Methanol reforming hydrogen production reactor

Abstract

The invention relates to the technical field of methanol catalytic reforming hydrogen production, and discloses a methanol reforming hydrogen production reactor. The invention relates to a methanol reforming hydrogen production reactor, which comprises: a reaction tank; the fixing assembly is arranged at the bottom in the reaction tank; the reforming reaction assembly is fixed in the reaction tank through the fixing assembly; the feeding hole is formed in the bottom of the side surface of the reaction tank; the discharging hole is formed in the top of the side face of the reaction tank and is formed in the side, opposite to the feeding hole, of the reaction tank; and the waste gas exhaust pipeline is arranged at the top of the reaction tank. According to the methanol reforming hydrogen production reactor provided by the invention, the reforming reaction assembly is formed by taking the specially-made methanol reforming hydrogen production catalyst and the Pd / ceramic membrane as raw materials, so that efficient methanol reforming hydrogen production can be realized.

Description

Technical Field

[0001] The present invention relates to the technical field of methanol catalytic reforming hydrogen production, and in particular to a methanol reforming hydrogen production reactor. Background Art

[0002] With the growing global demand for clean energy, hydrogen, as an efficient and clean energy carrier, has garnered widespread attention. Methanol reforming hydrogen production technology, with its advantages such as a wide range of raw material sources, low cost, and convenient storage and transportation, has become a hot topic in hydrogen production research. The hydrogen production reactor is a core component of the methanol reforming hydrogen production process, and its performance directly impacts hydrogen production efficiency, cost, and product hydrogen quality.

[0003] Based on this, it is of great practical significance to develop an efficient methanol reforming hydrogen production reactor with high methanol conversion rate. Summary of the Invention

[0004] The purpose of the present invention is to provide a methanol reforming hydrogen production reactor, which has a high methanol conversion rate.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] A methanol reforming hydrogen production reactor, comprising:

[0007] reaction tank;

[0008] A fixing assembly, the fixing assembly being arranged at the bottom of the reaction tank;

[0009] a reforming reaction assembly, wherein the reforming reaction assembly is fixed inside the reaction tank via the fixing assembly;

[0010] A feed hole, the feed hole being arranged at the bottom of the side of the reaction tank;

[0011] A discharge hole is provided at the top of the side of the reaction tank and on the opposite side of the feed hole;

[0012] An exhaust gas pipe is provided on the top of the reaction tank;

[0013] The partition is arranged around the four sides of the reforming reaction component and isolates the internal cavity of the reaction tank into an exhaust gas exhaust cavity and a safety cavity.

[0014] Furthermore, the reforming reaction component comprises:

[0015] Box;

[0016] A feed pipe, the feed pipe is arranged at the bottom of the side of the box body and extends to the outside of the reaction tank through the feed hole;

[0017] A discharge pipe is provided at the top of the side of the box body and on the opposite side of the feed pipe, and extends to the outside of the reaction tank through the discharge hole;

[0018] A catalytic layer and a permeable membrane layer, wherein the catalytic layer and the permeable membrane layer are stacked inside the box, with the first layer on the feed pipe side being the catalytic layer and the first layer on the discharge pipe side being the permeable membrane layer;

[0019] An exhaust gas exhaust window is correspondingly arranged on the top of the catalytic layer.

[0020] Furthermore, the catalytic layer is formed by pressing a methanol reforming hydrogen production catalyst.

[0021] Furthermore, the preparation method of the methanol reforming hydrogen production catalyst comprises the following steps:

[0022] 1) Ce(NO3)3, Zr(NO3)4 and dodecyl ammonium bromide are placed in water and ultrasonically dispersed, then precipitated with a NaOH solution, filtered, and the filter residue is calcined to obtain a Ce / Zr mesoporous carrier;

[0023] 2) placing the Ce / Zr mesoporous support obtained in step 1) in an H2PtCl6 solution, immersing it in water, and reducing it to obtain Pt@Ce / Zr;

[0024] 3) adding the n-octanol solution of Zn(NO3)6 dropwise to the n-octanol solution of 2-methylimidazole and stirring to obtain a ZIF-8 precursor mixed solution;

[0025] 4) placing the Pt@Ce / Zr obtained in step 2) in the ZIF-8 precursor mixed solution obtained in step 3), allowing to stand, centrifuging, washing, and drying to obtain ZIF-8-encapsulated Pt@Ce / Zr;

[0026] 5) The ZIF-8-wrapped Pt@Ce / Zr obtained in step 4) is placed in a CuSO4 solution and reduced at a constant potential to obtain Cu@ZIF-8-wrapped Pt@Ce / Zr, i.e., the methanol reforming hydrogen production catalyst.

[0027] Furthermore, in step 1), the molar ratio of Ce(NO3)3, Zr(NO3)4 and dodecylammonium bromide is (2-3):1:1.

[0028] Furthermore, in step 1), the calcination treatment is specifically: calcination treatment at 250-300° C. for 3 hours.

[0029] Furthermore, in step 2), the concentration of the H2PtCl6 solution is 0.05 mol / L.

[0030] Furthermore, in step 2), the mass volume ratio of the Ce / Zr mesoporous carrier and the H2PtCl6 solution is 1g: (4-6)mL.

[0031] Furthermore, in step 2), the immersion treatment is specifically: immersion treatment at 40-60° C. for 20-40 minutes.

[0032] Furthermore, in step 2), the reduction is specifically: reduction at 300-320°C.

[0033] Furthermore, in step 3), the concentration of the Zn(NO3)6 n-octanol solution is 0.5 mol / L.

[0034] Furthermore, in step 3), the concentration of the 2-methylimidazole n-octanol solution is 1 mol / L.

[0035] Furthermore, in step 3), the molar ratio of Zn(NO3)6 to 2-methylimidazole is 1:(1-1.5).

[0036] Furthermore, in step 3), the stirring is specifically: controlling the stirring speed to 100 r / min and stirring at room temperature for 3 minutes.

[0037] Furthermore, in step 4), the mass volume ratio of the Pt@Ce / Zr and ZIF-8 precursor mixed solution is 1 g: (5-15) mL.

[0038] Furthermore, in step 4), the standing is specifically: standing at room temperature for 30 to 60 minutes.

[0039] Furthermore, in step 5), the concentration of the CuSO4 solution is 0.1 mol / L.

[0040] Furthermore, in step 5), the constant potential reduction is specifically: constant potential reduction at a working voltage of 2V for 20 to 40 minutes.

[0041] Furthermore, the permeable membrane layer is a Pd / ceramic membrane.

[0042] Furthermore, the preparation method of the Pd / ceramic membrane comprises the following steps:

[0043] 1) Place the porous alumina ceramic sheet in a PdCl2 solution, immerse it in water, and dry it to obtain a Pd-adsorbed alumina ceramic sheet. 2+ Alumina ceramic sheet;

[0044] 2) The Pd adsorbed 2+ The alumina ceramic sheet is placed in a mixed gas of sulfur dioxide and hydrogen for reduction to obtain the Pd / ceramic film.

[0045] Furthermore, in step 1), the concentration of the PdCl2 solution is 0.1 mol / L.

[0046] Furthermore, in step 1), the immersion treatment is specifically: immersion treatment at 60-100° C. for 2 hours.

[0047] Furthermore, in step 2), the mixed gas of sulfur dioxide and hydrogen is 50% sulfur dioxide + 50% hydrogen.

[0048] Furthermore, in step 2), the reduction is specifically: reduction at 60-80° C. for 1 hour.

[0049] Compared with the prior art, the present invention has the following beneficial effects:

[0050] The methanol reforming hydrogen production catalyst provided by the present invention has a methanol conversion rate of up to 100%, a carbon monoxide content in the product of up to 0.04%, high catalytic methanol reforming hydrogen production activity, and low carbon monoxide selectivity;

[0051] The Pd / ceramic membrane provided by the present invention has a hydrogen permeability of up to 100%, a carbon dioxide permeability of up to 0.03%, and a carbon monoxide permeability of up to 0%, and has good selective permeability to hydrogen;

[0052] The present invention provides a methanol reforming hydrogen production reactor, which uses a specially prepared methanol reforming hydrogen production catalyst and a Pd / ceramic membrane as raw materials to form a reforming reaction component, and can achieve efficient methanol reforming hydrogen production. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Various other advantages and benefits will become apparent to those skilled in the art upon reading the detailed description of the preferred embodiment below. The accompanying drawings are for illustration purposes only and are not to be considered as limiting the present invention. The same reference symbols are used throughout the drawings to represent the same components. In the drawings:

[0054] Figure 1 This is a schematic diagram of the planar structure of a methanol reforming hydrogen production reactor;

[0055] Figure 2 Schematic diagram of the planar structure of the reforming reaction component;

[0056] In the figure, 1. fixed component; 2. reforming reaction component; 201. feed pipe; 202. discharge pipe; 203. catalytic layer; 204. permeable membrane layer; 205. exhaust window; 3. feed hole; 4. discharge hole; 5. exhaust pipe; 6. partition; 601. exhaust chamber; 602. safety chamber. DETAILED DESCRIPTION

[0057] Various exemplary embodiments of the present invention are now described in detail. This detailed description should not be considered as a limitation of the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention. It should be understood that the terms used in the present invention are only for describing specific embodiments and are not intended to limit the present invention.

[0058] In addition, for numerical ranges in the present invention, it is understood that each intervening value between the upper and lower limits of the range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated value or intervening value in the stated range is also included in the present invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

[0059] Unless otherwise indicated, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may also be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of any conflict with any incorporated document, the contents of this specification shall prevail.

[0060] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments described herein without departing from the scope or spirit of the invention. Other embodiments will be apparent to those skilled in the art from the description of the invention. The description and examples are intended to be exemplary only.

[0061] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0062] In the following examples, the preparation method of the methanol reforming hydrogen production catalyst comprises the following steps:

[0063] 1) Ce(NO3)3, Zr(NO3)4 and dodecylammonium bromide were placed in water at a molar ratio of (2-3):1:1, and ultrasonically dispersed for 30 minutes. The mixture was then precipitated with a 0.1 mol / L NaOH solution, filtered, and the filter residue was calcined at 250-300°C for 3 hours to obtain a Ce / Zr mesoporous support.

[0064] 2) placing the Ce / Zr mesoporous support obtained in step 1) in a 0.05 mol / L H2PtCl6 solution at a mass volume ratio of 1 g to H2PtCl6 solution, immersing the support at 40-60°C for 20-40 min, and then reducing the support at 300-320°C to obtain Pt@Ce / Zr;

[0065] 3) According to the molar ratio of Zn(NO3)6 to 2-methylimidazole of 1: (1 to 1.5), a 0.5 mol / L n-octanol solution of Zn(NO3)6 was added dropwise to a 1 mol / L n-octanol solution of 2-methylimidazole, the stirring speed was controlled at 100 r / min, and the mixture was stirred at room temperature for 3 min to obtain a ZIF-8 precursor mixed solution;

[0066] 4) placing the Pt@Ce / Zr obtained in step 2) into the ZIF-8 precursor mixed solution obtained in step 3) at a mass volume ratio of 1 g:(5-15) mL of the Pt@Ce / Zr to ZIF-8 precursor mixed solution, standing at room temperature for 30-60 min, centrifuging, washing, and drying to obtain ZIF-8-encapsulated Pt@Ce / Zr;

[0067] 5) The ZIF-8-encapsulated Pt@Ce / Zr obtained in step 4) is placed in a CuSO4 solution with a concentration of 0.1 mol / L, and is subjected to constant potential reduction at an operating voltage of 2 V for 20 to 40 min to obtain Cu@ZIF-8-encapsulated Pt@Ce / Zr, i.e., the methanol reforming hydrogen production catalyst.

[0068] Example 1

[0069] A methanol reforming hydrogen production catalyst

[0070] 1) Ce(NO3)3, Zr(NO3)4 and dodecylammonium bromide were placed in water at a molar ratio of 2:1:1, ultrasonically dispersed for 30 minutes, and then precipitated with a 0.1 mol / L NaOH solution. The mixture was filtered, and the filter residue was calcined at 250°C for 3 hours to obtain a Ce / Zr mesoporous support;

[0071] 2) placing the Ce / Zr mesoporous support obtained in step 1) in a 0.05 mol / L H2PtCl6 solution at a mass volume ratio of 1 g to 4 mL, immersing the support at 40°C for 20 min, and then reducing the support at 300°C to obtain Pt@Ce / Zr;

[0072] 3) According to the molar ratio of Zn(NO3)6 to 2-methylimidazole of 1:1, a 0.5 mol / L n-octanol solution of Zn(NO3)6 was added dropwise to a 1 mol / L n-octanol solution of 2-methylimidazole, and the stirring speed was controlled at 100 r / min. The mixture was stirred at room temperature for 3 min to obtain a ZIF-8 precursor mixed solution;

[0073] 4) placing the Pt@Ce / Zr obtained in step 2) into the ZIF-8 precursor mixed solution obtained in step 3) at a mass volume ratio of 1 g:5 mL of the Pt@Ce / Zr to ZIF-8 precursor mixed solution, allowing the mixture to stand at room temperature for 30 min, centrifuging, washing, and drying to obtain ZIF-8-encapsulated Pt@Ce / Zr;

[0074] 5) The ZIF-8-wrapped Pt@Ce / Zr obtained in step 4) was placed in a CuSO4 solution with a concentration of 0.1 mol / L, and reduced at a constant potential for 20 min at an operating voltage of 2 V to obtain Cu@ZIF-8-wrapped Pt@Ce / Zr, i.e., the methanol reforming hydrogen production catalyst.

[0075] Example 2

[0076] A methanol reforming hydrogen production catalyst

[0077] 1) Ce(NO3)3, Zr(NO3)4 and dodecylammonium bromide were placed in water at a molar ratio of 2:1:1, ultrasonically dispersed for 30 minutes, and then precipitated with a 0.1 mol / L NaOH solution. The mixture was filtered, and the filter residue was calcined at 280°C for 3 hours to obtain a Ce / Zr mesoporous support;

[0078] 2) placing the Ce / Zr mesoporous support obtained in step 1) in a 0.05 mol / L H2PtCl6 solution at a mass volume ratio of 1 g to 5 mL, immersing the support at 50°C for 30 min, and then reducing the support at 310°C to obtain Pt@Ce / Zr;

[0079] 3) According to the molar ratio of Zn(NO3)6 to 2-methylimidazole of 1:1.2, a 0.5 mol / L n-octanol solution of Zn(NO3)6 was added dropwise to a 1 mol / L n-octanol solution of 2-methylimidazole, the stirring speed was controlled at 100 r / min, and the mixture was stirred at room temperature for 3 min to obtain a ZIF-8 precursor mixed solution;

[0080] 4) placing the Pt@Ce / Zr obtained in step 2) into the ZIF-8 precursor mixed solution obtained in step 3) at a mass volume ratio of 1 g:10 mL of the Pt@Ce / Zr to ZIF-8 precursor mixed solution, standing at room temperature for 40 min, centrifuging, washing, and drying to obtain ZIF-8-encapsulated Pt@Ce / Zr;

[0081] 5) The ZIF-8-wrapped Pt@Ce / Zr obtained in step 4) was placed in a CuSO4 solution with a concentration of 0.1 mol / L, and reduced at a constant potential for 30 min at an operating voltage of 2 V to obtain Cu@ZIF-8-wrapped Pt@Ce / Zr, i.e., the methanol reforming hydrogen production catalyst.

[0082] Example 3

[0083] A methanol reforming hydrogen production catalyst

[0084] 1) Ce(NO3)3, Zr(NO3)4 and dodecylammonium bromide were placed in water at a molar ratio of 3:1:1, ultrasonically dispersed for 30 minutes, and then precipitated with a 0.1 mol / L NaOH solution. The mixture was filtered, and the filter residue was calcined at 300°C for 3 hours to obtain a Ce / Zr mesoporous support;

[0085] 2) placing the Ce / Zr mesoporous support obtained in step 1) in a 0.05 mol / L H2PtCl6 solution at a mass volume ratio of 1 g to 6 mL, immersing the support at 60°C for 40 min, and then reducing the support at 320°C to obtain Pt@Ce / Zr;

[0086] 3) According to the molar ratio of Zn(NO3)6 to 2-methylimidazole of 1:1.5, a 0.5 mol / L n-octanol solution of Zn(NO3)6 was added dropwise to a 1 mol / L n-octanol solution of 2-methylimidazole, the stirring speed was controlled at 100 r / min, and the mixture was stirred at room temperature for 3 min to obtain a ZIF-8 precursor mixed solution;

[0087] 4) placing the Pt@Ce / Zr obtained in step 2) into the ZIF-8 precursor mixed solution obtained in step 3) at a mass volume ratio of 1 g:15 mL of the Pt@Ce / Zr to ZIF-8 precursor mixed solution, standing at room temperature for 60 min, centrifuging, washing, and drying to obtain ZIF-8-encapsulated Pt@Ce / Zr;

[0088] 5) The ZIF-8-wrapped Pt@Ce / Zr obtained in step 4) was placed in a CuSO4 solution with a concentration of 0.1 mol / L, and reduced at a constant potential for 40 min at an operating voltage of 2 V to obtain Cu@ZIF-8-wrapped Pt@Ce / Zr, i.e., the methanol reforming hydrogen production catalyst.

[0089] Comparative Example 1

[0090] A methanol reforming hydrogen production catalyst

[0091] 1) Ce(NO3)3 and dodecylammonium bromide were placed in water at a molar ratio of 2:1, ultrasonically dispersed for 30 minutes, and then precipitated with a 0.1 mol / L NaOH solution. The mixture was filtered, and the filter residue was calcined at 280°C for 3 hours to obtain a Ce mesoporous support;

[0092] 2) placing the Ce mesoporous support obtained in step 1) in a 0.05 mol / L H2PtCl6 solution at a mass volume ratio of 1 g to 5 mL, immersing the solution at 50°C for 30 min, and then reducing the solution at 310°C to obtain Pt@Ce;

[0093] 3) According to the molar ratio of Zn(NO3)6 to 2-methylimidazole of 1:1.2, a 0.5 mol / L n-octanol solution of Zn(NO3)6 was added dropwise to a 1 mol / L n-octanol solution of 2-methylimidazole, the stirring speed was controlled at 100 r / min, and the mixture was stirred at room temperature for 3 min to obtain a ZIF-8 precursor mixed solution;

[0094] 4) placing the Pt@Ce obtained in step 2) into the ZIF-8 precursor mixed solution obtained in step 3) at a mass volume ratio of 1 g:10 mL of the Pt@Ce to ZIF-8 precursor mixed solution, allowing the mixture to stand at room temperature for 40 min, centrifuging, washing, and drying to obtain ZIF-8-encapsulated Pt@Ce;

[0095] 5) The ZIF-8-wrapped Pt@Ce obtained in step 4) was placed in a CuSO4 solution with a concentration of 0.1 mol / L, and reduced at a constant potential for 30 min at an operating voltage of 2 V to obtain Cu@ZIF-8-wrapped Pt@Ce, i.e., the methanol reforming hydrogen production catalyst.

[0096] Comparative Example 2

[0097] A methanol reforming hydrogen production catalyst

[0098] 1) placing Zr(NO3)4 and dodecylammonium bromide in water at a molar ratio of 1:1, ultrasonically dispersing the mixture for 30 minutes, then precipitating the mixture with a 0.1 mol / L NaOH solution, filtering the mixture, and calcining the residue at 280°C for 3 hours to obtain a Zr mesoporous support;

[0099] 2) placing the Zr mesoporous support obtained in step 1) in a 0.05 mol / L H2PtCl6 solution at a mass volume ratio of 1 g to 5 mL, immersing the support at 50°C for 30 min, and then reducing the solution at 310°C to obtain Pt@Zr;

[0100] 3) According to the molar ratio of Zn(NO3)6 to 2-methylimidazole of 1:1.2, a 0.5 mol / L n-octanol solution of Zn(NO3)6 was added dropwise to a 1 mol / L n-octanol solution of 2-methylimidazole, the stirring speed was controlled at 100 r / min, and the mixture was stirred at room temperature for 3 min to obtain a ZIF-8 precursor mixed solution;

[0101] 4) placing the Pt@Zr obtained in step 2) into the ZIF-8 precursor mixed solution obtained in step 3) at a mass volume ratio of 1 g:10 mL of the Pt@Zr to ZIF-8 precursor mixed solution, allowing the mixture to stand at room temperature for 40 min, centrifuging, washing, and drying to obtain ZIF-8-encapsulated Pt@Zr;

[0102] 5) The ZIF-8-encapsulated Pt@Zr obtained in step 4) was placed in a CuSO4 solution with a concentration of 0.1 mol / L and reduced at a constant potential for 30 min at an operating voltage of 2 V to obtain Cu@ZIF-8-encapsulated Pt@Zr, i.e., the methanol reforming hydrogen production catalyst.

[0103] Comparative Example 3

[0104] A methanol reforming hydrogen production catalyst

[0105] 1) Ce(NO3)3, Zr(NO3)4 and dodecylammonium bromide were placed in water at a molar ratio of 2:1:1, ultrasonically dispersed for 30 minutes, and then precipitated with a 0.1 mol / L NaOH solution. The mixture was filtered, and the filter residue was calcined at 280°C for 3 hours to obtain a Ce / Zr mesoporous support;

[0106] 2) According to the molar ratio of Zn(NO3)6 to 2-methylimidazole of 1:1.2, a 0.5 mol / L n-octanol solution of Zn(NO3)6 was added dropwise to a 1 mol / L n-octanol solution of 2-methylimidazole, the stirring speed was controlled at 100 r / min, and the mixture was stirred at room temperature for 3 min to obtain a ZIF-8 precursor mixed solution;

[0107] 3) placing the Ce / Zr mesoporous support obtained in step 1) into the ZIF-8 precursor mixed solution obtained in step 3) at a mass volume ratio of 1 g:10 mL of the Ce / Zr mesoporous support and the ZIF-8 precursor mixed solution, standing at room temperature for 40 min, centrifuging, washing, and drying to obtain ZIF-8-encapsulated Ce / Zr;

[0108] 4) The ZIF-8-wrapped Ce / Zr obtained in step 3) was placed in a CuSO4 solution with a concentration of 0.1 mol / L, and subjected to constant potential reduction for 30 min at an operating voltage of 2 V to obtain Cu@ZIF-8-wrapped Ce / Zr, i.e., the methanol reforming hydrogen production catalyst.

[0109] Comparative Example 4

[0110] A methanol reforming hydrogen production catalyst

[0111] 1) Ce(NO3)3, Zr(NO3)4 and dodecylammonium bromide were placed in water at a molar ratio of 2:1:1, ultrasonically dispersed for 30 minutes, and then precipitated with a 0.1 mol / L NaOH solution. The mixture was filtered, and the filter residue was calcined at 280°C for 3 hours to obtain a Ce / Zr mesoporous support;

[0112] 2) placing the Ce / Zr mesoporous support obtained in step 1) in a 0.05 mol / L H2PtCl6 solution at a mass volume ratio of 1 g to 5 mL, immersing the support at 50°C for 30 min, and then reducing the support at 310°C to obtain Pt@Ce / Zr;

[0113] 3) According to the molar ratio of Zn(NO3)6 to 2-methylimidazole of 1:1.2, a 0.5 mol / L n-octanol solution of Zn(NO3)6 was added dropwise to a 1 mol / L n-octanol solution of 2-methylimidazole, the stirring speed was controlled at 100 r / min, and the mixture was stirred at room temperature for 3 min to obtain a ZIF-8 precursor mixed solution;

[0114] 4) According to the mass volume ratio of the Pt@Ce / Zr and ZIF-8 precursor mixed solution being 1 g:10 mL, the Pt@Ce / Zr obtained in step 2) was placed in the ZIF-8 precursor mixed solution obtained in step 3), and the mixture was allowed to stand at room temperature for 40 minutes, centrifuged, washed, and dried to obtain ZIF-8-coated Pt@Ce / Zr, i.e., the methanol reforming hydrogen production catalyst.

[0115] Comparative Example 5

[0116] A methanol reforming hydrogen production catalyst

[0117] 1) Ce(NO3)3, Zr(NO3)4 and dodecylammonium bromide were placed in water at a molar ratio of 2:1:1, ultrasonically dispersed for 30 minutes, and then precipitated with a 0.1 mol / L NaOH solution. The mixture was filtered, and the filter residue was calcined at 280°C for 3 hours to obtain a Ce / Zr mesoporous support;

[0118] 2) According to the mass volume ratio of Ce / Zr mesoporous support and H2PtCl6 solution of 1g:5mL, the Ce / Zr mesoporous support obtained in step 1) was placed in a H2PtCl6 solution with a concentration of 0.05mol / L, immersed at 50°C for 30min, and then reduced at 310°C to obtain Pt@Ce / Zr, i.e., the methanol reforming hydrogen production catalyst.

[0119] Methanol reforming hydrogen production catalyst catalytic methanol reforming hydrogen production performance testing

[0120] In the laboratory, methanol reforming hydrogen production catalysts prepared in Examples 1 to 3 and Comparative Examples 1 to 5 were used as catalysts to catalyze methanol reforming hydrogen production. The methanol content and carbon monoxide content in the product were detected, and the methanol conversion rate was calculated. The catalytic performance test results are shown in Table 1.

[0121] Methanol conversion rate = [(initial methanol content - product methanol content) / initial methanol content] × 100%;

[0122] Table 1 Catalytic performance test results

[0123]

[0124]

[0125] As can be seen from the data in Table 1, the methanol reforming hydrogen production catalyst provided by the present invention has a methanol conversion rate of up to 100%, and the carbon monoxide content in the product can reach 0.04%. It has high catalytic methanol reforming hydrogen production activity and low carbon monoxide selectivity;

[0126] Based on this, in the following examples, the methanol reforming hydrogen production reactor uses the methanol reforming hydrogen production catalyst prepared in Example 2 as a raw material, and is pressed at 150 KPa in a nitrogen atmosphere for 3 minutes to obtain the catalytic layer.

[0127] In the following examples, the preparation method of the Pd / ceramic membrane comprises the following steps:

[0128] 1) The porous alumina ceramic sheet was placed in a PdCl2 solution with a concentration of 0.1 mol / L, immersed at 60-100°C for 2 h, and dried to obtain a Pd-adsorbed alumina ceramic sheet. 2+ Alumina ceramic sheet;

[0129] 2) The Pd adsorbed 2+ The alumina ceramic piece is placed in a mixed gas of sulfur dioxide and hydrogen (50% sulfur dioxide + 50% hydrogen) and reduced at 60-80° C. for 1 hour to obtain the Pd / ceramic film.

[0130] Example 4

[0131] A Pd / ceramic film

[0132] 1) The porous alumina ceramic sheet was placed in a PdCl2 solution with a concentration of 0.1 mol / L, immersed at 60°C for 2 h, and dried to obtain a Pd-adsorbed alumina ceramic sheet. 2+ Alumina ceramic sheet;

[0133] 2) The Pd adsorbed 2+ The alumina ceramic piece is placed in a mixed gas of sulfur dioxide and hydrogen (50% sulfur dioxide + 50% hydrogen) and reduced at 60° C. for 1 hour to obtain the Pd / ceramic film.

[0134] Example 5

[0135] A Pd / ceramic film

[0136] 1) The porous alumina ceramic sheet was placed in a PdCl2 solution with a concentration of 0.1 mol / L, immersed at 80°C for 2 h, and dried to obtain a Pd-adsorbed alumina ceramic sheet. 2+ Alumina ceramic sheet;

[0137] 2) The Pd adsorbed 2+ The alumina ceramic piece is placed in a mixed gas of sulfur dioxide and hydrogen (50% sulfur dioxide + 50% hydrogen) and reduced at 70° C. for 1 hour to obtain the Pd / ceramic film.

[0138] Example 6

[0139] A Pd / ceramic film

[0140] 1) The porous alumina ceramic sheet was placed in a PdCl2 solution with a concentration of 0.1 mol / L, immersed at 100°C for 2 h, and dried to obtain a Pd-adsorbed alumina ceramic sheet. 2+ Alumina ceramic sheet;

[0141] 2) The Pd adsorbed 2+ The alumina ceramic piece is placed in a mixed gas of sulfur dioxide and hydrogen (50% sulfur dioxide + 50% hydrogen) and reduced at 80° C. for 1 hour to obtain the Pd / ceramic film.

[0142] Pd / ceramic membrane selective permeability detection

[0143] The hydrogen permeability, carbon dioxide permeability, and carbon monoxide permeability of the Pd / ceramic membranes, porous alumina ceramic sheets, and Pt membranes prepared in Examples 4 to 6 were tested. The selective permeability test results are shown in Table 2.

[0144] Table 2 Selective permeability test results

[0145]

[0146] As can be seen from the data in Table 2, the Pd / ceramic membrane provided by the present invention has a hydrogen permeability of up to 100%, a carbon dioxide permeability of up to 0.03%, and a carbon monoxide permeability of up to 0%, and has good selective permeability to hydrogen.

[0147] Based on this, in the following examples, the methanol reforming hydrogen production reactor uses the Pd / ceramic membrane prepared in Example 5 as the permeable membrane layer.

[0148] Example 7

[0149] Combine Figures 1-2 In this embodiment, a methanol reforming hydrogen production reactor includes:

[0150] reaction tank;

[0151] A fixing assembly 1, wherein the fixing assembly 1 is arranged at the bottom of the reaction tank;

[0152] A reforming reaction component 2, wherein the reforming reaction component 2 is fixed inside the reaction tank by the fixing component 1;

[0153] A feed hole 3, the feed hole 3 is arranged at the bottom of the side of the reaction tank;

[0154] A discharge hole 4 is provided at the top of the side of the reaction tank and on the opposite side of the feed hole 3;

[0155] An exhaust gas pipe 5 is provided on the top of the reaction tank;

[0156] A partition 6 is provided around the reforming reaction assembly 2 to separate the internal cavity of the reaction tank into an exhaust gas exhaust cavity 601 and a safety cavity 602;

[0157] Wherein, the reforming reaction component 2 comprises:

[0158] Box;

[0159] A feed pipe 201 is provided at the bottom of the side of the box body and extends to the outside of the reaction tank through the feed hole 3;

[0160] The discharge pipe 202 is arranged at the top of the side of the box body and on the opposite side of the feed pipe 201, and extends to the outside of the reaction tank through the discharge hole 4;

[0161] The catalytic layer 203 and the permeable membrane layer 204 are stacked inside the box, with the first layer on the feed pipe 201 side being the catalytic layer 203 and the first layer on the discharge pipe 202 side being the permeable membrane layer 204;

[0162] The exhaust gas exhaust window 205 is correspondingly arranged on the top of the catalyst layer 203.

[0163] It can be understood that when methanol catalytic reforming is performed using a methanol reforming hydrogen production reactor provided in this embodiment, the mixed steam of methanol and water is directly introduced into the interior of the reforming reaction assembly 2 through the feed hole 3 and the feed pipe 201, and directly contacts the catalyst layer 203 in the reforming reaction assembly 2, thereby realizing the feed of raw materials and starting the catalytic reforming of methanol;

[0164] In the methanol reforming hydrogen production reactor provided in this embodiment, the first layer on the feed pipe 201 side of the reforming reaction assembly 2 is set as the catalytic layer 203, the purpose of which is to enable the mixed steam of methanol and water to quickly contact the catalyst, thereby avoiding energy consumption and waste of raw materials;

[0165] The reaction equation for methanol catalytic reforming in a methanol reforming hydrogen production reactor provided in this embodiment is as follows:

[0166] CH3OH+H2O→3H2+CO2;

[0167] As can be seen from the reaction equation, the main products obtained from the catalytic reforming of methanol are hydrogen and carbon dioxide. Hydrogen is the target product of the catalytic reforming of methanol and can pass through the permeable membrane layer 204 in the reforming reaction component 2 and eventually be discharged from the reaction tank through the discharge pipe 202 and the discharge hole 4 to achieve hydrogen production. Carbon dioxide is the main by-product of the catalytic reforming of methanol. In the methanol reforming hydrogen production reactor provided in this embodiment, carbon dioxide cannot pass through the permeable membrane layer 204 in the reforming reaction component 2. Therefore, in this embodiment, an exhaust gas exhaust window 205 is provided on the top of the catalytic layer 203 to allow carbon dioxide to be discharged from the reforming reaction component 2, thereby achieving by-product separation and hydrogen purification.

[0168] In addition, carbon dioxide has a high density and is more likely to form deposits at the bottom of the catalytic layer 203. Therefore, it seems more reasonable to set the exhaust gas exhaust window 205 at the bottom of the catalytic layer 203. However, the methanol reforming hydrogen production reactor provided in this embodiment has the exhaust gas exhaust window 205 set at the top of the catalytic layer 203. The purpose is to use the high density of carbon dioxide to generate a certain downward pressure on the mixed steam of methanol and water that has just been introduced into the catalytic layer 203, thereby playing a certain "sealing" role, thereby preventing the mixed steam of methanol and water from overflowing the reforming reaction assembly 2 through the exhaust gas exhaust window 205 before being catalytically reformed, resulting in a waste of raw materials. As the catalytic reforming of methanol proceeds, the content of carbon dioxide gradually increases, so it overflows from the top of the catalytic layer 203, thereby achieving the discharge of carbon dioxide.

[0169] In a methanol reforming hydrogen production reactor provided in this embodiment, a partition 6 is provided around the reforming reaction assembly 2. The partition 6 is used to divide the upper end of the reaction tank into a waste gas exhaust chamber 601, which is used to enrich the carbon dioxide exhausted from each waste gas exhaust window 205 and ultimately exhaust it uniformly through the waste gas exhaust pipe 5.

[0170] At the same time, the provision of the partition plate 6 of the methanol reforming hydrogen production reactor provided in this embodiment not only isolates the exhaust gas exhaust chamber 601 at the upper end, but also isolates the safety chamber 602 at the lower end. The provision of the safety chamber 602 can improve the safety of the methanol reforming hydrogen production reactor to a certain extent. Specifically, when the reforming reaction assembly 2 leaks, the pressure inside the safety chamber 602 will increase. At this time, the input of raw materials is cut off and the hydrogen in the reaction tank is emptied in time, which can effectively improve the overall safety of the reactor and avoid human and economic losses.

[0171] In addition, the methanol catalytic reforming process also produces a by-product of carbon monoxide, the reaction equation of which is shown below:

[0172] CH3OH→CO+2H2;

[0173] In a methanol reforming hydrogen production reactor provided in this embodiment, carbon monoxide is also unable to pass through the permeable membrane layer 204 in the reforming reaction assembly 2. Therefore, the discharge method of carbon monoxide is the same as that of carbon dioxide, that is, it is discharged from the reaction tank through the exhaust gas exhaust window 205 and the exhaust gas exhaust pipe 5. Carbon monoxide is highly harmful, so the emission of carbon monoxide must be reduced. Based on this, a methanol reforming hydrogen production reactor provided in this embodiment has a feed hole 3 and a feed pipe 201 arranged at the bottom of the reaction tank and the box. The purpose is to allow carbon monoxide to fully contact with the catalyst, utilize the Cu@ZIF-8 in the catalyst to convert carbon monoxide into carbon dioxide, and reduce the emission of carbon monoxide.

[0174] In the methanol reforming hydrogen production reactor provided in this embodiment, by stacking the catalytic layer 203 and the permeable membrane layer 204 in multiple layers, methanol catalytic reforming can be achieved more thoroughly, reducing feedstock waste and avoiding a decrease in methanol conversion rate due to partial catalyst deactivation, thereby avoiding economic losses.

[0175] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. Although the present invention has been described in detail with reference to the above embodiments, ordinary technicians in the field should understand that the specific implementation methods of the present invention can still be modified or replaced by equivalents. Any modification or equivalent replacement that does not depart from the spirit and scope of the present invention should be covered by the scope of protection of the claims of the present invention.

Claims

1. A methanol reforming hydrogen production reactor, characterized in that: include: reaction tank; A fixing assembly, the fixing assembly being arranged at the bottom of the reaction tank; a reforming reaction assembly, wherein the reforming reaction assembly is fixed inside the reaction tank via the fixing assembly; A feed hole, the feed hole being arranged at the bottom of the side of the reaction tank; A discharge hole is provided at the top of the side of the reaction tank and on the opposite side of the feed hole; An exhaust gas pipe is provided on the top of the reaction tank; The partition is arranged around the four sides of the reforming reaction component and isolates the internal cavity of the reaction tank into an exhaust gas exhaust cavity and a safety cavity.

2. A methanol reforming hydrogen production reactor according to claim 1, characterized in that: The reforming reaction component comprises: Box; A feed pipe, the feed pipe is arranged at the bottom of the side of the box body and extends to the outside of the reaction tank through the feed hole; A discharge pipe is provided at the top of the side of the box body and on the opposite side of the feed pipe, and extends to the outside of the reaction tank through the discharge hole; A catalytic layer and a permeable membrane layer, wherein the catalytic layer and the permeable membrane layer are stacked inside the box, with the first layer on the feed pipe side being the catalytic layer and the first layer on the discharge pipe side being the permeable membrane layer; An exhaust gas exhaust window is correspondingly arranged on the top of the catalytic layer.

3. A methanol reforming hydrogen production reactor according to claim 2, characterized in that: The catalytic layer is formed by pressing a methanol reforming hydrogen production catalyst.

4. A methanol reforming hydrogen production reactor according to claim 3, characterized in that: The pressing is specifically as follows: pressing at 150 KPa for 3 minutes in a nitrogen atmosphere.

5. A methanol reforming hydrogen production reactor according to claim 3, characterized in that: The preparation method of the methanol reforming hydrogen production catalyst comprises the following steps: 1) Ce(NO3)3, Zr(NO3)4 and dodecyl ammonium bromide are placed in water and ultrasonically dispersed, then precipitated with a NaOH solution, filtered, and the filter residue is calcined to obtain a Ce / Zr mesoporous carrier; 2) placing the Ce / Zr mesoporous support obtained in step 1) in an H2PtCl6 solution, immersing it in water, and reducing it to obtain Pt@Ce / Zr; 3) adding the n-octanol solution of Zn(NO3)6 dropwise to the n-octanol solution of 2-methylimidazole and stirring to obtain a ZIF-8 precursor mixed solution; 4) placing the Pt@Ce / Zr obtained in step 2) in the ZIF-8 precursor mixed solution obtained in step 3), allowing to stand, centrifuging, washing, and drying to obtain ZIF-8-encapsulated Pt@Ce / Zr; 5) The ZIF-8-wrapped Pt@Ce / Zr obtained in step 4) is placed in a CuSO4 solution and reduced at a constant potential to obtain Cu@ZIF-8-wrapped Pt@Ce / Zr, i.e., the methanol reforming hydrogen production catalyst.

6. A methanol reforming hydrogen production reactor according to claim 5, characterized in that: In step 1), the molar ratio of Ce(NO3)3, Zr(NO3)4 and dodecylammonium bromide is (2-3):1:1; In step 1), the calcination treatment is specifically: calcination treatment at 250-300° C. for 3 hours; In step 2), the concentration of the H2PtCl6 solution is 0.05 mol / L; In step 2), the mass volume ratio of the Ce / Zr mesoporous carrier and the H2PtCl6 solution is 1g: (4-6)mL; In step 2), the immersion treatment is specifically: immersion treatment at 40-60° C. for 20-40 minutes; In step 2), the reduction is specifically: reducing at 300-320°C; In step 3), the concentration of the Zn(NO3)6 n-octanol solution is 0.5 mol / L; In step 3), the concentration of the 2-methylimidazole n-octanol solution is 1 mol / L; In step 3), the molar ratio of Zn(NO3)6 to 2-methylimidazole is 1:(1-1.5); In step 3), the stirring is specifically as follows: controlling the stirring speed to 100 r / min and stirring at room temperature for 3 min; In step 4), the mass volume ratio of the Pt@Ce / Zr and ZIF-8 precursor mixed solution is 1 g: (5-15) mL; In step 4), the standing is specifically: standing at room temperature for 30 to 60 minutes; In step 5), the concentration of the CuSO4 solution is 0.1 mol / L; In step 5), the constant potential reduction is specifically: constant potential reduction at a working voltage of 2V for 20 to 40 minutes.

7. A methanol reforming hydrogen production reactor according to claim 2, characterized in that: The permeable membrane layer is a Pd / ceramic membrane.

8. A methanol reforming hydrogen production reactor according to claim 7, characterized in that: The preparation method of the Pd / ceramic film comprises the following steps: 1) Place the porous alumina ceramic sheet in a PdCl2 solution, immerse it in water, and dry it to obtain a Pd-adsorbed alumina ceramic sheet. 2+ Alumina ceramic sheet; 2) The Pd adsorbed 2+ The alumina ceramic sheet is placed in a mixed gas of sulfur dioxide and hydrogen for reduction to obtain the Pd / ceramic film.

9. A methanol reforming hydrogen production reactor according to claim 8, characterized in that: In step 1), the concentration of the PdCl2 solution is 0.1 mol / L; In step 1), the immersion treatment is specifically: immersion treatment at 60-100° C. for 2 hours; In step 2), the mixed gas of sulfur dioxide and hydrogen is 50% sulfur dioxide + 50% hydrogen; In step 2), the reduction is specifically: reduction at 60-80° C. for 1 h.

Images