CN112569996B - Catalyst for preparing perhalogenated ethylene and preparation method and application thereof - Google Patents
Catalyst for preparing perhalogenated ethylene and preparation method and application thereof Download PDFInfo
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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Abstract
The invention relates to a catalyst for catalyzing and producing perhalogenated ethylene, which at least comprises nitrides and/or carbides of VIII group and/or VIB group and/or IIB group metals as catalyst active components, and the preparation method comprises the steps of (1) preparing a metal oxide precursor; step (2), temperature programming, reducing, nitriding and/or carbonizing; and (3) passivating to obtain the catalyst.
Description
Technical Field
The application relates to a catalyst and a preparation method thereof, in particular to a catalyst for preparing perhalogenated ethylene and a preparation method thereof.
Background
CTFE is an important commercial monomer in the production of fluoropolymers, and can be used for preparing a series of fluorine coatings, fluorine resins, fluorine rubbers, fluorine-chlorine lubricating oil and the like. These fluorine-containing materials have excellent chemical inertness and weather resistance, and have wide applications in the fields of advanced technologies, military aerospace, electronic industry and the like. Various methods have been used to prepare CTFE, and the existing production processes mainly include: the method comprises a trifluorotrichloroethane metal zinc powder reduction dechlorination method, a trifluorotrichloroethane catalytic hydrogenation dechlorination method, a trifluorotrichloroethane catalytic dechlorination method under the participation of ethylene and oxygen, a trifluorotrichloroethane electrochemical reduction method, a tetrafluoromonochloroethane cracking method and the like.
EP0459463A discloses the performance of a support for the preparation of chlorotrifluoroethylene by catalytic hydrogenationThe effect is that when alumina is used as the carrier, the conversion rate of the trifluorotrichloroethane is lower than 50%, and the conversion rate is compared with Pd-Hg/Al 2 O 3 The catalyst used in the former case was 1.3g, the Pd loading was 0.5% and the conversion was 54.7% and the catalyst used in the latter case was 0.6g, the Pd loading was 2% and the conversion was 63.9% of the activity of Pd-Hg/C.
US5089454 discloses that when the reaction temperature is 200-300 deg.c, the conversion rate of chlorotrifluoroethylene is over 40%, active carbon, alumina, titania and other material are used as carrier, one or several alkali metal and alkali earth metal salt are used as assistant, and VIII metal is used as active catalyst component.
CN1460549A discloses a catalyst for preparing chlorotrifluoroethylene and trifluoroethylene by catalytic hydrogenation and dechlorination of 1, 2-trifluoro-2, 1-trichloroethane, which is characterized in that noble metal palladium and metal copper are used as main active components, alkali metal lithium and rare earth metal or metal lanthanum are added as modification aids, and coconut shell activated carbon is used as a carrier; the dosage of the noble metal palladium is 0.5 to 0.4 percent of the total weight of the catalyst; the dosage of the adopted metallic copper is 1 to 12 percent of the total weight of the catalyst; the dosage of the adopted metal lithium is 0.2 to 2 percent of the total weight of the catalyst; the dosage of the rare earth metal or the metal lanthanum is 0.5 to 4 percent of the total weight of the catalyst. The conversion rate of raw materials can reach 100 percent, and the highest CTFE selectivity can reach 84.7 percent.
CN105457651A discloses a hydrodechlorination catalyst, which consists of a main catalyst, an auxiliary agent and a carrier; the main catalyst is Pd and Cu; the auxiliary agent is selected from one, two or more than three of Mg, ca, ba, co, mo, ni, sm and Ce; the main catalyst and the auxiliary agent are loaded on the activated carbon carrier. The preparation method comprises the following steps: adding activated carbon into an acid or alkali solution, carrying out water bath reflux treatment at 60-90 ℃ for 2-4 h, washing and drying; dipping or co-dipping the pretreated activated carbon step by adopting soluble salt solution of the main catalyst and the auxiliary agent under the vacuum or normal pressure condition; drying the impregnated activated carbon at the drying temperature of 90-120 ℃; and reducing the dried activated carbon to obtain the catalyst. A metal alloy phase is formed on the surface of the carrier between the first active component and the second active component, so that the activity is moderate, the product selectivity is improved, and the service life of the catalyst is prolonged. The conversion rate of the raw materials can reach 97.8%, and the highest CTFE selectivity can reach 96.2%.
CN105944734A discloses a catalyst for preparing chlorotrifluoroethylene by catalytic hydrodechlorination of trifluorotrichloroethane, which comprises a first catalyst, a second catalyst, an auxiliary agent and a carrier, wherein the first catalyst is one of cobalt or rhodium, the dosage of the first catalyst is 0.1-15% of the total mass of the catalyst, the second catalyst is one of chromium or manganese, the dosage of the second catalyst is 0.5-22% of the total mass of the catalyst, and the auxiliary agent is alkali metal potassium or rare earth metal rhenium, the dosage of the auxiliary agent is 0.1-5% of the total mass of the catalyst. The catalyst of the invention shows high activity in the reaction of preparing the chlorotrifluoroethylene by the hydrogenation and dechlorination of the trichlorotrifluoroethane, has mild reaction conditions and good operation stability, and is suitable for the process of preparing the chlorotrifluoroethylene by the hydrogenation and dechlorination of the trichlorotrifluoroethane.
These catalysts all have certain disadvantages such as consumption of expensive materials, low product yield, poor stability, etc., and the applicant has recognized that there is a continuing need in the art for further improvements in catalysts for the production of CTFE. The invention provides a catalyst with good selectivity, conversion rate and stability for producing vinyl halide (such as CTFE and the like) and a preparation method thereof.
Disclosure of Invention
The invention provides a catalyst for producing perhalogenated ethylene (such as CTFE) and a preparation method thereof, and also provides a method for producing halogenated ethylene.
The starting perhaloethane employed in the present invention is a perhaloethane corresponding to the formula:
CF a Cl b -CF d Cl f
wherein a is 0 to 3, b is 1 to 3, and a + b =3; d is 0 to 3, f is 1 to 3, and d + f =3; and b + f is 2 to 6.
Preferred perhaloethanes are 1, 2-dichlorotetrafluoroethane (fluorocarbon 114) or 1, 2-trichloro-1, 2-trifluoroethane (fluorocarbon 113), with 1, 2-trichloro-1, 2-trifluoroethane being particularly preferred.
The product is a perhaloethylene corresponding to the formula:
CF m Cl n ＝CF x Cl y
wherein m is 0 to 2, n is 0 to 2, and m + n =2; and x is 0 to 2, y is 0 to 2, and x + y =2. The preferred product is chlorotrifluoroethylene.
The catalyst for producing perhalogenated ethylene provided by the invention at least comprises the nitride and/or carbide of metal of VIII group and/or VIB group and/or IIB group as the active component of the catalyst.
Furthermore, the catalyst for producing the perhalogenated ethylene provided by the invention also comprises a carrier, and nitrides and/or carbides of VIII group and/or VIB group and/or IIB group metals are used as catalyst active components. Preferably, the content of the catalyst active component is 0.5 to 30wt%. More preferably, the content of the active component is 1 to 20wt%, or 2 to 15wt%, or 5 to 15wt%.
Preferably, the active component is a combination of at least two nitrides, a combination of at least two carbides, a combination of at least two nitrogen/carbides, a bimetal nitride or a bimetal carbide, nitrogen/carbide means a metal compound containing both a nitride and a carbide of a metal element.
Preferably, the active component is selected from at least two of cobalt nitride, molybdenum nitride, nickel nitride, zinc nitride, titanium nitride, iron nitride, and tungsten nitride.
Preferably, the active component is cobalt nitride and molybdenum nitride, or molybdenum nitride and nickel nitride, or cobalt nitride and zinc nitride, or molybdenum nitride and zinc nitride, or nickel nitride and zinc nitride, or iron nitride and tungsten nitride, or nickel nitride and molybdenum nitride, the molar ratio of the two nitrides being from 1.
