CN115254163A - Catalyst, preparation method thereof and application of catalyst in preparation process of hexafluorobutadiene - Google Patents
Catalyst, preparation method thereof and application of catalyst in preparation process of hexafluorobutadiene Download PDFInfo
- Publication number
- CN115254163A CN115254163A CN202210777816.XA CN202210777816A CN115254163A CN 115254163 A CN115254163 A CN 115254163A CN 202210777816 A CN202210777816 A CN 202210777816A CN 115254163 A CN115254163 A CN 115254163A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- reaction
- hexafluorobutadiene
- carbon layer
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
-
- 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
Landscapes
- 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 relates to the field of electronic special gas, in particular to a catalyst, a preparation method thereof and application thereof in a preparation process of hexafluorobutadiene, wherein the catalyst comprises a base material consisting of layered structure minerals; the surface of the base material is coated with a carbon layer; the carbon layer is doped with nitrogen atoms; the carbon layer also supports a metal halide. The catalyst can effectively reduce the energy required by the conversion of the 1, 4-dihaloperfluorobutane into the hexafluorobutadiene, so that the selectivity of the reaction and the reaction speed are also rapidly improved, the slurry method is adopted for preparing the hexafluorobutadiene, the overall reaction is mild and controllable, high-activity and easily-degradable raw materials are not required, the difficulty of the reaction and the difficulty of subsequent treatment are greatly reduced, the reaction can be efficiently carried out under a milder condition, the preparation method is simple, special protection treatment is not required, the cost is low, and the industrial use can be facilitated.
Description
Technical Field
The invention relates to the field of electronic special gas, in particular to a catalyst, a preparation method thereof and application thereof in a preparation process of hexafluorobutadiene.
Background
Semiconductor chips have become a fundamental strategic industry as the foundation of the information industry. Large scale integrated circuits and high speed high capacity memory chips are the core of IT industry, and with the continuous development of electronic industry, the requirement for etching line width is narrower and narrower in the processing process. The heart of the etching technology is the development of a plasma etchant, hexafluorobutadiene (C)4F6) The etching gas is a new generation of integrated circuit etching gas with excellent performance, can be used for dry etching of ultra-large integrated circuits with the width smaller than 90nm and even narrower, has high selectivity and high accuracy, and is more suitable for etching process with high aspect ratio.
Hexafluorobutadiene has many etching advantages at the 0.13 μm level of technology, which is superior to C4F8The method has higher selection ratio of the photoresist to the silicon nitride, can improve the stability of etching when in use, and improves the etching rate and the uniformity, thereby improving the excellent rate of products. The hexafluorobutadiene also has very low greenhouse effect (the GWP is only 290, and the hexafluorobutadiene can be completely decomposed in 2d in the atmosphere), has small harm to the ozone layer, and is an environment-friendly dry etching gas.
There are many methods for preparing hexafluorobutadiene, wherein the route capable of realizing industrial production can be divided into the following 5 types according to the number of raw materials and reaction steps:
(1) 1, 2-difluorodichloroethylene is taken as a raw material, and the hexafluorobutadiene is finally synthesized through 4 steps;
(2) Using trifluorochloroethylene as a raw material, and finally synthesizing hexafluorobutadiene through 3 steps;
(3) Trifluoro bromoethylene is used as a raw material, and the hexafluorobutadiene is prepared through two-step reaction;
(4) Tetrafluoroethylene is used as a reaction raw material, and the hexafluorobutadiene is obtained through two-step reaction preparation;
(5) 1, 4-dihaloperfluorobutane is used as a reaction raw material, and the hexafluorobutadiene is prepared through one-step reaction.
The method 5 has a good development potential due to the advantage of short reaction route.
In 1985, bargia 6 first reported a process for the preparation of hexafluorobutadiene by the IF removal of α, ω -diiodoperfluoroalkanes. 1.4-diiodoperfluorobutane is reacted with an organometallic compound (which may be an alkyl magnesium, a halogenated aryl magnesium, a dialkyl magnesium, a diaryl magnesium, an alkyl compound of zinc and cadmium, and an alkyl lithium or an aryl lithium) in an aprotic organic solvent (a nonpolar solvent or a polar aprotic ether, a cyclic ether), and preferably, the hexafluorobutadiene is prepared by dropwise adding a hexane solution containing butyl lithium to an anhydrous ether solution containing 1.4-diiodoperfluorobutane at-80 deg.C, then naturally raising to room temperature and heating to boiling and holding for 30min, and the yield of the hexafluorobutadiene can reach 97.5%.
Although the preparation of perfluorodiene from alpha, omega-diiodoperfluoroalkane has the advantages of few steps and high yield, the organic metal compound is expensive, high in chemical activity, easy to decompose and difficult to treat, so that the large-scale production has certain danger, and the industrial production is difficult.
MIKI, jun and YoshiMI et al report (EP 1247791) the use of I-CF2-CF2-CF2-CF2And (3) mixing the-I and Zn, heating to 120 ℃, maintaining for 30 minutes, adding a certain amount of DMF to initiate reaction, and reacting for 30 minutes to obtain a mixed gas with the content of the perfluorobutadiene of 65 percent. The yield thereof was found to be 54.4%.
Although the method is simple in reaction operation, 1, 4-diiodoperfluorobutane can generate cyclization and hydrogen substitution reaction in the process due to the use of polar organic matters such as NN-dimethylformamide and the like, so that the yield of byproducts is overhigh, and the further development of the method is limited.
Disclosure of Invention
The invention provides a catalyst, a preparation method thereof and application thereof in a preparation process of hexafluorobutadiene, aiming at overcoming the defects of high raw material danger and overhigh yield of byproducts in the preparation process of hexafluorobutadiene in the prior art.
In order to realize the purpose of the invention, the invention is realized by the following technical scheme:
in a first aspect, the present invention provides a catalyst which can be used to catalyze the conversion of 1, 4-dihaloperfluorobutane to hexafluorobutadiene;
the catalyst comprises a substrate composed of a layered structure mineral;
the surface of the base material is coated with a carbon layer;
the carbon layer is doped with nitrogen atoms;
the carbon layer also supports a metal halide.
The catalyst comprises the base materials formed by the layered structure minerals, because the base materials are supported in a scattered manner from one layer to the other, a large number of gaps are formed among the layers of the base materials, so that reactants can be filled in the gaps in the process of catalytic reaction, and because the reactants are adsorbed on the surface of the layer, the whole reaction system is divided into a plurality of micro-reaction areas by the gaps formed inside the base materials. Since each micro-reaction zone is internally and separately carried out, and each micro-reaction zone is kept constant due to the reaction conditions, the selectivity of the reaction of the 1, 4-dihaloperfluorobutane in the micro-reaction zone when being converted into the hexafluorobutadiene and the reaction speed are also rapidly improved.
Meanwhile, the carbon layer is coated on the surface of the base material, so that the surface roughness of the base material is increased, reactants are easier to load, the reactants can stably stay in gaps among the base materials, and the stability of the reaction conditions of a micro-reaction area is ensured. At the same time, the carbon layer has good electrical conductivity, which can act as an electron mediator, thereby promoting the transfer of electrons from the metal to the 1, 4-dihaloperfluorobutane, increasing the reaction rate of the 1, 4-dihaloperfluorobutane inside the micro-reaction zone.
In addition, because the carbon layer is also doped with nitrogen atoms, firstly, the doping of the nitrogen atoms can improve the polarity of the carbon layer, and the nitrogen atoms can generate coordination with the 1, 4-dihaloperfluorobutane, so that the two effects are combined with each other to improve the adsorption and adsorption effects on the 1, 4-dihaloperfluorobutane and reduce the activation energy on the reaction.
Finally, because the carbon layer is also loaded with the metal halide, the carbon layer can be used as a dehalogenation assistant to improve the dehalogenation effect of the metal on the 1, 4-dihaloperfluorobutane in the micro-reaction area, compared with a control group without the metal halide, the conversion rate of an experimental group added with the metal halide is obviously improved, and the reaction is milder.
Preferably, the lamellar structure mineral comprises one or more of mica, montmorillonite, pyrophyllite, serpentine, talc, chlorite in combination.
The layered structure minerals have the advantages of easily available raw materials and low price, and have the characteristics of simple treatment method and no need of excessive maintenance compared with other porous materials in the prior art. Therefore, the industrial production difficulty is effectively reduced.
Preferably, the metal halide includes any one or combination of halides of zinc, magnesium, aluminum, iron, manganese, copper.
In a second aspect of the present invention, there is provided a process for preparing the above catalyst,
the method comprises the following steps:
(1) Coating a carbon precursor on the surface of a base material consisting of layered structure minerals;
(2) Heat treating to convert the carbon precursor into a carbon layer;
(3) And (3) soaking the substrate coated with the carbon layer in a metal halide solution to load metal halide in the carbon layer, and drying to obtain the catalyst.
The catalyst of the invention has simple preparation method, does not need special protection treatment, and is beneficial to industrialized use. The catalyst of the invention only needs to fully strip the lamellar structure mineral into pieces and coat a layer of carbon precursor on the surface of the lamellar structure mineral, and then the carbon precursor can be converted into a carbon layer by a heat treatment mode.
The coated carbon precursor is various, for example, the substrate can be immersed in a solution containing the carbon precursor by an immersion method, and the carbon layer can be obtained after the immersion is finished and dried.
Preferably, the carbon precursor is polydopamine or polyvinylpyrrolidone.
