CN110713844A - Method for co-producing methane and light liquid tar by catalytic hydro-gasification two-step method - Google Patents
Method for co-producing methane and light liquid tar by catalytic hydro-gasification two-step method Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/08—Production of synthetic natural gas
Abstract
A method for co-producing methane and light liquid tar by a catalytic hydro-gasification two-step method belongs to the technical field of coal chemical industry, solves the problems existing in the technology for preparing natural gas by catalytic hydro-gasification of coal, and adopts the following solution: loading a univalent, binary or multivariate catalyst consisting of alkali metal salt, alkaline earth metal salt and transition metal salt onto raw coal or biomass, sequentially carrying out catalytic hydropyrolysis and catalytic hydro-gasification reactions on the raw material loaded with the catalyst and a gasifying agent in a two-stage pressurized fluidized bed, and catalyzing carbon-hydrogen and CO/CO by the catalyst2Hydrogen reaction to produce methane and light liquid tar, the first stage pyrolysis temperature being 450-; the second stage gasification temperature is 850-. The flow rate of the gasifying agent is controlled to be 0.5-10 times of the fluidization number of the solid particles under the selected reaction conditions. The invention has the advantages of wide raw material adaptability, high carbon conversion rate, high methane conversion rate and high catalyst recovery rate, 99.9 percent of catalyst can be recovered and purifiedThe yield of light liquid tar is high, and the gasification agent is cheap; the pressurized fluidized bed reactor is used, and the large-scale amplification is easy.
Description
Technical Field
The invention belongs to the technical field of coal chemical industry, relates to a method for co-producing methane and light liquid tar by a catalytic hydro-gasification two-step method, and particularly relates to process conditions, reaction raw materials, a gasification agent, a catalyst and a catalyst recovery mode for a pressurized fluidized bed two-step catalytic hydro-gasification process.
Background
In recent years, the demand of China for natural gas is on a rapid growth trend, and the development of coal-based natural gas technology is an effective means for making up for the shortage of natural gas resources in China. The prior coal-to-natural gas technology comprises a steam-oxygen two-step method, catalytic gasification and hydro-gasification, wherein the steam-oxygen two-step method represented by a Lurgi furnace and a pressurized fluidized bed coal catalytic gasification technology realize industrial operation, and the hydro-gasification technology is not reported in related industrial application. From the perspective of preparing substitute natural gas, the coal hydro-gasification technology has the shortest path, single product component, higher thermal efficiency (79.6%) and methane yield (40-50%). However, the coal hydro-gasification process needs to be carried out at a relatively high reaction temperature and hydrogen pressure (900-.
The problem of low reactivity of carbon in the hydro-gasification process can be solved by carrying out catalytic hydro-gasification of coal (CCHG) by introducing a catalyst. The coal catalytic hydrogenation gasification process can ensure that the coal hydrogenation gasification process obtains high carbon conversion rate and methane yield under mild reaction conditions (750-. In the catalytic coal hydro-gasification process, the target products mainly comprise methane and light liquid tar, if the coal needs to obtain higher carbon conversion rate, the reaction conditions are not too mild, but the harsher reaction conditions can cause secondary cracking of the tar to a deeper degree, so that the yield of the tar with higher added value is reduced. In addition, the pure hydrogen atmosphere has higher cost when being applied to the coal catalytic hydrogenation gasification process, the hydrogen atom utilization rate is lower, and the load of the subsequent hydrogen separation and purification process is larger.
Disclosure of Invention
The invention solves the problems of the technology for preparing natural gas by catalytic hydro-gasification of coal, and provides a method for co-producing methane and light liquid tar by a catalytic hydro-gasification two-step method, which has the advantages of high carbon conversion rate, high yield of methane and light liquid tar and low cost of a gasification agent.
The invention applies the catalytic hydro-gasification process to a two-stage pressurized fluidized bed reactor, and realizes more than 90 percent of carbon conversion rate and higher yield of methane and light tar in shorter retention time of solid particles.
