CN103816921B - Catalyst for hydrogen production via methanol steam reforming as well as preparing method and hydrogen production method thereof - Google Patents

Abstract

The invention discloses a multi-active component methanol steam reforming hydrogen production catalyst and a preparation method thereof. The catalyst includes Pt oxides, Pd oxides, Cu oxides, Fe oxides, and Zn oxides. oxides, rare earth metal oxides, transition metal oxides. Among them, the noble metal Pt content accounts for 0.5% to 2% of the total mass of the catalyst, the content of Pd accounts for 1% to 5% of the total mass of the catalyst, the oxides of Cu account for 5% to 15% of the total mass of the catalyst, and the oxides of Fe account for the total mass of the catalyst. 2% to 10% of the mass, Zn oxides account for 10% to 25% of the total mass of the catalyst, rare earth metal oxides account for 5% to 45% of the total mass of the catalyst, and the rest are transition metal oxides. The invention adopts the impregnation method, the co-precipitation method and the gel-sol method and the catalyst prepared by a special process can be used in a wide temperature range of 250-550 °C, the methanol conversion rate is greater than 90%, and the hydrogen content in the reformed gas is greater than 70mol%. . It has high activity, good reforming property and strong operability, and is suitable for non-uniform temperature methanol steam reforming hydrogen production system.

Description

Methanol steam reforming hydrogen production catalyst and its preparation method, hydrogen production method

technical field

The invention belongs to the technical field of hydrogen production technology, and relates to a catalyst, in particular to a multi-active component methanol steam reforming hydrogen production catalyst; at the same time, the invention relates to the preparation of the aforementioned methanol steam reforming hydrogen production catalyst Method; In addition, the present invention also relates to a hydrogen production method using the above methanol steam reforming hydrogen production catalyst.

Background technique

In recent years, with the development of proton exchange membrane fuel cells, especially their application in automobiles and distributed power generation, there is an urgent need for small, efficient, and decentralized mobile hydrogen production systems to supply raw hydrogen. As a result, various hydrogen production systems have emerged, as well as various hydrogen production methods.

For example, Chinese patent CN202519022U discloses a methanol steam reforming hydrogen production equipment, which includes a liquid storage container, a heat exchanger, a gasification chamber, a reforming chamber, and a separation chamber. The equipment includes one or more heating units to control the temperature of the parts of the hydrogen production equipment that need temperature control; the heating units are heated by the residual gas output from the separation chamber or/and the produced hydrogen. The transmission channel between the reforming chamber and the separation chamber passes through a preheating temperature control mechanism, which is used to heat the gas output from the reforming chamber; The buffer between them makes the temperature of the gas output from the reforming chamber the same or close to the temperature of the separation chamber.

Another example is the hydrogen production method provided by Chinese Patent Publication No. CN101033059. This hydrogen production method has attracted widespread attention because it does not require external heating and is easy to realize on-site heating. In this method, the relaxation gas is used to heat the system, and the result is uneven heating of various parts of the system. The most direct and most influential factor is the catalytic activity of the catalyst.

All methanol hydrogen production catalysts currently on the market, whether they are copper catalysts or noble metal catalysts and other catalysts, have their own activity temperature, either at 200-300 ° C, or at 350-450 ° C, or at 400 ° C or above, so the temperature distribution is uneven When the catalysts on the market are applied in the system, the catalytic activity will be low and the catalyst efficiency will be low. That is, the catalysts on the market will have limitations in the application of non-uniform temperature systems.

In view of this, there is an urgent need to design a new methanol hydrogen production catalyst in order to overcome the above-mentioned defects of existing catalysts.

Contents of the invention

The technical problem to be solved by the present invention is to provide a catalyst for hydrogen production by steam reforming of methanol. In the process of hydrogen production, the coordination of various components can make the catalyst have a high temperature in a wide temperature range. activity.

At the same time, the present invention also provides a method for preparing a catalyst for hydrogen production by steam reforming of methanol. During the process of hydrogen production, the prepared catalyst can undergo the coordinated action of various components, so that the catalyst can be used in a wide temperature range. Has a high activity.

In addition, the present invention further provides a hydrogen production method of a methanol steam reforming hydrogen production catalyst, which can make the catalyst have high activity in a wide temperature range through the coordinated action of various components.