When the carbon precursor is polydopamine, a polydopamine layer, namely one of the carbon precursors, can be formed on the surface of the base material by only dipping the base material in a solution containing dopamine components and adjusting the pH value of the solution.
When the carbon precursor is polyvinylpyrrolidone, the substrate is only required to be soaked in a solution containing polyvinylpyrrolidone components, and after the soaking is finished and the drying is carried out, the polyvinylpyrrolidone, namely the other carbon precursor, can be formed on the surface of the substrate.
The carbon precursor in the invention selects polydopamine or polyvinylpyrrolidone, and the polydopamine or polyvinylpyrrolidone has nitrogen atoms in the carbon precursor, so that the nitrogen atoms still remain in the carbon layer after heat treatment, and no component containing nitrogen is added into the carbon layer.
Preferably, the heat treatment conditions in the step (2) are as follows: under the protection of inert gas, heating to 400 to 650 ℃ and keeping for 3 to 12h.
In the process of forming the carbon layer on the surface of the substrate in the present invention, in order to ensure stable formation of the carbon layer, it is necessary to perform heat treatment under protection of inert gas so as to prevent thermal oxidation degradation of the carbon layer. Meanwhile, the carbon precursor is carbonized at the temperature of 400-650 ℃, so that the layered structure mineral is not changed into a structure, and the stability is ensured.
In a third aspect of the invention, there is also provided a process for the preparation of hexafluorobutadiene,
the method comprises the following steps:
(S.1) mixing the catalyst, metal powder and an organic solvent to form slurry, and refluxing and stirring to enable the zinc powder to enter an interlayer gap of the catalyst;
(S.2) dropwise adding 1, 4-dihaloperfluorobutane into the slurry, uniformly mixing, and adding alkyl aluminum to initiate reaction;
(S.3) collecting the generated hexafluorobutadiene.
The preparation process of the hexafluorobutadiene in the invention is obviously different from the prior art in that: the reaction system of the prior art is usually in a solution system, while the reaction system of the present invention is in a slurry formed by mixing a catalyst, a metal powder and an organic solvent.
As mentioned above, the present invention forms a large number of voids between layers of the substrate so that reactants can fill these voids to form micro-reaction regions during the catalytic reaction, and thus each micro-reaction region is independently performed inside, and each micro-reaction region is kept constant due to the reaction conditions, so that the energy required for the conversion of 1, 4-dihaloperfluorobutane into hexafluorobutadiene in the micro-reaction region is effectively reduced, and the selectivity of the reaction and the reaction rate are rapidly increased.
In addition, the method does not need to use high-activity and easily-decomposed raw materials for the hexafluorobutadiene, so that the difficulty of reaction and the difficulty of subsequent treatment are greatly reduced, and the reaction can be efficiently carried out under milder conditions.
Preferably, the reaction temperature in step (S.2) is 60 to 85 ℃.
Preferably, in the step (s.1), the mass ratio of the catalyst, the metal powder and the organic solvent is (1 to 3): 1: (1 to 3);
preferably, in the step (s.1), the metal powder is a single powder or an alloy powder of more than one of zinc, magnesium, aluminum, tin, copper and iron.
Preferably, the solvent is a polar aprotic solvent.
Further preferably, the polar aprotic solvent comprises any one or a combination of more of dimethyl sulfoxide, acetone, acetonitrile, dimethylformamide, dimethylacetamide or hexamethylphosphoramide.
Preferably, the particle size of the metal powder is in a range of 0.5 to 2 μm.
In some views of the prior art, the particle size of the metal powder generally has a significant influence on the dehalogenation reaction, and it is generally considered that the particle size of the metal powder cannot be too small, and the too small metal powder induces an increase in side reactions. According to the invention, because the reaction process is carried out in the interlayer gaps of the substrate, and the reaction in each micro-reaction area is relatively independent, the generation of side reactions can be reduced in the micro-reaction process, so that metal powder with a smaller particle size range can be selected in the process of selecting the particle size range of the metal powder, the side reactions can be reduced when the metal powder reaches the micro-nano scale, and the reaction rate can be effectively increased. When the particle diameter of the metal powder is too large, it is difficult to enter the interlayer gap between the base materials, resulting in a decrease in the efficiency of the reaction.
Preferably, the amount of the substance of the alkylaluminum initiator is 1 to 5% of the amount of the substance of 1, 4-dihaloperfluorobutane;
the amount of the 1, 4-dihaloperfluorobutane substance is 10 to 50 percent of the amount of the metal powder substance.
Therefore, the invention has the following beneficial effects:
(1) The catalyst can effectively reduce the energy required by the 1, 4-dihaloperfluorobutane in the conversion of the 1, 4-dihaloperfluorobutane into the hexafluorobutadiene, so that the selectivity and the reaction speed of the reaction are also rapidly improved;
(2) According to the method, the slurry method is adopted to prepare the hexafluorobutadiene, the overall reaction is mild and controllable, high-activity and easily-decomposed raw materials are not needed, the difficulty in the reaction and the difficulty in subsequent treatment are greatly reduced, and the reaction can be efficiently carried out under a milder condition;
(3) The preparation method is simple, does not need special protection treatment, has low cost and can be beneficial to industrial use.
Drawings
Fig. 1 is an electron micrograph of catalyst A1.
FIG. 2 is an electron micrograph of single mica platelets in catalyst A1.
FIG. 3 is a gas phase detection chart of crude hexafluorobutadiene in example 1.
Detailed Description
The invention is further described with reference to the drawings and the detailed description. Those skilled in the art will be able to implement the invention based on these teachings. Furthermore, the embodiments of the present invention described in the following description are generally only a part of the embodiments of the present invention, and not all of the embodiments. Therefore, all other embodiments obtained by a person of ordinary skill in the art based on the embodiments of the present invention without any creative effort shall fall within the protection scope of the present invention.
[ PREPARATION OF CATALYST ]
The preparation method of the catalyst used in the invention is as follows:
[ catalyst A1 ]: washing 100 parts of flake mica powder by acid, cleaning by distilled water, dispersing in 200 parts of water, then dropwise adding 20 parts of dopamine hydrochloride, stirring and dispersing uniformly, adjusting the pH to 9.5, continuing stirring for 1h, filtering out the mica powder, heating to 500 ℃ under the protection of nitrogen, carrying out heat treatment for 6h to obtain flake mica coated with a carbon layer, then soaking the flake mica in 5wt% zinc chloride solution for 30min, filtering, and carrying out vacuum drying for 3h at 100 ℃ to obtain the catalyst A1. The electron micrographs of the catalyst A1 and the monolithic mica therein are shown in FIGS. 1 to 2.
[ catalyst A2 ]: washing 100 parts of flake mica powder with acid, washing with distilled water, dispersing in 200 parts of water, then dropwise adding 20 parts of dopamine hydrochloride, stirring and dispersing uniformly, adjusting the pH to 9.5, continuing stirring for 1h, filtering out the mica powder, heating to 500 ℃ under the protection of nitrogen, carrying out heat treatment for 6h to obtain flake mica coated with a carbon layer, then soaking the flake mica in an aluminum chloride solution containing 5wt% for 30min, filtering, and carrying out vacuum drying for 3h at 100 ℃ to obtain the catalyst A2.
[ catalyst A3 ]: washing 100 parts of flake mica powder with acid, washing with distilled water, dispersing in 200 parts of water, then dropwise adding 20 parts of dopamine hydrochloride, stirring and dispersing uniformly, adjusting the pH to 9.5, continuing stirring for 1h, filtering out the mica powder, heating to 500 ℃ under the protection of nitrogen, carrying out heat treatment for 6h to obtain flake mica coated with a carbon layer, then soaking the flake mica in 5wt% copper bromide solution for 30min, filtering, and carrying out vacuum drying for 3h at 100 ℃ to obtain the catalyst A3.
[ catalyst A4 ]: pickling 100 parts of flaky talcum powder, cleaning with distilled water, dispersing in 200 parts of water, then dropwise adding 20 parts of dopamine hydrochloride, uniformly stirring and dispersing, adjusting the pH to 9.5, continuously stirring for 1h, filtering out mica powder, heating to 650 ℃ under the protection of nitrogen, carrying out heat treatment for 4h to obtain flaky mica coated with a carbon layer, then soaking the flaky mica in 5wt% zinc chloride solution for 30min, filtering, and carrying out vacuum drying for 3h at 100 ℃ to obtain the catalyst A4.
[ catalyst A5 ]: washing 100 parts of sheet montmorillonite with acid, washing with distilled water, dispersing in 200 parts of water containing 20% polyvinylpyrrolidone, stirring and dispersing for 1h, filtering out mica powder, heating to 400 ℃ under the protection of nitrogen, carrying out heat treatment for 12h to obtain sheet mica coated with a carbon layer, then soaking the sheet mica in a zinc chloride solution containing 5wt% of carbon for 30min, filtering, and carrying out vacuum drying at 100 ℃ for 3h to obtain the catalyst A5.
[ catalyst A6 ]: after 100 parts of flake mica is subjected to acid washing and distilled water washing, the flake mica is dispersed in 200 parts of water containing 20% of polyoxyethylene, stirred and dispersed for 1 hour, mica powder is filtered out, the temperature is raised to 400 ℃ under the protection of nitrogen, heat treatment is carried out for 12 hours, the flake mica coated with a carbon layer is obtained, then the flake mica is soaked in a zinc chloride solution containing 5wt% of zinc chloride for 30 minutes, filtered and dried in vacuum for 3 hours at the temperature of 100 ℃, and the catalyst A6 is obtained.
