A supported catalyst for hydrogen production from methane hydrogen sulfide reforming, its preparation method and application

Abstract

This invention discloses a supported methane hydrogen sulfide reforming catalyst for hydrogen production, its preparation method, and its application. The catalyst includes a support, and ferric oxide and alkaline earth metal oxides supported on the support. The support is a titanium-modified SBA-15 molecular sieve. The catalyst preparation method includes the following steps: dissolving a triblock copolymer P123, adding an acidic solution to adjust the pH to 2-4; then adding a titanium source and a silicon source, mixing thoroughly, and carrying out a crystallization reaction; further washing, drying, and calcining to obtain the support; mixing the support with an iron-containing compound and an alkaline earth metal compound, impregnating, drying, and calcining to obtain the supported methane hydrogen sulfide reforming catalyst for hydrogen production. The methane hydrogen sulfide reforming catalyst provided by this invention exhibits good thermal stability and higher reactivity during use. It solves the problems of poor dispersion, poor thermal stability, and low feed conversion rate existing in current hydrogen sulfide methane reforming catalysts for hydrogen production.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of catalytic materials, and particularly relates to a hydrogen sulfide and methane reforming hydrogen catalyst and a preparation method thereof. BACKGROUND

[0002] In recent years, with the continuous deepening of social industrialization process, the continuous development of emerging industries and the increasing environmental problems, the world energy structure is quietly changing. Hydrogen energy will become one of the main energies in the future world due to its safety, high efficiency, renewability, cleanliness, low carbon and easy storage. Hydrogen energy development and utilization has become an important way of global energy revolution.

[0003] At present, the main source of hydrogen is natural gas (CH4) and steam reforming of hydrogen (SMR). However, this process will produce a large amount of greenhouse gas CO2, and more seriously, most of the natural gas reservoirs contain hydrogen sulfide, which is easy to cause pipeline corrosion and catalyst poisoning.

[0004] As early as 1939, a patent proposed to prepare CS2 by reacting CH4 and H2S. However, it was not until 1991 that Papayannako (International Association for Hydrogen Energy. 1991) first realized that the H2S and CH4 reforming reaction (H2SMR) was an effective hydrogen production technology route. Moreover, hydrogen can be produced while by-producting CS2 with high added value, which is a technology with broad application prospect. However, due to the highly endothermic reaction, the high thermodynamic limit makes the research progress of this technology slow, and at present, it is mainly focused on kinetics, thermodynamics and simulation. No high-efficiency and stable catalyst system has been developed. The design difficulty of the catalyst for this process lies in the resistance to high temperature and H2S corrosion. Papayannak (Applied Catalysis A: General. 1996) studied the methane hydrogen sulfide reforming reaction of Pt / Al2O3 catalyst in the temperature range of 700-800℃, and proposed the LHHW reaction mechanism. Martinez-Salazar et al. (International Journal of Hydrogen Energy. 2015) prepared Mo, Cr / ZrO2-La2O3 and Mo, Cr / ZrO2-SBA15 catalysts, and found that the former showed higher reforming reaction activity, and the H2 yield reached 64% at 1073K-1123K temperature interval, while the latter formed ZrSiO4 mixed phase and had poor stability. SUMMARY

[0005] In view of the deficiencies in the prior art, the main purpose of the present application is to provide a supported hydrogen production catalyst for methane and hydrogen sulfide reforming, a preparation method and application thereof, the hydrogen production catalyst for methane and hydrogen sulfide reforming provided by the present application has good thermal stability and higher reactivity during use. The problems of poor dispersion performance, easy carbon deposition, poor thermal stability, low raw material conversion rate and the like of the hydrogen production catalyst for methane and hydrogen sulfide reforming are solved.

[0006] In order to achieve the above-mentioned purposes, the technical solutions provided by the present application include the following aspects:

[0007] The first aspect provides a supported hydrogen production catalyst for methane and hydrogen sulfide reforming, the catalyst comprising a carrier, and iron sesquioxide and alkaline earth metal oxide supported on the carrier, wherein the carrier is a titanium-modified SBA-15 molecular sieve (Ti / SBA-15 molecular sieve), the content of the iron sesquioxide is 5-50wt% based on the weight of the catalyst, the content of the alkaline earth metal oxide is 0.1-10wt%, and the content of the carrier is 40-90wt%.

[0008] Further, in the supported hydrogen production catalyst for methane and hydrogen sulfide reforming, the specific surface area of the catalyst is 200-1500m 2 / g, preferably 300-1000m 2 / g.

[0009] Further, in the supported hydrogen production catalyst for methane and hydrogen sulfide reforming, the pore size of the catalyst is 4-20nm, preferably 5-15nm.

[0010] The second aspect provides a preparation method of a supported hydrogen production catalyst for methane and hydrogen sulfide reforming, comprising the following steps:

[0011] (1) under the condition of contact, a triblock copolymer P123 is dissolved, an acidic solution is added to adjust the pH value to 2-4, and a mixed solution is obtained;

[0012] (2) under the condition of contact, a titanium source, a silicon source and the mixed solution obtained in step (1) are fully mixed and uniformly mixed, then reacted, and then further washed, dried and calcined to obtain a carrier;

[0013] (3) the carrier obtained in step (2) is mixed with an iron-containing compound and an alkaline earth metal compound, impregnation is completed, and then dried and calcined to obtain a supported hydrogen production catalyst for methane and hydrogen sulfide reforming.

[0014] Further, in the preparation method of the supported hydrogen production catalyst for methane and hydrogen sulfide reforming, the acidic solution in step (1) can be selected from inorganic acids, specifically at least one of hydrochloric acid, nitric acid and sulfuric acid, preferably hydrochloric acid, and more preferably the mass concentration of the acidic solution is 10-40wt%.

[0015] Further, in the preparation method of the supported hydrogen production catalyst for methane-hydrogen sulfide reforming, the silicon source in step (2) can be selected from one or more of tetraethyl orthosilicate (TEOS), sodium silicate, silica sol, and the like, and is preferably tetraethyl orthosilicate.

[0016] Further, in the preparation method of the supported hydrogen production catalyst for methane-hydrogen sulfide reforming, the titanium source in step (2) can be one or more of tetrabutyl titanate, titanium tetrachloride, titanium isopropoxide, and titanium sulfate, and is preferably tetrabutyl titanate.

[0017] Further, in the preparation method of the supported hydrogen production catalyst for methane-hydrogen sulfide reforming, the molar ratio of the titanium source (calculated as Ti element), the silicon source (calculated as Si element), and the triblock copolymer (calculated as P123) in step (2) is 1:2-200:0.1-10.

[0018] Further, in the preparation method of the supported hydrogen production catalyst for methane-hydrogen sulfide reforming, the titanium source, the silicon source, and the mixed solution obtained in step (1) are contacted and mixed under water bath conditions in step (2), the water bath temperature is 20-100°C, preferably 40-60°C, and the mixing time is 12-36h, preferably 15-25h.

[0019] Further, in the preparation method of the supported hydrogen production catalyst for methane-hydrogen sulfide reforming, the crystallization temperature in step (2) is 80-150°C, preferably 90-120°C, and the reaction time is 24-60h, preferably 36-50h.

[0020] Further, in the preparation method of the supported hydrogen production catalyst for methane-hydrogen sulfide reforming, the drying conditions in step (2) are: the drying temperature is 50-200°C, preferably 80-120°C; and the drying time is 1-24h, preferably 4-12h.

[0021] Further, in the preparation method of the supported hydrogen production catalyst for methane-hydrogen sulfide reforming, the calcination conditions in step (2) are: the calcination temperature is 200-1000°C, preferably 400-800°C; and the calcination time is 1-24h, preferably 4-8h.

[0022] Further, in the preparation method of the supported hydrogen production catalyst for methane-hydrogen sulfide reforming, the iron-containing compound in step (3) can be selected from at least one of an iron-containing inorganic acid salt and an iron-containing organic acid salt, and is preferably ferric nitrate and / or ferric chloride.

[0023] Further, in the preparation method of the supported hydrogen production catalyst for methane and hydrogen sulfide reforming, the alkali earth metal compound in step (3) can be at least one selected from alkali earth metal chloride, alkali earth metal inorganic acid salt and alkali earth metal organic acid salt, the alkali earth metal can be at least one of magnesium and calcium, and preferably magnesium; and the specific alkali earth metal compound is preferably at least one of magnesium nitrate and magnesium chloride.

[0024] Further, in the preparation method of the supported hydrogen production catalyst for methane and hydrogen sulfide reforming, the drying condition in step (3) is that the drying temperature is 50-200°C, and preferably 80-120°C; and the drying time is 1-24h, and preferably 4-12h.

[0025] Further, in the preparation method of the supported hydrogen production catalyst for methane and hydrogen sulfide reforming, the calcination condition in step (3) is that the calcination temperature is 200-1000°C, and preferably 400-800°C; and the calcination time is 1-24h, and preferably 4-8h.

[0026] Further, in the preparation method of the supported hydrogen production catalyst for methane and hydrogen sulfide reforming, the content of the ferric oxide is 5-50wt% based on the weight of the catalyst; the content of the alkali earth metal oxide is 0.1-10wt%; and the content of the carrier is 40-90wt%.

[0027] The third aspect of the present application provides a supported hydrogen production catalyst for methane and hydrogen sulfide reforming obtained by the above preparation method.

[0028] The fourth aspect of the present application provides a hydrogen production process for methane and hydrogen sulfide reforming, in which raw materials of methane and hydrogen sulfide enter a reactor, and the reactor is filled with the above supported hydrogen production catalyst for methane and hydrogen sulfide reforming or the supported hydrogen production catalyst for methane and hydrogen sulfide reforming obtained by the above preparation method.

[0029] Further, in the hydrogen production process for methane and hydrogen sulfide reforming, the hydrogen production catalyst for methane and hydrogen sulfide reforming needs to be sulfided before use, and the sulfidation operation can adopt any one of the existing catalyst sulfidation methods, such as passing hydrogen sulfide at a temperature of 100-800°C for 0.5-10h.

[0030] Further, in the hydrogen production process for methane and hydrogen sulfide reforming, the volume ratio of methane to hydrogen sulfide is 1:0.25-10.

[0031] Further, in the hydrogen production process for methane and hydrogen sulfide reforming, the reaction temperature is 500-1100°C, and preferably 700-900°C; the reaction pressure is 0.1MPa-5MPa, and preferably 0.1MPa-3MPa; the volume space velocity is 100h -1 -3000h -1 , and preferably 300h-1 ~2000h -1 .

[0032] Compared with the prior art, the supported hydrogen production catalyst for methane hydrogen sulfide reforming and the preparation method thereof have the following technical effects:

[0033] 1. The application provides a supported hydrogen production catalyst for methane hydrogen sulfide reforming, which has a titanium in-situ modified SBA-15 molecular sieve as a carrier and has diiron trioxide as an active metal, has high hydrogen sulfide decomposition performance, has good high-temperature resistance and sulfur resistance, and has high raw material conversion rate in a methane hydrogen sulfide reforming reaction process. Meanwhile, the introduction of titanium elements can play a synergistic effect with the active metal component iron, improve the dispersity of the active metal component iron on the carrier, and improve the catalytic reaction activity of the catalyst.

[0034] 2. In the preparation method of the supported hydrogen production catalyst for methane hydrogen sulfide reforming, titanium elements are introduced in the preparation of the SBA-15 molecular sieve through an in-situ synthesis method, and the interaction between titanium and the active metal component iron can improve the dispersity of the active metal component iron on the carrier and improve the catalytic reaction activity of the catalyst.

[0035] 3. In the hydrogen production catalyst for methane hydrogen sulfide reforming and the preparation method thereof, the addition of the alkaline earth metal oxide additive can strengthen the interaction between the active metal and the carrier, promote the dispersity of the iron elements on the surface of the carrier, and further improve the high-temperature reaction activity of the catalyst. BRIEF DESCRIPTION OF DRAWINGS

[0036] Figure 1 TEM image of the catalyst obtained in Example 1. DETAILED DESCRIPTION

[0037] The catalyst, the preparation method and the application thereof will be further illustrated through the following examples, but the application should not be considered to be limited to the following examples.

[0038] Unless otherwise clearly indicated, throughout the specification and claims, the term "comprise" or variations such as "comprises" or "comprising" will be understood to imply the inclusion of a stated element or group of elements but not the exclusion of any other element or group of elements.

[0039] In the following examples and comparative examples, the experimental methods are all conventional methods in the field unless otherwise specified. The experimental materials used in the following examples are all purchased from conventional biochemical reagent stores unless otherwise specified.

[0040] The analysis method of the present application: the specific surface area and pore distribution are measured by low-temperature liquid nitrogen physical adsorption method.

[0041] In the present application, the calculation formula of CH4 conversion rate is as follows: CH4 ×100%

[0042] Wherein, A CH4,in is the chromatographic peak area of methane at the inlet of the reactor, and A CH4,out is the chromatographic peak area of methane at the outlet of the reactor.

[0043] The hydrogen catalyst for methane and hydrogen sulfide reforming provided by the present application has good thermal stability and higher reaction activity during use. The problems of poor dispersion performance, easy carbon deposition, poor thermal stability, low raw material conversion rate and the like of the hydrogen catalyst for methane and hydrogen sulfide reforming are solved.

[0044] Example 1

[0045] 8.0g of P123 is weighed and dissolved in water, then 38wt% hydrochloric acid solution is added dropwise to adjust the pH to 3.2, 15.0g of tetraethyl orthosilicate and 2.4g of tetrabutyl titanate are added, and stirring is carried out at 38℃ under water bath conditions for 24h, the mixed solution is loaded into a reaction kettle, and reaction is carried out at 100℃ for 36h, then the reaction product is taken out, filtered and washed to neutral, dried in a 100℃ oven for 24h, and then placed in a muffle furnace at 550℃ for calcination for 4h to obtain a Ti-SBA-15 carrier. 10.0g of Ti-SBA-15 molecular sieve is added to a mixed solution of iron nitrate and magnesium nitrate, impregnated, dried at 110℃ for 8h, and calcined at 800℃ for 4h to obtain a catalyst, in terms of oxide mass, the content of iron sesquioxide is 25.5wt%, the content of magnesium oxide is 5.0wt%, and the rest is the carrier.

[0046] Figure 1 It is a TEM diagram of the catalyst, and it can be seen from the diagram that the metal dispersion is good. The BET properties of the catalyst are shown in Table 1.

[0047] The catalyst is applied to the hydrogen production reaction of methane and hydrogen sulfide reforming, first, hydrogen sulfide is introduced at a temperature of 250℃ for 8h, raw material gas with H2S:CH4 being 4:1 is introduced at a space velocity of 600h -1 -1, and reaction is carried out at a high temperature of 800℃ under a pressure of 0.1MPa, the CH4 conversion rate reaches 53.3%, and the conversion rate still maintains at 50.1% after 300h.

[0048] Example 2

[0049] ​Take 350.2g of P123 in water, after dissolving, add 38wt% hydrochloric acid solution to adjust pH to 3.2, add 300.5g of tetraethyl orthosilicate, 3.0g of titanium isopropoxide, then stir for 15h under 45℃ water bath condition, put the mixed solution into the reaction kettle, and place it at 100℃ for 36h, then take out the reaction product, wash it to neutral, dry it in 100℃ oven for 24h, and then put it into the muffle furnace at 550℃ for 4h to obtain Ti-SBA-15 carrier. Take 10.0g of Ti-SBA-15 molecular sieve, immerse it in the mixed solution of ferric chloride and magnesium nitrate, dry it at 110℃ for 8h, and calcine it at 800℃ for 6h to obtain the catalyst, in terms of oxide mass, the catalyst contains 25.0wt% of iron trioxide, 3.2wt% of magnesium oxide, and the rest is carrier. The properties of the catalyst are shown in Table 1.

[0050] The catalyst is applied to the reaction of hydrogen production by methane and hydrogen sulfide reforming. First, hydrogen sulfide is pre-sulfided at 250℃ for 8h, and the raw gas with H2S:CH4 ratio of 4:1 is fed at space velocity of 600h-1, 0.1MPa, and 800℃ to carry out the reaction. The CH4 conversion rate reaches 52.5%, and the conversion rate still maintains at 50.4% after 300h. -1

[0051] Example 3

[0052] Take 25.5g of P123 in water, after dissolving, add 30wt% hydrochloric acid solution to adjust pH to 3.2, add 36.7g of tetraethyl orthosilicate, 3.0g of tetrabutyl titanate, then stir for 20h under 45℃ water bath condition, put the mixed solution into the reaction kettle, and place it at 110℃ for 36h, then take out the reaction product, wash it to neutral, dry it in 120℃ oven for 18h, and then put it into the muffle furnace at 600℃ for 4h to obtain Ti-SBA-15 carrier. Take 10.0g of Ti-SBA-15 molecular sieve, immerse it in the mixed solution of ferric chloride and magnesium nitrate, dry it at 110℃ for 8h, and calcine it at 800℃ for 4h to obtain the catalyst, in terms of oxide mass, the catalyst contains 6.5wt% of iron trioxide, 5.6wt% of magnesium oxide, and the rest is carrier. The properties of the catalyst are shown in Table 1.

[0053] The catalyst is applied to the reaction of hydrogen production by methane and hydrogen sulfide reforming. First, hydrogen sulfide is pre-sulfided at 350℃ for 6h, and the raw gas with H2S:CH4 ratio of 4:1 is fed at space velocity of 600h-1, 0.1MPa, and 800℃ to carry out the reaction. The CH4 conversion rate reaches 40.5%, and the conversion rate still maintains at 38.3% after 300h. -1

[0054] Example 4

[0055] ​​Take 59.6g of P123 in water, after dissolving, add 38wt% hydrochloric acid solution to adjust pH to 3.2, add 62.2g of tetraethyl orthosilicate, 5g of tetrabutyl titanate, and stir for 15h under 45℃ water bath condition, then put the mixture into a reaction kettle, and react at 110℃ for 48h, then take out the reaction product, wash until neutral, dry in 100℃ oven for 10h, and then put into muffle furnace at 450℃ for 4h to obtain Ti-SBA-15 carrier. Take 10.0g of Ti-SBA-15 molecular sieve, immerse in a mixed solution of iron nitrate and calcium nitrate, dry at 110℃ for 8h, and calcine at 850℃ for 4h to obtain the catalyst, in terms of oxide mass, the catalyst contains 46.3wt% of iron sesquioxide, 2.3wt% of calcium oxide, and the rest is carrier. The properties of the catalyst are shown in Table 1.

[0056] The catalyst is applied to the reaction of hydrogen production by methane and hydrogen sulfide reforming. First, hydrogen sulfide is pre-sulfided at 250℃ for 8h, and the raw gas with H2S:CH4 ratio of 4:1 is fed at space velocity of 600h-1, 0.2MPa, and 800℃ to carry out the reaction, and the CH4 conversion rate reaches 56.5%, and the conversion rate still maintains at 53.3% after 300h. -1

[0057] Example 5

[0058] Take 59.6g of P123 in water, after dissolving, add 38wt% hydrochloric acid solution to adjust pH to 3.2, add 62.2g of tetraethyl orthosilicate, 5g of tetrabutyl titanate, and stir for 15h under 45℃ water bath condition, then put the mixture into a reaction kettle, and react at 110℃ for 48h, then take out the reaction product, wash until neutral, dry in 100℃ oven for 10h, and then put into muffle furnace at 450℃ for 4h to obtain Ti-SBA-15 carrier. Take 10.0g of Ti-SBA-15 molecular sieve, immerse in a mixed solution of iron nitrate and calcium nitrate, dry at 110℃ for 8h, and calcine at 850℃ for 4h to obtain the catalyst, in terms of oxide mass, the catalyst contains 46.3wt% of iron sesquioxide, 2.3wt% of calcium oxide, and the rest is carrier. The properties of the catalyst are shown in Table 1.

[0059] The catalyst is applied to the reaction of hydrogen production by methane and hydrogen sulfide reforming. First, hydrogen sulfide is pre-sulfided at 250℃ for 8h, and the raw gas with H2S:CH4 ratio of 4:1 is fed at space velocity of 600h-1, 0.2MPa, and 800℃ to carry out the reaction, and the CH4 conversion rate reaches 56.5%, and the conversion rate still maintains at 53.3% after 300h. -1

[0060] Example 6

[0061] ​​36.7 g of P123 was dissolved in water, and the pH was adjusted to 3.2 by adding 38 wt% hydrochloric acid solution. 18.8 g of silica gel and 1.0 g of tetrabutyl titanate were added, and the mixture was stirred in a 40℃ water bath for 15 h. The mixture was then transferred to a reaction vessel and reacted at 105℃ for 40 h. The reaction product was then removed, filtered, washed until neutral, dried in a 100℃ oven for 12 h, and calcined in a muffle furnace at 650℃ for 4 h to obtain the Ti-SBA-15 support. 10.0 g of Ti-SBA-15 molecular sieve was impregnated in a mixed solution of ferric nitrate and magnesium chloride, dried at 110℃ for 8 h, and calcined at 850℃ for 6 h. The resulting catalyst, by oxide mass, contained 32.4 wt% ferric oxide, 2.8 wt% magnesium oxide, and the remainder was the support. The properties of the catalyst are shown in Table 1.

[0062] The catalyst was applied to the hydrogen production reaction of methane hydrogen sulfide reforming. First, hydrogen sulfide was introduced for pre-sulfurization at 250°C for 6 hours. The feed gas ratio of H2S:CH4 was 4:1, and the reaction was carried out at a space velocity of 800 h⁻¹. -1 The reaction was carried out at 0.1 MPa and 800℃, and the CH4 conversion rate reached 48.4%, which remained at 45.7% after 300 h.

[0063] Example 7

[0064] 61.2 g of P123 was dissolved in water, and the pH was adjusted to 3.2 by adding 38 wt% hydrochloric acid solution. 17.0 g of tetraethyl orthosilicate and 2.0 g of titanium chloride were added, and the mixture was stirred in a 40℃ water bath for 15 h. The mixture was then transferred to a reaction vessel and reacted at 105℃ for 40 h. The reaction product was then removed, filtered, washed until neutral, dried in a 100℃ oven for 12 h, and calcined in a muffle furnace at 650℃ for 4 h to obtain the Ti-SBA-15 support. 10.0 g of Ti-SBA-15 molecular sieve was impregnated in a mixed solution of ferric nitrate and calcium nitrate, dried at 110℃ for 8 h, and calcined at 750℃ for 4 h. The resulting catalyst, by oxide mass, contained 26.5 wt% ferric oxide, 4.2 wt% calcium oxide, and the remainder was the support. The properties of the catalyst are shown in Table 1.

[0065] The catalyst was applied to the hydrogen production reaction of methane hydrogen sulfide reforming. First, hydrogen sulfide was introduced for pre-sulfurization at 300°C for 7 hours. The feed gas ratio of H2S:CH4 was 2:1, and the reaction was carried out at a space velocity of 800 h⁻¹. -1 The reaction was carried out at 0.3 MPa and 900℃, and the CH4 conversion rate reached 50.9%, which remained at 46.5% after 300 h.

[0066] Example 8

[0067] 48.9 g of P123 was dissolved in water, and the pH was adjusted to 3.2 by adding 38 wt% hydrochloric acid solution. Then, 13.6 g of tetraethyl orthosilicate and 1.0 g of tetrabutyl titanate were added, and the mixture was stirred in a water bath at 40 °C for 15 h. The mixture was then transferred to a reaction vessel and reacted at 105 °C for 40 h. The reaction product was then removed, filtered, washed until neutral, dried in an oven at 100 °C for 12 h, and calcined in a muffle furnace at 650 °C for 4 h to obtain the Ti-SBA-15 support. 10.0 g of Ti-SBA-15 molecular sieve was impregnated in a mixed solution of ferric nitrate and magnesium nitrate, dried at 110 °C for 8 h, and calcined at 750 °C for 4 h. The resulting catalyst, by mass of oxides, contained 30.6 wt% ferric oxide, 3.3 wt% magnesium oxide, and the remainder was the support. The properties of the catalyst are shown in Table 1.

[0068] The catalyst was applied to the hydrogen production reaction of methane hydrogen sulfide reforming. First, hydrogen sulfide was introduced for pre-sulfurization at 250°C for 6 hours. The feed gas ratio of H2S:CH4 was 4:1, and the reaction was carried out at a space velocity of 800 h⁻¹. -1 The reaction was carried out at 0.1 MPa and 900℃, and the CH4 conversion rate reached 64.7%, which remained at 62.6% after 300 h.

[0069] Comparative Example 1

[0070] The process was essentially the same as in Example 1, except that tetrabutyl titanate was not added during the preparation of the support. The initial CH4 conversion of the catalyst reached 25.3%, which decreased to 12.5% ​​after 300 hours.

[0071] Comparative Example 2

[0072] The process was essentially the same as in Example 1, except that no alkaline earth metal compounds were used in the catalyst preparation. The initial CH4 conversion of the catalyst reached 32.3%, which decreased to 18.6% after 300 hours.

[0073] Comparative Example 3

[0074] Compared to Example 2, no titanium isopropoxide was added during the support preparation, the support was not modified with Ti, and no alkaline earth metal compounds were introduced during catalyst preparation. The initial CH4 conversion of the catalyst reached 16.3%, which decreased to 8.2% after 300 h.

[0075] Table 1 Catalyst Properties

[0076] Catalyst S BET / (m 2 / g)]]> V p / (cm 3 / g)]]> D p (nm) Example 1 650.4 1.3 8.0 Example 2 432.6 0.6 5.5 Example 3 522.5 1.0 7.6 Example 4 761.4 1.3 6.8 Example 5 610.2 1.1 7.2 Example 6 550.8 1.2 8.7 Example 7 620.4 1.2 7.7 Example 8 482.3 0.7 5.8

Claims

1. A supported catalyst for hydrogen production by reforming of methane and hydrogen sulfide, said catalyst comprising a support, and diiron trioxide and an alkaline earth metal oxide supported on the support, wherein, The carrier is a titanium modified SBA-15 molecular sieve, the content of the diiron trioxide is 5-50wt% based on the weight of the catalyst, the content of the alkaline earth metal oxide is 0.1-10wt%, and the content of the carrier is 40-90wt%. The specific surface area of the catalyst is 200-1500 m 2 / g.

2. The supported catalyst for hydrogen production by reforming of methane and hydrogen sulfide according to claim 1, characterized in that: The specific surface area of the catalyst is 300-1000 m 2 / g.

3. The supported catalyst for hydrogen production by reforming of methane and hydrogen sulfide according to claim 1, characterized in that: The pore size of the catalyst is 4-20nm.

4. The supported catalyst for hydrogen production by methane-hydrogen sulfide reforming according to claim 3, characterized in that: The pore size of the catalyst is 5-15nm.

5. A preparation method of the supported methane hydrogen sulfide reforming hydrogen production catalyst according to any one of claims 1-4, comprising the following steps: (1) under contact conditions, dissolving the triblock copolymer P123, then adding an acidic solution to adjust the pH value to 2-4 to obtain a mixed solution; (2) under contact conditions, mixing the titanium source and the silicon source with the mixed solution obtained in step (1) uniformly, then performing a crystallization reaction, and then further performing washing, drying and calcination to obtain the carrier; (3) mixing the carrier obtained in step (2) with the iron-containing compound and the alkaline earth metal compound, performing impregnation, then performing drying and calcination to obtain the supported methane hydrogen sulfide reforming hydrogen production catalyst.

6. The process for preparing a supported catalyst for hydrogen production by methane-hydrogen sulfide reforming according to claim 5, characterized by: The acidic solution in step (1) is selected from at least one of hydrochloric acid, nitric acid and sulfuric acid.

7. The process for preparing a supported catalyst for hydrogen production by methane-hydrogen sulfide reforming according to claim 6, characterized in that: The acidic solution in step (1) is hydrochloric acid.

8. The process for preparing a supported catalyst for hydrogen production by methane-hydrogen sulfide reforming according to claim 6, characterized by: The mass concentration of the acidic solution in step (1) is 10-40wt%.

9. The process for preparing a supported catalyst for hydrogen production by methane-hydrogen sulfide reforming according to claim 5, characterized by: The silicon source in step (2) is selected from one or more of tetraethyl orthosilicate, sodium silicate and silica sol.

10. The process for preparing a supported catalyst for hydrogen production by methane-hydrogen sulfide reforming according to claim 9, characterized by: The silicon source in step (2) is tetraethyl orthosilicate.

11. The process for preparing the supported catalyst for hydrogen production by methane and hydrogen sulfide reforming according to claim 5, characterized by: The titanium source in step (2) is selected from one or more of tetrabutyl titanate, titanium tetrachloride, titanium isopropoxide and titanium sulfate.

12. The process for preparing a supported catalyst for hydrogen production by methane-hydrogen sulfide reforming according to claim 11, characterized by: The titanium source in step (2) is tetrabutyl titanate.

13. The process for preparing a supported catalyst for hydrogen production by methane-hydrogen sulfide reforming according to claim 5, characterized by: In step (2), the molar ratio of the titanium source (calculated based on Ti element), the silicon source (calculated based on Si element) and the triblock copolymer (calculated based on P123) is 1:2-200:0.1-10.

14. The process for preparing a supported catalyst for hydrogen production by methane and hydrogen sulfide reforming according to claim 5, characterized by: In step (2), the titanium source, the silicon source and the mixed solution obtained in step (1) are contacted and mixed under water bath conditions, the water bath temperature is 20-100℃, and the mixing time is 12-36h.

15. The process for preparing a supported catalyst for hydrogen production by methane-hydrogen sulfide reforming according to claim 14, characterized by: In step (2), the titanium source, the silicon source and the mixed solution obtained in step (1) are contacted and mixed under water bath conditions, the water bath temperature is 40-60℃, and the mixing time is 15-25h.

16. The process for preparing a supported catalyst for hydrogen production by methane and hydrogen sulfide reforming according to claim 5, characterized by: The crystallization temperature in step (2) is 80-150℃, and the reaction time is 24-60h.

17. The process for preparing a supported catalyst for hydrogen production by methane-hydrogen sulfide reforming according to claim 16, characterized by: The crystallization temperature in step (2) is 90-120℃, and the reaction time is 36-50h.

18. The process for preparing a supported catalyst for hydrogen production by methane and hydrogen sulfide reforming according to claim 5, characterized by: The drying condition in step (2) is that the drying temperature is 50-200℃, and the drying time is 1-24h.

19. The process for preparing a supported catalyst for hydrogen production by methane-hydrogen sulfide reforming according to claim 18, characterized by: The drying condition in step (2) is that the drying temperature is 80-120℃, and the drying time is 4-12h.

20. The process for preparing a supported catalyst for hydrogen production by methane and hydrogen sulfide reforming according to claim 5, characterized by: The calcination condition in step (2) is that the calcination temperature is 200-1000℃, and the calcination time is 1-24h.

21. The process for preparing a supported catalyst for hydrogen production by methane and hydrogen sulfide reforming according to claim 20, characterized by: The calcination condition in step (2) is that the calcination temperature is 400-800℃, and the calcination time is 4-8h.

22. The process for preparing a supported catalyst for hydrogen production by methane and hydrogen sulfide reforming according to claim 5, characterized by: The iron-containing compound in step (3) is selected from at least one of iron-containing inorganic acid salts and iron-containing organic acid salts.

23. The process for preparing a supported catalyst for hydrogen production by methane-hydrogen sulfide reforming according to claim 22, characterized by: The iron-containing compound in step (3) is iron nitrate and / or iron chloride.

24. The process for preparing a supported catalyst for hydrogen production by methane and hydrogen sulfide reforming according to claim 5, characterized by: The alkaline earth metal compound in step (3) is at least one selected from alkaline earth metal chloride, alkaline earth metal inorganic acid salt and alkaline earth metal organic acid salt, and the alkaline earth metal is at least one of magnesium and calcium.

25. The process for preparing a supported catalyst for hydrogen production by methane and hydrogen sulfide reforming according to claim 24, characterized by: The alkaline earth metal in step (3) is magnesium, and the specific alkaline earth metal compound is at least one of magnesium nitrate and magnesium chloride.

26. The process for preparing a supported catalyst for hydrogen production by methane and hydrogen sulfide reforming according to claim 5, characterized by: The drying condition in step (3) is that the drying temperature is 50-200°C, and the drying time is 1-24h.

27. The process for preparing a supported catalyst for hydrogen production by methane and hydrogen sulfide reforming according to claim 26, characterized by: The drying condition in step (3) is that the drying temperature is 80-120°C, and the drying time is 4-12h.

28. The process for preparing a supported catalyst for hydrogen production by methane and hydrogen sulfide reforming according to claim 5, characterized by: The calcination condition in step (3) is that the calcination temperature is 200-1000°C, and the calcination time is 1-24h.

29. The process for preparing a supported catalyst for hydrogen production by methane and hydrogen sulfide reforming according to claim 28, characterized by: The calcination condition in step (3) is that the calcination temperature is 400-800°C, and the calcination time is 4-8h.

30. The process for preparing a supported catalyst for hydrogen production by methane and hydrogen sulfide reforming according to claim 5, characterized by: The content of the ferric oxide is 5-50wt% based on the weight of the catalyst; the content of the alkaline earth metal oxide is 0.1-10wt%; and the content of the carrier is 40-90wt%.

31. A supported hydrogen production catalyst for the reforming of methane and hydrogen sulfide, which is prepared by the method of any one of claims 5-30.

32. A process for the reforming of methane and hydrogen sulfide to produce hydrogen, wherein the raw materials methane and hydrogen sulfide are introduced into a reactor, and the reactor is filled with the supported hydrogen production catalyst for the reforming of methane and hydrogen sulfide of any one of claims 1-4 or prepared by the method of any one of claims 5-31.

33. The process for hydrogen production by reforming of methane and hydrogen sulfide according to claim 32, characterized in that: The hydrogen production catalyst for the reforming of methane and hydrogen sulfide needs to be sulfided before use, and the sulfidation operation is any one of the existing catalyst sulfidation methods.

34. The process for hydrogen production by reforming of methane and hydrogen sulfide according to claim 33, characterized in that: The sulfidation operation is carried out by introducing hydrogen sulfide at a temperature of 300-900°C for 0.5-5h.

35. The process of claim 32 wherein the hydrogen is produced by reforming methane and hydrogen sulfide. The volume ratio of methane to hydrogen sulfide is 1:0.25-10.

36. The process for hydrogen production by reforming of methane and hydrogen sulfide according to claim 32, characterized in that: The reaction temperature is 500-1100℃, the reaction pressure is 0.1-5 MPa, the volume space velocity is 100-3000 h -1 -3000 h -1 .

37. The process for hydrogen production by reforming of methane and hydrogen sulfide according to claim 36, characterized in that: The reaction temperature is 700-900°C, the reaction pressure is 0.1-3 MPa, the volume space velocity is 300-2000 h -1 -1,000 h -1 .

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