阅读说明：本技术 整体式催化剂及其制备方法和应用以及使用其的甲醇水蒸气重整制氢方法 (Monolithic catalyst, preparation method and application thereof, and methanol steam reforming hydrogen production method using monolithic catalyst ) 是由 张磊 翁幼云 翁玉冰 于 2019-10-18 设计创作，主要内容包括：本发明提供了一种整体式催化剂及其制备方法和应用以及使用其的甲醇水蒸气重整制氢方法,涉及催化剂制备技术领域。所述整体式涂层催化剂包括多孔材料基体,所述多孔材料基体上负载有催化涂层,所述催化涂层上负载有活性金属；所述催化涂层包括Al氧化物、Ce氧化物、Zr氧化物和LaCrO<Sub>3</Sub>中的至少一种；所述活性金属包括Cu。将该整体式催化剂应用于重整制氢反应中具有较高的原料转化率,催化得到的重整气中氢气含量较高,一氧化碳含量相对较低,有效缓解了现有重整制氢反应中原料转化率低、重整气中一氧化碳含量较高的问题。(The invention provides an integral catalyst, a preparation method and application thereof, and a methanol steam reforming hydrogen production method using the integral catalyst, and relates to the technical field of catalyst preparation. The monolithic coated catalyst comprises a porous material substrate, wherein a catalytic coating is loaded on the porous material substrate, and an active metal is loaded on the catalytic coating; the catalytic coating comprises Al oxide, Ce oxide, Zr oxide and LaCrO 3 At least one of; the active metal includes Cu. The monolithic catalyst has higher raw material conversion rate when being applied to reforming hydrogen production reaction, the reformed gas obtained by catalysis has higher hydrogen content and relatively lower carbon monoxide content, and the problems of low raw material conversion rate and higher carbon monoxide content in the reformed gas in the existing reforming hydrogen production reaction are effectively solvedTo a problem of (a).)

1. A monolithic catalyst comprising a porous material substrate having a catalytic coating supported thereon, the catalytic coating having an active metal supported thereon;

the catalytic coating comprises Al oxide, Ce oxide, Zr oxide and LaCrO₃At least one of;

the active metal includes Cu.

2. The monolithic catalyst according to claim 1, wherein the porous material matrix is a honeycomb ceramic;

preferably, the honeycomb ceramic comprises a combination of one or more of an oxide ceramic, a carbide ceramic, a nitride ceramic, and a boride ceramic;

more preferably, the specific surface area of the honeycomb ceramic is 3000-10000M²/M³The density of the holes of the honeycomb ceramic is 200-2000 holes/cm²。

3. The monolithic catalyst as recited in claim 1, wherein the mass of the catalytic coating layer is 5 to 40 wt% of the mass of the porous material matrix;

preferably, the mass of the catalytic coating is 10-20 wt% of the mass of the porous material matrix.

4. The monolithic catalyst according to claim 1, wherein the content of the active metal is 4-30 wt% of the mass of the porous material matrix calculated by oxide;

preferably, the content of the active metal is 5-15 wt% of the mass of the porous material matrix calculated by oxide.

5. A method for preparing a monolithic catalyst according to any of claims 1 to 4, comprising the steps of:

firstly, the catalytic coating is loaded on the porous material, then the oxide of the active metal is loaded on the catalytic coating, and the integral catalyst is obtained by reduction.

6. The method for preparing a monolithic catalyst according to claim 5, comprising in particular the steps of:

preparing gel by taking at least one salt of Al salt, Ce salt and Zr salt as a raw material through a sol-gel method, then immersing a porous material substrate into the gel to enable the gel to be uniformly loaded on the porous material substrate, and sintering to obtain a catalyst precursor A with a catalytic coating loaded on the porous material substrate; then, uniformly loading an oxide of an active metal on the catalytic coating in the catalyst precursor A by adopting a solution impregnation method, sintering to obtain a catalyst precursor B, and reducing to obtain an integral catalyst;

preferably, the preparation method specifically comprises the following steps:

with La (NO)₃)₂、Cr(NO₃)₂·9H₂Preparing gel from O and citric acid by sol-gel method, immersing porous material matrix in the gel to make the gel uniformly loaded on the porous material matrix, and sintering to obtain the catalystA catalyst precursor A with a coating layer loaded on a porous material substrate; and then, uniformly loading the oxide of the active metal on the catalytic coating in the catalyst precursor A by adopting a solution impregnation method, sintering to obtain a catalyst precursor B, and reducing to obtain the monolithic catalyst.