In order to solve the problems of the technologies described above, the present invention adopts the following technical solutions:

A methanol steam reforming catalyst for hydrogen production. The catalyst is composed of five elements, Pt, Pd, Cu, Fe, and Zn. The active component is a functional composite metal oxide as a carrier. The functional composite metal oxide Including rare earth metal oxides, transition metal oxides;

The catalyst specifically includes: PtO, PdO, _CuO , _Fe2O3 , ZnO, rare earth metal oxides, transition metal oxides;

Among them, the content of noble metal Pt accounts for 0.5% to 2% of the total mass of the catalyst, the content of Pd accounts for 1% to 5% of the total mass of the catalyst, _CuO accounts for 5% to 15% of the total mass of the catalyst, and _Fe2O3 accounts for 2% to 10% of the total mass of the catalyst, ZnO accounts for 10% to 25% of the total mass of the catalyst, rare earth metal oxides account for 5% to 45% of the total mass of the catalyst, and the rest are transition metal oxides;

The rare earth metal includes one or more of lanthanum, cerium, neodymium, europium, and praseodymium; the transition metal includes one or more of zirconium, yttrium, molybdenum, niobium, manganese, and cobalt.

A catalyst for hydrogen production by steam reforming of methanol, said catalyst comprising: oxides of Pt, oxides of Pd, oxides of Cu, oxides of Fe, oxides of Zn, rare earth metal oxides, transition metal oxides ;

As a preferred version of the present invention, the noble metal Pt content accounts for 0.5% to 2% of the total mass of the catalyst, the content of Pd accounts for 1% to 5% of the total mass of the catalyst, and the oxide of Cu accounts for 5% to 15% of the total mass of the catalyst. , Fe oxides account for 2% to 10% of the total catalyst mass, Zn oxides account for 10% to 25% of the total catalyst mass, rare earth metal oxides account for 5% to 45% of the total catalyst mass, and the rest are transition metals oxide.

As a preferred solution of the present invention, the rare earth metal includes one or more of lanthanum, cerium, neodymium, europium and praseodymium.

As a preferred solution of the present invention, the transition metal includes one or more of zirconium, yttrium, molybdenum, niobium, manganese, and cobalt.

A kind of preparation method of above-mentioned catalyst, described preparation method comprises:

The carrier adopts co-precipitation method or gel-sol method. The precipitate or sol of the carrier is dried at 110-180°C, decomposed at 260-480°C, and roasted at 400-750°C. The obtained solid is impregnated with active components into the carrier by impregnation method superior.

As a preferred solution of the present invention, the method specifically includes: the carrier is prepared by co-precipitation method or gel-sol method, the precipitate or sol of the carrier is dried at 120-150°C for 6-15 hours, and decomposed at 300-400°C 2-6 hours, roasting at 450-650° C. for 3-6 hours, the obtained solids are pressed into tablets or extruded into strands, and the active components are impregnated onto the carrier by impregnation; the carrier includes rare earth metal oxides and transition metal oxides.

As a preferred version of the present invention, the preparation method specifically includes the following steps:

Carrier preparation steps: use rare earth nitrates and transition metal nitrates to obtain precipitates by co-precipitation method, or use gel-sol method to generate gels; precipitates or sols are dried at 120-150°C for 6-15 hours, and dried at 300- Decompose at 400°C for 2-6 hours, roast at 450-650°C for 3-6 hours, and the resulting solid is formed by pressing or extruding to obtain a sheet-shaped or strip-shaped carrier; the co-precipitation method is a mixed aqueous solution of rare earth nitrates and transition metal nitrates First, use ammonia water or sodium carbonate to co-precipitate to obtain a precipitate; the gel-sol method means that rare earth metal nitrates and transition metal nitrates react with organic acids such as citric acid in aqueous solution to form gels;

Catalyst preparation steps: impregnate the active components onto the carrier by impregnation, that is, soak the formed sheet or strip carrier in the prepared mixture of platinum nitrate, palladium nitrate, copper nitrate, iron nitrate and zinc nitrate Soak in aqueous solution for 12-24 hours, then dry at 120-150°C for 6-15 hours, and roast at 350-650°C for 3-6 hours; the catalyst finally obtained is composed of five elements: Pt, Pd, Cu, Fe, and Zn. Functional composite metal oxides are used as a carrier, and the functional composite metal oxides include rare earth metal oxides and transition metal oxides;

The catalyst specifically includes: PtO, PdO, CuO, Fe ₂ O ₃ , ZnO, rare earth metal oxides, and transition metal oxides; wherein, the content of noble metal Pt accounts for 0.5% to 2% of the total mass of the catalyst, and the content of Pd accounts for 1%-5% of the total mass, CuO 5%-15% of the total mass of the catalyst, Fe ₂ O ₃ 2%-10% of the total mass of the catalyst, ZnO 10%-25% of the total mass of the catalyst, rare earth metals Oxides account for 5% to 45% of the total mass of the catalyst, and the rest are transition metal oxides; the rare earth metals include one or more of lanthanum, cerium, neodymium, europium, and praseodymium; transition metals include zirconium, yttrium, and molybdenum , niobium, manganese, cobalt in one or more.

A hydrogen production method utilizing the above methanol steam reforming hydrogen production catalyst, the hydrogen production method comprising the steps of:

The hydrogen production method includes a reforming step, and the catalyst in the reforming chamber in the reforming step is the above-mentioned methanol steam reforming hydrogen production catalyst.

As a preferred solution of the present invention, the hydrogen production temperature in the reforming chamber is controlled in the range of 250-550°C, the molar ratio of water to methanol is 1-1.6, and the reaction is carried out at a space velocity of 2.8h ^-1 .

The hydrogen production method specifically includes the following steps:

Step S1, quick start step; the hydrogen production system uses the quick start device to provide starting energy to start; specifically includes:

The first heating mechanism of the first starting device is energized for a set time, and methanol is introduced into the first gasification pipeline after the first heating mechanism reaches the set temperature; since the first gasification pipeline is tightly wound around the first heating mechanism Above, the temperature of methanol gradually increases; the first gasification pipeline outputs the gasified methanol, and then ignites and burns through the ignition mechanism; or, the first gasification pipeline outputs the gasified methanol, and the output methanol temperature reaches the spontaneous combustion point, methanol spontaneously ignites directly after being output from the first gasification pipeline;

The gasified methanol provides start-up energy for hydrogen production equipment through combustion and release of heat; at the same time, the combustion of methanol output from the first gasification pipeline also heats the second gasification pipeline of the second start-up device, turning the second gasification tube Methanol gasification in the road;

After the vaporized methanol is output from the second gasification pipeline, the first starting device is closed, and the methanol output from the second gasification pipeline of the second starting device is heated for the reforming chamber, and at the same time, the second gasification pipeline is heated , to vaporize the methanol in the second gasification pipeline; the inner wall of the reforming chamber is provided with a heating pipeline, and a catalyst is placed in the heating pipeline; heating;

Step S2, after the system is started, the hydrogen production system provides the energy required for operation through the hydrogen produced by the hydrogen production equipment; when the hydrogen production system is running and produces enough hydrogen, turn off the quick start device, and part of the hydrogen produced by the hydrogen production equipment or / and residual gas are burned to maintain the operation of hydrogen production equipment; the hydrogen production process specifically includes:

The methanol and water in the liquid storage container are transported to the heat exchanger of the hydrogen production equipment through the raw material delivery device for heat exchange, and enter the gasification chamber for gasification after heat exchange; the vaporized methanol vapor and water vapor enter the reforming chamber, A catalyst is installed in the reforming chamber, and the temperature of the lower and middle parts of the reforming chamber is 300°C to 420°C; the catalyst specifically includes: PtO, PdO, CuO, Fe ₂ O ₃ , ZnO, rare earth metal oxides, and transition metal oxides; Among them, the content of noble metal Pt accounts for 0.5% to 2% of the total mass of the catalyst, the content of Pd accounts for 1% to 5% of the total mass of the catalyst, _CuO accounts for 5% to 15% of the total mass of the catalyst, and _Fe2O3 accounts for 2% to 10% of the total mass of the catalyst, ZnO accounts for 10% to 25% of the total mass of the catalyst, rare earth metal oxides account for 5% to 45% of the total mass of the catalyst, and the rest are transition metal oxides; the rare earth metals include lanthanum, cerium, One or more of neodymium, europium, and praseodymium; transition metals include one or more of zirconium, yttrium, molybdenum, niobium, manganese, and cobalt;

The temperature of the upper part of the reforming chamber is 400°C to 570°C; the reforming chamber and the separation chamber are connected through a connecting pipeline, and all or part of the connecting pipeline is arranged on the upper part of the reforming chamber, which can pass through the high temperature of the upper part of the reforming chamber. Continue to heat the gas output from the reforming chamber; the connecting pipeline serves as a buffer between the reforming chamber and the separation chamber, so that the temperature of the gas output from the reforming chamber is the same as or close to the temperature of the separation chamber;

The temperature in the separation chamber is set at 350°C to 570°C; a membrane separator is installed in the separation chamber, and hydrogen is obtained from the gas-producing end of the membrane separator; the raw material delivery device provides power to transport the raw material in the liquid storage container to the hydrogen production equipment; the raw material conveying device provides a pressure of 0.15 to 5 MPa for the raw material, so that the hydrogen produced by the hydrogen production equipment has sufficient pressure; the hydrogen produced by the hydrogen production equipment is transported to the membrane separation device for separation. The difference between the internal and external pressure of the membrane separation device for separating hydrogen is greater than or equal to 0.7M Pa; the membrane separation device is a membrane separation device that vacuum-plates palladium-silver alloy on the surface of porous ceramics, and the coating layer is palladium-silver alloy. The quality of palladium-silver alloy Percent palladium accounts for 75% to 78%, silver accounts for 22% to 25%;

After the hydrogen production equipment starts to produce hydrogen, part of the hydrogen or/and residual gas produced by the hydrogen production equipment is burned to maintain the operation of the hydrogen production equipment.

The beneficial effect of the present invention is that: the methanol steam reforming hydrogen production catalyst and its preparation method proposed by the present invention, in the process of hydrogen production, through the coordinated action of each component, the catalyst has a very high temperature in a wide temperature range. High activity. Provide technical guarantee for hydrogen production equipment with uneven temperature in hydrogen production system such as mobile on-site hydrogen production equipment.

Description of drawings

Fig. 1 is a flow chart of the method for preparing a catalyst for hydrogen production by steam reforming of methanol according to the present invention.

detailed description

Preferred embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings.

Embodiment one

The present invention discloses a multi-active component methanol steam reforming catalyst for hydrogen production. The catalyst consists of five elements, Pt, Pd, Cu, Fe, and Zn, as active components, and uses a functional composite metal oxide as a carrier. , the functional composite metal oxides include rare earth metal oxides and transition metal oxides.

The catalyst specifically includes: oxides of Pt, oxides of Pd, CuO, Fe ₂ O ₃ , ZnO, oxides of rare earth metals, oxides of transition metals. Among them, the content of noble metal Pt accounts for 0.5% to 2% of the total mass of the catalyst, the content of Pd accounts for 1% to 5% of the total mass of the catalyst, _CuO accounts for 5% to 15% of the total mass of the catalyst, and _Fe2O3 accounts for 2% to 10% of the total mass of the catalyst, ZnO accounts for 10% to 25% of the total mass of the catalyst, rare earth metal oxides account for 5% to 45% of the total mass of the catalyst, and the rest are transition metal oxides.

The rare earth metals include one or more of lanthanum, cerium, neodymium, europium, and praseodymium (of course, other rare earth metals can also be imagined by those skilled in the art); transition metals include zirconium, yttrium, molybdenum, One or more of niobium, manganese and cobalt (of course other transition metals are also possible).

In this example, Pt oxide accounts for 1% of the total mass of the catalyst, Pd oxide accounts for 2% of the total mass of the catalyst, CuO accounts for 10% of the total mass of the catalyst, Fe2O3 accounts for 5% of the total mass of the catalyst, and ZnO accounts for 5% of the total mass of the catalyst. 10%, rare earth metal oxides account for 30% of the total mass of the catalyst, and transition metal oxides account for 42% of the total mass of the catalyst.

Embodiment two

In this embodiment, Pt oxide accounts for 2% of the total mass of the catalyst, Pd oxide accounts for 5% of the total mass of the catalyst, CuO accounts for 15% of the total mass of the catalyst, Fe2O3 accounts for 10% of the total mass of the catalyst, and ZnO accounts for 10% of the total mass of the catalyst. 15%, the rare earth metal oxide accounts for 5% of the total mass of the catalyst, and the transition metal oxide accounts for 48% of the total mass of the catalyst.

Embodiment three

In this embodiment, Pt oxide accounts for 0.5% of the total mass of the catalyst, Pd oxide accounts for 1% of the total mass of the catalyst, CuO accounts for 5% of the total mass of the catalyst, Fe2O3 accounts for 2% of the total mass of the catalyst, and ZnO accounts for 2% of the total mass of the catalyst. 25%, the rare earth metal oxide accounts for 5% of the total mass of the catalyst, and the transition metal oxide accounts for 48% of the total mass of the catalyst.

The hydrogen production process is carried out in a reforming chamber with a temperature change range of 250°C to 550°C. The test data of the above examples are as follows,

Embodiment four

The present invention also discloses a method for preparing the methanol steam reforming hydrogen production catalyst described in the above examples. The preparation method includes: the carrier adopts a co-precipitation method or a gel-sol method, and the precipitate or sol of the carrier is deposited at 110 Dried at ~180°C, decomposed at 260~480°C, calcined at 400~750°C, and the obtained solid is impregnated with active components on the carrier by impregnation method.

Preferably, the method specifically includes: the carrier is prepared by co-precipitation method or gel-sol method, the precipitate or sol of the carrier is dried at 120-150°C for 6-15 hours, decomposed at 300-400°C for 2-6 hours, and dried at 450°C Calcined at ~650°C for 3-6 hours, the resulting solid is pressed into tablets or extruded into strips, and the active component is impregnated onto the carrier by impregnation; the carrier includes rare earth metal oxides and transition metal oxides.

Specifically, please refer to Figure 1. In this embodiment, the preparation method of the methanol steam reforming hydrogen production catalyst specifically includes the following steps:

Step S1, the preparation step of the carrier: using rare earth nitrates and transition metal nitrates to obtain precipitates by co-precipitation method, or using gel-sol method to generate gel; the precipitates or sols are dried at 120-150° C. for 6-15 hours, Decompose at 300-400°C for 2-6h (the chemical reaction of decomposition is: MCO3 (or MOH)-MO+CO2 (or H2O), where M represents metal and MO represents metal oxide), and roast at 450-650°C for 3 hours ~6h, the obtained solid is formed by pressing or extruding to obtain a sheet or strip-shaped carrier; the co-precipitation method is that the mixed aqueous solution of rare earth nitrate and transition metal nitrate is first co-precipitated with ammonia water or sodium carbonate to obtain a precipitate; Colloid-sol method is that rare earth metal nitrates and transition metal nitrates react with organic acids such as citric acid in aqueous solution to form gels.

Step S2, the preparation step of the catalyst: the active component is impregnated onto the carrier by the impregnation method, that is, the above-mentioned shaped sheet or strip carrier is soaked in the prepared platinum nitrate, palladium nitrate, copper nitrate, iron nitrate, nitric acid Soak in the mixed aqueous solution of zinc for 12-24 hours, then dry at 120-150°C for 6-15 hours, and roast at 350-650°C for 3-6 hours.

The catalyst finally obtained is composed of five elements of Pt, Pd, Cu, Fe, and Zn as active components, and functional composite metal oxides are used as supports, and the functional composite metal oxides include rare earth metal oxides, transition metal oxides . The catalyst specifically includes: PtO, PdO, CuO, Fe ₂ O ₃ , ZnO, rare earth metal oxides, and transition metal oxides; wherein, the content of noble metal Pt accounts for 0.5% to 2% of the total mass of the catalyst, and the content of Pd accounts for 1%-5% of the total mass, CuO 5%-15% of the total mass of the catalyst, Fe ₂ O ₃ 2%-10% of the total mass of the catalyst, ZnO 10%-25% of the total mass of the catalyst, rare earth metals Oxides account for 5% to 45% of the total mass of the catalyst, and the rest are transition metal oxides; the rare earth metals include one or more of lanthanum, cerium, neodymium, europium, and praseodymium; transition metals include zirconium, yttrium, and molybdenum , niobium, manganese, cobalt in one or more.

Embodiment five

The present invention also discloses a hydrogen production method using the methanol steam reforming hydrogen production catalyst with multiple active components. The hydrogen production method includes the following steps:

The hydrogen production method includes a reforming step. In the reforming step, the catalyst in the reforming chamber is the methanol steam reforming hydrogen production catalyst with multiple active components described in the above examples; the temperature of the reforming chamber is controlled at 250-550°C (of course It can also be within the range of 200-650°C), the molar ratio of water to methanol is 1-1.6 (or 1-2.8 or other ratios), and the reaction is carried out under the condition of space velocity of 2.8h ^-1 .

Embodiment six

The difference between this embodiment and Embodiment 5 is that in this embodiment, the hydrogen production method specifically includes the following steps:

[Step S1] Quick start step (of course, the hydrogen production method may not include this step); the hydrogen production system is started by using the quick start device to provide start energy. Specifically include:

The first heating mechanism of the first starting device is energized for a set time, and methanol is introduced into the first gasification pipeline after the first heating mechanism reaches the set temperature; since the first gasification pipeline is tightly wound around the first heating mechanism Above, the temperature of methanol gradually increases; the first gasification pipeline outputs the gasified methanol, and then ignites and burns through the ignition mechanism; or, the first gasification pipeline outputs the gasified methanol, and the output methanol temperature reaches the spontaneous combustion point, methanol spontaneously ignites directly after being output from the first gasification pipeline;

The gasified methanol provides start-up energy for hydrogen production equipment through combustion and release of heat; at the same time, the combustion of methanol output from the first gasification pipeline also heats the second gasification pipeline of the second start-up device, turning the second gasification tube Methanol gasification in the road;

After the vaporized methanol is output from the second gasification pipeline, the first starting device is closed, and the methanol output from the second gasification pipeline of the second starting device is heated for the reforming chamber, and at the same time, the second gasification pipeline is heated , to vaporize the methanol in the second gasification pipeline; the inner wall of the reforming chamber is provided with a heating pipeline, and a catalyst is placed in the heating pipeline; heating.

[Step S2] After the system is started, the hydrogen production system provides the energy required for operation through the hydrogen produced by the hydrogen production equipment; when the hydrogen production system is running and produces enough hydrogen, turn off the quick start device, and the part produced by the hydrogen production equipment Hydrogen or/and residual gas is burned to maintain the operation of hydrogen production equipment.

The process for preparing hydrogen specifically includes:

The methanol and water in the liquid storage container are transported to the heat exchanger of the hydrogen production equipment through the raw material delivery device for heat exchange, and enter the gasification chamber for gasification after heat exchange; the vaporized methanol vapor and water vapor enter the reforming chamber, A catalyst is installed in the reforming chamber, and the temperature in the lower and middle parts of the reforming chamber is 250°C to 420°C (or lower).

The catalyst specifically includes: PtO, PdO, CuO, Fe ₂ O ₃ , ZnO, rare earth metal oxides, and transition metal oxides; wherein, the content of noble metal Pt accounts for 0.5% to 2% of the total mass of the catalyst, and the content of Pd accounts for 1%-5% of the total mass, CuO 5%-15% of the total mass of the catalyst, Fe ₂ O ₃ 2%-10% of the total mass of the catalyst, ZnO 10%-25% of the total mass of the catalyst, rare earth metals Oxides account for 5% to 45% of the total mass of the catalyst, and the rest are transition metal oxides; the rare earth metals include one or more of lanthanum, cerium, neodymium, europium, and praseodymium; transition metals include zirconium, yttrium, and molybdenum , niobium, manganese, cobalt in one or more.

The temperature at the upper part of the reforming chamber is 400°C to 550°C (it can be higher); The high temperature of the upper part of the reforming chamber continues to heat the gas output from the reforming chamber; the connecting pipeline acts as a buffer between the reforming chamber and the separation chamber, so that the temperature of the gas output from the reforming chamber is the same as that of the separation chamber or close.

The temperature in the separation chamber is set at 350° C. to 570° C.; the separation chamber is provided with a membrane separator, and hydrogen is obtained from the gas-producing end of the membrane separator.

In this embodiment, the raw material delivery device provides power to transport the raw material in the liquid storage container to the hydrogen production equipment; the raw material delivery device provides the raw material with a pressure of 0.15-5 MPa, so that the hydrogen produced by the hydrogen production equipment The pressure; the hydrogen produced by the hydrogen production equipment is transported to the membrane separation device for separation, and the difference between the internal and external pressures of the membrane separation device used to separate hydrogen is greater than or equal to 0.7MPa. The membrane separation device is a membrane separation device that vacuum-plates palladium-silver alloy on the surface of porous ceramics. The coating layer is palladium-silver alloy. The mass percentage of palladium-silver alloy is 75%-78% palladium and 22%-25% silver.

After the hydrogen production equipment starts to produce hydrogen, part of the hydrogen or/and residual gas produced by the hydrogen production equipment is burned to maintain the operation of the hydrogen production equipment.

In summary, the methanol steam reforming hydrogen production catalyst and its preparation method proposed by the present invention, through the coordination of various components in the hydrogen production process, make the catalyst have a high active. Provide technical guarantee for hydrogen production equipment with uneven temperature in hydrogen production system such as mobile on-site hydrogen production equipment.

The description and application of the invention herein is illustrative and is not intended to limit the scope of the invention to the above-described embodiments. Variations and changes to the embodiments disclosed herein are possible, and substitutions and equivalents for various components of the embodiments are known to those of ordinary skill in the art. It should be clear to those skilled in the art that the present invention can be realized in other forms, structures, arrangements, proportions, and with other components, materials and components without departing from the spirit or essential characteristics of the present invention. Other modifications and changes may be made to the embodiments disclosed herein without departing from the scope and spirit of the invention.

Claims (2)

1. a kind of preparation method of catalyst for preparing hydrogen by reforming methanol and water vapour it is characterised in that described catalyst with pt, pd, cu, Five kinds of elementary composition active components of fe, zn, using feature metal composite oxide as carrier, described feature composition metal oxygen Compound includes rare-earth oxide, transition metal oxide；

Described preparation method includes:

Carrier adopts coprecipitation or agglutinating nature yeast, the precipitate of carrier or colloidal sol to be dried, and decomposes, roasting, gained solid is adopted With in impregnation active component to carrier；

Described preparation method specifically includes following steps:

The preparation process of carrier: using rare earth nitrate and transition metal nitrate, thing is precipitated using coprecipitation, or adopts Generate gel with agglutinating nature yeast；Precipitate or colloidal sol in 120～150 DEG C of drying 6～15h, decompose 2 at 300～400 DEG C～ 6h, in 450～650 DEG C of roasting 3～6h, gained solid, through tabletting or extruded moulding, obtains lamellar or bar shaped carrier；Co-precipitation Method is that the mixed aqueous solution of rare earth nitrate and transition metal nitrate is carried out being co-precipitated and must be precipitated with ammonia or sodium carbonate first Thing；Agglutinating nature yeast is rare-earth metal nitrate and transition metal nitrate reacts raw in aqueous with citric acid organic acid Become gel；

The preparation process of catalyst: using in impregnation active component to carrier, that is, going up the described lamellar of molding or bar Shape carrier be soaked in the mixed aqueous solution of the platinum nitrate preparing, Palladous nitrate., copper nitrate, ferric nitrate, zinc nitrate soak 12～ 24h, then in 120～150 DEG C of drying 6～15h, 350～650 DEG C of roasting 3～6h；The catalyst finally obtaining with pt, pd, cu, Five kinds of elementary composition active components of fe, zn, using feature metal composite oxide as carrier, described feature composition metal oxygen Compound includes rare-earth oxide, transition metal oxide；

Described catalyst specifically includes: pto, pdo, cuo, fe₂o₃, zno, rare-earth oxide, transition metal oxide；Its In, the content of 0.5%～2%, the pd that noble metal pt content accounts for catalyst gross mass accounts for the 1%～5% of catalyst gross mass, Cuo accounts for 5%～15%, fe of catalyst gross mass₂o₃2%～10%, the zno accounting for catalyst gross mass accounts for catalyst gross mass 10%～25%, rare-earth oxide accounts for the 5%～45% of catalyst gross mass, remaining be transition metal oxide；Institute State rare earth metal and include one or more of lanthanum, cerium, neodymium, europium, praseodymium；Transition metal include zirconium, yttrium, molybdenum, niobium, manganese, in cobalt One or more.

2. a kind of hydrogen production process using catalyst for preparing hydrogen by reforming methanol and water vapour is it is characterised in that described hydrogen production process includes Following steps:

Hydrogen production process includes reforming step, and in reforming step, the catalyst of reformer chamber is according to preparation side described in claim 1 The catalyst for preparing hydrogen by reforming methanol and water vapour that method is obtained；

In 250～550 DEG C of scopes, water is 1～1.6 with the mol ratio of methanol to the hydrogen manufacturing temperature control of reformer chamber, in air speed 2.8h^-1 Under conditions of react；

Described hydrogen production process specifically includes following steps:

Step s1, quick starting step；Described hydrogen generating system utilizes device for rapidly starting to provide the startup energy to start；Concrete bag Include:

First heating arrangements energising setting time of the first starter, to first after the first heating arrangements reach design temperature Gasification pipe is passed through methanol；Because the first gasification pipe is closely wound on the first heating arrangements, methanol temperature is stepped up； First gasification pipe exports vaporized methanol, then passes through ignition mechanism ignition；Or, the first gasification pipe output quilt The methanol of gasification, and the methanol temperature exporting reaches self-ignition point, methanol direct spontaneous combustion after the first gasification pipe exports；

The methanol of gasification passes through combustion heat release, provides for hydrogen producer and starts the energy；Meanwhile, the methanol of the first gasification pipe output Burning is also the second gasification pipe heating of the second starter, by the methanol gasifying in the second gasification pipe；

After exporting the methanol of gasification in the second gasification pipe, close the first starter, by the second gas of the second starter The methanol changing pipeline output heats for reformer chamber, heats the second gasification pipe, by the methanol gasifying in the second gasification pipe simultaneously； Described reformer chamber inwall is provided with heating pipeline, is placed with catalyst in heating pipeline；It is described that described device for rapidly starting passes through heating Heating pipeline is attached most importance to the heating of whole room；

After step s2, system start-up, hydrogen generating system passes through the energy needed for hydrogen offer operation that hydrogen producer is obtained；Treat hydrogen manufacturing System operation is obtained enough hydrogen, closes device for rapidly starting, and the hydrogen partial that hydrogen producer is obtained or/and residual air pass through combustion Burn and maintain hydrogen producer to run；Hydrogen production process specifically includes:

First alcohol and water in described liquid container is delivered to the heat exchanger heat exchange of hydrogen producer by raw material conveying device, changes Vaporizer gasification is entered after heat；Methanol vapor after gasification and vapor enter reformer chamber, and reformer chamber is provided with catalyst, reform Room bottom and middle portion temperature are 250 DEG C～420 DEG C；Described catalyst specifically includes: pto, pdo, cuo, fe₂o₃, zno, rare earth gold Belong to oxide, transition metal oxide；Wherein, noble metal pt content accounts for the content of 0.5%～2%, pd of catalyst gross mass 1%～5%, the cuo accounting for catalyst gross mass accounts for 5%～15%, fe of catalyst gross mass₂o₃Account for the 2% of catalyst gross mass ～10%, zno account for the 10%～25% of catalyst gross mass, and rare-earth oxide accounts for the 5%～45% of catalyst gross mass, Remaining is transition metal oxide；Described rare earth metal includes one or more of lanthanum, cerium, neodymium, europium, praseodymium；Transition metal bag Include one or more of zirconium, yttrium, molybdenum, niobium, manganese, cobalt；

The temperature on described reformer chamber top is 400 DEG C～550 DEG C；Reformer chamber is connected by connecting line with separation chamber, connecting tube The all or part on road is arranged at the top of reformer chamber, can continue heating from reformer chamber output by the high temperature on reformer chamber top Gas；Described connecting line as between reformer chamber and separation chamber buffering so that from reformer chamber output gas temperature with The temperature of separation chamber is identical or close；

The described temperature separating interior is set as 350 DEG C～570 DEG C；Separate interior and be provided with membrane separator, from the product of membrane separator Gas end obtains hydrogen；

Described raw material conveying device provides power, by the feedstock transportation in liquid container to hydrogen producer；Described raw material is defeated Device is sent to provide the pressure of 0.15～5mpa so that the hydrogen that hydrogen producer is obtained has enough pressure to raw material；Described system Hydrogen storage equipment be obtained hydrogen be delivered to membrane separation device carries out separate, for separate hydrogen membrane separation device inside and outside pressure it Difference is more than or equal to 0.7m pa；Described membrane separation device is the membrane separation device in porous ceramic surface Vacuum Deposition palladium-silver, plating Film layer is palladium-silver, and the mass percent palladium of palladium-silver accounts for 75%～78%, and silver accounts for 22%～25%；

After described hydrogen producer starts hydrogen manufacturing, the hydrogen partial that hydrogen producer is obtained or/and residual air maintain hydrogen manufacturing to set by burning Received shipment row.