CN111097426B - Copper-based gas phase catalyst and preparation method and application thereof - Google Patents

Copper-based gas phase catalyst and preparation method and application thereof Download PDF

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CN111097426B
CN111097426B CN201911399609.XA CN201911399609A CN111097426B CN 111097426 B CN111097426 B CN 111097426B CN 201911399609 A CN201911399609 A CN 201911399609A CN 111097426 B CN111097426 B CN 111097426B
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copper
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CN111097426A (en
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汤峤永
姚素梅
肖鑫
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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
    • B01J23/80—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 zinc, cadmium or mercury
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • 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
    • 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
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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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  • 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 fluorine chemical catalysts, and particularly relates to a copper-based gas-phase catalyst, and a preparation method and application thereof. The copper-based gas phase catalyst comprises the following components in parts by mass: a. the first component of the catalyst is copper or an oxide thereof, and the mass fraction is 20-50%; b. the second component of the catalyst is one or oxides of zinc, nickel and cerium, and the mass fraction is 5-30%; c. the third component of the catalyst is alumina or silicon oxide, and the mass fraction is 20-75%. The catalyst can react under mild conditions, and has low requirements on reaction equipment; the catalyst has high catalytic activity and high selectivity, and almost no by-product is generated; the catalyst of the invention has simple preparation, easily obtained and cheap raw materials, easy molding and large-scale production.

Description

Copper-based gas phase catalyst and preparation method and application thereof
Technical Field
The invention belongs to the field of fluorine chemical catalysts, and particularly relates to a copper-based gas-phase catalyst, 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 existing catalyst of the gas phase method mostly uses noble metals, so that the cost is higher, or the catalyst is complicated to prepare and is easy to generate side reaction.
Therefore, a catalyst which has high selectivity, high stability and simple preparation under mild conditions is needed to be suitable for preparing hexafluoroisopropanol by gas-phase catalytic hydrogenation of hexafluoroacetone.
Disclosure of Invention
The invention aims to provide a copper-based gas phase catalyst, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
the copper-based gas phase catalyst is characterized by comprising the following components in parts by mass:
a. the first component of the catalyst is copper or an oxide thereof, and the mass fraction is 20-50%;
b. the second component of the catalyst is one or the oxide of zinc, nickel and cerium, and the mass fraction is 5-30%;
c. the third component of the catalyst is alumina or silicon oxide, and the mass fraction is 20-75%.
Wherein the molar ratio of the metal elements of the first component, the second component and the third component is as follows: 20-40:10:50-70.
Preferably, the molar ratio of the metal elements of the first component, the second component and the third component is: 40:10:50.
A method for preparing said copper-based gas phase catalyst, comprising the steps of: dissolving metal soluble salts of a first component, a second component and a third component of the catalyst in water, dripping ammonia water to the pH value of 7.0, standing at room temperature for aging and precipitation for 3 hours, filtering, washing, drying at 90-140 ℃, roasting for 2-6 hours under the air atmosphere of 300-800 ℃, and tabletting to obtain the catalyst.
Preferably, the catalyst is prepared by dissolving the metal soluble salts of the first, second and third components in water, adding ammonia water dropwise to pH 7.0, aging and precipitating at room temperature for 3 hours, filtering, washing, drying at 120 ℃, roasting at 500 ℃ for 4 hours in an air atmosphere, and tabletting.
The invention also comprises the application of the copper-based gas phase catalyst, which is applied to the preparation of hexafluoropropanol by the gas phase catalytic hydrogenation of hexafluoroacetone hydrate; the method specifically comprises the following steps: the catalyst is filled in a fixed bed reactor, hydrogen-nitrogen mixed gas and gasified hexafluoroacetone hydrate are 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 the hydrogen to the hexafluoroacetone is 3-20; the reaction space velocity is 50-1000h -1 。
The vaporization temperature of hexafluoroacetone hydrate was 110 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the catalyst can react under mild conditions, and has low requirements on reaction equipment; the catalyst has high catalytic activity and high selectivity, and almost no by-product is generated; the catalyst of the invention has simple preparation, easily obtained and cheap raw materials, easy molding and large-scale production.
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: dissolving 6.08g of Cu (NO3) 2.3H 2O, 3.65g of Zn (NO3) 2.6H 2O and 25.76g of aluminum nitrate nonahydrate in 50ml of water, dripping 25% of ammonia water to the pH value of about 7.0, standing at room temperature for aging and precipitation for 3 hours, filtering, washing, drying at 120 ℃, roasting at 500 ℃ for 4 hours in an air atmosphere, and tabletting to obtain the catalyst, wherein the catalyst is marked as Cu20-Zn10-Al 70.
Example 2: the procedure was carried out in the same manner as in the preparation of example one except that 12.16g of Cu (NO3) 2.3H 2O, 3.65g of Zn (NO3) 2.6H 2O and 18.4g of aluminum nitrate nonahydrate were weighed. This catalyst is designated as Cu40-Zn10-Al 50.
Example 3: the procedure was carried out in the same manner as in the preparation of example one except that 12.16g of Cu (NO3) 2.3H 2O, 2.45g of Ni (NO3)2 and 18.4g of aluminum nitrate nonahydrate were weighed. This catalyst was designated as Cu40-Ni10-Al 50.
Example 4: the procedure was carried out in the same manner as in the preparation of example one except that 12.16g of Cu (NO3) 2.3H 2O, 2.52g of Ce (NO3) 2.6H 2O and 18.4g of aluminum nitrate nonahydrate were weighed. This catalyst is designated as Cu40-Ce10-Al 50.
Example 5: the procedure was carried out in the same manner as in the preparation of example one except that 12.16g of Cu (NO3) 2.3H 2O, 3.65g of Zn (NO3) 2.6H 2O and 16.65g of 30% silica sol were weighed. This catalyst is designated as Cu40-Ce10-Si 50.
Example 6: this is a comparative example, a commercial 5% Pd/C catalyst was purchased.
Example 7: the catalysts of examples 1-6 were each subjected to a vapor phase hydrogenation of hexafluoroacetone.
The reaction test was carried out in a fixed bed reactor, and 5.0ml (20-40 mesh) of each sample prepared by the above method (examples 1-6) was charged into a stainless steel reaction tube (inner diameter 10mm, length 300mm), and reduced at 250 ℃ for 2 hours, the reducing gas was a mixed hydrogen-nitrogen gas containing 30% hydrogen, hydrogen was introduced after reduction, hexafluoroacetone trihydrate as a raw material was pumped in at a reaction temperature of 200 ℃, an operation pressure of normal pressure, and a reaction space velocity of 300 hours -1 . The reaction product is separated by the condenser and the liquid product is analyzed and measured by the gas chromatography. The reaction results are shown in table 1.
TABLE 1
Catalyst and process for preparing same Conversion rate% Selectivity%
Cu20-Zn10-Al70 98.3 99.8
Cu40-Zn10-Al50 99.6 100
Cu40-Ni10-Al50 99.2 100
Cu40-Ce10-Al50 99.0 99.5
Cu40-Zn10-Si50 98.9 100
5％Pd/C 92.3 97.2
As can be seen from Table 1, compared with the traditional palladium-carbon catalyst sold on the market, the catalyst prepared by the invention has very high catalytic activity, the conversion rate of hexafluoroacetone is more than 99%, the selectivity of hexafluoroisopropanol is close to hundred percent, and almost no by-product is generated.
Example eight: the reaction stability of the catalyst Cu40-Zn10-Al50 was examined on the reaction apparatus of example seven, and the reaction conditions were the same as those of example seven. The change of the reactivity with time is shown in Table 2.
TABLE 2
Time of day 2 10 30 50 100 200 300 500
Conversion rate% 98.9 99.6 99.5 99.3 99.2 99.2 99.3 99
Selectivity% 100 100 100 100 100 100 100 100
The result shows that the catalyst always shows higher reaction activity and selectivity, particularly strong catalytic stability within 500 hours of reaction time.
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 (4)

1. The application of the copper-based gas phase catalyst is characterized in that the copper-based gas phase catalyst is applied to the preparation of hexafluoropropanol by the gas phase catalytic hydrogenation of hexafluoroacetone hydrate; the method specifically comprises the following steps: the catalyst is filled in a fixed bed reactor, hydrogen-nitrogen mixed gas and vaporized hexafluoroacetone hydrate are 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 the hydrogen to the hexafluoroacetone is 3-20; the reaction space velocity is 50-1000h -1 ；
The catalyst comprises the following components:
a. the first component of the catalyst is copper or an oxide thereof, and the mass fraction is 20-50%;
b. the second component of the catalyst is one or the oxide of zinc, nickel and cerium, and the mass fraction is 5-30%;
c. the third component of the catalyst is alumina or silicon oxide, and the mass fraction is 20-75%;
wherein the molar ratio of the metal elements of the first component, the second component and the third component is 20-40:10: 50-70.
2. Use of the copper-based gas phase catalyst according to claim 1, wherein the catalyst is prepared by a process comprising the steps of: dissolving metal soluble salts of a first component, a second component and a third component of the catalyst in water, dripping ammonia water to the pH value of 7.0, standing at room temperature for aging and precipitation for 3 hours, filtering, washing, drying at 90-140 ℃, roasting for 2-6 hours under the air atmosphere of 300-800 ℃, and tabletting to obtain the catalyst.
3. Use of a copper-based gas-phase catalyst according to claim 2, wherein the catalyst is prepared by a process comprising the steps of: dissolving metal soluble salts of a first component, a second component and a third component of the catalyst in water, then dropwise adding ammonia water to a pH value of 7.0, standing at room temperature for aging and precipitation for 3 hours, filtering, washing, drying at 120 ℃, roasting for 4 hours at 500 ℃ under an air atmosphere, and tabletting and forming to obtain the catalyst.
4. Use of a copper-based gas-phase catalyst according to claim 1, characterized in that the vaporization temperature of hexafluoroacetone hydrate is 110 ℃.
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CN111790401A (en) * 2020-06-22 2020-10-20 山东东岳高分子材料有限公司 Catalyst for synthesizing hexafluoroisopropanol, preparation method and application

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CN102125847A (en) * 2010-12-30 2011-07-20 厦门大学 Copper nickel silicon catalyst for preparing ethylene glycol and preparation method thereof
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
CN102974382A (en) * 2012-11-22 2013-03-20 天津大学 Catalyst for preparing ethanol by virtue of acetate hydrogenation and preparation method thereof
CN103785408A (en) * 2014-02-12 2014-05-14 常州大学 Catalyst for preparing methyl glycolate through dimethyl oxalate hydrogenation and synthetic method of catalyst
CN105562004A (en) * 2016-02-18 2016-05-11 河南能源化工集团研究院有限公司 Preparation method of copper-based catalyst for selective hydrogenation of dimethyl oxalate
CN106179351A (en) * 2016-06-27 2016-12-07 浙江大学 A kind of Cu Ni/Al2o3preparation method of catalyst and products thereof and application
CN108404918A (en) * 2018-03-14 2018-08-17 天津大学 Tumer ester through hydrogenation produces the copper zinc SiO 2 catalyst and preparation method thereof of ethyl alcohol
CN108499564A (en) * 2018-03-13 2018-09-07 浙江师范大学 Catalyst in a kind of building-up process of methyl glycollate and preparation method thereof, application

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4467124A (en) * 1980-11-11 1984-08-21 Central Glass Company Limited Preparation of 1,1,1,3,3,3-hexafluoropropane-2-ol by vapor phase catalytic reaction of hexafluoroacetone hydrate with hydrogen
CN101016230A (en) * 2007-02-13 2007-08-15 上海三爱富新材料股份有限公司 Method of batch fractionating and purifying 1,1,1,3,3,3-hexafluoroisopropanol
CN101456791A (en) * 2007-12-13 2009-06-17 中国科学院兰州化学物理研究所 Method for producing 1,2-propanediol by using biological base glycerol
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
CN102125847A (en) * 2010-12-30 2011-07-20 厦门大学 Copper nickel silicon catalyst for preparing ethylene glycol and preparation method thereof
CN102974382A (en) * 2012-11-22 2013-03-20 天津大学 Catalyst for preparing ethanol by virtue of acetate hydrogenation and preparation method thereof
CN103785408A (en) * 2014-02-12 2014-05-14 常州大学 Catalyst for preparing methyl glycolate through dimethyl oxalate hydrogenation and synthetic method of catalyst
CN105562004A (en) * 2016-02-18 2016-05-11 河南能源化工集团研究院有限公司 Preparation method of copper-based catalyst for selective hydrogenation of dimethyl oxalate
CN106179351A (en) * 2016-06-27 2016-12-07 浙江大学 A kind of Cu Ni/Al2o3preparation method of catalyst and products thereof and application
CN108499564A (en) * 2018-03-13 2018-09-07 浙江师范大学 Catalyst in a kind of building-up process of methyl glycollate and preparation method thereof, application
CN108404918A (en) * 2018-03-14 2018-08-17 天津大学 Tumer ester through hydrogenation produces the copper zinc SiO 2 catalyst and preparation method thereof of ethyl alcohol

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