CN111111672B - Catalyst with hydrogen storage performance and preparation method and application thereof - Google Patents
Catalyst with hydrogen storage performance and preparation method and application thereof Download PDFInfo
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- CN111111672B CN111111672B CN201911404638.0A CN201911404638A CN111111672B CN 111111672 B CN111111672 B CN 111111672B CN 201911404638 A CN201911404638 A CN 201911404638A CN 111111672 B CN111111672 B CN 111111672B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
- C07C29/145—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones with hydrogen or hydrogen-containing gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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Abstract
The invention belongs to the field of catalysts, and particularly relates to a catalyst with hydrogen storage performance, and a preparation method and application thereof. The catalyst with hydrogen storage property comprises the following components: a metal hydrogen storage material and a metal boride; the mass ratio of the metal hydrogen storage material to the metal boride is 10-5: 1. Catalyst and gaseous H of the present application2A reversible reaction occurs to produce a solid solution of the metal and a metal hydride. Hydrogen molecules contact the surface of the alloy, are firstly adsorbed on the surface of the alloy molecules, then H-H bonds are dissociated to form atomic hydrogen, and the atomic hydrogen reduces hexafluoroacetone into hexafluoroisopropanol under the action of a hydrogenation catalyst. The catalyst can react under mild conditions, and has low requirements on reaction equipment; the catalyst of the present invention has high catalytic activity and high selectivity, and almost no by-product is generated.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a catalyst with hydrogen storage performance, and a preparation method and application thereof.
Background
Hexafluoroisopropanol (CF)3CHOHCF3HFIP for short) is an important fluorine-containing intermediate, and can be used for preparing high-end fluorine-containing fine chemicals such as anesthetics, surfactants and the like. Since HFIP is highly polar, miscible with water and many organic agents, resistant to heat and allows uv light to pass through, these properties make it an ideal solvent for many polymer systems, including polyamides, polyesters, polyacrylonitriles, polyacetals and hydrolyzed polyvinyl esters.
The synthesis method of hexafluoroisopropanol mainly uses hexafluoroacetone as raw material, and can be divided into hexafluoroacetone reduction with metal hydride, hexafluoroacetone reaction with Grignard reagent and catalytic hydrogenation according to the difference of reducing agent. The reaction is a main industrial method for producing hexafluoroisopropanol at present, and can be divided into two processes of liquid phase hydrogenation and gas phase hydrogenation. U.S. Pat. No. 4,3607952 uses PtO catalysts, U.S. Pat. No. 4,647,647,142 uses Pd/C or Pd/A2O3The catalyst is used for liquid phase hydrogenation reaction, and high yield is obtained, but the liquid phase hydrogenation method has high reaction pressure and long time, and is difficult to realize continuous operation. The gas phase hydrogenation process has low reaction pressure, high conversion rate and selectivity, convenient catalyst regeneration, less three wastes and continuous operation. U.S. Pat. No. 4,974612 in 1964, usesThe catalyst is Cu-Cr2O3(1-2: 1) the product was obtained in about 40% yield. U.S. patent reports US3532755, US4467124 and FR2479803 use hexafluoroacetone hydrate as raw material, Pd or nickel series and Ni-Cr-Cu mixture as catalyst, and the reaction temperature is 40-200 ℃. Chinese patent CN102274734 discloses a Pd-Cu-K/C catalyst, which obtains better yield. The julian recent chemical research institute also reports that the catalytic hydrogenation process using Ni-Cr-Cu as a catalyst has a raw material conversion rate of 90% and a product selectivity of 96%. However, the current catalysts of the gas phase method generally have complex reaction and are easy to generate side reaction.
Disclosure of Invention
The invention aims to provide a catalyst with hydrogen storage performance, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the catalyst with hydrogen storage performance comprises the following components in parts by mass: a metal hydrogen storage material and a metal boride;
the mass ratio of the metal hydrogen storage material to the metal boride is 10-5: 1.
The metal hydrogen storage material is AB5Type rare earth-based hydrogen storage alloy, AB2Type Laves phase hydrogen storage alloy A-B type Ti-Fe hydrogen storage alloy, A2B-type Mg-based hydrogen storage alloy, V-based solid solution type hydrogen storage alloy and rare earth-magnesium-nickel-based hydrogen storage alloy.
The AB5The rare-earth hydrogen-storage alloy is LaNi5；AB2The Laves phase hydrogen storage alloy is ZrMn2(ii) a The A-B type Ti-Fe hydrogen storage alloy is Mg2Ni; the V-based solid solution type hydrogen storage alloy is V0.8Ti0.2(ii) a The rare earth-magnesium-nickel base hydrogen storage alloy is La0.67Mg0.33Ni3.0。
The metal boride is one of Co-B, Ni-B, Pd-B alloys.
The preparation method of the metal boride comprises the following steps: NaBH4Preparing 0.01-10 mol/L solution, dissolving soluble metal salt in deionized water to prepare 0.05-5mol/L solution, stirring NaBH4 under magnetic force at room temperatureSlowly dripping into soluble metal salt solution, filtering the obtained powder, and vacuum drying to obtain the amorphous metal boride alloy.
The soluble metal salt is Co (NO)3)2 、CoCl2、Ni(NO3)2 、NiCl2、PdCl2One kind of (1).
The invention also comprises a preparation method of the catalyst with hydrogen storage performance, which comprises the following steps: firstly, mechanically grinding a metal hydrogen storage material into 200-mesh 600-mesh alloy powder, then mixing metal boride and metal hydrogen storage material powder, putting a mixed sample into a mechanical ball mill, and setting the ball milling time to be 3-48h, the ball milling rotation speed to be 200-mesh 600r/min and the ball-to-material ratio to be 12:1-2: 1; after the ball milling is finished, the metal with catalytic activity is obtained and is attached to the surface of the hydrogen storage alloy in an amorphous state.
The invention also comprises application of the catalyst with hydrogen storage performance, and is characterized in that the catalyst is applied to the preparation of hexafluoroisopropanol by gas-phase catalytic hydrogenation of hexafluoroacetone. The method specifically comprises the following steps: filling a catalyst with hydrogen storage performance in a fixed bed reactor, introducing hydrogen-nitrogen mixed gas, wherein the hydrogen content is 10-50%, the reduction temperature is 150-350 ℃, the reduction time is 1-3 hours, and the molar ratio of hydrogen to hexafluoroacetone is 3-20: 1.
Compared with the prior art, the invention has the beneficial effects that:
catalyst and gaseous H of the present application2A reversible reaction occurs to produce a solid solution of the metal and a metal hydride. Hydrogen molecules contact the surface of the alloy, are firstly adsorbed on the surface of the alloy molecules, then H-H bonds are dissociated to form atomic hydrogen, and the atomic hydrogen is reduced into hexafluoroisopropanol by the reduction of hexafluoroacetone under the action of a hydrogenation catalyst. The catalyst can react under mild conditions, and has low requirements on reaction equipment; the catalyst of the present invention has high catalytic activity and high selectivity, and almost no by-product is generated.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention will be further described in detail with reference to the following preferred embodiments.
Example 1: the preparation method of the catalyst with hydrogen storage performance comprises the following steps: firstly, a metal hydrogen storage material LaNi is used5Mechanically grinding into alloy powder of 200-; after the ball milling is finished, the obtained metal with catalytic activity is attached to the surface of the hydrogen storage alloy in an amorphous state and is marked as catalyst La-Co 5.
The preparation method of the Co-B comprises the following steps: NaBH4Preparing into 0.01-10 mol/L solution, soluble metal salt Co (NO)3)2Dissolving in deionized water to obtain 0.05-5mol/L solution, and magnetically stirring at room temperature4Slowly dripping into soluble metal salt solution, filtering the obtained powder, and vacuum drying to obtain the amorphous metal boride alloy. The preparation methods of other metal boride alloys are the same, and are not described in detail herein.
Example 2, example 2 differed from example 1 only in that the metal boride Co-B was labeled as catalyst La-Co10 at 10:1 with the metal hydrogen storage material powder.
Example 3: example 3 differs from example 1 only in that the metal boride Co-B is labeled as catalyst La-Co8 with the metal hydrogen storage material powder at 8: 1.
Example 4: example 4 differs from example 1 only in that the metal boride Co-B is in combination with the metal hydrogen storage material La0.67Mg0.33Ni3.0At a ratio of 8:1, marked as La-Mg-Ni-Co 8.
Example 5: the catalyst obtained in the example 1-4 is applied to the preparation of hexafluoroisopropanol by the gas phase catalytic hydrogenation of hexafluoroacetone. The method specifically comprises the following steps: filling a catalyst with hydrogen storage performance in a fixed bed reactor, introducing hydrogen-nitrogen mixed gas, reducing at 200 ℃ for 3 hours, wherein the molar ratio of hydrogen to hexafluoroacetone is 5: 1. A comparison of the reactivity of the different catalysts is shown in table 1. 5% Pd/C is a catalyst for traditional gas phase hydrogenation.
TABLE 1
As can be seen from Table 1, the catalyst of the present invention can react under mild conditions, and has low requirements for reaction equipment; the catalyst of the present invention has high catalytic activity and high selectivity, and almost no by-product is generated.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (3)
1. The application of the catalyst with hydrogen storage performance is characterized in that the catalyst is applied to the preparation of hexafluoroisopropanol by gas-phase catalytic hydrogenation of hexafluoroacetone; wherein, the catalyst with hydrogen storage performance comprises the following components: a metal hydrogen storage material and a metal boride; the mass ratio of the metal hydrogen storage material to the metal boride is 10-5: 1;
the metal hydrogen storage material is LaNi5Or La0.67Mg0.33Ni3.0One kind of (1); the metal boride is one of Co-B, Ni-B, Pd-B alloys;
the catalyst with hydrogen storage performance is prepared by the following steps: firstly, mechanically grinding a metal hydrogen storage material into alloy powder of 200-600 meshes, then mixing metal boride and metal hydrogen storage material powder, putting a mixed sample into a mechanical ball mill, and setting the ball milling time to be 3-48h, the ball milling rotation speed to be 200-600r/min and the ball material ratio to be 12:1-2: 1; after the ball milling is finished, the metal with catalytic activity is obtained and is attached to the surface of the hydrogen storage alloy in an amorphous state.
2. The use of a catalyst having hydrogen storage properties according to claim 1, wherein the metal boride is prepared by: NaBH4Preparing into 0.01-10 mol/L solution, dissolving soluble metal saltDeionized water is prepared into 0.05-5mol/L solution, NaBH is stirred under magnetic force at room temperature4Slowly dripping into soluble metal salt solution, filtering the obtained powder, and vacuum drying to obtain amorphous metal boride alloy, wherein the soluble metal salt is Co (NO)3)2、CoCl2、Ni(NO3)2、NiCl2、PdCl2To (3) is provided.
3. The use of the catalyst with hydrogen storage capability as claimed in claim 1, wherein the catalyst with hydrogen storage capability is loaded in a fixed bed reactor, mixed gas of hydrogen and nitrogen is introduced, the hydrogen content is 10-50%, the reduction temperature is 150-350 ℃, the reduction time is 1-3 hours, and the molar ratio of hydrogen to hexafluoroacetone is 3-20: 1.
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| CN102274734B (en) * | 2010-06-13 | 2013-10-16 | 中化蓝天集团有限公司 | Catalyst used for gas phase catalytic hydrogenation of hexafluoroacetone hydrate for preparing hexafluoroisopropanol and preparation method and application thereof |
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