[ catalyst A7 ]: washing 100 parts of sheet mica powder with acid, washing with distilled water, dispersing in 200 parts of water, then dropwise adding 20 parts of dopamine hydrochloride, stirring and dispersing uniformly, adjusting the pH value to 9.5, continuing stirring for 1h, filtering out the mica powder, heating to 500 ℃ under the protection of nitrogen, carrying out heat treatment for 6h, and naturally cooling the sheet mica coated with the carbon layer to obtain the catalyst A7.
[ PRODUCTION OF HEXAFLUOROBUTENE ]
Example 1
A preparation method of hexafluorobutadiene comprises the following steps:
after the air in a 2000ml tower kettle with a thermocouple is completely replaced by nitrogen, 200g of catalyst A1, 200g (3 mol) of nano zinc powder (average particle size is 500 nm) and 400g of dimethyl sulfoxide are added, and the mixture is heated, refluxed and stirred for 1h, so that the zinc powder enters gaps among the layers of the catalyst to form slurry. Adjusting the temperature of the system to 80 ℃, adding 136g (0.3 mol) of 1, 4-diiodoperfluorobutane into the system, continuously mixing for 30min, then adding 0.35g (3 mmol) of triethylaluminum to initiate reaction, collecting a crude product after the reaction for 3h, placing the crude product in a low-temperature cold trap at the temperature of-90 ℃, after the reaction is finished, fully gasifying the crude product at normal temperature, freezing the gasified gas into a high-pressure steel cylinder, and weighing to obtain 45.8g of a crude product of the hexafluorobutadiene (the yield is 94.2%, the purity is 98.3%), wherein a GC diagram is shown in figure 3.
Example 2
A preparation method of hexafluorobutadiene comprises the following steps:
after the air in a 2000ml column reactor equipped with a thermocouple was completely replaced with nitrogen, 300g of catalyst A2, 100g (1.5 mol) of ultrafine zinc powder (average particle size 1 μm) and 300g of dimethyl sulfoxide were added, and the mixture was heated, refluxed and stirred for 1 hour to allow the zinc powder to enter the gaps between the catalyst layers to form a slurry. Adjusting the temperature of the system to 85 ℃, adding 340g (0.75 mol) of 1, 4-diiodoperfluorobutane into the system, continuously mixing for 30min, then adding 4.38g (38 mmol) of triethylaluminum to initiate reaction, collecting a crude product after 4h of reaction, placing the crude product in a low-temperature cold trap at the temperature of-90 ℃, after the reaction is finished, fully gasifying the crude product at normal temperature, freezing the gasified gas into a high-pressure steel cylinder, and weighing to obtain 115.5g of crude hexafluorobutadiene (the yield is 95.1 percent, and the purity is 98.5 percent).
Example 3
A preparation method of hexafluorobutadiene comprises the following steps:
after the air in a 2000ml tower kettle with a thermocouple is completely replaced by nitrogen, 200g of catalyst A3, 100g (1.5 mol) of nano zinc powder (with the average particle size of 500 nm) and 100g of dimethyl sulfoxide are added, and the mixture is heated, refluxed and stirred for 1 hour, so that the zinc powder enters the gaps between the layers of the catalyst to form slurry. Adjusting the temperature of the system to 85 ℃, adding 136g (0.3 mol) of 1, 4-diiodoperfluorobutane into the system, continuously mixing the mixture for 30min, then adding 0.7g (6 mmol) of triethylaluminum to initiate a reaction, collecting a crude product after the reaction for 4h, putting the crude product into a low-temperature cold trap at the temperature of-90 ℃, after the reaction is finished, placing the crude product at normal temperature for full gasification, freezing the gasified gas into a high-pressure steel cylinder, and weighing to obtain 40.5g of crude hexafluorobutadiene (the yield is 93.5 percent, and the purity is 99.3 percent).
Example 4
A preparation method of hexafluorobutadiene comprises the following steps:
after the air in a 2000ml column reactor with a thermocouple was completely replaced with nitrogen, 200g of catalyst A4, 96g (4 mol) of ultrafine magnesium powder (average particle size: 2 μm), and 250g of acetonitrile were added, and the mixture was heated, refluxed, and stirred for 1 hour to cause the magnesium powder to enter gaps between layers of the catalyst, thereby forming a slurry. Adjusting the temperature of the system to 60 ℃, adding 181g (0.4 mol) of 1, 4-diiodoperfluorobutane into the system, continuously mixing for 30min, then adding 1.16g (3 mmol) of triethylaluminum to initiate reaction, collecting a crude product after the reaction is carried out for 2.5h, putting the crude product into a low-temperature cold trap at the temperature of-90 ℃, after the reaction is finished, placing the crude product at normal temperature for full gasification, freezing the gasified gas into a high-pressure steel cylinder, and weighing to obtain 61.8g of a crude product of the hexafluorobutadiene (the yield is 95.3%, and the purity is 98.1%).
