CN109721028B - Method for preparing hydrogen by reforming methane and hydrogen sulfide - Google Patents
Method for preparing hydrogen by reforming methane and hydrogen sulfide Download PDFInfo
- Publication number
- CN109721028B CN109721028B CN201711023753.4A CN201711023753A CN109721028B CN 109721028 B CN109721028 B CN 109721028B CN 201711023753 A CN201711023753 A CN 201711023753A CN 109721028 B CN109721028 B CN 109721028B
- Authority
- CN
- China
- Prior art keywords
- hydrogen sulfide
- methane
- catalyst
- carrier
- perovskite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The method for preparing hydrogen by reforming methane and hydrogen sulfide comprises the following steps of carrying out contact reaction on hydrogen sulfide and methane and a catalyst with the following mass composition: 5% -65% of Fe2O31% -20% of Co2O315% -94% of LaMO3Wherein LaMO3Is a carrier with a perovskite structure, and M is at least one selected from Co, Fe and Ni. The invention takes perovskite type oxide as a carrier to load Fe2O3And Co2O3As active components, firstly the perovskite type oxide has very good stability at high temperature and is suitable for high-temperature reaction, and secondly the perovskite type oxideThe compound has rich oxygen vacancies, contains rich lattice oxygen and is beneficial to the activation of methane and hydrogen sulfide, and the iron oxide and the cobalt oxide are used as double active components, so that the conversion rate of the methane and the hydrogen sulfide can be effectively improved, the reaction temperature is reduced, the reactant has higher conversion rate at relatively lower temperature, and the energy consumption is reduced.
Description
Technical Field
The invention relates to a method for preparing hydrogen by reforming methane hydrogen sulfide, in particular to a method for catalyzing the reforming of methane hydrogen sulfide by adopting a catalyst with a perovskite structure, and belongs to the catalyst technology in the field of hydrogen preparation by reforming methane.
Background
The sulfur in natural gas exists mainly in the form of H2S and the balance of organic sulfur such as mercaptan, thioether and the like, and the organic sulfur can be converted into H through hydrogenation2S。H2S is a gas with strong toxicity, malodor and strong corrosiveness, so the sulfur-containing natural gas can bring a series of complex problems to well drilling, gas production, gas transmission and the like, and can cause the breakage of a drilling tool and the severe corrosion of an oil pipe, a gas pipe and the like, thereby causing huge economic loss. Therefore, H is properly disposed of or utilized2S is also a serious problem in the petrochemical industry in China.
At present, H in China2The S utilization technique is also dominated by the Claus process, with the main product being sulfur. However, the international sulfur market is saturated at present, and the sulfur price drops all the way, so H is used2S is a raw material for producing sulfur, so that development of H is urgently needed2S using a new method. A great deal of H is carried out on Chinese scientists2Research on hydrogen production by S decomposition, e.g. by using a double reaction process consisting of redox reaction and electrolysis reaction2When the acid tail gas is treated, the sulfur in the acid tail gas is recovered, and high-purity hydrogen can be prepared. The prepared hydrogen can be reused in the hydrodesulfurization process of fuel oil, and the comprehensive utilization of hydrogen is realized. The process is feasible through the research of the enlarged test of Shenghua oil refinery at the university of petroleum (east China). For example, the great-continuous-substance research institute develops a super-adiabatic combustion technology, which is applied to hydrogen sulfide decomposition hydrogen production and utilizes H under the condition of not using a catalyst and an external heating source2S is subjected to super-adiabatic partial oxidative decomposition in a porous medium to remove H2S and hydrogen can be recovered, and the pollution emission is obviously reduced. The technology can be used for treating the workers containing toxic and harmful componentsIndustrial waste gas. Up to now, the vast majority of the foreign industrial hydrogen comes from CH4The hydrogen production technology is mature, the production cost is low, but CO and CO are generated in the process2The difficulty is caused to the emission reduction of greenhouse gas, and the raw material also needs to be subjected to a desulfurization process, so that the energy consumption of the whole process is increased.
H2S and CH4The products of reforming are hydrogen and easily liquefiable stored CS2This is H2S is a novel way of utilization and is therefore of particular interest. At present, there is no H in China2S and CH4The reforming hydrogen production aspect of (1). Foreign scientists already in the United states, Mexico, and other countries are engaged in H2S and CH4The research on the reforming hydrogen production process mainly takes kinetics, thermodynamics and simulation as main researches. Thermodynamic analysis was performed by Huang et al in the United states and analysis found that the reaction temperature exceeded 1000 deg.CoC methane can be completely converted, and the conversion rate of hydrogen sulfide is lower, 1000oC is only 30%; Martinez-Salazar et al Pair Mo/La in Mexico2O3-ZrO2The catalyst is subjected to kinetic analysis and simulation, the reaction temperature is 850 ℃ and CH4/H2S =1/12, at H2In the case of a large excess of S, the methane conversion is only 82%.
