CN111135842B - Catalyst for catalytic conversion of impurities in octafluorocyclobutane, and preparation method and application thereof - Google Patents
Catalyst for catalytic conversion of impurities in octafluorocyclobutane, and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a catalyst for catalytic conversion of impurities in octafluorocyclobutane, and a preparation method and application thereof1And X2The active component palladium content is 0.2-1.5 wt%, and the auxiliary agent X10.1-2.5 wt% of auxiliary agent X2The content is 0.05-0.8 wt%. The invention can reduce the content of alkene fluorocarbon impurities in the octafluorocyclobutane to below 1 ppmv. The invention has the advantages of good catalyst performance, high separation efficiency and simple operation.
Description
Technical Field
The invention belongs to the field of fine chemical engineering, and particularly relates to a catalyst for catalytic conversion of impurities in octafluorocyclobutane, and a preparation method and application thereof.
Background
Perfluorocycloalkanes have wide applications in high voltage insulation, aerosols, sprays, very large scale integrated circuit etchants, heat pump working fluids, etc., with octafluorocyclobutane (also known as perfluorocyclobutane) being particularly important. The octafluorocyclobutane has stable chemical property, no toxicity, zero ozone consumption index value and low greenhouse effect, and is a green environment-friendly special gas. With the implementation of Montreal protocol and the rapid growth of electronic industry, the function of octafluorocyclobutane is increasingly important, the usage amount is increased year by year, and the octafluorocyclobutane has wide application in high-voltage insulation, aerosol, spray, very large scale integrated circuit etchant, heat pump working fluid and the like.
Octafluorocyclobutane is used as one of etching or cleaning gases in a common semiconductor process, and as the size of a semiconductor device is smaller, the requirement on etching precision is stricter and higher, and the requirement on the purity of the octafluorocyclobutane is higher and higher. The existing purification methods of octafluorocyclobutane mainly comprise the following three methods:
the first is an adsorption process. The adsorption method removes impurities in octafluorocyclobutane by using an adsorbent, and commonly used adsorbents include modified activated carbon, metal oxides and the like. The existing adsorbent has poor selectivity and complex preparation process, and further description and research on the regeneration and recycling processes of the adsorbent are not provided. For example, chinese patent publication No. CN107694509A discloses an adsorbent for removing hexafluoropropylene in octafluorocyclobutane, which is formed by compounding metal oxide and metal and is grown on a wire mesh packing, but no data indicates its adsorption effect and adsorbent reusability.
The second is a rectification process. The rectification method is a commonly used method for purifying the octafluorocyclobutane, but due to the fact that the impurity types are more, particularly, impurities with the boiling point close to that of the octafluorocyclobutane cannot meet the preset separation requirement through the conventional rectification method. In addition, azeotropic distillation and extractive distillation methods are also adopted, but the methods have high equipment cost and complex process.
The third is a catalytic process. Chinese patent publication No. CN104529691A discloses a catalytic conversion method of impurities in perfluoroalkane, and AlF is used as a catalyst3And metal high-valence fluoride, the catalyst can convert most of the impurities of the hydrogen-containing fluorocarbon and/or alkene fluorocarbon, but the conversion is difficult to complete, and particularly after a period of reaction, the catalyst effect is obviously poor.
Disclosure of Invention
Aiming at the defects of the existing technology for purifying octafluorocyclobutane, the invention aims to provide a catalyst for catalytically converting impurities in octafluorocyclobutane, which has the advantages of good catalyst performance, high separation efficiency and simple operation, and a preparation method and application thereof.
In order to solve the technical problems, the invention is realized by the following technical scheme: the catalyst for catalytic conversion of impurities in octafluorocyclobutane is composed of an active component and an auxiliary agent, wherein the active component is palladium, and the auxiliary agent is X1And X2The active component palladium content is 0.2-1.5 wt% (wt%, mass percentage content), and the auxiliary agent X10.1-2.5 wt% of auxiliary agent X2The content is 0.05-0.8 wt%.
As a preferred embodiment of the present invention, wherein X1One selected from Mo, Co, Ni and Ag, X2One selected from Y, La, Sc and Ce.
The preparation method of the catalyst for catalytically converting impurities in octafluorocyclobutane comprises the following steps:
(1) active carbon pretreatment: mixing activated carbon and 2-10 wt% of nitric acid aqueous solution according to the mass ratio of 1: 3-8, uniformly stirring, treating at 60-90 ℃ for 1-4 h, washing to be neutral by deionized water, and drying at 100-120 ℃ to obtain pretreated activated carbon for later use;
(2) preparing a catalyst precursor: will contain X1And a compound containing X2Adding the compound into distilled water, heating to 80-100 ℃, and obtaining a solution containing auxiliary components for later use after the compound is completely dissolved and cooled; dissolving a palladium-containing compound into dilute hydrochloric acid to obtain a solution containing an active component, mixing the solution containing the active component with a solution containing an auxiliary component, adjusting the pH value of the solution to 4-7, adding the pretreated activated carbon obtained in the step (1), soaking for 2-5 h in the same volume, and drying at 100-120 ℃ to obtain a catalyst precursor;
(3) reduction treatment: roasting the catalyst precursor obtained in the step (2) at the temperature of 150-300 ℃ for 4-8 h, and finally carrying out reduction treatment on the catalyst precursor by using a mixed gas of hydrogen and nitrogen at the temperature of 100-250 ℃ for 4-8 h to obtain the catalyst.
As preferred embodiments of the present inventionIn one embodiment, the palladium-containing compound is palladium chloride or palladium nitrate, and X is1And X2The compound of (b) is a corresponding nitrate compound or other water-soluble compound.
In a preferred embodiment of the present invention, the diluted hydrochloric acid is 2 to 8% by mass.
As a preferred embodiment of the invention, octafluorocyclobutane containing alkene fluorocarbon impurities is reacted with hydrogen under the action of a catalyst, and a reaction product is collected and subjected to hydrogen separation, rectification and purification to obtain the treated octafluorocyclobutane.
As a preferred embodiment of the present invention, the olefinic fluorocarbon impurity is 1-C4F8、2-C4F8And C2F4。
As a preferred embodiment of the present invention, the content of olefinic fluorocarbon impurities in the octafluorocyclobutane is 100ppmv or less.
As a preferred embodiment of the invention, the octafluorocyclobutane has a purity of > 99.99%.
In a preferred embodiment of the present invention, the molar ratio of octafluorocyclobutane to hydrogen is 1:0.0005 to 0.01, the reaction temperature is 30 to 150 ℃, the pressure is 0.1 to 0.5MPa, and the contact time is 0.5 to 20 s.
In the invention, under the action of a catalyst, crude octafluorocyclobutane is reacted with hydrogen, so that impurities with a boiling point close to that of the octafluorocyclobutane are converted into substances with a higher boiling point than that of the octafluorocyclobutane, and the subsequent separation and purification are facilitated.
In the invention, the catalyst can be loaded into a fixed bed reactor, octafluorocyclobutane containing alkene fluorocarbon and hydrogen enter the reactor to contact with the catalyst for reaction, and the treated gas is collected. After hydrogen separation and rectification purification, 1-C in octafluorocyclobutane can be obtained4F8、2-C4F8And C2F4Respectively to below 1 ppmv.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following beneficial effects:
(1) the catalyst prepared by the invention is added with a proper amount of auxiliary agent X1And X2Improving the activity of the catalyst, leading the impurities in the octafluorocyclobutane to be converted as much as possible and being beneficial to the subsequent separation, 1-C4F8The conversion rate of the catalyst is more than 98.5 percent and can reach 99.3 percent at most, 2-C4F8The conversion rate of (C) is more than 98.3%, and can be up to 99.1%2F4The conversion rate is more than 98.1 percent and can reach 98.8 percent at most.
(2) The separation efficiency is high, and the content of alkene fluorocarbon impurities in the octafluorocyclobutane can be reduced to below 1 ppmv.
(3) The method has simple operation, can effectively remove alkene fluorocarbon impurities in the octafluorocyclobutane through hydrotreating and conventional separation and rectification operations, and obviously simplifies the process.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
The catalyst is prepared by the following steps:
(1) active carbon pretreatment: mixing activated carbon and 5 wt% nitric acid aqueous solution according to the mass ratio of 1: 3, uniformly stirring after mixing, treating for 4 hours at the temperature of 60 ℃, washing to be neutral by deionized water, and drying for 5 hours at the temperature of 120 ℃ to obtain the pretreated activated carbon.
(2) Preparing a catalyst precursor: adding cobalt nitrate and yttrium nitrate into distilled water, stirring and heating to 80 ℃, and obtaining a solution containing auxiliary components after the cobalt nitrate and the yttrium nitrate are completely dissolved and cooled for later use; dissolving palladium chloride into dilute hydrochloric acid with the mass fraction of 2% to obtain a solution containing an active component, mixing the solution containing the active component with a solution containing an auxiliary component, adjusting the pH value of the solution to 6 by using sodium carbonate to obtain a mixed solution, adding pretreated activated carbon into the mixed solution, soaking for 3 hours in an equal volume, and drying for 6 hours at 120 ℃ after soaking to obtain a catalyst precursor.
(3) Reduction treatment: and roasting the catalyst precursor obtained in the process at the temperature of 250 ℃ for 4h, and finally, carrying out reduction treatment on the catalyst precursor for 5h by using a mixed gas of hydrogen and nitrogen at the temperature of a bed layer of 200 ℃ to obtain the supported catalyst. The catalyst comprises the following components: 0.5 wt% Pa-1.0 wt% Co-0.25 wt% Y/C.
The method for catalytically converting impurities in octafluorocyclobutane by using the catalyst comprises the following steps:
the alkene-containing fluorocarbon impurity (1-C)4F8：21ppmv，2-C4F8：33ppmv，C2F4: 23ppmv), and octafluorocyclobutane with purity of more than 99.99 percent is contacted with a catalyst for hydrotreating, and the reaction conditions are as follows: the mol ratio of octafluorocyclobutane to hydrogen is 1:0.003, the reaction temperature is 60 ℃, the pressure is 0.3MPa, the contact time is 5s, the treated gas is collected, and the reaction temperature is 1-C4F8、2-C4F8And C2F4The conversion rates of (a) were 98.6%, 98.7% and 98.2%, respectively. After hydrogen separation and rectification purification, 1-C in octafluorocyclobutane is detected4F8Is 0.2ppmv, 2-C4F8Is 0.4ppmv, C2F4Is 0.4 ppmv.
Example 2
The catalyst is prepared by the following steps:
(1) active carbon pretreatment: mixing activated carbon and 2 wt% nitric acid aqueous solution according to the mass ratio of 1: 5, uniformly stirring after mixing, treating for 2 hours at the temperature of 90 ℃, washing to be neutral by deionized water, and drying for 4 hours at the temperature of 100 ℃ to obtain the pretreated activated carbon.
(2) Preparing a catalyst precursor: adding silver nitrate and cerium nitrate into distilled water, stirring and heating to 90 ℃, and obtaining a solution containing auxiliary components after the silver nitrate and the cerium nitrate are completely dissolved and cooled for later use; dissolving an active component palladium chloride into dilute hydrochloric acid with the mass fraction of 4% to obtain a solution containing the active component, mixing the solution containing the active component with a solution containing an auxiliary component, adjusting the pH value of the solution to 5 by using sodium carbonate to obtain a mixed solution, adding pretreated activated carbon into the mixed solution, soaking for 4 hours in an equal volume manner, and drying for 8 hours at 110 ℃ after the soaking is finished to obtain a catalyst precursor.
(3) Reduction treatment: and roasting the catalyst precursor obtained in the process at the temperature of 200 ℃ for 5 hours, and finally, reducing the catalyst precursor by using a mixed gas of hydrogen and nitrogen at the temperature of 220 ℃ of a bed layer for 8 hours to obtain the supported catalyst. The catalyst comprises the following components: 1.0 wt% Pa-1.5 wt% Ag-0.4 wt% Ce/C.
The method for catalytically converting impurities in octafluorocyclobutane by using the catalyst comprises the following steps:
the alkene-containing fluorocarbon impurity (1-C)4F8：25ppmv，2-C4F8：28ppmv，C2F4: 21ppmv), contacting octafluorocyclobutane with purity of more than 99.99% with a catalyst for hydrotreating, wherein the reaction conditions are as follows: the mol ratio of octafluorocyclobutane to hydrogen is 1:0.001, the reaction temperature is 30 ℃, the pressure is 0.2MPa, the contact time is 8s, the treated gas is collected, and the reaction temperature is 1-C4F8、2-C4F8And C2F4The conversion rates of (a) were 99.1%, 98.5% and 98.5%, respectively. After hydrogen separation and rectification purification, 1-C in octafluorocyclobutane is detected4F8Is 0.15ppmv, 2-C4F8Is 0.2ppmv, C2F4The content of (B) was 0.3 ppmv.
Example 3
The catalyst is prepared by the following steps:
(1) active carbon pretreatment: mixing activated carbon and 8 wt% nitric acid aqueous solution according to the mass ratio of 1: 4, uniformly stirring after mixing, treating for 3 hours at the temperature of 70 ℃, washing to be neutral by deionized water, and drying for 8 hours at the temperature of 120 ℃ to obtain the pretreated activated carbon.
(2) Preparing a catalyst precursor: adding molybdenum nitrate and yttrium nitrate into distilled water, stirring and heating to 80 ℃, and obtaining a solution containing auxiliary components after the molybdenum nitrate and the yttrium nitrate are completely dissolved and cooled for later use; dissolving an active component palladium chloride into dilute hydrochloric acid with the mass fraction of 6% to obtain a solution containing the active component, mixing the solution containing the active component with a solution containing an auxiliary component, adjusting the pH value of the solution to 6.5 by using sodium carbonate to obtain a mixed solution, adding pretreated active carbon into the mixed solution, soaking for 2 hours in the same volume, and drying for 6 hours at 110 ℃ after soaking to obtain a catalyst precursor.
(3) Reduction treatment: roasting the catalyst precursor obtained in the process at the temperature of 180 ℃ for 6 hours, and finally carrying out reduction treatment on the catalyst precursor for 4 hours by using a mixed gas of hydrogen and nitrogen at the bed temperature of 150 ℃ to obtain the supported catalyst. The catalyst comprises the following components: 1.5 wt% Pa-0.8 wt% Mo-0.5 wt% Y/C.
The method for catalytically converting impurities in octafluorocyclobutane by using the catalyst comprises the following steps:
the alkene-containing fluorocarbon impurity (1-C)4F8：31ppmv，2-C4F8：42ppmv，C2F4: 17ppmv), octafluorocyclobutane with purity of more than 99.99% is contacted with a catalyst for hydrotreating, and the reaction conditions are as follows: the mol ratio of octafluorocyclobutane to hydrogen is 1:0.008, the reaction temperature is 80 ℃, the pressure is 0.1MPa, the contact time is 3s, the treated gas is collected, and the reaction temperature is 1-C4F8、2-C4F8And C2F4The conversion rates of (a) were 99.3%, 99.1% and 98.1%, respectively. After hydrogen separation and rectification purification, 1-C in octafluorocyclobutane is detected4F8Is 0.1ppmv, 2-C4F8Is 0.2ppmv, C2F4Is 0.4 ppmv.
Example 4
The catalyst is prepared by the following steps:
(1) active carbon pretreatment: mixing activated carbon and a 4 wt% nitric acid aqueous solution according to a mass ratio of 1: 7, uniformly stirring, treating at the temperature of 80 ℃ for 1.5h, washing to be neutral by deionized water, and drying at the temperature of 110 ℃ for 6h to obtain the pretreated activated carbon.
(2) Preparing a catalyst precursor: adding nickel nitrate and scandium nitrate into distilled water, stirring and heating to 95 ℃, and obtaining a solution containing auxiliary components after the nickel nitrate and the scandium nitrate are completely dissolved and cooled for later use; dissolving an active component palladium nitrate into dilute hydrochloric acid with the mass fraction of 5% to obtain a solution containing the active component, mixing the solution containing the active component with a solution containing an auxiliary component, adjusting the pH value of the solution to 5.5 by using sodium carbonate to obtain a mixed solution, adding pretreated active carbon into the mixed solution, soaking for 5 hours in the same volume, and drying for 7 hours at 105 ℃ after soaking to obtain a catalyst precursor.
(3) Reduction treatment: and roasting the catalyst precursor obtained in the process at 220 ℃ for 8h, and finally, reducing the catalyst precursor by using a mixed gas of hydrogen and nitrogen at a bed temperature of 170 ℃ for 6h to obtain the supported catalyst. The catalyst comprises the following components: 0.8 wt% Pa-1.6 wt% Ni-0.6 wt% Sc/C.
The method for catalytically converting impurities in octafluorocyclobutane by using the catalyst comprises the following steps:
the alkene-containing fluorocarbon impurity (1-C)4F8：22ppmv，2-C4F8：40ppmv，C2F4: 18ppmv), the octafluorocyclobutane with the purity of more than 99.99 percent is contacted with a catalyst for hydrotreating, and the reaction conditions are as follows: the mol ratio of octafluorocyclobutane to hydrogen is 1:0.01, the reaction temperature is 90 ℃, the pressure is 0.5MPa, the contact time is 12s, the treated gas is collected, and the reaction temperature is 1-C4F8、2-C4F8And C2F4The conversion rates of (a) were 98.9%, 98.4% and 98.8%, respectively. After hydrogen separation and rectification purification, 1-C in octafluorocyclobutane is detected4F8Is 0.2ppmv, 2-C4F8Is 0.4ppmv, C2F4The content of (B) was 0.2 ppmv.
Example 5
The catalyst is prepared by the following steps:
(1) active carbon pretreatment: mixing activated carbon and 6 wt% nitric acid aqueous solution according to the mass ratio of 1: 6, uniformly stirring after mixing, treating for 2.5h at the temperature of 65 ℃, washing to be neutral by deionized water, and drying for 7h at the temperature of 120 ℃ to obtain the pretreated activated carbon.
(2) Preparing a catalyst precursor: adding cobalt nitrate and yttrium nitrate into distilled water, stirring and heating to 90 ℃, and obtaining a solution containing auxiliary components after the cobalt nitrate and the yttrium nitrate are completely dissolved and cooled for later use. Dissolving an active component palladium chloride into dilute hydrochloric acid with the mass fraction of 3% to obtain a solution containing the active component, mixing the solution containing the active component with a solution containing an auxiliary component, adjusting the pH value of the solution to 6 by using sodium carbonate to obtain a mixed solution, adding pretreated activated carbon into the mixed solution, soaking for 3 hours in an equal volume, and drying for 8 hours at 110 ℃ after soaking to obtain a catalyst precursor.
(3) Reduction treatment: and roasting the catalyst precursor obtained in the process at the temperature of 280 ℃ for 6h, and finally, carrying out reduction treatment on the catalyst precursor for 5h by using a mixed gas of hydrogen and nitrogen at the temperature of 240 ℃ of a bed layer to obtain the supported catalyst. The catalyst comprises the following components: 0.3 wt% Pa-0.6 wt% Co-0.1 wt% Y/C.
The method for catalytically converting impurities in octafluorocyclobutane by using the catalyst comprises the following steps:
the alkene-containing fluorocarbon impurity (1-C)4F8：22ppmv，2-C4F8：36ppmv，C2F4: 21ppmv), contacting octafluorocyclobutane with purity of more than 99.99% with a catalyst for hydrotreating, wherein the reaction conditions are as follows: the mol ratio of octafluorocyclobutane to hydrogen is 1:0.0008, the reaction temperature is 80 ℃, the pressure is 0.2MPa, the contact time is 5s, the treated gas is collected, and the reaction temperature is 1-C4F8、2-C4F8And C2F4The conversion rates of (a) were 98.5%, 98.3% and 98.4%, respectively. After hydrogen separation and rectification purification, 1-C in octafluorocyclobutane is detected4F8Is 0.2ppmv, 2-C4F8Is 0.4ppmv, C2F4Is 0.3 ppmv.
Comparative example 1
The alkene-containing fluorocarbon impurity (1-C)4F8：21ppmv，2-C4F8：33ppmv，C2F4: 23ppmv), octafluorocyclobutane with a purity of > 99.99%, which was purified by the same rectification method as in example 1 without being subjected to hydrogenation, and then detected as 1-C in octafluorocyclobutane4F8In an amount of 10ppmv, 2-C4F8In an amount of 21ppmv, C2F4Was present in an amount of 8 ppmv.
Claims (8)
1. Catalytic conversion octafluorocyclobutaneThe method for removing impurities in alkane is characterized in that octafluorocyclobutane containing alkene fluorocarbon impurities reacts with hydrogen under the action of a catalyst, a reaction product is collected, and the treated octafluorocyclobutane is obtained after hydrogen separation, rectification and purification1And X2The active component palladium content is 0.2-1.5 wt%, and the auxiliary agent X10.1-2.5 wt% of auxiliary agent X2The content is 0.05-0.8 wt%, wherein X1One selected from Mo, Co, Ni and Ag, X2One selected from Y, La, Sc and Ce.
2. The method of claim 1, wherein the catalyst is prepared by the steps of:
(1) active carbon pretreatment: mixing activated carbon and 2-10 wt% of nitric acid aqueous solution according to the mass ratio of 1: 3-8, uniformly stirring, treating at 60-90 ℃ for 1-4 h, washing to neutrality by using deionized water, and drying at 100-120 ℃ to obtain pretreated activated carbon for later use;
(2) preparing a catalyst precursor: will contain X1And a compound containing X2Adding the compound into distilled water, heating to 80-100 ℃, and obtaining a solution containing auxiliary components for later use after the compound is completely dissolved and cooled; dissolving a palladium-containing compound into dilute hydrochloric acid to obtain a solution containing an active component, mixing the solution containing the active component with a solution containing an auxiliary component, adjusting the pH value of the solution to 4-7, adding the pretreated activated carbon obtained in the step (1), soaking for 2-5 h in the same volume, and drying at 100-120 ℃ to obtain a catalyst precursor;
(3) reduction treatment: roasting the catalyst precursor obtained in the step (2) at the temperature of 150-300 ℃ for 4-8 h, and finally carrying out reduction treatment on the catalyst precursor by using a mixed gas of hydrogen and nitrogen at the temperature of 100-250 ℃ for 4-8 h to obtain the catalyst.
3. A catalytic converter according to claim 2The method for removing impurities in the fluorocyclobutane is characterized in that the palladium-containing compound is palladium chloride or palladium nitrate, and X is1And X2The compound of (b) is a corresponding nitrate compound or other water-soluble compound.
4. The method for catalytic conversion of impurities in octafluorocyclobutane according to claim 2, wherein the mass fraction of the dilute hydrochloric acid is 2 to 8%.
5. The method of claim 1, wherein the olefinic fluorocarbon impurity is 1-C4F8、2-C4F8And C2F4。
6. The method of claim 1, wherein the octafluorocyclobutane has an olefinic fluorocarbon impurity content of 100ppmv or less.
7. The method of claim 1, wherein the octafluorocyclobutane has a purity of > 99.99%.
8. The method of claim 1, wherein the molar ratio of octafluorocyclobutane to hydrogen is 1: 0.0005-0.01, the reaction temperature is 30-150 ℃, the pressure is 0.1-0.5 MPa, and the contact time is 0.5-20 s.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201911365565.9A CN111135842B (en) | 2019-12-26 | 2019-12-26 | Catalyst for catalytic conversion of impurities in octafluorocyclobutane, and preparation method and application thereof |
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| JP2023009764A (en) * | 2021-07-08 | 2023-01-20 | ダイキン工業株式会社 | Octafluorocyclobutane production method |
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