Example 5
A preparation method of hexafluorobutadiene comprises the following steps:
after the air in a 2000ml tower kettle with a thermocouple was completely replaced with nitrogen, 250g of catalyst A5, 54g (2 mol) of ultrafine aluminum powder (average particle size of 1 μm) and 250g of acetone were added, and the mixture was heated, refluxed and stirred for 1 hour to allow the aluminum powder to enter gaps between layers of the catalyst, thereby forming a slurry. Adjusting the temperature of the system to 65 ℃, adding 91g (0.2 mol) of 1, 4-diiodoperfluorobutane into the system, continuously mixing for 30min, then adding 0.24g (3 mmol) of triethylaluminum to initiate reaction, collecting a crude product after the reaction is carried out for 3.5h, placing the crude product in a low-temperature cold trap at the temperature of-90 ℃, after the reaction is finished, fully gasifying the crude product at normal temperature, freezing the gasified gas into a high-pressure steel cylinder, and weighing to obtain 30.8g of a crude product of the hexafluorobutadiene (the yield is 95.1%, and the purity is 97.9%).
Example 6
A preparation method of hexafluorobutadiene comprises the following steps:
after the air in a 2000ml column reactor equipped with a thermocouple was completely replaced with nitrogen, 300g of catalyst A2, 100g (1.5 mol) of ultrafine zinc powder (average particle size: 1 μm), and 300g of dimethyl sulfoxide were added, and the mixture was heated, refluxed, and stirred for 1 hour to allow the zinc powder to enter the gaps between the layers of the catalyst, thereby forming a slurry. Adjusting the temperature of the system to 85 ℃, adding 270g (0.75 mol) of 1, 4-dibromoperfluorobutane into the system, continuously mixing the mixture for 30min, then adding 0.86g (7.5 mmol) of triethylaluminum to initiate a reaction, collecting a crude product after the reaction for 4h, putting the crude product into a low-temperature cold trap at the temperature of-90 ℃, after the reaction is finished, placing the crude product at normal temperature for full gasification, freezing the gasified gas into a high-pressure steel cylinder, and weighing to obtain 116.1g of crude hexafluorobutadiene (the yield is 95.6 percent, and the purity is 97.6 percent).
Comparative example 1
A preparation method of hexafluorobutadiene comprises the following steps:
after the air in a 2000ml tower kettle with a thermocouple was completely replaced with nitrogen, 100g (1.5 mol) of nano zinc powder (average particle size 500 nm) and 100g of dimethyl sulfoxide were heated and refluxed and stirred for 1 hour to form a slurry. Adjusting the temperature of the system to 120 ℃, adding 136g (0.3 mol) of 1, 4-diiodoperfluorobutane into the system, continuously mixing for 30min, then adding 0.7g (6 mmol) of triethylaluminum to initiate reaction, collecting a crude product after the reaction is carried out for 5h, placing the crude product into a low-temperature cold trap at the temperature of-90 ℃, after the reaction is finished, fully gasifying the crude product at normal temperature, freezing the gasified gas into a high-pressure steel cylinder, and weighing to obtain 20.0g of a crude product of the hexafluorobutadiene (the yield is 46.3 percent, and the purity is 88.6 percent).
Comparative example 2
A preparation method of hexafluorobutadiene comprises the following steps:
after the air in a 2000ml tower kettle with a thermocouple is completely replaced by nitrogen, 200g of catalyst A6, 100g (1.5 mol) of nano zinc powder (with the average particle size of 500 nm) and 100g of dimethyl sulfoxide are added, and the mixture is heated, refluxed and stirred for 1 hour, so that the zinc powder enters the gaps between the layers of the catalyst to form slurry. Adjusting the temperature of the system to 85 ℃, adding 136g (0.3 mol) of 1, 4-diiodoperfluorobutane into the system, continuously mixing the mixture for 30min, then adding 0.7g (6 mmol) of triethylaluminum to initiate a reaction, collecting a crude product after the reaction for 4h, putting the crude product into a low-temperature cold trap at the temperature of-90 ℃, after the reaction is finished, placing the crude product at normal temperature for full gasification, freezing the gasified gas into a high-pressure steel cylinder, and weighing to obtain 31.4g of crude hexafluorobutadiene (the yield is 72.6 percent, and the purity is 94.9 percent).
