CN118179384A - System and method for combining methane hydrogen production with Buddha reaction - Google Patents
System and method for combining methane hydrogen production with Buddha reaction Download PDFInfo
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Abstract
The invention relates to the field of energy chemical engineering devices, and provides a system and a method for combining methane with Buddha reaction for hydrogen production, which are used for solving the problems that the utilization rate of carbon dioxide is low and the catalyst is easy to accumulate and deactivate in the methane dry reforming process in the prior art. The system can realize green co-production of hydrogen and carbon monoxide, reduce the poisoning risk of the catalyst and realize the recycling utilization of carbon dioxide.
Description
Technical Field
The invention relates to the field of energy chemical devices, in particular to a system and a method for producing hydrogen by methane and combining Buddha reaction.
Background
Natural gas plays an important role in energy consumption as a fossil energy source, and is converted into zero-carbon energy source and chemical products through technical innovation, so that the reduction of carbon emission is facilitated, and sustainable raw material sources can be provided for the chemical industry. Methane reforming is the most predominant natural gas conversion technology, and typically the reaction temperature is 700-1100 ℃, and methane reacts with steam to produce synthesis gas. The method is a strong endothermic reaction, the energy consumption of the reaction process is high, the H 2/CO ratio in the synthetic gas product is 3, and the hydrogen content is obviously higher than that of the synthetic gas of H 2/CO=2 required by downstream F-T synthesis, methanolysis and other reactions, so that an additional procedure is required to adjust the gas component ratio. A large amount of CO 2 emissions are generated during the reforming process, and a great pressure is brought to control of greenhouse gas emissions.
Methane dry reforming technology is a relatively popular natural gas conversion technology in recent years, and methane and carbon dioxide react to generate synthesis gas at 700-900 ℃. The H 2/CO ratio in the synthesis gas product generated by the reaction is 1, which is lower than the ratio requirements of the reactions such as F-T synthesis, methanolysis and the like in the downstream process, and the additional working procedure is also needed to adjust the gas components. In the reaction process, serious catalyst carbon deposition deactivation phenomenon exists, the prior art is still immature, and further development is needed.
The recycling of carbon dioxide becomes an important technical path for reducing carbon dioxide emission, meanwhile, the demands of the whole society on clean energy sources, especially hydrogen energy, are gradually growing, and how to clean and efficiently realize the process of carbon dioxide utilization and hydrogen energy production is becoming a technical problem to be solved in the field. Chinese patent publication No. CN103332650a discloses a system and a method for producing hydrogen and separating carbon dioxide by dry methane catalytic decomposition, which can separate and trap unreacted carbon dioxide, but only trap the carbon dioxide, which means that the carbon dioxide is not fully utilized, so that the method still has room for improving the utilization rate of carbon dioxide.
Disclosure of Invention
The invention provides a methane hydrogen production combined Buddha reaction system, which can realize green co-production of hydrogen and carbon monoxide, reduce the poisoning risk of the catalyst and realize the recycling utilization of carbon dioxide, so as to solve the problems that the utilization rate of the carbon dioxide is low and the catalyst is easy to accumulate and deactivate in the methane dry reforming process in the prior art. The invention also provides a method for combining methane with Buddha reaction, which has high yield and high product purity.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
The utility model provides a methane hydrogen manufacturing combines system of many alr reaction, including hydrogen manufacturing reactor and many alr reactor, be equipped with methane entry in the hydrogen manufacturing reactor, hydrogen export and hydrogen manufacturing side catalyst entry, be equipped with CO 2 entry in the many alr reactor, make CO side catalyst entry and CO export, hydrogen manufacturing side separator and hydrogen manufacturing side feed back valve are connected with making CO side catalyst entry in proper order to hydrogen manufacturing reactor's hydrogen export, the CO export of many alr reactor is connected with hydrogen manufacturing side catalyst entry through making CO side separator and making CO side feed back valve in proper order, hydrogen manufacturing side feed back valve and making CO side feed back valve still are equipped with inert gas entry, catalyst that fills in the system is difunctional catalytic carbon carrier.