7. The preparation method of the monolithic catalyst according to claim 5, wherein the temperature of the reduction is 250-350 ℃;

preferably, the reduction is carried out under an atmosphere of a protective gas, and the protective gas is H₂-N₂Mixing the gas;

more preferably, said H₂-N₂H in the mixed gas₂The content of (B) is 1 to 20 wt%.

8. The preparation method of the monolithic catalyst according to claim 5, further comprising the steps of pre-treating the porous material substrate and then loading the catalyst coating;

preferably, the step of pre-treating is to treat the porous material matrix with hydrochloric acid, and then to wash and dry the porous material matrix.

9. Use of the monolithic catalyst according to any one of claims 1 to 4 in a reforming hydrogen production reaction.

10. A method for producing hydrogen by reforming methanol steam, which is characterized in that the method for producing hydrogen by reforming methanol steam is catalyzed by using the monolithic catalyst of any one of claims 1 to 4.

Technical Field

The invention relates to the technical field of catalyst preparation, in particular to an integral catalyst, a preparation method and application thereof, and a method for preparing hydrogen by reforming methanol steam by using the integral catalyst.

Background

The energy is an indispensable factor for human survival and development, and hydrogen is taken as an important energy carrier, and the combustion product of the hydrogen is only water and does not cause any pollution to the environment, so the hydrogen is regarded as the cleanest energy. Hydrogen is the best choice as the fuel for the anode of a fuel cell because of its cleanliness. However, due to the special physical and chemical properties of hydrogen, the production of hydrogen has a high cost, and therefore, the development of a low-cost hydrogen production method is the key point for developing hydrogen energy.

The hydrogen produced by reforming the chemical raw materials and the steam has relatively high hydrogen percentage content, so that the cost of subsequently purifying the reformed gas is saved, and the hydrogen is a hot point of research in recent years. However, the product of hydrogen production from chemical raw materials, such as methanol, always contains a certain amount of CO, which is a substance that can cause poisoning of the proton membrane of the fuel cell, and therefore, how to reduce the CO content in the reformed gas is a key factor for whether to use methanol to produce hydrogen to provide a hydrogen source for the fuel cell. Meanwhile, the existing reforming hydrogen production catalysts are all particle catalysts. Although the particle catalyst has higher conversion rate, the bed heat is not easy to dissipate in the hydrogen production process, the sintering carbon deposit of the catalyst is easy to deactivate, and the bed pressure drop of the particle catalyst is 20 times of that of the monolithic catalyst, so the particle catalyst is only suitable for running at low space velocity, which obviously increases the cost of hydrogen production.

Therefore, it is necessary and urgent to develop a monolithic catalyst with high conversion rate, high hydrogen output, low carbon monoxide output, and high space velocity for hydrogen production by reforming.

In view of the above, the present invention is particularly proposed.

Disclosure of Invention

The first purpose of the invention is to provide a monolithic catalyst, which has a higher raw material conversion rate when applied to a reforming hydrogen production reaction, and the reformed gas obtained by catalysis has a higher hydrogen content and a lower carbon monoxide content.

The second purpose of the invention is to provide a preparation method of the monolithic catalyst, which has simple preparation process and convenient operation and is suitable for large-scale industrial production.

The third purpose of the invention is to provide the application of the monolithic catalyst, and the monolithic catalyst can be widely applied to reforming hydrogen production reaction.

The fourth purpose of the invention is to provide a method for preparing hydrogen by reforming methanol steam, wherein the method for preparing hydrogen by reforming methanol steam uses the monolithic catalyst for catalysis, and has the advantages of high methanol conversion rate, high hydrogen content in the reformed gas obtained by catalysis, and relatively low carbon monoxide content.

The monolithic catalyst provided by the invention comprises a porous material substrate, wherein a catalytic coating is loaded on the porous material substrate, and active metal is loaded on the catalytic coating;

the catalytic coating comprises Al oxide, Ce oxide, Zr oxide and LaCrO₃At least one of (1);

the active metal includes Cu.

Further, the porous material matrix is honeycomb ceramic;

preferably, the honeycomb ceramic comprises a combination of one or more of an oxide ceramic, a carbide ceramic, a nitride ceramic, and a boride ceramic;

more preferably, the specific surface area of the honeycomb ceramic is 3000-10000M²/M³The density of the holes of the honeycomb ceramic is 200-2000 holes/cm²。

Further, the mass of the catalytic coating is 5-40 wt% of that of the porous material substrate;

preferably, the mass of the catalytic coating is 10-20 wt% of the mass of the porous material matrix.

Further, the content of the active metal is 4-30 wt% of the mass of the porous material matrix calculated by oxide;

preferably, the content of the active metal is 5-15 wt% of the mass of the porous material matrix calculated by oxide.

The invention provides a preparation method of the monolithic catalyst, which comprises the following steps:

firstly, the catalytic coating is loaded on the porous material, then the oxide of the active metal is loaded on the catalytic coating, and the integral catalyst is obtained by reduction.

Further, the preparation method specifically comprises the following steps: preparing gel by taking at least one salt of Al salt, Ce salt and Zr salt as a raw material through a sol-gel method, then soaking a porous material substrate into the gel to enable the gel to be uniformly loaded on the porous material substrate, and sintering to obtain a catalyst precursor A with a catalytic coating loaded on the porous material substrate; and then, uniformly loading the oxide of the active metal on the catalytic coating in the catalyst precursor A by adopting a solution impregnation method, sintering to obtain a catalyst precursor B, and reducing to obtain the monolithic catalyst.

Preferably, the preparation method specifically comprises the following steps:

with La (NO)₃)₂、Cr(NO₃)₂·9H₂Preparing gel by taking O and citric acid as raw materials through a sol-gel method, then immersing the porous material substrate into the gel to enable the gel to be uniformly loaded on the porous material substrate, and sintering to obtain a catalyst precursor A with a catalytic coating loaded on the porous material substrate; and then, uniformly loading the oxide of the active metal on the catalytic coating in the catalyst precursor A by adopting a solution impregnation method, sintering to obtain a catalyst precursor B, and reducing to obtain the monolithic catalyst.

Further, the reduction temperature is 250-350 ℃;

preferably, the reduction is carried out under an atmosphere of a protective gas, and the protective gas is H₂-N₂Mixing the gas;

more preferably, said H₂-N₂H in the mixed gas₂The content of (B) is 1 to 20 wt%.

Further, the preparation method also comprises the steps of pretreating the porous material substrate and then loading the catalyst coating;

preferably, the step of pre-treating is to treat the porous material matrix with hydrochloric acid, and then to wash and dry the porous material matrix.

The invention provides an application of the monolithic catalyst in reforming hydrogen production reaction.

The invention provides a method for preparing hydrogen by reforming methanol steam, which uses the monolithic catalyst for catalysis.

Compared with the prior art, the invention has the beneficial effects that:

the monolithic catalyst provided by the invention comprises a porous material substrate, wherein a catalytic coating is loaded on the porous material substrate, and active metal is loaded on the catalytic coating; the catalytic coating comprises Al oxide, Ce oxide, Zr oxide and LaCrO₃At least one of; the active metal includes Cu. The monolithic catalyst has higher raw material conversion rate when being applied to reforming hydrogen production reaction, the hydrogen content in the reformed gas obtained by catalysis is higher, the carbon monoxide content is relatively lower, and due to the specific pore structure of the porous material matrix, the heat of the monolithic catalyst is easy to dissipate in the reforming hydrogen production process, the catalyst is not easy to sinter and inactivate, and the monolithic catalyst is further suitable for high space velocity (reaction space velocity WHSV of 5.8 h)^-1) The method effectively solves the problems that the conversion rate of raw materials is low, the content of carbon monoxide in reformed gas is high and the existing particle catalyst can not operate at high space velocity in the existing reforming hydrogen production reaction.

The preparation method of the monolithic catalyst comprises the steps of loading the catalytic coating on the porous material substrate, loading the copper oxide on the catalytic coating, and reducing to obtain the monolithic catalyst. The preparation method is simple in preparation process, convenient and fast to operate and suitable for large-scale industrial production.

The monolithic catalyst provided by the invention can be widely applied to reforming hydrogen production reaction.

According to the method for preparing hydrogen by reforming methanol steam, the monolithic catalyst is used for catalysis, and the method has the advantages of high methanol conversion rate, high hydrogen content in the reformed gas obtained by catalysis, and relatively low carbon monoxide content.

