CN111111672A - 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 PDF

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CN111111672A
CN111111672A CN201911404638.0A CN201911404638A CN111111672A CN 111111672 A CN111111672 A CN 111111672A CN 201911404638 A CN201911404638 A CN 201911404638A CN 111111672 A CN111111672 A CN 111111672A
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hydrogen storage
catalyst
metal
alloy
hydrogen
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CN111111672B (en
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姚素梅
陈爽
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Tianjin Changlu Chemical New Material Co ltd
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Tianjin Changlu Chemical New Material Co ltd
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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
    • 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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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 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 catalysts of the present application react reversibly with gaseous H2 to form metal solid solutions and metal hydrides. 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.

Description

Catalyst with hydrogen storage performance and preparation method and application thereof
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 (CF3CHOHCF3, HFIP for short) is an important fluorine-containing intermediate and can be used for preparing high-end fluorine-containing fine chemicals such as anesthetics and surfactants. 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 a hydrogenation reduction method using hexafluoroacetone as a raw material, and can be divided into a method of reducing hexafluoroacetone and a metal hydride, a method of reacting hexafluoroacetone with a Grignard reagent and a method of catalytic hydrogenation according to the difference of a 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 catalyst, U.S. Pat. No. 4,350,647,142, JP59204142 uses Pd/C or Pd/A2O3 catalyst to carry out liquid phase hydrogenation reaction, which achieves higher yield, but the liquid phase hydrogenation method has high reaction pressure and long reaction 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. patent GB974612 in 1964, using a Cu-Cr2O3 (1-2: 1) mixture as the catalyst, gave a product yield of about 40%. 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 one of AB5 type rare earth hydrogen storage alloy, AB2 type 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 AB5 type rare earth hydrogen storage alloy is LaNi 5; the AB2 type Laves phase hydrogen storage alloy is ZrMn 2; the A-B type Ti-Fe hydrogen storage alloy is Mg2 Ni; 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.
One of the metal boride Co-B, Ni-B, Pd-B alloys.
The preparation method of the metal boride comprises the following steps: NaBH4 is prepared into 0.01-10mol/L solution, soluble metal salt is dissolved in deionized water to prepare 0.05-5mol/L solution, NaBH4 is slowly dripped into the soluble metal salt solution at room temperature under the magnetic stirring, and the obtained powder is filtered and vacuum-dried to obtain the amorphous metal puffed boride alloy.
The soluble metal salt is one of CoNO3, CoCl2, NiNO3, NiCl2 and PdCl 2.
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 the application of the catalyst with hydrogen storage performance, which is characterized in that the catalyst 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, 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:
the catalysts of the present application react reversibly with gaseous H2 to form metal solid solutions and metal hydrides. 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, mechanically grinding a metal hydrogen storage material LaNi5 into alloy powder of 200-mesh and 600-mesh, then mixing metal boride Co-B and metal hydrogen storage material powder according to a ratio of 5:1, putting a mixed sample into a mechanical ball mill, and setting ball milling time to be 3-48h, ball milling rotation speed to be 200-mesh and 600r/min and ball material ratio to be 6: 1; 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 Ni-B comprises the following steps: NaBH4 is prepared into a 0.01-10mol/L solution, soluble metal salt CoNO3 is dissolved in deionized water to prepare a 0.05-5mol/L solution, NaBH4 is slowly dropped into the soluble metal salt solution under magnetic stirring at room temperature, and the obtained powder is filtered and vacuum-dried to obtain the amorphous metal puffed 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 ratio of the metal boride Co-B to the metal hydrogen storage material La0.67Mg0.33Ni3.0 is 8:1, labeled 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
Examples Catalyst and process for preparing same Conversion rate% Selectivity%
Example 1 La-Co5 99.8 100
Example 2 La-Co10 96.7 100
Example 3 La-Co8 98.1 100
Example 4 La-Mg-Ni-Co8 98.6 99.5
Comparative example 1 5％Pd/C 92.3 97.2
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 (9)

1. The catalyst with hydrogen storage performance is characterized by comprising 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.
2. The catalyst with hydrogen storage capability of claim 1, wherein the metal hydrogen storage material is one of AB5 type rare earth hydrogen storage alloy, AB2 type 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.
3. The catalyst with hydrogen storage capability of claim 2, wherein the AB5 type rare earth-based hydrogen storage alloy is LaNi 5; the AB2 type Laves phase hydrogen storage alloy is ZrMn 2; the A-B type Ti-Fe hydrogen storage alloy is Mg2 Ni;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。
4. The catalyst having hydrogen storage capability of claim 1 wherein said metal boride is one of the alloys Co-B, Ni-B, Pd-B.
5. The catalyst having hydrogen storage capability of claim 4, wherein the metal boride is prepared by a method comprising: NaBH4 is prepared into 0.01-10mol/L solution, soluble metal salt is dissolved in deionized water to prepare 0.05-5mol/L solution, NaBH4 is slowly dripped into the soluble metal salt solution under magnetic stirring at room temperature, and the obtained powder is filtered and vacuum-dried to obtain the amorphous metal boride alloy.
6. The catalyst with hydrogen storage capability of claim 5, wherein the soluble metal salt is one of CoNO3, CoCl2, NiNO3, NiCl2 and PdCl 2.
7. A method for preparing a catalyst having hydrogen storage properties according to any one of claims 1 to 6, comprising the steps of: 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.
8. Use of a catalyst having hydrogen storage properties according to any one of claims 1 to 6 in the preparation of hexafluoroisopropanol by gas phase catalytic hydrogenation of hexafluoroacetone.
9. The use of the catalyst with hydrogen storage capability as claimed in claim 8, 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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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113976120A (en) * 2021-11-30 2022-01-28 西安工业大学 Preparation method of high-activity CoB catalyst

Citations (2)

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Publication number Priority date Publication date Assignee Title
CN1325837A (en) * 2000-05-26 2001-12-12 中国石油化工集团公司 Process for preparing alcohol by hydrogenating relative ketone
CN102274734A (en) * 2010-06-13 2011-12-14 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

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN1325837A (en) * 2000-05-26 2001-12-12 中国石油化工集团公司 Process for preparing alcohol by hydrogenating relative ketone
CN102274734A (en) * 2010-06-13 2011-12-14 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

Non-Patent Citations (3)

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Title
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郜余军 等: "球磨时间对 MmNi3.9Co0.45Mn0.4Al0.25-CoB复合储氢合金电化学性能的影响", 《稀有金属》 *
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113976120A (en) * 2021-11-30 2022-01-28 西安工业大学 Preparation method of high-activity CoB catalyst
CN113976120B (en) * 2021-11-30 2023-12-01 西安工业大学 Preparation method of high-activity CoB catalyst

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