The invention integrates a hydrogen production reactor and a Buddha reactor, wherein one end of the hydrogen production reactor is used for inputting methane, the other end is connected with the inlet of a hydrogen production side separator, and the other end is connected with the outlet of a CO production side feed back valve; one end of the Buddha reactor is input into the CO 2, the other end is connected with the inlet of the CO-side separator, and the other end is connected with the outlet of the hydrogen production side feed back valve; the hydrogen production side separator receives the H 2 gas flow containing the catalyst from the hydrogen production reactor, and simultaneously outputs the catalyst to the hydrogen production side feed back valve; the CO-making side separator receives a CO gas stream containing the catalyst from the Buddha reactor and simultaneously outputs the catalyst to a CO-making side feed back valve; the hydrogen production side feed back valve and the CO production side feed back valve are connected with inert gas at the bottom, and the flow of the catalyst in the hydrogen production side separator and the CO production side separator is respectively controlled by regulating and controlling the inflow of the inert gas. The catalyst moves in the whole system and generates a specific oxidation-reduction reaction with the reaction atmosphere in a fluidized state in a hydrogen preparation reactor and a Buddha reactor, in the hydrogen preparation reactor, methane is converted into hydrogen and carbon under the catalysis of the catalyst, the carbon can be combined with the catalyst and then enters the Buddha reactor along with the catalyst, and in the Buddha reactor, carbon dioxide reacts with carbon carried by the catalyst to be converted into CO.
Preferably, in the hydrogen production reactor, the methane inlet is arranged at the bottom of the hydrogen production reactor, the hydrogen outlet is arranged at the top of the hydrogen production reactor, and the hydrogen production side catalyst inlet is arranged at the side surface of the hydrogen production reactor.
The H 2 product is output from the upper end of the hydrogen production side separator.
Preferably, in the Buddha reactor, the CO 2 inlet is arranged at the bottom of the Buddha reactor, the CO outlet is arranged at the top of the Buddha reactor, and the CO-side catalyst inlet is arranged at the side of the Buddha reactor.
The CO product is output from the upper end of the CO side separator.
Preferably, the bifunctional catalytic carbon support comprises a wave-absorbing support material and a bifunctional catalytic active material coated on the surface of the wave-absorbing support material; the wave-absorbing carrier material is a mixture of SiC and oxide, the oxide is one or more materials of Al 2O3、SiO2 and ZrO 2, and the mass ratio of the SiC is 10-20%; the bifunctional catalytic active material is one or more of transition metal, la 2O3、K2 O and SrO.
Preferably, the mass ratio of SiC in the wave-absorbing carrier material is 10-20%, the mass ratio of Al 2O3 is 40-60%, the mass ratio of SiO 2 is 0-10%, and the mass ratio of ZrO 2 is 0-30%.
Preferably, the transition metal is Ni, fe, and Co.
Preferably, the loading mass ratio of the bifunctional catalytic active material in the bifunctional catalytic carbon carrier is 20-25%.
Preferably, the preparation step of the dual-function catalytic carbon carrier comprises the following steps:
(1) Adding oxides into SiC particles, mixing and grinding, controlling the particle size of the particles to be 300-400 meshes, calcining uniformly mixed powder in an air atmosphere at the calcining temperature of 1500 ℃, crushing and grinding the calcined product again, and controlling the average particle size to be 100-150 meshes to obtain the wave-absorbing carrier material;
(2) Preparing a precursor solution of a catalyst active component, dipping the precursor solution on a wave-absorbing carrier material, and then drying and calcining the precursor solution;
(3) And (3) carrying out reduction activation on the carbon carrier material by hydrogen to obtain the difunctional catalytic carbon carrier.
Preferably, in the step (2), the drying temperature is 110 to 150℃and the calcining temperature is 900 ℃.
Preferably, in the step (3), the reduction process is to use a mixed gas of 5% H 2、95% N2 to perform reduction activation under the condition of GHSV 300H -1, the heating rate is 10-15 ℃/min, the final temperature is 900 ℃, and the temperature is kept constant for 2 hours.
Preferably, heating devices are arranged on the outer sides of the hydrogen production reactor and the Buddha reactor respectively.
Preferably, the hydrogen production side feed back valve and the CO production side feed back valve are both U-shaped feed back valves, the hydrogen production side separator and the CO production side separator are both cyclone separators, and the heating device is a microwave heating device.