Comparative example 3
A preparation method of hexafluorobutadiene comprises the following steps:
after the air in a 2000ml tower kettle with a thermocouple is completely replaced by nitrogen, 200g of catalyst A7, 100g (1.5 mol) of nano zinc powder (with the average particle size of 500 nm) and 100g of dimethyl sulfoxide are added, and the mixture is heated, refluxed and stirred for 1h, so that the zinc powder enters gaps among layers of the catalyst to form slurry. Adjusting the temperature of the system to 85 ℃, adding 136g (0.3 mol) of 1, 4-diiodoperfluorobutane into the system, continuously mixing for 30min, then adding 0.7g (6 mmol) of triethylaluminum to initiate reaction, collecting a crude product after 4h of reaction, placing the crude product in a low-temperature cold trap at the temperature of-90 ℃, after the reaction is finished, fully gasifying the crude product at normal temperature, freezing the gasified gas into a high-pressure steel cylinder, and weighing to obtain 29.5g of a crude product of the hexafluorobutadiene (the yield is 68.2 percent, and the purity is 95.2 percent).
From the above results, it is understood that by comparing examples 1 to 5 with comparative example 1, the reaction temperature used in the preparation of hexafluorobutadiene can be effectively reduced by applying the catalyst of the present invention, and at a lower reaction temperature, one can maintain a higher yield and purity.
Meanwhile, by comparing with comparative example 2, we found that catalyst A6 in comparative example 2 does not contain nitrogen atoms in its carbon layer, resulting in a great decrease in the yield of crude hexafluorobutadiene during the reaction, indicating that the addition of nitrogen atoms has a non-negligible effect on the conversion of diiodoperfluorobutane into hexafluorobutadiene.
Furthermore, we found that the catalyst A6 of comparative example 2, which does not carry a metal halide in its carbon layer, also had a decrease in yield when compared with comparative example 2, indicating that the addition of a metal halide also had a non-negligible effect on the conversion of diiodoperfluorobutane to hexafluorobutadiene.
Claims (10)
1. A catalyst, characterized in that,
comprises a substrate composed of a layered structure mineral;
the surface of the base material is coated with a carbon layer;
the carbon layer is doped with nitrogen atoms;
the carbon layer also supports a metal halide.
2. A catalyst according to claim 1,
the lamellar structure mineral comprises one or more of mica, montmorillonite, pyrophyllite, serpentine, talc and chlorite.
3. A catalyst according to claim 1,
the metal halide comprises any one or combination of halides of zinc, magnesium, aluminum, iron, manganese and copper.
4. A process for preparing the catalyst as claimed in any of claims 1 to 3, characterized in that,
the method comprises the following steps:
(1) Coating a carbon precursor on the surface of a base material consisting of layered structure minerals;
(2) Heat treating to convert the carbon precursor into a carbon layer;
(3) And (3) soaking the substrate coated with the carbon layer in a metal halide solution to load metal halide in the carbon layer, and drying to obtain the catalyst.
5. The method of claim 4,
the carbon precursor is polydopamine or polyvinylpyrrolidone.
6. The method of claim 4,
the heat treatment conditions in the step (2) are as follows: heating to 400-650 ℃ under the protection of inert gas, and keeping for 3-12h.
7. A method for preparing hexafluorobutadiene, which is characterized in that,
the method comprises the following steps:
(S.1) mixing the catalyst of any one of claims 1 to 3 with metal powder and an organic solvent to form slurry, and refluxing and stirring to enable the zinc powder to enter an interlayer gap of the catalyst;
(S.2) dropwise adding 1, 4-dihaloperfluorobutane into the slurry, uniformly mixing, and adding alkyl aluminum to initiate reaction;
(S.3) collecting the generated hexafluorobutadiene.
8. The process according to claim 7, wherein the reaction mixture is a mixture of at least two of the above-mentioned monomers,
in the step (S.1), the mass ratio of the catalyst to the metal powder to the organic solvent is (1 to 5): 1: (1 to 5);
the metal powder is single substance powder or multiple alloy powder of any one of zinc, magnesium, aluminum, tin, copper and iron;
the solvent is a polar aprotic solvent.
9. The process according to claim 7 or 8, wherein the reaction mixture is a mixture of at least two of the above-mentioned monomers,
the particle size range of the metal powder is 0.5-2 mu m.