Detailed Description

The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

According to one aspect of the present invention, a monolithic catalyst includes a porous material substrate having a catalytic coating supported thereon, the catalytic coating having an active metal supported thereon;

the catalytic coating comprises Al oxide, Ce oxide, Zr oxide and LaCrO₃At least one of (1);

the active metal includes Cu.

The monolithic catalyst provided by the invention comprises a porous material substrate, wherein a catalytic coating is loaded on the porous material substrate, and active metal is loaded on the catalytic coating; the catalytic coating comprises Al oxide, Ce oxide, Zr oxide and LaCrO₃At least one of; the active metal includes Cu. The monolithic catalyst has higher raw material conversion rate when being applied to reforming hydrogen production reaction, the hydrogen content in the reformed gas obtained by catalysis is higher, the carbon monoxide content is relatively lower, and due to the specific pore structure of the porous material matrix, the heat of the monolithic catalyst is easy to dissipate in the reforming hydrogen production process, the catalyst is not easy to sinter and inactivate, and the monolithic catalyst is further suitable for high space velocity (reaction space velocity WHSV of 5.8 h)^-1) The lower operation effectively relieves the raw materials in the existing reforming hydrogen production reactionLow conversion rate, high carbon monoxide content in the reformed gas and the problem that the existing particle catalyst can not run at high space velocity.

In a preferred embodiment of the invention, the catalytic coating comprises at least one of Al oxide, Ce oxide, Zr oxide, meaning that the catalytic coating may consist of one or more of Al oxide, Ce oxide, Zr oxide. For example, the catalytic coating may be an Al oxide; may also be Ce oxide; the oxide may be Zr oxide, and may be Ce-Zr oxide.

In a preferred embodiment, the Al oxide catalytic coating can increase the specific surface area of the catalyst and the dispersion degree of the active component, thereby increasing the catalytic activity. The Ce oxide has good catalytic performance as a catalytic coating, CeO₂With oxygen storage and release function in CeO₂The cerium-zirconium solid solution composite oxide formed by doping Zr4+ in the cerium-zirconium solid solution composite oxide improves CeO₂Has higher oxygen storage and release capacity and better thermal stability. Meanwhile, the cerium-zirconium solid solution composite oxide is used as a coating material of the monolithic catalyst, so that the loading area of the active component can be increased, and the catalytic performance can be improved. And the active metal Cu has better activity at low temperature and high selectivity to hydrogen.

More preferably, the catalytic coating is Al₂O₃、CeO₂、ZrO₂Or CeO₂-ZrO₂One of binary oxides. AlO (aluminum oxide)₃The specific surface area of the catalyst and the dispersion degree of the active components can be improved, and the catalytic activity is improved. Rare earth catalytic material CeO₂Has the functions of storing and releasing oxygen and good catalytic performance in CeO₂The cerium-zirconium solid solution composite oxide formed by doping Zr4+ in the cerium-zirconium solid solution composite oxide improves CeO₂Has higher oxygen storage and release capacity and better thermal stability. The cerium-zirconium solid solution composite oxide is used as a coating material of the monolithic catalyst, so that the loading area of the active component can be increased, and the catalytic performance is improved.

As a preferred embodiment, LaCrO is used₃As coating material for monolithic catalyst, can be increasedThe loading area of the active component improves the catalytic performance.

In a preferred embodiment of the present invention, the porous material matrix is a honeycomb ceramic;

as a preferred embodiment, because the selected honeycomb ceramic matrix material has good thermal conductivity and high heat transfer efficiency, and a large number of directional or random holes are dispersed in the honeycomb ceramic, the ceramic with a specific pore structure is used as the matrix of the monolithic catalyst, and the catalyst can be operated at high space velocity.

In the above preferred embodiment, the honeycomb ceramic comprises a combination of one or more of oxide ceramic, carbide ceramic, nitride ceramic, and boride ceramic;

as a preferred embodiment, among the oxide ceramics, there are single oxide ceramics such as alumina, composite oxide ceramics such as mullite, etc.; carbide ceramics such as silicon carbide and the like; the nitride ceramics include silicon nitride, boron nitride, etc., boride ceramics, such as titanium diboride ceramics.

More preferably, the honeycomb ceramic is a carbide ceramic, and the carbide ceramic is a silicon carbide (SiC) honeycomb ceramic.

In a preferred embodiment of the present invention, the honeycomb ceramic has a specific surface area of 3000 to 10000M²/M³The density of the holes of the honeycomb ceramic is 200-2000 holes/cm²。

Typical but non-limiting preferred embodiments of the specific surface area of the above-described honeycomb ceramic are: 3000M²/M³、4000M²/M³、5000M²/M³、6000M²/M³、7000M²/M³、8000M²/M³、 9000M²/M³And 10000M²/M³. Typical but non-limiting preferred embodiments of the cell density of the above-described honeycomb ceramics are: 200 holes/cm²400 pores/cm²600 wells/cm²800 holes/cm²1000 pores/cm²1200 cells/cm²1400 pores/cm²1600 holes/cm²1800 holes/cm²And 2000 holes/cm²。

In a preferred embodiment of the invention, the mass of the catalytic coating is 5-40 wt% of the mass of the porous material matrix;

in a preferred embodiment, the mass of the catalytic coating is 5-40 wt% of the mass of the porous material substrate, and if the mass of the catalytic coating is smaller, the coating amount is insufficient, and the mass is larger, so that the coating amount may be too large, which may cause non-uniformity of the coating amount.

Typical but non-limiting preferred embodiments of the quality of the catalytic coating described above are: 5 wt%, 10 wt%, 13.37 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt% and 40 wt%.

Preferably, the mass of the catalytic coating is 10-20 wt% of the mass of the porous material matrix.

More preferably, the mass of the catalytic coating is 13.37 wt% of the mass of the porous material substrate.

In the invention, the quality of the catalytic coating is further adjusted and optimized, so that the catalytic effect of the monolithic catalyst is further optimized.

In a preferred embodiment of the invention, the content of the active metal is 4-30 wt% of the mass of the porous material matrix calculated by oxide;

in a preferred embodiment, the content of the active metal is 4 to 30 wt% of the mass of the porous material matrix in terms of oxide; wherein the mass of the active metal is too small, the loading amount of the active component is insufficient, the mass is too large, and the active component is easy to agglomerate.

Typical but non-limiting preferred embodiments of the mass of the above-mentioned active metal component oxide are: 4 wt%, 8 wt%, 10 wt%, 10.62 wt%, 15 wt%, 18 wt%, 20 wt%, 25 wt%, 28 wt% and 30 wt%.

Preferably, the content of the active metal is 5-15 wt% of the mass of the porous material matrix calculated by oxide.

More preferably, the content of the active metal is 10.62 wt% of the mass of the porous material matrix calculated by oxide.

According to one aspect of the present invention, a method for preparing the monolithic catalyst described above comprises the steps of:

firstly, the catalytic coating is loaded on the porous material, then the oxide of the active metal is loaded on the catalytic coating, and the integral catalyst is obtained by reduction.

The preparation method of the monolithic catalyst comprises the steps of loading the catalytic coating on the porous material substrate, loading the oxide of the active metal on the catalytic coating, and reducing to obtain the monolithic catalyst. The preparation method is simple in preparation process, convenient and fast to operate and suitable for large-scale industrial production.

In a preferred embodiment of the present invention, the preparation method specifically comprises the following steps: preparing gel by taking at least one salt of Al salt, Ce salt and Zr salt as a raw material through a sol-gel method, then immersing a porous material substrate into the gel to enable the gel to be uniformly loaded on the porous material substrate, and sintering to obtain a catalyst precursor A with a catalytic coating loaded on the porous material substrate; and then, uniformly loading the oxide of the active metal on the catalytic coating in the catalyst precursor A by adopting a solution impregnation method, sintering to obtain a catalyst precursor B, and reducing to obtain the monolithic catalyst.

In a preferred embodiment of the present invention, the preparation method specifically comprises the following steps:

with La (NO)₃)₂、Cr(NO₃)₂·9H₂Preparing gel by taking O and citric acid as raw materials through a sol-gel method, then immersing the porous material substrate into the gel to enable the gel to be uniformly loaded on the porous material substrate, and sintering to obtain a catalyst precursor A with a catalytic coating loaded on the porous material substrate; and then, uniformly loading the oxide of the active metal on the catalytic coating in the catalyst precursor A by adopting a solution impregnation method, sintering to obtain a catalyst precursor B, and reducing to obtain the monolithic catalyst.

In a preferred embodiment of the invention, the temperature of the reduction is 250 to 350 ℃; at the above reduction temperatures, the monolithic catalyst has a very good effect.

Typical but non-limiting preferred embodiments of the above reduction temperatures are: 250 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃ and 350 ℃.

Preferably, the reduction is carried out under an atmosphere of a protective gas, and the protective gas is H₂-N₂Mixing the gas;

more preferably, said H₂-N₂The content of H2 in the mixed gas is 1-20 wt%.

In a preferred embodiment of the present invention, the preparation method further comprises the steps of pre-treating the porous material substrate, and then loading the catalyst coating;

as a preferred embodiment, the preparation method further comprises the step of pretreating the porous material substrate to remove impurities, so as to facilitate the loading of the catalytic coating at a later stage.

Preferably, the step of pre-treating is to treat the porous material matrix with hydrochloric acid, and then to wash and dry the porous material matrix.

More preferably, the preparation method of the monolithic catalyst specifically comprises the following steps:

(a) soaking the porous material matrix with hydrochloric acid with the concentration of 3-10 wt% for 2-10 h, then washing with deionized water, drying, and roasting at 500-600 ℃ for 2-10 h to obtain a pretreated porous material matrix;

(b) preparing a salt solution with the concentration of 1-3 mol/L by taking one of Al salt, Ce salt or Zr salt as a raw material, dropwise adding 1-10 wt% of ammonia water into the solution under high-speed stirring, adjusting the pH value to 2-7 to form gel, and aging the gel for 5-48 h to obtain a spare gel;

(c) soaking the porous material substrate pretreated in the step (a) in the gel aged in the step (b) for 1-10 hours, taking out the gel, blowing residual liquid in the pores, drying, and roasting at 400-600 ℃ for 2-10 hours; repeating the steps for 3-5 times until the catalytic coating accounts for 5-40 wt% of the mass of the porous material matrix, and preparing a catalyst precursor A;

(d) soaking the catalyst precursor A prepared in the step (c) in 1-5 mol/l of Cu (NO) by adopting a solution soaking method₃)₂.3H₂Soaking in O solution for 1-10h, drying, and roasting at 400-600 deg.C for 3 h; repeating the step for 2-5 times until CuO accounts for 4-30% of the mass of the porous material matrix, and preparing a catalyst precursor B;

(e) putting the catalyst precursor B prepared in the step (d) in H₂-N₂Reducing for 2-8h at the temperature of 250 ℃ and 350 ℃ in mixed atmosphere to obtain the monolithic catalyst.

Preferably, the preparation method of the monolithic catalyst specifically comprises the following steps:

(a) soaking the porous material matrix with hydrochloric acid with the concentration of 3-10 wt% for 2-10 h, then washing with deionized water, drying, and roasting at 500-600 ℃ for 2-10 h to obtain a pretreated porous material matrix;

(b) la (NO)₃)₂、Cr(NO₃)₂·9H₂Preparing solutions with the concentration of 1-3 mol/L from O and citric acid serving as raw materials, mixing the solutions together, stirring at a high speed until gel is formed, and aging the gel for 5-48 hours to prepare a standby gel;

(c) soaking the porous material substrate pretreated in the step (a) in the gel aged in the step (b) for 1-10 hours, taking out the gel, blowing residual liquid in the pores, drying, and roasting at 700-900 ℃ for 2-7 hours; repeating the steps for 3-5 times until the catalytic coating accounts for 5-40 wt% of the mass of the porous material matrix, and preparing a catalyst precursor A;

(d) soaking the catalyst precursor A prepared in the step (c) in 1-5 mol/l of Cu (NO) by adopting a solution soaking method₃)₂.3H₂Soaking in O solution for 1-10h, drying, and roasting at 400-600 deg.C for 3 h; repeating the step for 2-5 times until CuO accounts for 4-30% of the mass of the porous material matrix to prepare a catalyst precursor B;

(e) putting the catalyst precursor B prepared in the step (d) in H₂-N₂Reducing for 2-8h at the temperature of 250 ℃ and 350 ℃ in mixed atmosphere to obtain the integral typeA catalyst.

According to one aspect of the invention, the monolithic catalyst is used in a reforming hydrogen production reaction.

The monolithic catalyst provided by the invention can be widely applied to reforming hydrogen production reaction.

According to one aspect of the invention, a method for producing hydrogen by methanol steam reforming is catalyzed by using the monolithic catalyst.

According to the method for preparing hydrogen by reforming methanol steam, the monolithic catalyst is used for catalysis, and the method has the advantages of high methanol conversion rate, high hydrogen content in the reformed gas obtained by catalysis, and relatively low carbon monoxide content.

The technical solution of the present invention will be further described with reference to examples and comparative examples.