Preferably, the microwave heating device is divided into a plurality of areas along the flowing direction of the catalyst, and each area is provided with a microwave antenna and an infrared temperature measuring probe.
The microwave heating device is respectively arranged at the outer sides of the hydrogen production reactor and the Buddha reactor, the catalysts in the two reactors are heated, the microwave heating area is divided into a plurality of areas along the flowing direction of catalyst particles, each area is provided with a microwave antenna and an infrared temperature measuring probe, and the output power can be regulated and controlled according to the temperature distribution of the bed layer.
A method for producing hydrogen by combining methane with a Buddha reaction, which uses the system and comprises the following steps:
s1, loading a catalyst into a hydrogen production reactor, and then purging a system gas path by using inert gas;
S2, when the catalyst in the system is stable in circulating motion, inert gas input except a hydrogen production side feed back valve and a CO production side feed back valve is disconnected, and methane and CO 2 are respectively input into a hydrogen production reactor and a Buddha reactor;
S3, the catalyst in the system is stable in circulating motion, the temperature of the hydrogen production reactor is controlled to be 500-750 ℃, the temperature of the Buddha reactor is controlled to be 600-950 ℃, and products are collected at a hydrogen outlet of the hydrogen production reactor and a CO outlet of the Buddha reactor respectively.
The method integrates methane cracking reaction and Buddha reaction by using a chemical chain method to realize the co-production of hydrogen and carbon monoxide.
Preferably, the step S3 further comprises controlling the moving speed of the catalyst in the hydrogen production reactor to be 0.5-3.4m/S, and controlling the moving speed of the catalyst in the Buddha reactor to be 0.1-2.6m/S.
Therefore, the invention has the following beneficial effects:
(1) The method for realizing the CO-production of the hydrogen and the carbon monoxide by integrating the methane cracking reaction and the Buddha reaction by using the chemical chain method can realize clean and efficient hydrogen energy production and carbon dioxide resource utilization, the method utilizes methane cracking to produce the hydrogen, the purity of the obtained hydrogen is higher, impurities such as CO, NO x、SOx and the like are not existed, the poisoning risk of a catalyst in the application scene of a downstream fuel cell is avoided, the conversion of the carbon dioxide into the CO is realized, and the resource utilization of the carbon dioxide is realized;
(2) The whole system can realize continuous production of H 2 and CO in the double-function catalytic carbon carrier circulating oxidation-reduction reaction, and can realize accurate matching of H 2/CO proportion of a synthetic gas product by regulating and controlling the mixing proportion for downstream F-T synthesis, methanolysis reaction and other scenes;
(3) Compared with the traditional methods such as electric heating, gas heating and the like, the introduction of the microwave heating method obviously improves the energy consumption and the system response speed, and improves the economy and the production flexibility of the method;
(4) The device has compact overall design, simple method and good technical economy;
(5) By researching the reaction process design, the development of the difunctional catalytic carbon carrier, the microwave-assisted thermal catalytic process design, the methane hydrogen production reaction/Buddha reaction protocol and the like, compared with the prior art, the chemical chain conversion system and the carbon carrier catalyst for the methane hydrogen production combined Buddha reaction have the advantages of combined production of blue hydrogen and CO, recycling of carbon dioxide, low energy consumption of the integration process, high response speed, compact design, high reaction activity and good cycle stability.
Drawings
Fig. 1 is a schematic structural view of the present invention.
Wherein, 1-hydrogen production reactor, 2-Buduo Ab reactor, 3-hydrogen production side separator, 4-CO production side separator, 5-hydrogen production side feed back valve, 6-CO production side feed back valve, 7-heating device.
Detailed Description
The invention is further described below in connection with the detailed description and the accompanying drawings.
Example 1
A chemical chain conversion system for combining methane with Budohal reaction, the structure of which is shown in figure 1, comprising: the device comprises a hydrogen production reactor 1, a Buddha reactor 2, a hydrogen production side separator 3, a CO production side separator 4, a hydrogen production side feed back valve 5, a CO production side feed back valve 6, a heating device 7 and a bifunctional catalytic carbon carrier;
The diameter of the hydrogen production reactor 1 is 30cm, the height is 4m, the bottom of the hydrogen production reactor 1 is provided with a methane inlet, the top of the hydrogen production reactor 1 is provided with a hydrogen outlet, and the side surface of the hydrogen production reactor is provided with a hydrogen production side catalyst inlet; the diameter of the Buddha reactor 2 is 20cm, the height is 7m, the bottom of the Buddha reactor 2 is provided with a CO 2 inlet, the top is provided with a CO outlet, and the side face is provided with a catalyst inlet on the side of preparing CO; the hydrogen production side separator 3 and the CO production side separator 4 are cyclone separators; the hydrogen production side feed back valve 5 and the CO production side feed back valve 6 are U-shaped feed back valves, and the bottoms of the U-shaped feed back valves are respectively provided with an inert gas inlet; the heating device 7 is a microwave heating device and is respectively arranged at the outer sides of the hydrogen production reactor 1 and the Buduo-Alar reactor 2, the side surfaces of the hydrogen production reactor 1 and the Buduo-Alar reactor 2 are wrapped, the height 1m of the external heating device 7 of the hydrogen production reactor 1 is divided into four areas at intervals of 0.25m, the height 2m of the external heating device 7 of the Buduo-Alar reactor 2 is divided into 4 areas at intervals of 0.5m, and a microwave antenna and an infrared temperature measuring probe are arranged in each area;
The methane inlet of the hydrogen production reactor 1 is connected with a pipeline for transporting methane raw materials, the hydrogen outlet is connected with the inlet of the hydrogen production side separator 3 through a pipeline, and the hydrogen production side catalyst inlet is connected with the outlet of the CO production side feed back valve 6 through a pipeline; the CO 2 inlet of the Buddha reactor 2 is connected with a pipeline for transporting CO 2 raw material, the CO outlet is connected with the inlet of the CO preparing side separator 4 through a pipeline, and the CO preparing side catalyst inlet is connected with the outlet of the hydrogen preparing side feed back valve 5 through a pipeline; the outlet of the hydrogen production side separator 3 is connected with the inlet of the hydrogen production side feed back valve 5 through a pipeline, and the outlet of the CO production side separator 4 is connected with the inlet of the CO production side feed back valve 6 through a pipeline; the inert gas inlets of the hydrogen production side feed back valve 5 and the CO production side feed back valve 6 are connected with a pipeline for transporting inert gas; the catalyst filled in the system is a granular difunctional catalytic carbon carrier;
When the system is operated, the hydrogen production side separator 3 receives the H 2 airflow containing the double-function catalytic carbon carrier from the hydrogen production reactor 1, outputs the H 2 product from the upper hydrogen outlet, and simultaneously outputs the double-function catalytic carbon carrier to the hydrogen production side feed back valve 5; the CO preparing side separator 4 receives the CO gas flow containing the double-function catalytic carbon carrier from the Buddha reactor 2, outputs CO products from an upper CO outlet, and simultaneously outputs the double-function catalytic carbon carrier to the CO preparing side feed back valve 6; the hydrogen production side U-shaped feed back valve 4 and the CO production side U-shaped feed back valve 6 are connected with inert gas at the bottoms, and respectively control the flow of the difunctional catalytic carbon carriers transmitted from the hydrogen production side separator 3 and the CO production side separator 4.
Example 2
A method for producing hydrogen from methane in combination with a butcher reaction using the system of example 1, comprising the steps of:
s1, loading a difunctional catalytic carbon carrier into a hydrogen production reactor, wherein the loading capacity is 10kg, and then purging a system gas path by using inert gas;
S2, disconnecting inert gas input except a hydrogen production side feed back valve and a CO production side feed back valve when the circulation movement of the difunctional catalytic carbon carrier in the system is stable, and inputting methane and CO 2 into a hydrogen production reactor and a Buddha reactor at flow rates of 3.4m/S and 2.6m/S respectively;
S3, the circulation movement of the bifunctional catalytic carbon carrier in the system is stable, the temperature at the position with the height of 0.5m of the bed layer of the hydrogen production reactor is controlled to be 600 ℃, the temperature at the position with the height of 1.0m of the bed layer of the Buddha reactor is controlled to be 800 ℃, the flowing speed of the bifunctional catalytic carbon carrier in the hydrogen production reactor is controlled to be 0.8m/S by regulating and controlling the air inlet speeds of methane and CO 2, the flowing speed of the bifunctional catalytic carbon carrier in the Buddha reactor is controlled to be 0.5m/S, and products are collected at a hydrogen outlet of the hydrogen production reactor and a CO outlet of the Buddha reactor respectively;
The difunctional catalytic carbon carrier in S1 is prepared by the following steps:
(1) Mixing particles of SiC and Al 2O3、SiO2, wherein the mass ratio is controlled as follows: siC: al 2O3：SiO2 = 0.2:0.77:0.03, ball milling the mixed particles, screening the mixed particles after ball milling, controlling the particle size of the particles to be 300-400 meshes, then calcining the particles in an air atmosphere at a heating rate of 1 ℃/min, calcining at a temperature of 1500 ℃ for 6 hours, naturally cooling, taking a calcined product, ball milling again, and screening the product after ball milling to obtain the wave-absorbing carrier material with the particle size of 100-150 meshes;
(2) Preparing Ni (NO 3)2、Fe(NO3)3、Sr(NO3)2、KNO3 mixed solution, controlling the total concentration of cations to be 3mol/L, controlling the ion concentration ratio Ni to Fe to Sr to K=0.6 to 0.25 to 0.1 to 0.05, loading the Ni on a wave-absorbing carrier material by an isovolumetric impregnation method, heating to 120 ℃ at 5 ℃/min for drying treatment for 5 hours, and heating to 500 ℃ at a heating rate of 1 ℃/min for calcining treatment for 5 hours;
(3) And (3) placing the cooled catalyst material into a reduction furnace, heating to 900 ℃ at a speed of 1 ℃/min under the atmosphere of 5% H 2, keeping the temperature for 6 hours, carrying out reduction treatment, and naturally cooling to obtain the bifunctional catalytic carbon carrier.
Example 3
A method for producing hydrogen from methane in combination with a butcher reaction, using the system of example 1, the steps of which differ from those of example 2 in the use of a bifunctional catalytic carbon support prepared by:
(1) Mixing particles of SiC and Al 2O3、SiO2, wherein the mass ratio is controlled as follows: siC: al 2O3：ZrO2 = 0.2:0.7:0.1, ball milling the mixed particles, screening the mixed particles after ball milling, controlling the particle size of the particles to be 300-400 meshes, then calcining the particles in an air atmosphere at a heating rate of 1 ℃/min, calcining at a temperature of 1500 ℃ for 6 hours, naturally cooling, taking a calcined product, ball milling again, and screening the product after ball milling to obtain the wave-absorbing carrier material with the particle size of 100-150 meshes;
(2) Preparing Ni (NO 3)2、Co(NO3)2、Sr(NO3)2、KNO3 mixed solution, controlling the total concentration of cations to be 3mol/L, controlling the ion concentration ratio Ni to Co to be Sr to be K=0.4 to be 0.35 to be 0.05 to be 0.2), loading the Ni on a wave-absorbing carrier material by an isovolumetric impregnation method, heating to 120 ℃ at 5 ℃/min for drying treatment for 5 hours, and heating to 500 ℃ at a heating rate of 1 ℃/min for calcining treatment for 5 hours;
(3) And (3) placing the cooled catalyst material into a reduction furnace, heating to 900 ℃ at a speed of 1 ℃/min under the atmosphere of 5% H 2, keeping the temperature for 6 hours, carrying out reduction treatment, and naturally cooling to obtain the bifunctional catalytic carbon carrier.
Example 4
A method for producing hydrogen from methane in combination with a butcher reaction, using the system of example 1, the steps of which differ from example 2 in the temperatures of the hydrogen production reactor and the butcher reactor, specifically by:
s1, loading a difunctional catalytic carbon carrier into a hydrogen production reactor, wherein the loading capacity is 10kg, and then purging a system gas path by using inert gas;
s2, disconnecting inert gas input except a hydrogen production side feed back valve and a CO production side feed back valve when the circulation movement of the difunctional catalytic carbon carrier in the system is stable, and inputting methane and CO 2 into a hydrogen production reactor and a Buddha reactor at flow rates of 2.04m/S and 1.56m/S respectively;
s3, the circulation movement of the bifunctional catalytic carbon carrier in the system is stable, the temperature at the position with the height of 0.5m of the bed layer of the hydrogen production reactor is controlled to be 450 ℃, the temperature at the position with the height of 1.0m of the bed layer of the Buddha reactor is controlled to be 700 ℃, the flow speed of the bifunctional catalytic carbon carrier in the hydrogen production reactor is controlled to be 0.5 m/S by regulating the inlet speeds of methane and CO 2, the flow speed of the bifunctional catalytic carbon carrier in the Buddha reactor is controlled to be 0.1 m/S, and products are collected at a hydrogen outlet of the hydrogen production reactor and a CO outlet of the Buddha reactor respectively;
The difunctional catalytic carbon carrier in S1 is prepared by the following steps:
(1) Mixing particles of SiC and Al 2O3、SiO2, wherein the mass ratio is controlled as follows: siC: al 2O3：SiO2 = 0.2:0.77:0.03, ball milling the mixed particles, screening the mixed particles after ball milling, controlling the particle size of the particles to be 300-400 meshes, then calcining the particles in an air atmosphere at a heating rate of 1 ℃/min, calcining at a temperature of 1500 ℃ for 6 hours, naturally cooling, taking a calcined product, ball milling again, and screening the product after ball milling to obtain the wave-absorbing carrier material with the particle size of 100-150 meshes;
(2) Preparing Ni (NO 3)2、Fe(NO3)3、Sr(NO3)2、KNO3 mixed solution, controlling the total concentration of cations to be 3mol/L, controlling the ion concentration ratio Ni to Fe to Sr to K=0.6 to 0.25 to 0.1 to 0.05, loading the Ni on a wave-absorbing carrier material by an isovolumetric impregnation method, heating to 120 ℃ at 5 ℃/min for drying treatment for 5 hours, and heating to 500 ℃ at a heating rate of 1 ℃/min for calcining treatment for 5 hours;
(3) And (3) placing the cooled catalyst material into a reduction furnace, heating to 900 ℃ at a speed of 1 ℃/min under the atmosphere of 5% H 2, keeping the temperature for 6 hours, carrying out reduction treatment, and naturally cooling to obtain the bifunctional catalytic carbon carrier.
Example 5
A method for producing hydrogen from methane in combination with a butcher reaction, using the system of example 1, the steps of which differ from example 2 in the temperatures of the hydrogen production reactor and the butcher reactor, specifically by:
s1, loading a difunctional catalytic carbon carrier into a hydrogen production reactor, wherein the loading capacity is 10kg, and then purging a system gas path by using inert gas;
s2, disconnecting inert gas input except a hydrogen production side feed back valve and a CO production side feed back valve when the circulation movement of the difunctional catalytic carbon carrier in the system is stable, and inputting methane and CO 2 into a hydrogen production reactor and a Buddha reactor at flow rates of 4.08m/S and 3.12m/S respectively;
s3, the circulation movement of the difunctional catalytic carbon carrier in the system is stable, the temperature at the position with the height of 0.5m of the bed layer of the hydrogen production reactor is controlled to be 750 ℃, the temperature at the position with the height of 1.0m of the bed layer of the Buddha reactor is controlled to be 1000 ℃, the flowing speed of the difunctional catalytic carbon carrier in the hydrogen production reactor is 3.4m/S by regulating and controlling the air inlet speed of methane and CO 2, the flowing speed of the difunctional catalytic carbon carrier in the Buddha reactor is 2.6m/S, and products are respectively collected at a hydrogen outlet of the hydrogen production reactor and a CO outlet of the Buddha reactor;
The difunctional catalytic carbon carrier in S1 is prepared by the following steps:
(1) Mixing particles of SiC and Al 2O3、SiO2, wherein the mass ratio is controlled as follows: siC: al 2O3：SiO2 = 0.2:0.77:0.03, ball milling the mixed particles, screening the mixed particles after ball milling, controlling the particle size of the particles to be 300-400 meshes, then calcining the particles in an air atmosphere at a heating rate of 1 ℃/min, calcining at a temperature of 1500 ℃ for 6 hours, naturally cooling, taking a calcined product, ball milling again, and screening the product after ball milling to obtain the wave-absorbing carrier material with the particle size of 100-150 meshes;
(2) Preparing Ni (NO 3)2、Fe(NO3)3、Sr(NO3)2、KNO3 mixed solution, controlling the total concentration of cations to be 3mol/L, controlling the ion concentration ratio Ni to Fe to Sr to K=0.6 to 0.25 to 0.1 to 0.05, loading the Ni on a wave-absorbing carrier material by an isovolumetric impregnation method, heating to 120 ℃ at 5 ℃/min for drying treatment for 5 hours, and heating to 500 ℃ at a heating rate of 1 ℃/min for calcining treatment for 5 hours;
(3) And (3) placing the cooled catalyst material into a reduction furnace, heating to 900 ℃ at a speed of 1 ℃/min under the atmosphere of 5% H 2, keeping the temperature for 6 hours, carrying out reduction treatment, and naturally cooling to obtain the bifunctional catalytic carbon carrier.
Comparative example 1
A method for producing hydrogen from methane in combination with a butcher reaction, using the system of example 1, the steps of which differ from example 2 in the flow rates of the bifunctional catalytic carbon support in the hydrogen production reactor and the butcher reactor, specifically as follows:
s1, loading a difunctional catalytic carbon carrier into a hydrogen production reactor, wherein the loading capacity is 10kg, and then purging a system gas path by using inert gas;
s2, disconnecting inert gas input except a hydrogen production side feed back valve and a CO production side feed back valve when the circulation movement of the difunctional catalytic carbon carrier in the system is stable, and inputting methane and CO 2 into a hydrogen production reactor and a Buddha reactor at flow rates of 6m/S and 4m/S respectively;
S3, the circulation movement of the difunctional catalytic carbon carrier in the system is stable, the temperature of the hydrogen production reactor is controlled to be 400 ℃, the temperature of the Buddha reactor is controlled to be 600 ℃, the flow speed of the difunctional catalytic carbon carrier in the hydrogen production reactor is controlled to be 4 m/S by regulating and controlling the air inlet speed of methane and CO 2, the flow speed of the difunctional catalytic carbon carrier in the Buddha reactor is 3 m/S, and products are collected at a hydrogen outlet of the hydrogen production reactor and a CO outlet of the Buddha reactor respectively;
The difunctional catalytic carbon carrier in S1 is prepared by the following steps:
(1) Mixing particles of SiC and Al 2O3、SiO2, wherein the mass ratio is controlled as follows: siC: al 2O3：SiO2 = 0.2:0.77:0.03, ball milling the mixed particles, screening the mixed particles after ball milling, controlling the particle size of the particles to be 300-400 meshes, then calcining the particles in an air atmosphere at a heating rate of 1 ℃/min, calcining at a temperature of 1500 ℃ for 6 hours, naturally cooling, taking a calcined product, ball milling again, and screening the product after ball milling to obtain the wave-absorbing carrier material with the particle size of 100-150 meshes;
(2) Preparing Ni (NO 3)2、Fe(NO3)3、Sr(NO3)2、KNO3 mixed solution, controlling the total concentration of cations to be 3mol/L, controlling the ion concentration ratio Ni to Fe to Sr to K=0.6 to 0.25 to 0.1 to 0.05, loading the Ni on a wave-absorbing carrier material by an isovolumetric impregnation method, heating to 120 ℃ at 5 ℃/min for drying treatment for 5 hours, and heating to 500 ℃ at a heating rate of 1 ℃/min for calcining treatment for 5 hours;
(3) And (3) placing the cooled catalyst material into a reduction furnace, heating to 900 ℃ at a speed of 1 ℃/min under the atmosphere of 5% H 2, keeping the temperature for 6 hours, carrying out reduction treatment, and naturally cooling to obtain the bifunctional catalytic carbon carrier.
The product yields at the hydrogen outlet of the hydrogen production reactor and at the CO outlet of the butcher reactor for examples 2-5 and comparative example 1 are shown in the following table, wherein the methane conversion and CO 2 conversion were calculated by the following methods:
，
The residual methane content was detected at the hydrogen outlet of the hydrogen production reactor, the residual CO 2 content was detected at the CO outlet of the Buddha reactor, and the detection results are shown in Table 1.
TABLE 1 Hydrogen, CO production for examples 2-5 and comparative example 1
As can be seen from the table, the invention realizes the joint production of hydrogen and CO and the resource utilization of carbon dioxide.
The reaction temperature in comparative example 1 is lower, and the flow speed is higher under the drive of the high gas speed of the catalyst, so that the conversion rate of methane and CO 2 is low.
Claims (10)
1. The utility model provides a methane hydrogen manufacturing combines system of cloth multi-alr reaction, which is characterized by including hydrogen manufacturing reactor (1) and cloth multi-alr reactor (2), be equipped with methane entry in hydrogen manufacturing reactor (1), hydrogen export and hydrogen manufacturing side catalyst entry, be equipped with CO 2 entry in cloth multi-alr reactor (2), CO manufacturing side catalyst entry and CO export, hydrogen export of hydrogen manufacturing reactor (1) loops through hydrogen manufacturing side separator (3) and hydrogen manufacturing side feed back valve (5) and is connected with CO manufacturing side catalyst entry, CO export of cloth multi-alr reactor (2) loops through CO manufacturing side separator (4) and CO manufacturing side feed back valve (6) and is connected with hydrogen manufacturing side catalyst entry, hydrogen manufacturing side feed back valve (5) and CO manufacturing side feed back valve (6) still are equipped with the inert gas entry, the catalyst that fills in the system is difunctional catalytic carbon carrier.
2. The system for combining methane and bunyall reactions according to claim 1 wherein in said hydrogen production reactor (1), the methane inlet is at the bottom of the hydrogen production reactor (1), the hydrogen outlet is at the top of the hydrogen production reactor (1), the hydrogen production side catalyst inlet is at the side of the hydrogen production reactor (1).
3. A system for producing hydrogen from methane in combination with a butoxide reaction according to claim 1 or 2, characterized in that in the butoxide reactor (2), the CO 2 inlet is at the bottom of the butoxide reactor (2), the CO outlet is at the top of the butoxide reactor (2), and the CO side catalyst inlet is at the side of the butoxide reactor (2).
4. The system for producing hydrogen from methane in combination with a butcher reaction according to claim 1, wherein the bi-functional catalytic carbon support comprises a wave-absorbing support material and a bi-functional catalytic active material coated on the surface of the wave-absorbing support material; the wave-absorbing carrier material is a mixture of SiC and oxide, the oxide is one or more materials of Al 2O3、SiO2 and ZrO 2, and the mass ratio of the SiC is 10-20%; the bifunctional catalytic active material is one or more of transition metal, la 2O3、K2 O and SrO.
5. A methane-producing Co-bundear reaction system in accordance with claim 4, wherein said transition metals are Ni, fe and Co.
6. A methane-producing co-bundear reaction system according to claim 4 or 5, wherein the dual-function catalytic carbon support has a dual-function catalytic active material loading mass ratio of 20-25%.
7. A methane hydrogen production combined brazier reaction system according to claim 1,2 or 4, characterized in that the outside of the hydrogen production reactor (1) and the brazier reactor (2) are respectively provided with a heating device (7).
8. The methane-hydrogen-production combined Buddha reaction system according to claim 7, wherein the hydrogen-production side feed back valve (5) and the CO-production side feed back valve (6) are both U-shaped feed back valves, the hydrogen-production side separator (3) and the CO-production side separator (4) are both cyclone separators, and the heating device (7) is a microwave heating device.
9. A process for producing hydrogen from methane in combination with a butcher reaction, characterized in that it uses a system according to any one of claims 1 to 8, comprising the steps of:
s1, loading a catalyst into a hydrogen production reactor, and then purging a system gas path by using inert gas;
S2, when the catalyst in the system is stable in circulating motion, inert gas input except a hydrogen production side feed back valve and a CO production side feed back valve is disconnected, and methane and CO 2 are respectively input into a hydrogen production reactor and a Buddha reactor;
S3, the catalyst in the system is stable in circulating motion, the temperature of the hydrogen production reactor is controlled to be 500-750 ℃, the temperature of the Buddha reactor is controlled to be 600-950 ℃, and products are collected at a hydrogen outlet of the hydrogen production reactor and a CO outlet of the Buddha reactor respectively.
10. The method for producing hydrogen from methane in combination with a butcher reaction according to claim 9, wherein S3 further comprises controlling the catalyst moving speed in the hydrogen production reactor to be 0.5-3.4m/S and the catalyst moving speed in the butcher reactor to be 0.1-2.6m/S.
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