10. The method of producing hexafluorobutadiene according to claim 7,
the amount of the substance of the alkylaluminum initiator in the step (S.2) is 1 to 5 percent of the amount of the substance of the 1, 4-dihaloperfluorobutane;
the amount of the 1, 4-dihaloperfluorobutane substance is 10 to 50 percent of the amount of the metal powder substance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210777816.XA CN115254163B (en) | 2022-07-04 | 2022-07-04 | Catalyst, preparation method thereof and application of catalyst in preparation process of hexafluorobutadiene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210777816.XA CN115254163B (en) | 2022-07-04 | 2022-07-04 | Catalyst, preparation method thereof and application of catalyst in preparation process of hexafluorobutadiene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115254163A true CN115254163A (en) | 2022-11-01 |
| CN115254163B CN115254163B (en) | 2023-06-30 |
Family
ID=83764474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210777816.XA Active CN115254163B (en) | 2022-07-04 | 2022-07-04 | Catalyst, preparation method thereof and application of catalyst in preparation process of hexafluorobutadiene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115254163B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5332708A (en) * | 1992-11-23 | 1994-07-26 | Phillips Petroleum Company | Catalyst compositions and catalytic processes |
| CN101774884A (en) * | 2010-01-14 | 2010-07-14 | 天津大学 | Preparation method of hexachlorobutadiene |
| CN107051566A (en) * | 2017-03-22 | 2017-08-18 | 湖北大学 | The method that the preparation method of azepine carbon coating cobalt catalyst and unsaturated compound based on above-mentioned catalyst are catalyzed transfer hydrogenation |
| WO2017189120A1 (en) * | 2016-04-29 | 2017-11-02 | Exxonmobil Chemical Patents Inc. | Organoaluminum activators on clays |
| WO2021259388A1 (en) * | 2020-06-24 | 2021-12-30 | 广东工业大学 | Method for using carbon coating to prepare low oxygen content, high thermal conductivity silicon nitride ceramic, and application thereof |
-
2022
- 2022-07-04 CN CN202210777816.XA patent/CN115254163B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5332708A (en) * | 1992-11-23 | 1994-07-26 | Phillips Petroleum Company | Catalyst compositions and catalytic processes |
| CN101774884A (en) * | 2010-01-14 | 2010-07-14 | 天津大学 | Preparation method of hexachlorobutadiene |
| WO2017189120A1 (en) * | 2016-04-29 | 2017-11-02 | Exxonmobil Chemical Patents Inc. | Organoaluminum activators on clays |
| CN107051566A (en) * | 2017-03-22 | 2017-08-18 | 湖北大学 | The method that the preparation method of azepine carbon coating cobalt catalyst and unsaturated compound based on above-mentioned catalyst are catalyzed transfer hydrogenation |
| WO2021259388A1 (en) * | 2020-06-24 | 2021-12-30 | 广东工业大学 | Method for using carbon coating to prepare low oxygen content, high thermal conductivity silicon nitride ceramic, and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115254163B (en) | 2023-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108946698B (en) | Method for preparing gamma-type graphite single alkyne nano carbon material based on benzene precursor | |
| CN110813359B (en) | Ruthenium-based ammonia synthesis catalyst with nitrogen-doped porous carbon material as carrier and preparation method thereof | |
| CN102167314A (en) | Method for preparing graphene | |
| EP3085666B1 (en) | Method for repairing reduced graphene oxide | |
| CN113546679B (en) | Ionic liquid-ruthenium-based catalyst for catalyzing hydrochlorination of acetylene as well as preparation method and application thereof | |
| CN113000061B (en) | Preparation method of banded graphite carbon nitride nanosheets | |
| CN115254163B (en) | Catalyst, preparation method thereof and application of catalyst in preparation process of hexafluorobutadiene | |
| CN111111740A (en) | Preparation and application of supported nitrogen-rich carbon-based solid base catalyst | |
| CN111167443B (en) | Novel ruthenium-based catalyst and preparation method and application thereof | |
| CN113134378A (en) | W18O49/g-C3N4Preparation method of/RGO semiconductor photocatalyst | |
| CN117225444A (en) | Photocatalytic material and preparation method and application thereof | |
| CN114768884B (en) | Immobilized catalyst for producing ethylene carbonate, preparation method and application | |
| CN115974655A (en) | Application of high-load copper monatomic catalyst in preparation of phenol by using hydrogen peroxide | |
| CN114477154A (en) | Preparation method of high-quality graphene | |
| CN116328774A (en) | Catalyst for methane catalytic pyrolysis hydrogen production and preparation method thereof | |
| CN111957334A (en) | Preparation method of composite ternary heterojunction photocatalyst | |
| CN112853385A (en) | Oxygen vacancy and Mn doped double-defect cerium dioxide nanosheet and preparation method and application thereof | |
| KR102082221B1 (en) | Method for preparing N-doped titanium carbide | |
| JP7448912B2 (en) | Metal composite, nitrogen-containing polycyclic compound, fired body and method for producing the same, oxygen reduction catalyst, oxygen generation catalyst, and hydrogen generation catalyst | |
| CN111468128A (en) | Preparation method of composite nanosheet catalyst | |
| KR20050006197A (en) | Method for producing organic alkyne compounds | |
| CN118059899A (en) | Composite copper powder catalyst for synthesizing organic silicon monomer and preparation method thereof | |
| CN114735687B (en) | Synthesis method of graphene | |
| CN115779968B (en) | Copper-based catalyst for preparing vinyl chloride by hydrochlorination of acetylene as well as preparation method and application thereof | |
| CN115532251B (en) | Layered transition metal boride material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |