CN101214921A - Method and device for coupled catalytic reforming-membrane separation reaction - Google Patents

Abstract

The invention discloses a method of preparing high-purity hydrogen with a coupled catalyst reformation-film separation reactor device and a device thereof. The method includes the following steps: a. substance with carbon-hydrogen and water vapor are heated to 300 DEG C to 1500 DEG C; the water vapor is fed into a reactor after the water-carbon ratio in the reactor is 1.0 to 10.0 through regulating the flow of the water vapor; b. the mixed gas and the reformed catalyst particles in the reactor fully contact, react and produce mixed gas with hydrogen; c. the mixed gas goes through high-selective hydrogen permeable film separation components arranged in the reactor; the hydrogen is timely separated in the reaction, high-purity hydrogen is collected. With the invention, the high-selective hydrogen permeable film separation components are directly arranged in the reactor, so that the hydrogen produced by catalyst reformation is timely separated from the mixed gas produced by the reaction of carbon-hydrogen raw material and the vapor, which can prevent methanation and other side effects and improve the hydrogen making efficiency; the reactor system coupled with film separation components has simple structure.

Description

Method and device for coupled catalytic reforming-membrane separation reaction

technical field

The invention relates to the field of hydrogen production, in particular to a method and device for coupling catalytic reforming-membrane separation reactions.

Background technique

As an efficient and clean secondary energy source, hydrogen has attracted more and more attention, and has been widely used in many industries. Expanding from the aerospace field in the past to today's civilian industry, especially the use of fuel cells, has brought good economic prospects and environmental protection advantages to the efficient and clean utilization of hydrogen energy, and has also promoted people's widespread attention to hydrogen energy; At present, the use of natural gas water coupling catalytic reforming-membrane separation reaction is still the most important way of large-scale hydrogen production. People have found through research that under certain catalyst and reaction conditions, various raw materials such as natural gas, methane, propane, methanol, Ethanol, ether, naphtha, coke oven gas, blast furnace gas, converter gas, coal bed methane, landfill gas, biomass and waste gasification gas or biogas, bio-oil, etc. can all undergo reforming reactions with water vapor to produce Hydrogen, which greatly expands the selection range of raw materials for hydrogen production, and also provides multiple production paths for vigorously developing hydrogen energy.

However, in the prior art, hydrogen reforming and hydrogen separation cannot be realized directly on one piece of equipment. Since hydrogen cannot be collected quickly, it is very easy to cause side reactions such as methanation, and the efficiency of hydrogen production is low.

Contents of the invention

The purpose of the present invention is to provide a method and device for coupling catalytic reforming-membrane separation reaction. The present invention simultaneously realizes reforming catalytic reaction and hydrogen separation in one reaction device, has a simple and compact structure, and has high hydrogen production efficiency.

The method for coupling catalytic reforming-membrane separation reaction of the present invention comprises the following steps:

a. Mix and heat hydrocarbons and water vapor to 300°C to 1500°C, and adjust the flow of water vapor so that the water-carbon ratio in the reactor is 1.0 to 10.0, and then send it into the reactor;

b. The mixed gas is in full contact with the reforming catalyst particles in the reactor to react to generate a mixed gas containing hydrogen;

c. The mixed gas passes through the high-selectivity hydrogen-permeable membrane separation module built in the reactor, and the hydrogen is separated in time during the reaction, and high-purity hydrogen is collected.

The main feature of the present invention is: directly build the highly selective hydrogen permeable membrane separation module into the fluidized bed reactor, so that the hydrogen gas produced by catalytic reforming can be separated in time from the mixed gas generated by the reaction of hydrocarbon-containing substances and steam, Side reactions such as methanation are avoided, and the efficiency of hydrogen production is improved; the reactor coupled with the membrane separation module has a simple and compact structure; it has good thermal stability and can prolong the life of the hydrogen permeable membrane; the purity of the hydrogen produced by the method is High, without further process treatment, directly obtain cheap hydrogen source.

The catalyst used in the method can be a metal catalyst, a bimetallic catalyst, a metal oxide catalyst or a combination of the above catalysts which can catalyze the reforming of raw materials and steam to generate hydrogen.

The hydrocarbon-containing substances in the method of the present invention, that is, common materials containing hydrocarbons, alcohols or ethers, etc., are specifically selected from one of the following or a mixture of more than one: natural gas, methane, propane, methanol, Ethanol, ether, naphtha, coke oven gas, blast furnace gas, converter gas, coal bed methane, landfill gas, biomass, waste gasification gas, biogas or bio-oil.

The coupled catalytic reforming-membrane separation reaction device used in the method of the present invention includes a reactor; wherein, a highly selective hydrogen permeable membrane separation module is directly built into the reactor to realize high-efficiency reforming of hydrocarbons to produce hydrogen the process of.

The space in the reactor is a reaction space, and the wall of the reactor is provided with a raw material feed hole, a catalyst feed port, a catalyst discharge port, and a residual gas outlet connected to the reaction space; the highly selective hydrogen permeable A hydrogen outlet is provided on the membrane separation module.

The further structure is that the highly selective hydrogen permeable membrane separation module is tubular, one end of the tubular membrane separation module is closed, and the other end is open, and the open end can pass through the wall of the reactor, and the outlet The hydrogen port is set at the opening end, and the hydrogen gas is collected by negative pressure and other means; the membrane separation module can also have holes at both ends, and the carrier gas such as water vapor or inert gas enters from one end and goes out from the other end to clean and pass through. The hydrogen in the membrane separation module is then separated to produce high-purity hydrogen. The highly selective hydrogen permeable membrane separation module can be a single pipe, multiple pipes or row pipes; the membrane separation module can be a separate high selectivity hydrogen permeable membrane material, or it can be attached to a porous support Highly selective hydrogen permeable membrane; the membrane separation module can be various forms of tubular structures such as round tubes and square tubes; the membrane separation module can be placed vertically, horizontally or obliquely in the reactor; its raw material inlet It can be single or multiple; the catalyst feed port can be single or multiple; similarly, the residual gas outlet can be single or multiple, or the residual gas can be discharged through the annular chamber, and the residual gas can be discharged through the residual gas outlet. The residual gas discharged from the gas port can also be input to the next coupled catalytic reforming-membrane separation reaction device for reuse.

Description of drawings

Fig. 1 is a flowchart of the method of the present invention;

Fig. 2 is a structural diagram of the device used in the inventive method;

Fig. 3 is an enlarged view of place A of Fig. 2;

Fig. 4 is an enlarged view at B of Fig. 2;

Explanation of reference signs:

1. Reactor, 2. Reaction space, 3. Catalyst feed inlet, 4. Catalyst discharge port, 5. Raw material feed hole, 6. Residual gas outlet, 7. Membrane separation module, 8. Hydrogen outlet.

Detailed ways

As shown in Figure 1, a method for coupling catalytic reforming-membrane separation reaction, the method comprises the following steps:

a. Heating the hydrocarbon-containing substance and water vapor to 400°C to 1200°C, and adjusting the flow of water vapor to make the water-carbon ratio in the reactor 1 be 1.0 to 10.0, and then send it into the reactor 1;

b. The mixed gas is in full contact with the reforming catalyst particles in the reactor 1 to react to generate a mixed gas containing hydrogen;

c. The mixed gas passes through the highly selective hydrogen-permeable membrane separation module 7 built in the reactor 1, and the hydrogen gas is separated in time during the reaction, and high-purity hydrogen gas is collected.

The hydrocarbon-containing substance used in the present invention is one of the following or a mixture of more than one: natural gas, methane, propane, methanol, ethanol, ether, naphtha, coke oven gas, blast furnace gas, converter gas, coal bed methane, One of landfill gas, biomass, waste gasification gas, biogas or bio-oil; in the present invention, the catalyst used can be a metal catalyst, a bimetallic catalyst, a metal oxidation catalysts or combinations of the above catalysts.

The coupled catalytic reforming-membrane separation reaction device used in the method of the present invention includes a reactor 1; wherein, a highly selective hydrogen permeable membrane separation module 7 is directly built into the reactor. Specifically, it can be: the space in the reactor 1 is a reaction space 2, and the wall of the reactor 1 is provided with a raw material feed hole 5, a catalyst feed port 3, and a catalyst discharge port 4 communicating with the reaction space 2. , residual gas outlet 6; the highly selective hydrogen permeable membrane separation assembly 7 (i.e. palladium membrane separator) is a plurality of exhaust pipes, one of the ends of the exhaust pipes passes through the top of the wall of the reactor 1 And immersed in the catalyst, the upper end of the exhaust pipe is provided with a hydrogen outlet 8, and the highly selectively permeable hydrogen is collected at the hydrogen outlet 8. Methane (or other hydrocarbon-containing substances) and water vapor enter from the bottom of the reactor 1 with a water-to-carbon ratio of 2.5 to 3 as raw materials, so that the nickel/alumina catalyst particles placed in the reactor 1 are fully fluidized, and the raw materials The inlet temperature of the gas is 650 degrees Celsius to 750 degrees Celsius; under the action of the catalyst, the raw material gas undergoes a reforming reaction to generate a mixture of H ₂ , CO, CO ₂ and unreacted methane and water; The hydrogen membrane separation module 7 is enriched in its cavity, and hydrogen gas with a purity of 99.99% to 99.999% is collected from the top of the highly selective hydrogen permeable membrane separation module 7, and the remaining gas is discharged through the residual gas outlet 6 Reactor 1 for further processing.

Claims (12)

1. one kind is utilized coupling catalytic reforming-film separation reaction device to produce the method for high-purity hydrogen, it is characterized in that this method comprises the steps:

A, will contain hydrocarbon material and water vapor is heated to 300 degrees centigrade to 1500 degrees centigrade, and, send into reactor by regulating after steam rates makes steam/hydrocarbons ratio in the reactor be 1.0 to 10.0;

B, gas mixture fully contact with reforming catalyst particle in the reactor, and reaction generates the gas mixture of hydrogen;

The membrane separation assemblies of c, the highly selective saturating hydrogen of gas mixture through being built in this reactor, hydrogen in time separates when reaction, collects and obtains highly purified hydrogen.

2. coupling catalytic reforming-film separation reaction the device that utilizes according to claim 1 is produced the method for high-purity hydrogen, it is characterized in that the residual air after above-mentioned c step is handled is imported next described coupling catalytic reforming-film separation reaction device and reused.

3. coupling catalytic reforming-film separation reaction the device that utilizes according to claim 1 is produced the method for high-purity hydrogen, it is characterized in that, describedly contain hydrocarbon material and be selected from one of following or more than one mixture: Sweet natural gas, methane, propane, methyl alcohol, ethanol, ether, petroleum naphtha, coke-oven gas, blast furnace gas, coal gas of converter, coal-seam gas, refuse embedded gas, biomass, refuse gasification gas, biogas or bio oil.

4. coupling catalytic reforming-film separation reaction the device that utilizes according to claim 1 is produced the method for high-purity hydrogen, it is characterized in that described catalyzer is the combination that energy catalytic reforming raw material and steam produce metal catalyst, bimetallic catalyst, metal oxide catalyst or the above-mentioned catalyzer of hydrogen.

5. coupling catalytic reforming-film separation reaction device comprises reactor, it is characterized in that, directly the membrane separation assemblies with the saturating hydrogen of highly selective is built in this reactor.

6. according to the described coupling catalytic reforming of claim 5-film separation reaction device, it is characterized in that, space in the described reactor is a reaction compartment, and the wall of reactor is provided with raw material feed port, catalyst feeds, catalyzer discharge opening, the residual air air outlet that communicates with reaction compartment; The membrane separation assemblies of the saturating hydrogen of described highly selective is provided with hydrogen opening.

7. according to the described coupling catalytic reforming of claim 5-film separation reaction device, it is characterized in that, the membrane separation assemblies of the saturating hydrogen of described highly selective is a tubulose, one end closure of this piped membrane separation assemblies, the other end perforate, the perforate end can pass the wall of described reactor, and described hydrogen opening is located at this perforate end.

8. coupling catalytic reforming according to claim 5-film separation reaction device, it is characterized in that: the two ends perforate of described membrane separation assemblies, carrier gas from an end enter, the other end goes out and cleans hydrogen through membrane separation assemblies, separates producing highly purified hydrogen again.

9. according to claim 7 or 8 described coupling catalytic reforming-film separation reaction devices, it is characterized in that the membrane separation assemblies of the saturating hydrogen of highly selective is individual tubes or many pipes or some pipes row.

10. coupling catalytic reforming according to claim 5-film separation reaction device is characterized in that: described membrane separation assemblies can be pipe or square tube.

11. want 5 described coupling catalytic reforming-film separation reaction devices according to right, it is characterized in that: the material of highly selective permeable hydrogen membrane can be metal, alloy, inorganics, organism one of them or its combination.

12. coupling catalytic reforming according to claim 5-film separation reaction device is characterized in that: described membrane separation assemblies can be for independent highly selective permeable hydrogen membrane material or attached to the highly selective permeable hydrogen membrane on the porous supporting body.

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