming, sea level rise and the like. The use of a large amount of fossil energy is also an important reason for the problem of air pollution in China at present. Therefore, the development of the alternative clean energy of fossil energy has great significance for national safety and economic development of China. When mankind faces the real threat of the annual reduction of fossil energy reserves, with the reduction of methanol cost and price, a trend has been developed to utilize methanol as a new source of petrochemical raw materials.
The synthesis gas refers to a mixed gas of carbon monoxide and hydrogen,CO and H in syngas2The ratio varies with the raw materials and the production method, and the molar ratio is 1/2-3/1. Syngas is one of the organic synthesis feedstocks and is also a source of hydrogen and carbon monoxide, and plays an important role in the chemical industry. The raw materials for the synthesis gas are various, and many carbonaceous resources such as coal, natural gas, petroleum or residual oil, etc. can be used to produce the synthesis gas. The synthesis gas can be converted into liquid and gas fuels, bulk chemicals and fine organic chemical products with high added value. The prior art, in which the source of the synthesis gas is mainly from fossil fuel, is not favorable for the popularization of green road policy for sustainable development, and the preparation of methanol from the synthesis gas separated in the step is severely limited by time and space. The full-component conversion technology achieves the characteristics of being produced and used without time and space limitations and greatly exerts the production flexibility. Therefore, the method for directly preparing the methanol from the synthesis gas by using the renewable biogas as the raw material has profound significance for the current national conditions of China.
Disclosure of Invention
The invention aims to overcome the defects that the prior methane needs to be subjected to carbon dioxide separation in advance and the like, and provides a method for preparing methanol by full-component thermocatalysis of methane, which does not need to separate components such as carbon dioxide in advance, enables all components in the methane to participate in reaction, effectively improves the conversion rate of methane and carbon dioxide, and efficiently prepares the methanol.
The invention also aims to provide a system for preparing methanol by full-component thermal catalysis of methane.
The above object of the present invention is achieved by the following technical solutions:
a method for preparing methanol by full-component thermal catalysis of marsh gas comprises the following steps:
providing dried and desulfurized biogas, mixing the biogas with steam to obtain mixed gas, carrying out dry-wet double reforming in the presence of a catalyst, reacting to obtain synthesis gas, and preparing to obtain methanol.
The invention introduces the water vapor to react with the methane, thereby not only avoiding the incomplete methane reaction from polluting the environment and reducing the energy utilization rate, but also inhibiting the generation of carbon deposition in the reaction. Meanwhile, the dry-wet double reforming is a combined double reforming mode of dry reforming and wet reforming of carbon dioxide-methane and water-methane, so that the utilization rate of carbon dioxide in the methane is improved, the hydrogen-carbon ratio in the reaction process is adjusted, and the reaction for preparing methanol from the synthesis gas in the later period is facilitated; in the reforming process, about 1/3 of methane participates in the dry reforming of carbon dioxide-methane, 2/3 of methane participates in the wet reforming of water-methane, and the hydrogen-carbon ratio of the obtained synthesis gas is about 2.2:1, thereby meeting the requirements of the synthesis gas for preparing methanol and recovering unconverted gas.
Preferably, the volume ratio of methane to the water vapor in the biogas is 3: 1.5-2.2 (preferably 3: 2). The amount of water vapor is determined according to the methane content in the biogas in order to allow the methane in the biogas to react completely.
Preferably, H in the desulfurized biogas2The volume content of S is less than 1.0 ppm.
In particular, CH in the biogas450-70% by volume of CO2The content is 30-50 vol%.
Preferably, when CO is contained in the biogas2And CH4When the volume ratio of (3) is less than 1/3, adding CO into the mixed gas2To CO2And CH4Is not less than 1/3, preferably CO2And CH4Is 0.43 to 1.0.
Preferably, when CO is contained in the biogas2And CH4When the volume ratio of the carbon dioxide to the carbon dioxide is more than or equal to 1/3, CO contained in the biogas2Has already enabled CH4Complete reaction without adding CO into the mixed gas2。
Preferably, the catalyst is selected from at least one of Ni-based catalyst, copper-zinc catalyst.
Preferably, the reaction temperature is 750-850 ℃ when preparing the synthesis gas.
Preferably, the synthesis gas is heated to 100-300 ℃ under the action of a catalyst to prepare the methanol.
Preferably, the catalyst for preparing methanol from synthesis gas is a copper-zinc catalyst, and a mature catalyst is selected.
The invention also claims a system for preparing methanol by converting the full-component methane through thermal catalysis and conversion into the synthesis gas, which comprises a methane tank 1, a methane preheating furnace 2, a wet-dry double reforming reactor 3, a waste heat recovery heat exchanger 4, a first water cooling heat exchanger 5, a first gas-liquid separation device 6, a first gas pressurization device 7, a carbon dioxide separation device 8 and a second gas pressurization device 9; a synthesis gas preheating furnace 10, a methanol synthesis reaction furnace 11, a heat recovery heat converter 12, a second water cooling heat exchanger 13 and a second gas-liquid separation device 14; the biogas in the biogas digester 1 enters a biogas preheating furnace 2, and the biogas is preheated to the required temperature; the preheated methane enters a dry-wet double reforming reactor 3 to prepare synthesis gas, the synthesis gas enters a waste heat recovery heat exchanger 4, the waste heat recovery heat exchanger 4 is communicated with a first water cooling heat exchanger 5, a gas passage of the first water cooling heat exchanger 5 is communicated with a first gas-liquid separation device 6, the separated gas enters a first gas pressurization device 7, the pressurized gas enters a carbon dioxide separation device 8, the synthesis gas after carbon dioxide separation enters a second gas pressurization device 9, the pressurized synthesis gas enters a synthesis gas preheating furnace 10, the synthesis gas enters a methanol synthesis reaction furnace 11 after preheating, the synthesis gas reacts in the reaction furnace to synthesize methanol, the obtained mixed gas containing methanol enters a heat converter 12 to realize heat recovery, the gas flowing out of the heat converter 12 enters a second water cooling heat exchanger 13 and then enters a second gas-liquid separation device 14, the liquid obtained by separation is the methanol.
Preferably, a pipeline for conveying gas is connected to the second gas-liquid separating device 14, and the pipeline is communicated to the second gas pressurizing device 9 to connect the unreacted CO and H separated in the second gas-liquid separating device 142And the gas is conveyed to a second gas supercharging device 9, enters a subsequent synthesis gas preheating furnace 10 again, enters a methanol synthesis reaction furnace 11 to participate in the reaction again, and is synthesized into methanol.
Preferably, a certain amount of untreated synthesis gas is generated in the gas channel of the first water-cooled heat exchanger 5, and the gas outlet of the first water-cooled heat exchanger 5 is communicated to the methanol synthesis reaction furnace, so that the synthesis gas participates in the reaction to synthesize methanol.
Preferably, the liquid outlet of the first gas-liquid separation device 6 is communicated to the second gas-liquid separation device 14, so that the water separated by the first gas-liquid separation device 6 can enter the second gas-liquid separation device 14 to be separated again.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel method for deeply utilizing marsh gas, which mainly utilizes marsh gas to directly prepare synthetic gas to prepare methanol and utilizes the reaction of methane in the marsh gas, carbon dioxide and water vapor to produce the biological methanol. The invention uses renewable methane as raw material to directly prepare environment-friendly chemical product methanol, and the components of methane, carbon dioxide, water and the like in the methane participate in the reaction. Compared with the methane combustion power generation utilization technology, the invention has obvious carbon emission reduction effect; compared with the methane fuel cell technology, the invention has high energy utilization efficiency; the steam is introduced to react with the methane, so that the incomplete methane reaction can be avoided, the environment is polluted, the energy utilization rate is reduced, and the generation of carbon deposition in the reaction can be inhibited; the methanol with high energy efficiency is obtained, and meanwhile, the environmental pollution caused by reaction waste is avoided. Meanwhile, a system for preparing methanol by full-component thermal catalysis of methane is provided, and substances such as tail gas and the like can be subjected to cyclic reaction on the premise of improving the methane conversion rate to the maximum extent, so that the emission of harmful substances is avoided, and the resource utilization maximization is realized.
Drawings
FIG. 1 is a schematic process flow diagram of an embodiment of the present invention.
Description of reference numerals: 1-a methane tank; 2-a methane preheating furnace; 3-dry-wet double reforming reactor; 4-a waste heat recovery heat exchanger; 5-a first water-cooled heat exchanger; 6-a first gas-liquid separation device; 7-a first gas pressurisation device; 8-a carbon dioxide separation unit; 9-a second gas pressurization device; 10-a synthesis gas preheating furnace; 11-methanol synthesis reaction furnace; 12-a heat recovery heat converter; 13-a second water-cooled heat exchanger; 14-a second gas-liquid separation device.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
The method provided by the embodiment of the invention comprises the following steps:
the biogas is firstly processed by a raw material gas purification and raw material water metering and conveying module to reach the desulfurization index of less than 1.0ppm, the processed purified biogas enters the next reaction stage, namely a purified gas dry-wet double reforming module, and the reaction process of the purified gas dry-wet double reforming module is dry-wet double reforming operation of purified gas and a combined double reforming mode of dry reforming and wet reforming of carbon dioxide-methane and water-methane. The synthesis gas after reaction enters the operation module for preparing the methanol from the synthesis gas, the synthesis gas preheating system preheats the reaction gas to the reaction temperature, the preheated synthesis gas enters the reactor for preparing the methanol from the synthesis gas to react to obtain the methanol, and the methanol is taken out of the reactor through the aqueous solution and enters the collecting device to obtain the biological methanol.
The main reaction equation is as follows:
3CH4+2H2O+CO2→4CO+8H2
CO+2H2→CH3OH
as shown in fig. 1, the embodiment of the present invention directly prepares a chemical intermediate synthesis gas by using renewable biogas as a raw material to produce liquid fuel methanol, and specifically includes the following steps:
biogas from livestock and poultry manure, forestry waste, municipal sludge and the like is firstly treated by a raw material gas purification and raw material water metering and conveying module, and the biogas (the specific composition is H)2S content 3000-4Content 60 vol.% CO2Content 40 vol%) is pumped to gas purification operation module by power equipment (induced draft fan), and the gas pumped by power equipment enters gas drying and desulfurizing tower to be dried and desulfurized, and the desulfurization index reaches <1.0 ppm. The processed purified methane enters the next reaction stage, namely a purified gas dry-wet double reforming module, and specifically, the reaction flow of the purified gas dry-wet double reforming module is dry-wet double reforming operation of purified gas and a combined double reforming mode of dry reforming and wet reforming of carbon dioxide-methane and water-methane, so that the utilization rate of carbon dioxide in the methane is improved, the hydrogen-carbon ratio in the reaction process is adjusted, and the reaction for preparing methanol from synthesis gas in the later stage is facilitated. And (3) the reacted synthesis gas enters an operation module for preparing methanol from synthesis gas, specifically, the synthesis gas preheating system preheats the reaction gas to a reaction temperature, the preheated synthesis gas enters a reactor for preparing methanol from synthesis gas to react to obtain methanol, and the methanol is taken out of the reactor through an aqueous solution and enters a collecting device to obtain the biological methanol. The auxiliary work required for the whole process is carried out by auxiliary utility operation modules, namely: the system comprises a purified water preparation module, a cooling water storage and cooling module, a power equipment module, a heat supply combustion boiler module and a necessary power supply module.
Purified biogas (CH) after dehydration and desulfurization treatment in a gas purification operation module4Content 60 vol.% CO240 vol%) into two parts, one part (accounting for about 50 vol% of the total gas) is used as fuel to enter a heat supply combustion boiler module to provide heat for reaction; and the other part (accounting for 50 volume percent of the total gas quantity) serving as the reaction gas of the dry-wet double reforming enters a power equipment operation module (a secondary compressor) for pressurization (the pressure after pressurization is controlled to be about 0.8 MPa), and the pressurized gas enters the dry-wet double reforming operation module after passing through a buffer system, a flow control system and a metering system. In the reaction process, in order to adjust the hydrogen-carbon ratio, the module is provided with a module operation of pure water metering and conveying, and then the conveying and metering of pure water required for the reaction and the conveying and metering of pure water required for cooling are completed. Therefore, the function of conveying reaction raw materials is realized, and the function of recovering heat of waste heat is realized. In the clean gas dry-wet double reforming module, the heat required for the dry-wet double reforming reaction of the biogas is provided by the combustion of the biogas, and during this reforming process about 1/3 volumes of methane participate in the dry reforming of carbon dioxide-methane, 2/3 volumesThe methane participates in the wet reforming of water-methane, and the resulting synthesis gas has a hydrogen-to-carbon ratio of about 2.2:1 (i.e., H in the synthesis gas)2The molar ratio of the catalyst to CO is about 2.2:1), and meets the requirements of preparing methanol from synthesis gas and recovering unconverted gas. In the operation module for preparing methanol from synthesis gas, the product is subjected to gas-liquid separation after two-stage condensation heat exchange, and the two-stage condensation heat exchange has the following functions: the first stage of condensation heat exchange aims at realizing heat recovery, the second stage of condensation heat exchange aims at deep cooling of the product, further realizes recovery of methanol and water and separation of unreacted gas, and the separated methanol and water are automatically discharged as the product; and the separated unreacted gas enters a synthesis gas pressurization operation system for recycling. In the auxiliary utility operation module, the purified water preparation operation module comprises a purified water preparation system and a purified water storage system as long as a sufficient amount of purified water is provided for the reaction process. The cooling water storage and cooling water operation module mainly provides the necessary cooling water for deep cooling and the heat exchange of the water after the heat exchange for the whole system, and the cooling effect is ensured. The power equipment operation module mainly comprises a power pump, a multi-stage supercharger system and the like and provides transmission power for material conveying of equipment. The fired boiler operation module primarily provides the necessary heat for equipment operation. The power supply operation module of the necessary equipment mainly provides necessary electric energy for a control system, power equipment and the like of the equipment.
The system shown in fig. 1 works as follows: the biogas in the biogas digester 1 enters a biogas preheating furnace 2, the biogas is preheated to the required temperature (usually 750-.
The preheated methane enters a dry-wet double reforming reactor 3 to prepare synthesis gas, the synthesis gas enters a waste heat recovery heat exchanger 4, the waste heat recovery heat exchanger 4 is communicated with a first water cooling heat exchanger 5, a gas passage of the first water cooling heat exchanger 5 is communicated with a first gas-liquid separation device 6, the separated gas enters a first gas pressurization device 7, the pressurized gas enters a carbon dioxide separation device 8, the synthesis gas after carbon dioxide separation enters a second gas pressurization device 9, the pressurized synthesis gas enters a synthesis gas preheating furnace 10, the synthesis gas enters a methanol synthesis reaction furnace 11 after preheating, the synthesis gas reacts in the reaction furnace to synthesize methanol, the obtained mixed gas containing methanol enters a heat converter 12 to realize heat recovery, the gas flowing out of the heat converter 12 enters a second water cooling heat exchanger 13 and then enters a second gas-liquid separation device 14, the separated liquid is methanol which can be collected and stored by a collecting device.
The second gas-liquid separator 14 is connected with a pipeline for conveying gas, the pipeline is communicated to the second gas supercharging device 9, and the gas separated by the second gas-liquid separator 14 contains H2CO and the like, the gas enters the second gas supercharging device 9 through the pipeline, enters the subsequent synthesis gas preheating furnace 10 again, then enters the methanol synthesis reaction furnace 11 to participate in the reaction again, synthesizes methanol, realizes effective recovery of tail gas, can not be discharged to the atmosphere, and further can not pollute the environment.
The new water replenishing system may specifically adopt a system in which a pipeline for replenishing new water is communicated to the first water cooling heat exchanger 5, the new water is heated for the first time by using the waste heat of the gas flowing out of the waste heat recovery heat exchanger 4, a water outlet of the first water cooling heat exchanger 5 is communicated to a water inlet channel of the waste heat recovery heat exchanger 4, so that the new water is reheated in the waste heat recovery heat exchanger 4, a water outlet of the waste heat recovery heat exchanger 4 is communicated to the biogas preheating furnace 2 through a pipeline, so that the new water heated in the waste heat recovery heat exchanger 4 enters the biogas preheating furnace 2 through a pipeline, and after preheating, steam is formed and enters the dry-wet double reforming reactor 3 to participate in the reaction.
A certain amount of untreated synthesis gas is in the gas channel of the first water cooling heat exchanger 5, and the gas outlet of the first water cooling heat exchanger 5 is communicated to the methanol synthesis reaction furnace, so that the synthesis gas participates in the reaction to synthesize methanol.
The liquid outlet of the first gas-liquid separating device 6 is communicated to the second gas-liquid separating device 14, so that the water separated by the first gas-liquid separating device 6 can enter the second gas-liquid separating device 14 to be separated again.
Each heat exchanger allows the heat in the system to be fully recovered, which can recover about 60% of the released heat.
Example 1
After biogas is desulfurized by a gas purification operation module, under the treatment of a raw material water metering and conveying module, methane and steam are mixed according to the volume ratio of 3:2, and a nickel-based catalyst is used in an environment at 800 ℃ to react to generate synthesis gas (CO and H) with the methane conversion rate of about 100 percent and the carbon dioxide conversion rate of more than 50 percent2) Then synthesis gas (CO and H)2) Under the condition of processing by an operation module for preparing methanol from synthesis gas at 300 ℃, the reaction reaches the yield of 192.5mol/h of methanol, the product is led into a water solution collecting device to obtain the methanol, and simultaneously tail gas enters the synthesizing device again for circular reaction.
Example 2
After biogas is desulfurized by a gas purification operation module, under the treatment of a raw material water metering and conveying module, methane and steam are mixed according to the volume ratio of 3:2, and synthesis gas (CO and H) is generated by using a nickel-based catalyst under the environment of 850 ℃ and with the methane conversion rate of about 100 percent and the carbon dioxide conversion rate of over 60 percent2) Then synthesis gas (CO and H)2) In the environment of 300 ℃, under the treatment of an operation module for preparing methanol from synthesis gas, the reaction reaches the yield of about 211.4mol/h, the product is led into a water solution collecting device to obtain methanol, and simultaneously tail gas enters the synthesizing device again for circular reaction.
Example 3
After biogas is desulfurized by a gas purification operation module, under the treatment of a raw material water metering and conveying module, methane and steam are mixed according to the volume ratio of 3:2, and synthesis gas (CO and H) is generated by using a nickel-based catalyst under the environment of 750 ℃ and with the methane conversion rate of about 80% and the carbon dioxide conversion rate of more than 40%2) Then synthesis gas (CO and H)2) In the environment of 300 ℃, under the treatment of an operation module for preparing methanol from synthesis gas, the reaction reaches the yield of about 153.7mol/h, the product is introduced into a water solution collecting device to obtain methanol, and simultaneously tail gas enters the synthesizing device again for circular reaction.
Example 4
After the biogas is desulfurized by a gas purification operation module, under the treatment of a raw material water metering and conveying module, methane and water vapor are mixed according to the volume ratio of 3:2, and in an environment of 800 ℃,using a nickel-based catalyst, the reaction produces syngas (CO and H) at a methane conversion of about 100% and a carbon dioxide conversion of greater than 50%2) Then synthesis gas (CO and H)2) Under the condition of processing by an operation module for preparing methanol from synthesis gas at the temperature of 100 ℃, the reaction reaches the yield of about 148.2mol/h of methanol, the product is led into a water solution collecting device to obtain the methanol, and simultaneously tail gas enters the synthesizing device again for circular reaction.
Example 5
After biogas is desulfurized by a gas purification operation module, under the treatment of a raw material water metering and conveying module, methane and steam are mixed according to the volume ratio of 3:2, and a nickel-based catalyst is used in an environment at 800 ℃ to react to generate synthesis gas (CO and H) with the methane conversion rate of about 100 percent and the carbon dioxide conversion rate of more than 50 percent2) Then synthesis gas (CO and H)2) Under the condition of processing by an operation module for preparing methanol from synthesis gas at 200 ℃, the reaction reaches the yield of about 159.7mol/h of methanol, the product is led into a water solution collecting device to obtain the methanol, and simultaneously tail gas enters the synthesizing device again for circular reaction.
In summary, the embodiment of the present invention provides a new method for deep utilization of biogas, which mainly uses biogas to directly prepare methanol from syngas, and uses methane, carbon dioxide and steam in biogas to pass through a raw material gas purification and raw material water metering transportation module, a purified gas dry-wet double reforming module, a syngas methanol module and an auxiliary public engineering operation module, that is: 4 main body operation modules such as a purified water preparation module, a cooling water storage and cooling module, a power equipment module, a heat supply combustion boiler module and a necessary power supply module are used for producing the biological methanol. The method uses renewable methane as raw material to directly prepare the environment-friendly chemical product methanol. Compared with the methane combustion power generation utilization technology, the invention has obvious carbon emission reduction effect; compared with the methane fuel cell technology, the invention has high energy utilization efficiency; the steam is introduced to react with the methane, so that the incomplete methane reaction can be avoided, the environment is polluted, the energy utilization rate is reduced, and the generation of carbon deposition in the reaction can be inhibited; the methanol with high energy efficiency is obtained, and meanwhile, the environmental pollution caused by reaction waste is avoided.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A method for preparing methanol by full-component thermal catalysis of marsh gas is characterized by comprising the following steps: providing dried and desulfurized biogas, mixing the biogas with steam to obtain mixed gas, carrying out dry-wet double reforming in the presence of a catalyst, reacting to obtain synthesis gas, and preparing to obtain methanol.
2. The method of claim 1, wherein the volume ratio of methane to the water vapor in the biogas is 3: 2.
3. the method of claim 1, wherein the desulfurized biogas is H-enriched2The volume content of S is less than 1.0 ppm.
4. Method according to claim 1, characterized in that CH is present in the biogas450-70% of CO2The content is 30-50%.
5. The method of claim 1, wherein the CO is present in the biogas2And CH4When the volume ratio of (3) is less than 1/3, adding CO into the mixed gas2To CO2And CH4The volume ratio of (A) is more than or equal to 1/3.
6. The method of claim 1, wherein the catalyst is selected from at least one of Ni-based catalysts, copper-based catalysts, and copper-zinc catalysts.
7. The method of claim 1, wherein the synthesis gas is prepared at a reaction temperature of 750 ℃ to 850 ℃.
8. The method of claim 1, wherein the synthesis gas is heated to 100 to 300 ℃ to produce methanol.
9. A system for preparing methanol by converting full-component methane through thermal catalysis and thermal catalysis into synthesis gas is characterized by comprising a methane tank (1), a methane preheating furnace (2), a dry-wet double reforming reactor (3), a waste heat recovery heat exchanger (4), a first water cooling heat exchanger (5), a first gas-liquid separation device (6), a first gas pressurization device (7), a carbon dioxide separation device (8) and a second gas pressurization device (9); a synthesis gas preheating furnace (10), a methanol synthesis reaction furnace (11), a heat recovery heat converter (12), a second water cooling heat exchanger (13) and a second gas-liquid separation device (14); the biogas in the biogas digester (1) enters a biogas preheating furnace (2) and is preheated to the required temperature; the preheated methane enters a dry-wet double reforming reactor (3) to prepare synthesis gas, the synthesis gas enters a waste heat recovery heat exchanger (4), the waste heat recovery heat exchanger (4) is communicated with a first water cooling heat exchanger (5), a gas channel of the first water cooling heat exchanger (5) is communicated with a first gas-liquid separation device (6), the separated gas enters a first gas pressure boosting device (7), the pressurized gas enters a carbon dioxide separation device (8), the synthesis gas after carbon dioxide separation enters a second gas pressure boosting device (9), the pressurized synthesis gas enters a synthesis gas preheating furnace (10), the synthesis gas enters a methanol synthesis reaction furnace (11) after preheating, the synthesis gas reacts in the reaction furnace to synthesize methanol, the obtained mixed gas containing the methanol enters a heat converter (12) to realize heat recovery, the gas flowing out of the heat converter (12) enters a second water cooling heat exchanger (13), then enters a second gas-liquid separation device (14) to obtain liquid, namely methanol.
10. A system according to claim 9, characterized in that the second gas-liquid separation device (14) is connected to a gas supply line which is connected to the second gas pressurisation device (9) and which connects the second gas-liquid separation device (14) to itSeparated unreacted CO and H2And the gas is conveyed to a second gas supercharging device (9) and enters a subsequent synthesis gas preheating furnace (10) again, and then enters a methanol synthesis reaction furnace (11) to participate in the reaction again to synthesize the methanol.
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