The design concept of the invention is as follows:
after entering a reactor, the raw material loaded with the catalyst is firstly subjected to catalytic hydro-pyrolysis in a low-temperature area of a first section to extract oil components with high added values in coal/biomass to a large extent, and semicoke generated after pyrolysis has high condensation degree and low reactivity and enters a high-temperature area of a second section to continue to be subjected to catalytic hydro-gasification to generate methane to a large extent. H2In the atmosphere, the catalyst mainly catalyzes the carbon-hydrogen reaction in the whole reaction process to play a role in hydrogen supply and bond breaking so as to meet the supply of sufficient hydrogen for generating volatile matters in the pyrolysis stage, generate more light liquid tar products, and generate more methane by breaking and hydrogenating carbon-carbon bonds in the gasification stage to a deeper degree. If at H2Mixing H in a certain proportion in atmosphere2And O, the hole expanding effect of the raw material with a lower surface can be realized, so that the catalytic hydrogenation of the raw material is more effective in the presence of the catalyst. If at H2Mixing CO or CO in a certain proportion in atmosphere2The catalyst loaded on the raw material can catalyze CO/CO while catalyzing carbon hydrogenation in coal/biomass in the reaction process2The methanation reaction is carried out to further improve the yield of the target product methane.
After the reaction, the transition metal element in the mono-component, binary or multi-component catalyst exists in the gasification residue as a metal simple substance or a metal oxide, and the catalyst can be recovered by an acid washing method. However, after the recovered catalyst is recycled for a certain number of times, the transition metal element needs to be purified by a precipitation-filtration-acid washing method to remove part of mineral substances which do not play a catalytic role, so that the activity of the catalyst is prevented from being adversely affected.
The invention is realized by the following technical scheme:
a method for co-producing methane and light liquid tar by a catalytic hydro-gasification two-step method comprises the following steps:
s1, loading a catalyst on the raw material for later use;
s2, first stage: catalytic hydropyrolysis reaction:
first, two-stage pressurized fluidized bed with N2Purging for 0.5 ~ 1h, blowing a gasifying agent into the two sections of pressurized fluidized beds, controlling the flow of the gasifying agent to be 0.5-10 times of the fluidization number of solid particles under the selected reaction conditions, adjusting the pressure in the two sections of pressurized fluidized beds to be 0.1-5MPa, adding the raw material of the supported catalyst prepared in the step S1 into the first section of the two sections of pressurized fluidized beds, and finally, carrying out catalytic hydropyrolysis reaction on the raw material of the supported catalyst in the atmosphere of the gasifying agent, wherein the pyrolysis temperature is 450 ℃ and 700 ℃, and the retention time of the solid particles is 0.1-1.0 h;
s3, second stage: catalytic hydro-gasification reaction: keeping the pressure in the two sections of pressurized fluidized beds and the flow rate of the gasifying agent, putting the material reacted in the step S2 into the second section of the two sections of pressurized fluidized beds, wherein the gasification temperature is 850-1100 ℃, the retention time of solid particles is 0.5-2.0h, and coproducing the target products of methane and light liquid tar in the steps S2 and S3.
Further, in the step S1, the raw material is a dry-based raw material, the dry-based raw material is one or more of dry-based biomass, lignite, bituminous coal or anthracite, and the raw material may have one or more of high ash characteristics, high cohesiveness, high sulfur characteristics or low reactivity.
Further, the catalyst described in step S1 is used to catalyze a carbon-hydrogen reaction and a CO/CO 2-hydrogen reaction, the catalyst is a unitary transition metal catalyst, or a multi-component catalyst composed of a transition metal catalyst and one or more of three types of catalysts, and the unitary transition metal catalyst is used as a reference catalyst in terms of atomic mass ratio, wherein the loading amount of the transition metal catalyst is 1% to 5%, and the loading amounts and proportions of the components of the multi-component catalyst are adjusted according to different coal types to remove part of minerals which do not play a catalytic role, so as to prevent the accumulation of the content thereof from causing fluxing action to result in slagging and hindering the catalytic action of the active component.
Further, the catalyst precursor is carbonate, nitrate, acetate or oxide, wherein the transition metal catalyst comprises one or two of Cu, Fe, Co, Ni and Mo, the alkali metal catalyst comprises K, Na, and the alkaline earth metal catalyst comprises Ca, Mg and Ba.
Further, the catalyst is recovered by an acid washing method, and the recovered catalyst needs to be purified and regulated after being recycled for a certain number of times.
Further, in step S2, the gasifying agent is pure hydrogen, or a mixture of hydrogen and one or more of carbon monoxide, carbon dioxide and steam.
Compared with the prior art, the invention has the beneficial effects that:
1. the raw materials of the invention have wide adaptability, and the selected catalyst does not react with mineral substances in coal and does not generate sulfur poisoning inactivation. The catalyst in the gasification residue can be recovered by a simple acid dissolution method, the recovery rate can reach 99.9 percent at most, and the catalyst can be circularly applied to the catalytic hydrogenation gasification process of coal.
2. The invention has high yield of methane and light liquid tar, and can simultaneously catalyze the carbon-hydrogen reaction and CO/CO reaction in mixed atmosphere by loading proper catalyst for reaction2And (3) hydrogen reaction, the stable carbon conversion rate of 92 percent can be achieved within 0.5-2.0h, the methane yield of 247 percent (based on carbon in coal) and the tar yield of 9.04 percent can be achieved, and the HCL yield (dry ashless base) can reach 3.36 weight percent.
3. The gasifying agent is cheap and easy to obtain, and the atom utilization rate of hydrogen is high.
4. The pressurized fluidized bed is applied to the catalytic hydro-gasification process and is easy to scale up.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
To explain technical solutions, structural features, and technical effects of the present invention in detail, the following detailed description is given with reference to the accompanying drawings in conjunction with the detailed description. The following examples are merely illustrative of the present invention and should not be construed as limiting the scope of the invention.
Example 1:
weighing 100g of low ash bituminous coal which is dried for 2.0h under vacuum at 100 deg.C, and mixing with 10.1g of Co (CH)3COO)2•4H2O and 4.4gCa (CH)3COO)2•H2And (4) loading O on the raw coal, and drying for later use. The reactor is preliminarily treated with N before the reaction2Purging for 30min, and then controlling the temperature of the first section of the reactor to 600 ℃ and the temperature of the second section to 850 ℃. After the set temperature is reached, the pressure of the reactor is increased to 3MPa2The atmosphere was maintained, and the gas inlet and outlet flow rates were controlled by mass flow meters to be 12 NL/min (3.5 times the minimum fluidization number). 100g of the catalyst-loaded starting material was charged into a silo before the start of the reaction, and then the feed silo was pressurized to 3.5 MPa. After the temperature and the pressure of the reaction system are stable, a lower end valve of the storage bin is opened, and the materials are injected into the first section of the 3MPa reactor at one time through the pressure of 3.5 MPa. After reacting for 30min, opening the valve of the distribution plate, and continuously dropping the raw materials to the second section of the reactor to react for 30 min. The non-condensable gases generated during the reaction were collected in a gas bag and the volume of the collected gases was recorded with a gas meter. Volatile matters generated in the early stage of the reaction enter the rear system through the reactor main body at the temperature higher than 400 ℃, are condensed and separated through the secondary condensation system, and are separated from coal dust before entering condensation by adding quartz wool at the front end of the outlet.
Taking out all residues after reaction, adding 500mL of 1.0 mol/L diluted hydrochloric acid, heating and stirring at the constant temperature of 60 ℃, filtering while hot after 1h, and washing until the filtered filtrate is not acidic. The filtrate was evaporated isothermally at 280 ℃ and concentrated to 60 ml. The amount of Co and Ca recovered from the concentrate was measured by an ion concentration meter (ICP) to calculate the recovery of Co and Ca.
Example 2:
weighing 100g of low ash bituminous coal which is dried for 2.0h under vacuum at 100 deg.C, and mixing with 10.1g of Co (CH)3COO)2•4H2O and 4.4gCa (CH)3COO)2•H2And (4) loading O on the raw coal, and drying for later use. The reactor is preliminarily treated with N before the reaction2Purging for 30min, controlling the temperature of the first section of the reactor to 600 ℃ and the temperature of the second section to 850 ℃, and increasing the pressure of the reactor to 80% H of 3MPa after the set temperature is reached2+20%CO2The atmosphere and the gas inlet flow rate controlled by a mass flow meter were all 15 NL/min (5 times the minimum fluidization number). 100g of the catalyst-loaded starting material was charged into a silo before the start of the reaction, and then the feed silo was pressurized to 3.5 MPa. After the temperature and the pressure of the reaction system are stable, a lower end valve of the storage bin is opened, and the materials are injected into the first section of the 3MPa reactor at one time through the pressure of 3.5 MPa. After reacting for 30min, the valve of the distribution plate is opened, and the raw materials continuously fall to the second section of the reactor to react for 2.0 h. The non-condensable gases generated during the reaction were collected in a gas bag and the volume of the collected gases was recorded with a gas meter. Volatile matters generated in the early stage of the reaction enter the rear system through the reactor main body at the temperature higher than 400 ℃, are condensed and separated through the secondary condensation system, and are separated from coal dust before entering condensation by adding quartz wool at the front end of the outlet.
Taking out all residues after reaction, adding 500mL of 1.0 mol/L diluted hydrochloric acid, heating and stirring at the constant temperature of 60 ℃, filtering while hot after 1h, and washing until the filtered filtrate is not acidic. The filtrate was evaporated isothermally at 280 ℃ and concentrated to 60 ml. The amount of Co recovered in the concentrate was measured by an ion concentration meter (ICP) to calculate the Co recovery rate.
Example 3:
weighing 100g of 75-1000um high-ash high-sulfur bituminous coal which is dried for 12 hours in vacuum at 100 ℃. 10.1g of Co (CH) will be taken3COO)2•4H2O、4.4g Ca(CH3COO)2•H2O and 5.7g CaO are loaded on raw coal and dried for standby. The reactor is preliminarily treated with N before the reaction2Purging for 30min, controlling the temperature of the first section to 450 ℃, controlling the temperature of the second section to 950 ℃, and increasing the pressure of the reactor to be H of 3MPa after the set temperature is reached2The atmosphere was maintained, and the gas inlet and outlet flow rates were controlled by mass flow meters to be 12 NL/min (3.5 times the minimum fluidization number). Load 100gThe raw materials with the catalyst are added into a storage bin before the reaction is started, and then the pressure of the feeding bin is increased to 3.5 MPa. After the temperature and the pressure of the reaction system are stable, a lower end valve of the storage bin is opened, and the materials are injected into the first section of the 3MPa reactor at one time through the pressure of 3.5 MPa. After reacting for 30min, the valve of the distribution plate is opened, and the raw materials continuously fall to the second section of the reactor to react for 2.0 h. The non-condensable gases generated during the reaction were collected in a gas bag and the volume of the collected gases was recorded with a gas meter. Volatile matters generated in the early stage of the reaction enter the rear system through the reactor main body at the temperature higher than 400 ℃, are condensed and separated through the secondary condensation system, and are separated from coal dust before entering condensation by adding quartz wool at the front end of the outlet.
Example 4:
weighing 100g of low ash bituminous coal and 30g of biomass which are dried for 2.0h in vacuum at 100 ℃, and mixing 10.1g of Co (CH)3COO)2•4H2O and 4.4gCa (CH)3COO)2•H2And (4) loading the O on the raw coal, mixing with the biomass, and drying for later use. The reactor is preliminarily treated with N before the reaction2Purging for 30min, controlling the temperature of the first section of the reactor to 600 ℃ and the temperature of the second section to 850 ℃, and increasing the pressure of the reactor to 80% H of 3MPa after the set temperature is reached2+20%CO2The atmosphere and the gas inlet flow rate controlled by a mass flow meter were all 15 NL/min (5 times the minimum fluidization number). 100g of the catalyst-loaded starting material was charged into a silo before the start of the reaction, and then the feed silo was pressurized to 3.5 MPa. After the temperature and the pressure of the reaction system are stable, a lower end valve of the storage bin is opened, and the materials are injected into the first section of the 3MPa reactor at one time through the pressure of 3.5 MPa. After reacting for 30min, the valve of the distribution plate is opened, and the raw materials continuously fall to the second section of the reactor to react for 2.0 h. The non-condensable gases generated during the reaction were collected in a gas bag and the volume of the collected gases was recorded with a gas meter. Volatile matters generated in the early stage of the reaction enter the rear system through the reactor main body at the temperature higher than 400 ℃, are condensed and separated through the secondary condensation system, and are separated from coal dust before entering condensation by adding quartz wool at the front end of the outlet.