Preferably, the active components are nitrogen/cobalt carbide and nitrogen/molybdenum carbide, or nitrogen/molybdenum carbide and nitrogen/nickel carbide, or nitrogen/cobalt carbide and nitrogen/zinc carbide, or nitrogen/molybdenum carbide and nitrogen/zinc carbide, or nitrogen/nickel carbide and nitrogen/zinc carbide, or nitrogen/iron carbide and nitrogen/tungsten carbide, or nitrogen/nickel carbide and nitrogen/molybdenum carbide; the two nitrogen/carbide molar ratios are 1.1 to 10, preferably 1.
Preferably, the active component is a nickel molybdenum bimetallic nitride, or a cobalt molybdenum bimetallic nitride.
Preferably, the carrier is alumina, titania, silica, molecular sieve.
The invention provides a preparation method of a catalyst for producing perhalogenated ethylene, which comprises the steps of (1) preparing a metal oxide precursor; step (2), temperature programming, reduction, nitridation and/or carbonization; and (3) passivating to obtain the catalyst.
Preferably, the step (1) is to weigh a certain amount of salt containing active metal components, roast the salt at high temperature for 2 to 6 hours in the air atmosphere, and obtain precursor metal oxide through tabletting and screening; or soaking the carrier in a first metal salt solution with a certain concentration, standing overnight at room temperature, drying at 80-160 ℃ for 2-10h in air atmosphere, roasting at air atmosphere for 2-6h, cooling, and drying to obtain the precursor metal oxide. Preferably, the second metal salt solution is impregnated after cooling and drying, and the precursor metal oxide is obtained through the same treatment mode as the first impregnation. Preferably, the calcination temperature is 400 to 800 ℃, more preferably 400 to 600 ℃.
Preferably, in the step (2), the precursor metal oxide is subjected to temperature programming reduction nitridation and/or carbonization in a vacuum heating furnace, before nitridation and/or carbonization, the vacuum pumping is performed, then nitrogen purging is performed, and then reducing gas is introduced for nitridation and/or carbonization; preferably, the temperature is raised to 300-400 ℃ at the speed of 8-15 ℃/min, and then raised to 600-800 ℃ at the final temperature of 0.3-5 ℃/min, preferably 650-750 ℃ or 700 ℃, and the temperature is kept for 2-5h at constant temperature; preferably, the nitriding and/or carbonizing is at atmospheric pressure.
In one embodiment, the reducing gas is ammonia gas, mixed gas of ammonia gas and hydrogen gas, organic amine, and mixed gas of ammonia gas and organic amine; more preferably, the reducing gas is a mixed gas of ammonia and hydrogen, and the volume ratio of the mixed gas of ammonia and hydrogen is 1.
In one embodiment, the reducing gas is one or more of ammonia, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, monopropylamine, dipropylamine, ethylenediamine, monoethanolamine, and diethanolamine; preferably, the reducing gas is one or more of ammonia, diethylamine and diethanolamine; most preferably, the reducing gas is a mixed gas of ammonia and diethylamine, and the mixing volume ratio is 1.
In one embodiment, the reducing gas is methane, ethane, propane, or a combination thereof.
Preferably, step (3) is carried out by cooling to room temperature in a reducing gas atmosphere after the nitriding and/or carbonizing are finished, and then carrying out O 2 And N 2 And (5) passivating the mixed gas. Preferably, O 2 And N 2 The volume ratio is 1; the passivation time is 5-20h.
The invention also provides application of the catalyst in preparing perhalogenated ethylene in a catalytic manner, in particular application in preparing chlorotrifluoroethylene.
The present invention also provides a process for the production of perhalogenated ethylene, which comprises dechlorinating one or more halogenated ethanes in the gas phase in the presence of a catalyst and at least one compound which will react with the chlorine from the dechlorination reaction in the presence of the catalyst in the gaseous reaction mixture.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention to these embodiments. It will be appreciated by those skilled in the art that the present invention encompasses all alternatives, modifications and equivalents as may be included within the scope of the claims.