H reported in the literature2S and CH4The reforming catalyst is mainly Fe catalyst and Mo catalyst, and the carrier is Al2O3. The reaction is generally carried out at temperatures above 800 ℃ so Al2O3The series of catalysts have the problem of poor high-temperature reaction performance.
Disclosure of Invention
Aims to solve the problem that Al is generally used in the hydrogen production reaction by reforming methane and hydrogen sulfide in the prior art2O3The series of catalysts have poor high-temperature stability, resulting in H2The invention aims to provide a method for preparing hydrogen by reforming methane and hydrogen sulfide, which catalyzes the reaction by using a catalyst with a perovskite structure and has the advantages of good high-temperature stability, high catalyst activity and H2High S conversion rate.
The technical scheme adopted by the invention is as follows:
the method for preparing hydrogen by reforming methane and hydrogen sulfide comprises the following steps of carrying out contact reaction on hydrogen sulfide and methane and a catalyst with the following mass composition:
Fe2O35%~65%
Co2O31%~20%
LaMO315%~94%
wherein LaMO3Is a carrier with a perovskite structure, and M is at least one selected from Co, Fe and Ni.
In the above method, as a further preferable aspect, the catalyst composition is:
Fe2O310%~40%
Co2O35~20%
in the method, the temperature of the methane hydrogen sulfide reforming reaction is 600-1200 ℃, preferably 700-800 ℃; the reaction pressure is 0.1 to 2MPa, preferably 0.1 to 1 MPa.
In the above process, the catalyst is prepared by the following method: preparing soluble salt of at least one of iron, nickel or cobalt into solution, adding lanthanum nitrate solution, adding citric acid solution or ethylene glycol, evaporating to form gel, taking out, drying, roasting to obtain perovskite type oxide carrier, loading iron and cobalt onto the carrier by adopting an impregnation method, drying, and roasting to obtain the catalyst.
In the above method, in the preparation of the catalyst, the soluble salt of iron, nickel or cobalt is preferably a nitrate. When the carrier is prepared, the citric acid solution or the ethylene glycol is used as a complexing agent, and the adding amount of the complexing agent is that the molar ratio of the citric acid solution or the ethylene glycol to the metal ions is 1: 1-5: 1, preferably 1: 1-3: 1; the reaction temperature is 30-90 ℃, preferably 50-80 ℃, and the reaction time is 3-8 hours, preferably 4-6 hours; stirring the mixture during the reaction process, wherein the stirring speed is 100-500 rpm, preferably 300-400 rpm; the drying temperature of the carrier is 60-200 ℃, preferably 80-150 ℃, and the drying time is 1-36 hours, preferably 8-24 hours; the roasting is carried out at 400-1000 ℃ for 2-15 hours, preferably at 600-900 ℃ for 3-8 hours. The impregnation method is equal-volume impregnation or over-volume impregnation.
Compared with the prior art, the invention has the following advantages:
the invention takes perovskite type oxide as a carrier to load Fe2O3And Co2O3The perovskite type oxide has rich oxygen vacancies and contains rich lattice oxygen, which is beneficial to the activation of methane and hydrogen sulfide, and the iron oxide and the cobalt oxide are used as double active components, so that the conversion rate of the methane and the hydrogen sulfide can be effectively improved, the reaction temperature is reduced, the reactant has higher conversion rate at relatively lower temperature, and the energy consumption is reduced. In addition, the catalyst has the advantages of low cost and easy obtainment of raw materials, simple preparation method and suitability for industrial application.
Drawings
FIG. 1X-ray diffraction pattern of the catalyst prepared in example 1.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
Catalysts were prepared in examples 1-7 and comparative examples 1-3:
example 1
49.15g of Fe (NO) are taken3)3·6H2O was placed in a 500mL beaker, 100mL of distilled water was added, and the mixture was placed in a water bath at 80 ℃ with a stirring speed of 400 rpm. 34.3g of La (NO) was taken3)3·6H2O, put into a beaker containing 100mL of distilled water, and stirred until the solution was completely dissolved. Then, the lanthanum nitrate solution is added dropwise into the ferric nitrate solution while stirring. 40g of citric acid is taken and put into a beaker with 100mL of the citric acid and stirred until the citric acid is completely dissolved, and after the mixed solution is stirred for 30 minutes, the citric acid solution is slowly added and stirred while being dropwise added. After stirring for 5 hours, the solution had dehydrated to a viscous gel, which was taken out into a drying oven at 110 ℃ and dried overnight. Then theTaking out the dried perovskite precursor, placing the perovskite precursor in a muffle furnace, heating from room temperature to 400 ℃ at the heating rate of 3 ℃/min, roasting at constant temperature for 3 hours, heating to 900 ℃ at the heating rate of 10 ℃/min, and roasting at constant temperature for 4 hours to obtain the carrier with the perovskite structure. Mixing Fe (NO)3)3·6H2O and Co (NO)3)3·6H2Placing O into a 100mL beaker, adding 50mL of distilled water, soaking the O onto the perovskite oxide carrier by using a rotary evaporator after dissolving, taking out the O, standing overnight in a 120 ℃ drying oven, and roasting in a 900 ℃ muffle furnace for 4 hours to obtain Fe2O3-Co2O3/LaFeO3Catalyst of which Fe2O3Supported in an amount of 15wt%, Co2O3The loading is 1 weight percent, and LaFeO3The carrier was 84 wt%.
FIG. 1 is Fe prepared by the above method2O3-Co2O3/LaFeO3XRD spectrum of 32 at 2 thetao、40o、46.5oAnd 57.5oThe characteristic diffraction peak of the ferric oxide appears, the peak shape is symmetrical and the peak intensity is better, which indicates that the ferric oxide crystal form is complete, and the ferric oxide catalyst prepared by the method is mainly dispersed on the surface of the carrier and is beneficial to the methane hydrogen sulfide reforming reaction controlled by diffusion. The cobalt oxide content is low, and the diffraction peak of the cobalt oxide cannot be seen on the graph.
Example 2
49.15g of Fe (NO) are taken3)3·6H2O was placed in a 500mL beaker, 100mL of distilled water was added, and the mixture was placed in a water bath at 80 ℃ with a stirring speed of 400 rpm. 34.3g of La (NO) was taken3)3·6H2O, put into a beaker containing 100mL of distilled water, and stirred until the solution was completely dissolved. Then, the lanthanum nitrate solution is added dropwise into the ferric nitrate solution while stirring. 40g of citric acid is taken and put into a beaker with 100mL of the citric acid and stirred until the citric acid is completely dissolved, and after the mixed solution is stirred for 30 minutes, the citric acid solution is slowly added and stirred while being dropwise added. After stirring for 5 hours, the solution had dehydrated to a viscous gel, which was taken out into a drying oven at 110 ℃ and dried overnight. Then taking out the driedAnd (3) placing the dried perovskite precursor into a muffle furnace, heating from room temperature to 400 ℃ at the heating rate of 3 ℃/min, roasting at constant temperature for 3 hours, heating to 900 ℃ at the heating rate of 10 ℃/min, and roasting at constant temperature for 4 hours to obtain the carrier with the perovskite structure. Taking Fe (NO)3)3·6H2O and Co (NO)3)3·6H2Putting O into a 100mL beaker, adding 50mL of distilled water, soaking the O on the perovskite oxide carrier by using a rotary evaporator after dissolving, taking out the O, standing overnight in a 120 ℃ drying oven, and roasting for 4 hours in a 900 ℃ muffle furnace to obtain Fe2O3-Co2O3/LaFeO3Catalyst of which Fe2O3Loading of 10wt% of Co2O3The loading capacity is 10 percent, and LaFeO3The carrier is 80 wt%.
Example 3
49.15g of Fe (NO) are taken3)3·6H2O was placed in a 500mL beaker, 100mL of distilled water was added, and the mixture was placed in a water bath at 80 ℃ with a stirring speed of 400 rpm. 34.3g of La (NO) was taken3)3·6H2O, put into a beaker containing 100mL of distilled water, and stirred until the solution was completely dissolved. Then, the lanthanum nitrate solution is added dropwise into the ferric nitrate solution while stirring. 40g of citric acid is taken and put into a beaker with 100mL of the citric acid and stirred until the citric acid is completely dissolved, and after the mixed solution is stirred for 30 minutes, the citric acid solution is slowly added and stirred while being dropwise added. After stirring for 5 hours, the solution had dehydrated to a viscous gel, which was taken out into a drying oven at 110 ℃ and dried overnight. And then taking out the dried perovskite precursor, placing the perovskite precursor in a muffle furnace, heating the perovskite precursor from room temperature to 400 ℃ at the heating rate of 3 ℃/min, roasting the perovskite precursor at constant temperature for 3 hours, heating the perovskite precursor to 900 ℃ at the heating rate of 10 ℃/min, and roasting the perovskite precursor at constant temperature for 4 hours to obtain the carrier with the perovskite structure. Taking Fe (NO)3)3·6H2O and Co (NO)3)3·6H2Putting O into a 100mL beaker, adding 50mL of distilled water, soaking the O on the perovskite oxide carrier by using a rotary evaporator after dissolving, taking out the O, standing overnight in a 120 ℃ drying oven, and roasting for 4 hours in a 900 ℃ muffle furnace to obtain Fe2O3-Co2O3/LaFeO3Catalyst of which Fe2O3Supported in an amount of 30wt%, Co2O3The loading amount is 5 percent, and LaFeO3The carrier was 65 wt%.
Example 4
49.15g of Fe (NO) are taken3)3·6H2O was placed in a 500mL beaker, 100mL of distilled water was added, and the mixture was placed in a water bath at 80 ℃ with a stirring speed of 400 rpm. 34.3g of La (NO) was taken3)3·6H2O, put into a beaker containing 100mL of distilled water, and stirred until the solution was completely dissolved. Then, the lanthanum nitrate solution is added dropwise into the ferric nitrate solution while stirring. 40g of citric acid is taken and put into a beaker with 100mL of the citric acid and stirred until the citric acid is completely dissolved, and after the mixed solution is stirred for 30 minutes, the citric acid solution is slowly added and stirred while being dropwise added. After stirring for 5 hours, the solution had dehydrated to a viscous gel, which was taken out into a drying oven at 110 ℃ and dried overnight. And then taking out the dried perovskite precursor, placing the perovskite precursor in a muffle furnace, heating the perovskite precursor from room temperature to 400 ℃ at the heating rate of 3 ℃/min, roasting the perovskite precursor at constant temperature for 3 hours, heating the perovskite precursor to 900 ℃ at the heating rate of 10 ℃/min, and roasting the perovskite precursor at constant temperature for 4 hours to obtain the carrier with the perovskite structure. Taking Fe (NO)3)3·6H2O and Co (NO)3)3·6H2Placing O into a 100mL beaker, adding 50mL of distilled water, soaking the O on the perovskite oxide carrier by using a rotary evaporator after dissolving, taking out the O after soaking, and then taking out the O120oC, standing overnight in a drying oven, and roasting for 4 hours in a muffle furnace at 900 ℃ to obtain Fe2O3- Co2O3/LaFeO3Catalyst of which Fe2O3Loading of 40wt% of Co2O3The loading amount is 5 percent, and LaFeO3The carrier was 55 wt%.
Example 5
49.15g of Fe (NO) are taken3)3·6H2O was placed in a 500mL beaker, 100mL of distilled water was added, and the mixture was placed in a water bath at 80 ℃ with a stirring speed of 400 rpm. 34.3g of La (NO) was taken3)3·6H2O, putting into a beaker with 100mL of distilled water, and stirringStirring until all the components are dissolved. Then, the lanthanum nitrate solution is added dropwise into the ferric nitrate solution while stirring. 40g of citric acid is taken and put into a beaker with 100mL of the citric acid and stirred until the citric acid is completely dissolved, and after the mixed solution is stirred for 30 minutes, the citric acid solution is slowly added and stirred while being dropwise added. After stirring for 5 hours, the solution had dehydrated to a viscous gel, which was taken out into a drying oven at 110 ℃ and dried overnight. And then taking out the dried perovskite precursor, placing the perovskite precursor in a muffle furnace, heating the perovskite precursor from room temperature to 400 ℃ at the heating rate of 3 ℃/min, roasting the perovskite precursor at constant temperature for 3 hours, heating the perovskite precursor to 900 ℃ at the heating rate of 10 ℃/min, and roasting the perovskite precursor at constant temperature for 4 hours to obtain the carrier with the perovskite structure. Taking Fe (NO)3)3·6H2O and Co (NO)3)3·6H2Putting O into a 100mL beaker, adding 50mL of distilled water, soaking the O on the perovskite oxide carrier by using a rotary evaporator after dissolving, taking out the O, standing overnight in a 120 ℃ drying oven, and roasting for 4 hours in a 900 ℃ muffle furnace to obtain Fe2O3- Co2O3/LaFeO3Catalyst of which Fe2O3Supported in an amount of 30wt%, Co2O3The loading capacity is 10 percent, and LaFeO3The carrier is 50 wt%.
Example 6
49.15g of Fe (NO) are taken3)3·6H2O was placed in a 500mL beaker, 100mL of distilled water was added, and the mixture was placed in a water bath at 80 ℃ with a stirring speed of 400 rpm. 34.3g of La (NO) was taken3)3·6H2O, put into a beaker containing 100mL of distilled water, and stirred until the solution was completely dissolved. Then, the lanthanum nitrate solution is added dropwise into the ferric nitrate solution while stirring. 40g of citric acid is taken and put into a beaker with 100mL of the citric acid and stirred until the citric acid is completely dissolved, and after the mixed solution is stirred for 30 minutes, the citric acid solution is slowly added and stirred while being dropwise added. After stirring for 5 hours, the solution had dehydrated to a viscous gel, which was taken out into a drying oven at 110 ℃ and dried overnight. Then taking out the dried perovskite precursor, placing the perovskite precursor in a muffle furnace, heating the perovskite precursor from room temperature to 400 ℃ at the heating rate of 3 ℃/min, roasting the perovskite precursor for 3 hours at constant temperature, and then heating the perovskite precursor for 10 ℃/minThe temperature is raised to 700 ℃, and the carrier with the perovskite structure is obtained after the constant temperature roasting for 4 hours. Taking Fe (NO)3)3·6H2O and Co (NO)3)3·6H2Putting O into a 100mL beaker, adding 50mL of distilled water, soaking the O on the perovskite oxide carrier by using a rotary evaporator after dissolving, taking out the O, standing overnight in a 120 ℃ drying oven, and roasting for 4 hours in a 900 ℃ muffle furnace to obtain Fe2O3- Co2O3/LaFeO3Catalyst of which Fe2O3Supported in an amount of 15wt%, Co2O3The loading amount is 5 percent, and LaFeO3The carrier is 80 wt%.
Example 7
49.15g of Fe (NO) are taken3)3·6H2O was placed in a 500mL beaker, 100mL of distilled water was added, and the mixture was placed in a water bath at 80 ℃ with a stirring speed of 400 rpm. 34.3g of La (NO) was taken3)3·6H2O, put into a beaker containing 100mL of distilled water, and stirred until the solution was completely dissolved. Then, the lanthanum nitrate solution is added dropwise into the ferric nitrate solution while stirring. 40g of citric acid is taken and put into a beaker with 100mL of the citric acid and stirred until the citric acid is completely dissolved, and after the mixed solution is stirred for 30 minutes, the citric acid solution is slowly added and stirred while being dropwise added. After stirring for 5 hours, the solution had dehydrated to a viscous gel, which was taken out into a drying oven at 110 ℃ and dried overnight. And then taking out the dried perovskite precursor, placing the perovskite precursor in a muffle furnace, heating the perovskite precursor from room temperature to 400 ℃ at the heating rate of 3 ℃/min, roasting the perovskite precursor at constant temperature for 3 hours, heating the perovskite precursor to 900 ℃ at the heating rate of 10 ℃/min, and roasting the perovskite precursor at constant temperature for 4 hours to obtain the carrier with the perovskite structure. Taking Fe (NO)3)3·6H2O and Co (NO)3)3·6H2Putting O into a 100mL beaker, adding 50mL of distilled water, soaking the O on the perovskite oxide carrier by using a rotary evaporator after dissolving, taking out the O, standing overnight in a 120 ℃ drying oven, and roasting for 4 hours in a 1000 ℃ muffle furnace to obtain Fe2O3- Co2O3/LaFeO3Catalyst of which Fe2O3Supported in an amount of 15wt%, Co2O3The loading amount is 5 percent, and LaFeO3The carrier is 80 wt%.
Comparative example 1
Weighing 116g of 80-100 mesh Al2O3The pellets were placed in a flask of a rotary evaporator and the water bath temperature was maintained at 65 ℃. 20g Fe (NO) are weighed out3)3·9H2And O is put into a 500mL beaker, 100mL of deionized water is added to prepare a solution, a vacuum pump is turned on after the solution is dissolved, the solution is sucked into the flask, and the rotating speed of the flask is 100 r/min. After the solution is completely evaporated, taking out Al2O3The pellets are dried in a drying oven at 110 ℃ for 24 hours and roasted in a muffle furnace at 900 ℃ for 3 hours to obtain the catalyst Fe2O3/Al2O3In which Fe2O315% by mass of Al2O3The mass content is 85%.
Comparative example 2
49.15g of Fe (NO) are taken3)3·6H2O was put into a 500mL beaker, 100mL of distilled water was added, and the beaker was placed in a water bath at 80 ℃ with a stirring speed of 400 rpm. 34.3g of La (NO) was taken3)3·6H2O, put into a beaker containing 100mL of distilled water, and stirred until the solution was completely dissolved. Then, the lanthanum nitrate solution is added dropwise into the ferric nitrate solution while stirring. 40g of citric acid is taken and put into a beaker with 100mL of the citric acid and stirred until the citric acid is completely dissolved, and after the mixed solution is stirred for 30 minutes, the citric acid solution is slowly added and stirred while being dropwise added. After stirring for 5 hours, the solution had dehydrated to a viscous gel, which was taken out into a drying oven at 110 ℃ and dried overnight. And then taking out the dried perovskite precursor, placing the perovskite precursor in a muffle furnace, heating the perovskite precursor from room temperature to 400 ℃ at the heating rate of 3 ℃/min, roasting the perovskite precursor at constant temperature for 3 hours, heating the perovskite precursor to 700 ℃ at the heating rate of 10 ℃/min, and roasting the perovskite precursor at constant temperature for 4 hours to obtain the carrier with the perovskite structure. Taking Fe (NO)3)3·6H2Placing O into a 100mL beaker, adding 50mL of distilled water, soaking the O on the perovskite oxide carrier by using a rotary evaporator after dissolving, taking out the O, standing overnight in a 120 ℃ drying oven, and roasting in a 900 ℃ muffle furnace for 4 hours to obtain Fe2O3/LaFeO3Catalyst of which Fe2O3The loading of (A) is 15wt%, LaFeO3The carrier was 85 wt%.
Comparative example 3
49.15g of Fe (NO) are taken3)3·6H2O was put into a 500mL beaker, 100mL of distilled water was added, and the beaker was placed in a water bath at 80 ℃ with a stirring speed of 400 rpm. 34.3g of La (NO) was taken3)3·6H2O, put into a beaker containing 100mL of distilled water, and stirred until the solution was completely dissolved. Then, the lanthanum nitrate solution is added dropwise into the ferric nitrate solution while stirring. 40g of citric acid is taken and put into a beaker with 100mL of the citric acid and stirred until the citric acid is completely dissolved, and after the mixed solution is stirred for 30 minutes, the citric acid solution is slowly added and stirred while being dropwise added. After stirring for 5 hours, the solution had dehydrated to a viscous gel, which was taken out into a drying oven at 110 ℃ and dried overnight. And then taking out the dried perovskite precursor, placing the perovskite precursor in a muffle furnace, heating the perovskite precursor from room temperature to 400 ℃ at the heating rate of 3 ℃/min, roasting the perovskite precursor at constant temperature for 3 hours, heating the perovskite precursor to 700 ℃ at the heating rate of 10 ℃/min, and roasting the perovskite precursor at constant temperature for 4 hours to obtain the carrier with the perovskite structure. Taking Co (NO)3)3·6H2Placing O into a 100mL beaker, adding 50mL of distilled water, soaking the O on the perovskite oxide carrier by using a rotary evaporator after dissolving, taking out the O after soaking, and then taking out the O120oC, standing overnight in a drying oven, and roasting for 4 hours in a muffle furnace at 900 ℃ to obtain Co2O3/LaFeO3Catalyst of which Co2O315% of LaFeO3The carrier was 85 wt%.
The catalyst is used for catalyzing the hydrogen production reaction of methane and hydrogen sulfide reforming: the test is carried out in a fixed bed reactor, 5mL of catalyst is taken and mixed with quartz sand with the same mesh number according to the volume ratio of 1: 1. The raw material gas is a mixed gas (10 vol% CH) of methane and hydrogen sulfide4，20vol％H2S，70vol%N2) The flow is 100mL/min, the preheating is carried out to 500 ℃, the reaction temperature is 600 ℃, 700 ℃, 800 ℃, 850 ℃, 900 ℃ and 950 ℃, and the reaction pressure is normal pressure. Starting to sample after the reaction is stableThe method adopts SP-3820 type gas chromatography on-line analysis, a 5A molecular sieve column and a Porapak Q column, and TCD detection. The evaluation results after 100h are shown in Table 1.
TABLE 1 different reaction temperatures H2Conversion of S
Claims (10)
1. The method for preparing hydrogen by reforming methane and hydrogen sulfide comprises the following steps of carrying out contact reaction on hydrogen sulfide and methane and a catalyst with the following mass composition:
Fe2O35%~65%
Co2O31%~20%
LaMO315%~94%
wherein LaMO3Is a carrier with a perovskite structure, and M is at least one selected from Co, Fe and Ni.
2. The method of claim 1, wherein the catalyst is comprised of:
Fe2O310%~40%
Co2O35~20%
LaMO340%~85%。
3. the method of claim 1, wherein the temperature of the methane hydrogen sulfide reforming reaction is 600 to 1200 ℃.
4. The method of claim 3, wherein the temperature of the methane hydrogen sulfide reforming reaction is 700 to 800 ℃.
5. The method according to claim 1, wherein the pressure of the methane hydrogen sulfide reforming reaction is 0.1 to 2 MPa.
6. The method according to claim 5, wherein the pressure of the methane hydrogen sulfide reforming reaction is 0.1 to 1 MPa.
7. The method of claim 1, wherein the catalyst is prepared by: preparing soluble salt of at least one of iron, nickel or cobalt into solution, adding lanthanum nitrate solution, adding citric acid solution or ethylene glycol, evaporating to form gel, taking out, drying, roasting to obtain perovskite type oxide carrier, loading iron and cobalt onto the carrier by adopting an impregnation method, drying, and roasting to obtain the catalyst.
8. The method of claim 7, wherein the catalyst is prepared by using a nitrate as the soluble salt of iron, nickel or cobalt.
9. The method according to claim 7, wherein the citric acid solution or ethylene glycol is added in an amount of 1: 1-5: 1 meter.
10. The method according to claim 7, wherein the perovskite-type oxide support is prepared at a reaction temperature of 30 to 90 ℃ for 3 to 8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711023753.4A CN109721028B (en) | 2017-10-27 | 2017-10-27 | Method for preparing hydrogen by reforming methane and hydrogen sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711023753.4A CN109721028B (en) | 2017-10-27 | 2017-10-27 | Method for preparing hydrogen by reforming methane and hydrogen sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109721028A CN109721028A (en) | 2019-05-07 |
| CN109721028B true CN109721028B (en) | 2020-09-11 |
Family
ID=66291951
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711023753.4A Active CN109721028B (en) | 2017-10-27 | 2017-10-27 | Method for preparing hydrogen by reforming methane and hydrogen sulfide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109721028B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112169817B (en) * | 2020-10-19 | 2022-10-04 | 宁夏大学 | Perovskite type composite oxygen carrier and application |
| CN114471643B (en) * | 2020-10-27 | 2023-09-01 | 中国石油化工股份有限公司 | Catalyst for hydrogen production and preparation method and application thereof |
| CN114029066B (en) * | 2021-10-28 | 2024-01-05 | 江苏大学 | Mo-based monoatomic high-entropy perovskite oxide desulfurization catalyst and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040129135A1 (en) * | 2002-03-05 | 2004-07-08 | Roark Shane E. | Dense, layered membranes for hydrogen separation |
| WO2010150063A1 (en) * | 2009-06-24 | 2010-12-29 | Eni S.P.A. | Process for upgrading natural gas with a high hydrogen sulfide content |
| JP2011212603A (en) * | 2010-03-31 | 2011-10-27 | Nippon Steel Corp | Reforming catalyst for tar-containing gas, method for manufacturing reforming catalyst and method for reforming tar-containing gas |
| CN102862959A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Applications and preparation of high-activity oxygen carrier in chemical looping circulation hydrogen production |
| CN103374430B (en) * | 2012-04-12 | 2015-07-22 | 中国石油化工股份有限公司 | High-stability oxygen carrier, preparation method and applications |
| WO2017062799A1 (en) * | 2015-10-07 | 2017-04-13 | Gas Technology Institute | Process for conversion of methane to higher hydrocarbons, including liquid fuels |
| US20170158502A1 (en) * | 2012-03-14 | 2017-06-08 | Board Of Regents, The University Of Texas System | Photochemical Processes and Compositions for Methane Reforming Using Transition Metal Chalcogenide Photocatalysts |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101351317B1 (en) * | 2011-12-12 | 2014-01-15 | 재단법인 포항산업과학연구원 | A method for preparing reducing gas by using cokes oven gas and by-product gas from steel works |
| KR102263022B1 (en) * | 2014-12-04 | 2021-06-11 | 재단법인 포항산업과학연구원 | Method for producing hydrogen from hydrogen psa off-gas of coke oven gas |
-
2017
- 2017-10-27 CN CN201711023753.4A patent/CN109721028B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040129135A1 (en) * | 2002-03-05 | 2004-07-08 | Roark Shane E. | Dense, layered membranes for hydrogen separation |
| WO2010150063A1 (en) * | 2009-06-24 | 2010-12-29 | Eni S.P.A. | Process for upgrading natural gas with a high hydrogen sulfide content |
| JP2011212603A (en) * | 2010-03-31 | 2011-10-27 | Nippon Steel Corp | Reforming catalyst for tar-containing gas, method for manufacturing reforming catalyst and method for reforming tar-containing gas |
| CN102862959A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Applications and preparation of high-activity oxygen carrier in chemical looping circulation hydrogen production |
| US20170158502A1 (en) * | 2012-03-14 | 2017-06-08 | Board Of Regents, The University Of Texas System | Photochemical Processes and Compositions for Methane Reforming Using Transition Metal Chalcogenide Photocatalysts |
| CN103374430B (en) * | 2012-04-12 | 2015-07-22 | 中国石油化工股份有限公司 | High-stability oxygen carrier, preparation method and applications |
| WO2017062799A1 (en) * | 2015-10-07 | 2017-04-13 | Gas Technology Institute | Process for conversion of methane to higher hydrocarbons, including liquid fuels |
Non-Patent Citations (7)
| Title |
|---|
| A.L. Martı＇nez-Salazar et al.Hydrogen production by methane reforming with H2S using Mo,Cr/ZrO2eSBA15 and Mo,Cr/ZrO2eLa2O3 catalysts.《international journal o f hydrogen energy》.2015,全文. * |
| CH4 and H2S reforming to CH3SH and H2 catalyzed by metal-promoted Mo6S8 clusters: a first-principles micro-kinetic study;William Taifan et al;《Catalysis Science & Technology》;20170706;全文 * |
| Production of hydrogen from hydrogen sulfide in presence of methane;A.M. El-Melih et al;《international journal o f hydrogen energy》;20161203;全文 * |
| Reformation of hydrogen sulfide to hydrogen in the presence of xylene;A.M. El-Melih;《Applied Energy》;20170622;全文 * |
| Severe Deactivation of a LaNiO3 Perovskite-Type Catalyst Precursor with H2S during Methane Dry Reforming;Jaime Gallego et al;《Energy & Fuels》;20090917;全文 * |
| Structural and textural properties of Fe2O3/g-Al2O3 catalysts and their importance in the catalytic reforming of CH4 with H2S for hydrogen n the catalytic reforming of CH4 with H2S for hydrogen;Felix Galindo-Hernandez et al;《Journal of Power Sources》;20150407;全文 * |
| Thermodynamic analyses of hydrogen production from sub-quality natural gas Part II: Steam reforming and autothermal steam reforming;Cunping Huang et al;《Journal of Power Sources》;20060502;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109721028A (en) | 2019-05-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mo et al. | Elucidating the special role of strong metal–support interactions in Pt/MnO 2 catalysts for total toluene oxidation | |
| Zhu et al. | Low-temperature SCR of NO with NH3 over CeO2 supported on modified activated carbon fibers | |
| CN109721028B (en) | Method for preparing hydrogen by reforming methane and hydrogen sulfide | |
| CN104759277B (en) | A kind of CeOx‑MnOx/ graphene low-temperature SCR catalyst for denitrating flue gas and preparation method thereof | |
| CN110508309B (en) | Carbon nitride supported chromium oxide catalyst and preparation method and application thereof | |
| CN110026228B (en) | Preparation of nitrogen-containing porous carbon material and H thereof2S-selective catalytic oxidation applications | |
| CN109762614B (en) | Cobaltosic oxide catalyst for methane catalytic combustion, preparation and application thereof | |
| CN101664689B (en) | Active carbon desulfurizer and preparation method thereof | |
| CN109721027B (en) | Method for producing hydrogen by reforming reaction of methane and hydrogen sulfide | |
| CN111644175A (en) | Ni-coal gangue catalyst, preparation method thereof and application thereof in tar steam reforming reaction | |
| CN114522688A (en) | Porous carbon loaded bimetallic catalyst and preparation and application thereof | |
| CN103785389A (en) | High-activity oxygen carrier and preparation method and application thereof | |
| CN110711584B (en) | Semicoke-loaded coke oil steam reforming catalyst and preparation method and application thereof | |
| CN109647400B (en) | Catalyst for preparing 1, 3-butadiene by high-efficiency carbon dioxide oxidation and 1-butylene dehydrogenation and preparation method thereof | |
| Zou et al. | Catalytic oxidation of NO on N-doped carbon materials at low temperature | |
| CN109250763B (en) | Method for preparing hydrogen by reforming hydrogen sulfide and methane | |
| CN104096571B (en) | Synthesis gas liquification catalyst and catalyzing method thereof, beds and preparation method | |
| CN109248689B (en) | Macroporous oxide catalyst | |
| CN108448123B (en) | Cerium-based catalyst for low-temperature water gas shift reaction and preparation method thereof | |
| CN112892569B (en) | Silicon carbide loaded cerium oxide catalyst and method for preparing sulfur by hydrogen sulfide selective oxidation under medium-high temperature condition by adopting same | |
| CN109718782B (en) | Method for preparing hydrogen by reforming methane and hydrogen sulfide | |
| CN102862956B (en) | The application of a kind of oxygen carrier with perovskite structure in hydrogen production of chemical chain and preparation | |
| CN113292519A (en) | Magnetic gold-cobalt composite catalyst and preparation method and application thereof | |
| CN112063431A (en) | Preparation method of large-scale magnetic CuFe2O4 oxygen carrier with industrial application | |
| CN106635245B (en) | A kind of oxygen carrier for burning chemistry chains, its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230831 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |