CN114620705A - Method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide - Google Patents
Method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide Download PDFInfo
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Abstract
The application relates to a method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide, which belongs to the technical field of carbonyl fluoride synthesis methods and comprises the following steps: s1, activating the catalyst, and dehydrating and activating the catalyst by using inert gas to obtain an activated catalyst; and S2, catalytic cracking, namely introducing hexafluoropropylene oxide and oxygen into a reaction container, and performing cracking reaction under the catalysis of the activated catalyst obtained in the step S1 to obtain carbonyl fluoride. This application adopts hexafluoropropylene oxide to carry out catalysis copyrolysis as raw materials and oxygen for the first time and prepares carbonyl fluoride, and the carbonyl fluoride of preparation has higher purity, and hexafluoropropylene oxide's utilization ratio is higher simultaneously.
Description
Technical Field
The application relates to the field of carbonyl fluoride synthesis technology, in particular to a method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide.
Background
Carbonyl fluoride (COF)2) Is an irritant, non-flammable, colorless, and toxic gas. As a cleaning and etching material of a new-generation industrial semiconductor device, carbonyl fluoride has extremely low global warming potential (GWP ≈ 1), extremely low ozone depletion potential (ODP ═ 0) and extremely low atmospheric lifetime (< 1a), and is an environment-friendly electronic gas. Carbonyl fluoride has certain advantages over nitrogen trifluoride in the aspects of process performance, environmental protection performance, tail gas treatment and carbon emission cost. Research on physicochemical properties, operational properties and biological activity of carbonyl fluoride has been conducted in nearly ten years by the research and development institution of new energy industry and technology and the research and development institution of global environment industry and technology of the japan industrial technology research institute, and it was confirmed that carbonyl fluoride is a promising substitute for gases such as nitrogen trifluoride.
Carbonyl fluoride as an etching gas and a cleaning gas for a Chemical Vapor Deposition (CVD) chamber in the manufacture of a new generation semiconductor industry has very low Global Warming Potential (GWP) compared with the traditional nitrogen trifluoride, and simultaneously, the cleaning performance of the carbonyl fluoride is excellent and the cleaning effect is not inferior to that of perfluorocarbon and nitrogen trifluoride. The carbonyl fluoride and water are reacted and decomposed into carbon dioxide which can be rapidly decomposed in the atmosphere, so that the use of the carbonyl fluoride can greatly reduce the equipment investment and energy consumption in the manufacture of the semiconductor industry, and has wide development potential.
Currently, production processes of carbonyl fluoride mainly include 1) a method of direct electrolytic fluorination of carbon monoxide, carbon dioxide, and trifluoromethane (japanese patent laid-open No. 2003-267712), but this reaction has many problems such as risk of explosion, many side reactions, low reaction yield of carbonyl fluoride, and severe heat generation; 2) the tetrafluoroethylene oxygen oxidation method has the same huge dangers, the activity of the tetrafluoroethylene is extremely high, the over-oxidation and even explosion dangers are easy to happen, the over-oxidation by-products are very complex, the separation of the products is very difficult, and the yield and the purity of the reaction are low.
In addition, chinese patent application publication No. CN102260160A discloses a method for preparing carbonyl fluoride and acetyl fluoride from hexafluoropropylene and oxygen as raw materials and silver oxide as a catalyst, wherein the ratio of carbonyl fluoride to acetyl fluoride is close to 1: 1. the chinese patent application with publication number CN106986757A discloses a method for oxidative cracking of symmetric perfluoro-2-butene into acetyl fluoride using silver oxide, molybdenum oxide and nickel oxide as catalysts.
In general, COF is relevant at home and abroad2The industrial production reports of (A) are few, most of the methods are applied to the field of organic synthesis, the purity of the organic compound is low, the requirement of electronic products on the purity is difficult to meet, and meanwhile, the methods cannot realize the complete utilization of raw materials. Therefore, the research is suitable for industrial production of COF2The new synthesis and purification technology of (1) realizes high-purity COF2The large-scale industrialized production is a technical difficulty to be solved at present.
Disclosure of Invention
In order to solve the problems that the purity of the conventional carbonyl fluoride synthesis process is low and the industrial production is not easy to realize, the application provides a method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide.
The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide adopts the following technical scheme:
the method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide comprises the following steps:
s1, activating the catalyst, and performing water removal and activation on the catalyst by using inert gas to obtain an activated catalyst;
and S2, catalytic cracking, namely introducing hexafluoropropylene oxide and oxygen into a reaction container, and performing cracking reaction under the catalysis of the activated catalyst obtained in the step S1 to obtain carbonyl fluoride.
Through adopting above-mentioned technical scheme, this application adopts hexafluoropropylene oxide to carry out catalytic cocracking with oxygen as raw materials for the first time and prepares carbonyl fluoride, because hexafluoropropylene oxide's epoxy bond is more active, consequently can just be opened under comparatively mild condition, produces carbonyl fluoride and acetyl fluoride. Because carbonyl on the acetyl fluoride is more active and is easier to crack into carbonyl fluoride, the carbonyl fluoride prepared by the method has higher purity, and the utilization rate of hexafluoropropylene oxide is higher. Meanwhile, the reaction is a weight increasing reaction and has higher atom utilization efficiency.
The inert gas may be conventionally selected from nitrogen, neon, helium, argon, and the like.
Optionally, in the step S1, the temperature for water removal activation is 280-.
Optionally, in step S1, the temperature for water removal activation is 300 ℃.
By adopting the technical scheme, the main purposes of dewatering and activating are to remove moisture adsorbed on the surface of the catalyst in the air and hydrolyze hydroxyl. If the temperature for dewatering activation is too low, the hydrolyzed hydroxyl on the surface of the catalyst is not easy to desorb; if the temperature for water removal activation is too high, the catalyst is easy to sinter and lose efficacy. Setting the temperature for water removal activation to 300 ℃ enables more efficient removal of water and hydrolyzed hydroxyl groups on the catalyst surface.
Optionally, in step S1, the water removal activation time is 1.5-2.5 h.
Optionally, in step S1, the water removal activation time is 2 h.
By adopting the technical scheme, when the dewatering activation time is too short, the hydrolyzed hydroxyl on the surface of the catalyst is not easy to desorb, and when the dewatering activation time is too long, the water and the surface hydroxyl on the surface of the catalyst are basically desorbed, so that the significance of continuous dewatering activation is not large, and the cost is increased. The time for water removal activation is limited to 2h, so that the production cost can be controlled on the basis of ensuring the water removal activation effect of the catalyst.
Optionally, in the step S2, the feeding volume ratio of hexafluoropropylene oxide to oxygen is 1 (2-10).
By adopting the technical scheme, the mechanism of the scheme is that oxygen is activated into oxygen free radicals through oxygen vacancies and lattice oxygen in the catalyst, and the oxygen free radicals further participate in the reaction. The volume ratio of the hexafluoropropylene oxide to the oxygen is controlled, so that the hexafluoropropylene oxide is easier to decompose, and the utilization rate of raw materials and the purity of a product are improved.
Optionally, in the step S2, the space velocity of hexafluoropropylene oxide is 20h-1～120h-1。
Optionally, in the step S2, the space velocity of hexafluoropropylene oxide is 30h-1～60h-1。
By adopting the technical scheme, the catalytic cracking condition of the hexafluoropropylene oxide is related to the feeding volume ratio of the hexafluoropropylene oxide to the oxygen, so that the airspeed of the hexafluoropropylene oxide needs to be correspondingly adjusted according to the feeding volume ratio of the hexafluoropropylene oxide to the oxygen.
Optionally, in the step S2, the temperature of the cracking reaction is 300-.
By adopting the technical scheme, the temperature of the cracking reaction needs to be strictly controlled, and if the temperature of the cracking reaction is too low, the reaction process is easy to slow or even impossible; if the temperature of the cracking reaction is too high, excessive decomposition of hexafluoropropylene oxide is easily caused, so that the purity of the final product carbonyl fluoride is reduced.
Optionally, the catalyst is a bimetal oxyfluoride, and the first metal of the catalyst is one of Fe, Co and Ni in the VIII subgroup metals; the second metal of the catalyst is one of La, Sm and Ce in rare earth metals.
By adopting the technical scheme, the adopted bimetallic oxyfluoride catalyst is specially adopted, the selected metals are two, the first metal is Fe, Co and Ni in VIII subgroup metals, and the second metal is one of La, Sm and Ce in rare earth metals. The VIII subgroup metal can provide Lewis acid sites with proper acid strength and proper acid amount, can effectively activate C-C bonds, and simultaneously, the Fe, Co and Ni metals have the characteristic of changeable valence states, so that certain fluorine vacancies or oxygen vacancies are easily generated. The rare earth metals La, Sm and Ce not only have changeable valence, but also have a large amount of lattice oxygen in oxyfluoride, and can effectively activate O2The molecule generates a large amount of oxygen free radicals, thereby efficiently catalyzing the hexafluoropropylene oxide. And the bimetallic oxyfluoride catalyst can stably exist in an acyl fluoride atmosphere, so that the stable catalytic activity is maintained. Belong to the same or twoThe metal oxyfluoride catalyst has improved corrosion resistance due to intermetallic lattice doping, and the lattice doping can generate more fluorine defects and oxygen defects and bring more Lewis acid sites and lattice free oxygen.
Optionally, in the catalyst, the molar ratio of the first metal to the second metal is 1: (0.2-1).
By adopting the technical scheme, the molar ratio of the first metal to the second metal needs to be strictly controlled, because different metal proportions can cause different degrees of lattice doping between two metal oxyfluorides, so that different degrees of oxygen vacancies and fluorine vacancies are brought, and different catalytic activities are brought.
Optionally, the precursors of the first metal and the second metal in the catalyst are both nitrates.
By adopting the technical scheme, the nitrate is used as the precursor because the nitrate does not introduce impurity ions, and meanwhile, the nitric acid is strong acid and is not easy to hydrolyze, so that the precipitation is more thorough.
Optionally, the fluorine source used in the preparation of the catalyst is 25% HF/N2And (4) mixing the gases.
By adopting the technical scheme, the selection of the fluorine source is very important when the bimetallic oxyfluoride catalyst is prepared, and the common fluorine source comprises pure HF and CHF3And CHF2Cl and the like, if pure HF is selected as a fluorine source, the fluorination capability of the pure HF is too strong, so that the surface of the catalyst is easy to generate violent structure rephotography, and the complete fluorination of the catalyst is caused. If CHF is selected3And CHF2Since the cracking temperature of the organic fluorine source such as Cl is higher than 300 ℃, the organic fluorine source is easily carbonized at high temperature, so that the surface carbon deposition of the catalyst is ineffective.
Optionally, the preparation process of the catalyst comprises the following steps:
a1, dissolving, namely dissolving a first metal nitrate and a second metal nitrate in water, then adding sodium hydroxide, and obtaining a cured product through precipitation, aging, suction filtration and water washing;
a2, roasting, namely roasting the condensate obtained in the step A1 to obtain a bimetallic oxide;
and A3, fluorination, namely placing the bimetal oxide obtained in the step A2 in a fluorine source for fluorination treatment to obtain the bimetal oxyfluoride catalyst.
Optionally, the step a3 specifically includes the following steps:
a31, primary fluorination, heating the system to the temperature of 280-320 ℃, and carrying out fluorination treatment for 110-130min to obtain primary fluoride;
a32, two-stage fluorination, further heating the system to 360-400 ℃, and carrying out fluorination treatment for 50-70min to obtain the bimetallic oxyfluoride catalyst;
by adopting the technical scheme, the existing common fluorination process is a one-section fluorination process for carrying out fluorination reaction at a higher temperature (if the fluorination treatment is only carried out at a low temperature, the fluorination degree is not enough, and the catalytic effect is poor). However, the inventor finds that the catalyst prepared by the special low-temperature one-stage fluorination and high-temperature two-stage fluorination processes has obviously better catalytic performance compared with the one-stage fluorination process. This is probably because, the fluorination process in one stage is directly performed at high temperature, the fluorination reaction is too violent, and the violent fluorination reaction easily causes violent structural rearrangement on the surface of the catalyst and even leads to complete fluorination of the catalyst.