Catalyst test conditions: CF is prepared by 2 Cl-CFCl 2 (R-113) and hydrogen mixture was fed to a reactor containing a catalyst bed (the reaction tube of the tubular reactor was used with an inner diameter of 12mm and a length of 50 cm), the contact time was 10 seconds, and the molar ratio of the feeds (R-113H 2 ) 1, temperature 500 ℃, and the exit gas from the reactor was collected and analyzed for composition. For NOTThe supported catalyst is prepared into catalyst particles of 40-60 meshes and is filled in a reaction tube.
1. Preparation of unsupported catalysts
Example 1
Weighing a certain amount of ammonium molybdate and cobalt nitrate, roasting for 4 hours at 500 ℃ in the air atmosphere, tabletting, and screening to obtain a precursor oxide. And (3) carrying out temperature programming reduction nitridation and/or carbonization on the precursor oxide in a vacuum heating furnace. Before nitriding and/or carbonizing, vacuumizing and then introducing nitrogen for purging, wherein the reducing gas is ammonia gas which is subjected to oxygen removal and dehydration through a 3A molecular sieve and calcium oxide, heating to 400 ℃ at a constant speed and normal pressure at a speed of 10 ℃/min, heating to 600 ℃ at a speed of 0.3 ℃/min, and keeping the temperature for 5 hours. Then with O at room temperature 2 And N 2 And passivating the mixed gas with the volume ratio of 1.
Examples 2 to 25
The conditions of example 1 were adjusted in terms of active ingredients and their contents, nitriding final temperature, nitriding gas, and the like, and the specific conditions are shown in table 1. Wherein the nickel source is nickel nitrate and the zinc source is zinc nitrate.
Example 26
The difference from example 1 is that the reducing gas is methane.
Comparative examples 1 to 6
Comparative example 1 differs from example 1 in that: the metal oxide catalyst is obtained without nitriding and/or carbonizing steps.
Comparative example 2 differs from comparative example 1 in that: the active components are nickel and molybdenum.
Comparative example 3 differs from comparative example 1 in that: the active components are cobalt and nickel.
Comparative example 4 differs from comparative example 1 in that: the active components are cobalt and zinc.
Comparative example 5 differs from comparative example 1 in that: the active components are molybdenum and zinc.
Comparative example 6 differs from comparative example 1 in that: the active components are nickel and zinc.
Table 1: unsupported catalyst component and test results
It can be seen that the combination of the nitrides and/or carbides of the metals such as cobalt, molybdenum, nickel, zinc and the like shows good catalytic performance for the reaction process of synthesizing CTFE from R-113.
It can be seen from the comparison of examples 1-5 that the catalysts obtained at different final nitriding temperatures have different performances, and the catalytic activity is different due to different sintering agglomeration degrees of the metal particles at different temperatures and different numbers of catalytic active sites; on the other hand, at different nitriding temperatures, the metal assumes different valence states, and the metal nitride sintered at a temperature of 700 ℃ has higher catalytic activity. It can be seen from comparing examples 3 and 6-9 that the catalyst product with better catalytic activity and selectivity can be obtained by using the combined reducing gas of organic amine, organic amine and ammonia gas, because the organic amine contains N and C elements at the same time, not only nitride but also partial carbide can be formed in the temperature programming process, and the formed nitrogen/carbide has better catalytic activity and selectivity.
2. Preparation of Supported catalysts
Example 27
Essentially as in example 1, the precursor oxide was prepared by a different method: soaking the carrier in an ammonium molybdate aqueous solution with a certain concentration according to an experimental set load amount, ageing overnight at room temperature, drying for 5h at 120 ℃ in an air atmosphere, and roasting for 4h at 500 ℃ in an air atmosphere; and then impregnating a second component of cobalt nitrate according to the same procedure to obtain a precursor oxide, thereby preparing the catalyst. Wherein the catalyst support is alumina (such as a commercially available alumina support).
Examples 28 to 52
Example 27 was adjusted in terms of the active ingredient and the content thereof, the nitriding final temperature, the nitriding gas, and the like, and specific conditions were as shown in table 2. Wherein the nickel source is nickel nitrate and the zinc source is zinc nitrate.
Example 53
The differences from example 27 are: the reducing gas is methane.
Comparative examples 7 to 12
Comparative example 7 differs from example 27 in that: the metal oxide catalyst is obtained without nitriding and/or carbonizing steps.
Comparative example 8 differs from comparative example 7 in that: the active components are nickel and molybdenum.
Comparative example 9 differs from comparative example 7 in that: the active components are cobalt and nickel.
Comparative example 10 differs from comparative example 7 in that: the active components are cobalt and zinc.
Comparative example 11 differs from comparative example 7 in that: the active components are molybdenum and zinc.
Comparative example 12 differs from comparative example 7 in that: the active components are nickel and zinc.
Table 2: supported catalyst component and test results
It can be seen that the combination of nitrides and/or carbides of metals such as cobalt, molybdenum, nickel, zinc and the like loaded on the carrier shows good catalytic performance in the reaction process of synthesizing CTFE from R-113, and the catalytic activity of the catalyst is obviously improved compared with that of a non-supported catalyst.
It can be seen from comparison of examples 27-32 that, as the content of active ingredient increases, the catalytic activity of the supported catalyst gradually increases, and there is a tendency of decreasing catalytic performance in the period of more than 20wt%, the main reason is that as the content of active ingredient increases, the active sites of the metal particles increase and then decrease, after reaching a certain content, the sintering agglomeration degree increases, the number of the catalytic active sites decreases, and the catalytic activity decreases; on the other hand, at different nitriding temperatures, the metals exhibit different valence states, and the metal nitride sintered at the temperature of 700 ℃ has higher catalytic activity. It can be seen from comparison of examples 30 and 33-36 that the catalyst product with better catalytic activity and selectivity can be obtained by using the combined reduction gas of organic amine, organic amine and ammonia gas, which reflects the same rule as that of the unsupported catalyst, but has higher catalytic activity and selectivity compared with the unsupported catalyst, because part of the carbide is formed, the dispersibility of the carbide is enhanced, and more active sites can be exposed for catalytic reaction.
All documents cited herein are incorporated by reference into this patent application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the appended claims.
Claims (6)
1. The use of a catalyst for the production of perhalogenated ethylene, characterized in that: at least comprises at least two of cobalt nitride, molybdenum nitride, nickel nitride, zinc nitride, titanium nitride, iron nitride and tungsten nitride as catalyst active components, or at least comprises nitrogen/cobalt carbide and nitrogen/molybdenum carbide, or nitrogen/cobalt carbide and nitrogen/nickel carbide, or nitrogen/cobalt carbide and nitrogen/zinc carbide, or nitrogen/molybdenum carbide and nitrogen/zinc carbide, or nitrogen/nickel carbide and nitrogen/zinc carbide, or nitrogen/iron carbide and nitrogen/tungsten carbide, or nitrogen/nickel carbide and nitrogen/molybdenum carbide as catalyst active components;
at least one raw material is 1, 2-dichlorotetrafluoroethane or 1, 2-trichloro-1, 2-trifluoroethane;
at least one product is chlorotrifluoroethylene.
2. Use according to claim 1, characterized in that: the catalyst also comprises a carrier, and the content of the active components of the catalyst is 0.5-30wt%.
3. Use according to claim 1, characterized in that: the active components are cobalt nitride and molybdenum nitride, or cobalt nitride and nickel nitride, or cobalt nitride and zinc nitride, or molybdenum nitride and zinc nitride, or nickel nitride and zinc nitride, or iron nitride and tungsten nitride, or nickel nitride and molybdenum nitride, and the molar ratio of the two nitrides is 1.
4. Use according to claim 1, characterized in that: the molar ratio of the two nitrogen/carbides is 1.1-10.
5. Use according to any one of claims 1 to 4, characterized in that: the preparation method of the catalyst comprises the steps of (1) preparing a metal oxide precursor; step (2), temperature programming, reduction, nitridation and/or carbonization; and (3) passivating to obtain the catalyst.
6. Use according to any one of claims 1 to 4, for the preparation of chlorotrifluoroethylene.
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| CN115364888B (en) * | 2022-10-25 | 2022-12-30 | 山东华夏神舟新材料有限公司 | Supported hydrodechlorination catalyst, preparation method and application thereof, and method for preparing chlorotrifluoroethylene by using catalyst |
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