Example 5: control experiment
Weighing 100g of low ash bituminous coal which is dried for 2.0h under vacuum at 100 deg.C, and mixing with 10.1g of Co (CH)3COO)2•4H2O and 4.4gCa (CH)3COO)2•H2And (4) loading O on the raw coal, and drying for later use. The reactor is preliminarily treated with N before the reaction2Purging for 30min, controlling the temperature of the reaction zone of the reactor to 850 ℃, and increasing the pressure of the reactor to 80% H of 3MPa after the set temperature is reached2+20%CO2The atmosphere and the gas inlet flow rate controlled by a mass flow meter were all 15 NL/min (5 times the minimum fluidization number). 100g of the catalyst-loaded starting material was charged into a silo before the start of the reaction, and then the feed silo was pressurized to 3.5 MPa. After the temperature and the pressure of the reaction system are stable, a lower end valve of the storage bin is opened, and the materials are injected into a 3MPa reactor at one time through the pressure of 3.5MPa to directly carry out catalytic hydro-gasification reaction. The non-condensable gases generated during the reaction were collected in a gas bag and the volume of the collected gases was recorded with a gas meter. Volatile matters generated in the early stage of the reaction enter the rear system through the reactor main body at the temperature higher than 400 ℃, are condensed and separated through the secondary condensation system, and are separated from coal dust before entering condensation by adding quartz wool at the front end of the outlet.
Example 6: recycling of catalyst
The catalyst acid solution recovered in example 2 was neutralized with ammonia water to PH 7, then sodium carbonate was added to precipitate and filter the Co catalyst, the filter cake was washed with deionized water several times and then dissolved and purified with acetic acid, and then the purified cobalt acetate solution was evaporated and concentrated. 100g of dry raw coal and 5.0g of CaCO were weighed in advance3Slowly pouring the mixture into the catalyst recovery solution in an ultrasonic environment, continuously stirring the mixture by using a mechanical stirrer to uniformly mix the coal sample and the mother solution, and keeping the temperature of a water bath constant at 30 ℃ in the ultrasonic process. After 2h, the ultrasound was switched off, the stirring was stopped and the water bath was kept thermostatted at 50 ℃ for 12 h. And after the impregnation is finished, taking out the materials in the water bath, placing the materials in the water bath in a vacuum environment at 105 ℃ for drying for 12 hours, and then grinding the materials until the materials are dried to 75-1000um for later use.
The other steps and reaction conditions were kept the same as in example 2.
The basic analysis data of the coal quality of the coal types used in the 6 examples are shown in Table 1.
The results of the gasification in the five examples of the invention run for different reaction times after the sample injection is completed are shown in table 2.
The catalyst recovery results of the present invention are shown in table 2.
Table 1 basic analytical data for coal quality.
Table 2 the results of the gasification after 0.5 h-2.0 h of operation after completion of the injection of the five examples (based on the carbon content in the coal).
By comparing example 1 and example 2 in table 2, it is found that the raw coal loaded with catalyst is applied to two-stage pressurized fluidized bed for catalytic hydro-gasification and pure H under mixed atmosphere2The methane yield can be higher within 1.0-2.0h compared with the methane yield under the atmosphere. Comparative example 2 and comparative example 5 it can be seen that a higher yield of light tar is obtained when the two-stage pressurized fluidized bed is subjected to catalytic hydro-gasification in a mixed atmosphere compared to a single-stage pressurized fluidized bed. The result of example 3 shows that the two-stage pressurized fluidized bed catalytic hydro-gasification can be suitable for coal types with high ash and sulfur characteristics and the like, and has good catalytic effect. The results of example 4 demonstrate that a two-stage pressurized fluidized bed catalytic hydro-gasification process can be applied to one or more of the feedstocks recited in claim 3.
From example 2, it can be seen that two-stage pressurized fluidized bed catalytic hydro-gasification is performed in a mixed atmosphere, the conversion rate of bituminous coal can reach 92.4% within 2.0h, which is higher than that in a pure hydrogen atmosphere, the yield of tar can reach 9.1%, and the yield of methane can reach 240% (based on carbon in coal), which indicates that the introduction of a relatively cheap mixed gas can not only promote the conversion of carbon in coal, but also the carbon in the mixed gas contributes to the generation of methane to a greater extent, so that the yield of methane is greatly improved. Example 6 results in conjunction with catalyst recovery indicate that the catalyst can be recovered by a simple acid wash and that the recovered and purified catalyst can be recycled for use in a two-stage pressurized fluidized bed catalytic hydro-gasification process. The high carbon conversion rate and high methane and tar yield of the coal break through the limitations of harsh reaction conditions, long reaction time and low conversion rate of the coal in the hydro-gasification process. The catalytic hydro-gasification process has no application precedent in the two-stage pressurized fluidized bed, which provides a practical reference basis and thought for further amplification and application of the preparation of methane and light tar by catalytic hydro-gasification of coal.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise embodiments disclosed, and any modifications or alterations which may be readily apparent to those skilled in the art are intended to be within the scope of the invention as defined by the appended claims. Therefore, the protection scope of the present invention shall be subject to the protection scope of the appended claims.
Claims (6)
1. A method for co-producing methane and light liquid tar by a catalytic hydro-gasification two-step method is characterized by comprising the following steps:
s1, loading a catalyst on the raw material for later use;
s2, first stage: catalytic hydropyrolysis reaction:
first, two-stage pressurized fluidized bed with N2Purging for 0.5 ~ 1h, blowing a gasifying agent into the two sections of pressurized fluidized beds, controlling the flow of the gasifying agent to be 0.5-10 times of the fluidization number of solid particles under the selected reaction conditions, adjusting the pressure in the two sections of pressurized fluidized beds to be 0.1-5MPa, adding the raw material of the supported catalyst prepared in the step S1 into the first section of the two sections of pressurized fluidized beds, and performing catalytic hydropyrolysis reaction on the raw material of the supported catalyst in the atmosphere of the gasifying agent at the pyrolysis temperature of 450-700 ℃;
s3, second stage: catalytic hydro-gasification reaction: keeping the pressure in the two sections of pressurized fluidized beds and the flow rate of the gasifying agent, feeding the material reacted in the step S2 into the second section of the two sections of pressurized fluidized beds, wherein the gasification temperature is 850-1100 ℃, and coproducing the target products, namely methane and light liquid tar, in the steps S2 and S3.
2. The method for co-producing methane and light liquid tar by the catalytic hydro-gasification two-step method according to claim 1, wherein: in the step S1, the raw material is a dry base raw material, and the dry base raw material is one or more of biomass, lignite, bituminous coal, and anthracite.
3. The method for co-producing methane and light liquid tar by the catalytic hydro-gasification two-step method according to claim 1, wherein: the catalyst of the step S1 is used for catalyzing carbon-hydrogen reaction and CO/CO2And (2) hydrogen reaction, wherein the catalyst is a unitary transition metal catalyst or a multi-component catalyst consisting of one or more of a transition metal catalyst and three catalysts, the unitary transition metal catalyst is taken as a reference catalyst according to the atomic mass ratio, the load capacity of the transition metal catalyst is 1-5%, and the load capacity and the proportion of each component of the multi-component catalyst are prepared according to different coal types.
4. The method for co-producing methane and light liquid tar by the catalytic hydro-gasification two-step method according to claim 3, wherein: the catalyst precursor is carbonate, nitrate, acetate or oxide, wherein the transition metal catalyst comprises one or two of Cu, Fe, Co, Ni and Mo, the alkali metal catalyst comprises one of K, Na, and the alkaline earth metal catalyst comprises one of Ca, Mg and Ba.
5. The method for co-producing methane and light liquid tar by the catalytic hydro-gasification two-step method according to claim 3, wherein: the catalyst is recovered by an acid washing method, and the purification and regulation of active components of the catalyst are needed after the recovered catalyst is recycled for a certain number of times.
6. The method for co-producing methane and light liquid tar by the catalytic hydro-gasification two-step method according to claim 1, wherein: in step S2, the gasifying agent is pure hydrogen, or a mixture of hydrogen and one or more of carbon monoxide, carbon dioxide and steam.
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| CN114991740A (en) * | 2022-06-21 | 2022-09-02 | 西安石油大学 | Method and system for cooling and saving energy of coal underground gasification produced gas |
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