Optionally, the temperature rise rate in step A31 and step A32 is 1.8-2.2 ℃/min.
By adopting the technical scheme, similarly, if the temperature rise speed is too high, the reaction process is easy to be too violent, and the violent fluorination reaction is easy to cause violent structural rearrangement on the surface of the catalyst, even the catalyst is completely fluorinated.
In summary, the present application includes at least one of the following beneficial technical effects:
1. according to the method, hexafluoropropylene oxide is used as a raw material to carry out catalytic co-cracking with oxygen for the first time to prepare carbonyl fluoride, and epoxy bonds of hexafluoropropylene oxide are more active, so that the carbonyl fluoride and acetyl fluoride can be opened under a relatively mild condition to generate the carbonyl fluoride and the acetyl fluoride, and the industrial production is easy to realize; the reactive carbonyl group on acetyl fluoride enables further cleavage of acetyl fluoride into carbonyl fluoride, and therefore the carbonyl fluoride finally obtained has higher purity.
2. The application specifically adopts a bimetallic oxyfluoride catalyst, and VIII subgroup metals not only can provide Lewis acid sites for activating C-C bonds, but also can generate certain fluorine vacancies or oxygen vacancies; the oxyfluoride of the rare earth metal elements has a large amount of lattice oxygen and can effectively activate O2The molecule generates a large amount of oxygen free radicals, thereby efficiently catalyzing the hexafluoropropylene oxide.
3. By limiting two kinds of metals in the bimetallic oxyfluoride catalyst, the bimetallic oxyfluoride catalyst can generate intermetallic lattice doping, the corrosion resistance of the catalyst is enhanced, and the stability of the catalyst in an acyl fluoride atmosphere is improved; in addition, more fluorine defects and oxygen defects can be generated by lattice doping, more Lewis acid sites and lattice free oxygen can be brought, and the catalytic effect is improved.
4. According to the method, hexafluoropropylene oxide and oxygen are cracked into high-purity carbonyl fluoride in one step under mild conditions, and meanwhile, the catalyst is low in preparation cost, easy to produce in an enlarged mode and beneficial to implementation of subsequent industrialization; meanwhile, the requirement on equipment of a fixed bed reactor required by catalysis is low, and the reaction cost is greatly reduced, so that the process is a green and environment-friendly process route.
Detailed Description
The present application will be described in further detail with reference to examples.
The embodiment of the application discloses a method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide.
Example 1
The preparation method of the catalyst comprises the following steps:
a1, dissolving, weighing 40.4g of ferric nitrate nonahydrate and 43.4g of cerous nitrate hexahydrate, dissolving in 1000mL of deionized water, adding 40g of sodium hydroxide after completely stirring and dissolving, continuing stirring, and then precipitating, aging, filtering, and washing to obtain a cured product.
And A2, roasting, namely taking the condensate obtained in the step A1, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ in a muffle furnace for 4 hours to obtain FeCo bimetallic oxide.
A3, fluorination, namely taking FeCo bimetal oxide in the step A2 for two-stage fluorination, and specifically comprising the following process steps:
a31, first-stage fluorination, and adding FeFe bimetal oxide in 25% HF/N2In the mixed gas, raising the temperature to 300 ℃ at room temperature for fluorination treatment for 2h, wherein the temperature raising speed is 2 ℃/min, and obtaining a section of fluoride;
a32, secondary fluorination, further heating the system from 300 ℃ to 380 ℃ for fluorination treatment for 1h at the heating speed of 2 ℃/min to obtain secondary fluoride; and tabletting and granulating the second-stage fluoride, and taking particles with the particle size of 0.3-0.7mm to obtain the bimetallic oxyfluoride catalyst.
The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide comprises the following steps:
s1, activating the catalyst, namely, filling 10ml of the FeFe bimetallic oxyfluoride catalyst prepared in the previous step into a fixed bed reactor with a GC online detection system, introducing 10ml/min inert gas nitrogen, heating to 300 ℃, and performing water removal and activation treatment for 2h to obtain the activated catalyst.
S2, catalytic cracking, namely heating the temperature to 350 ℃, closing nitrogen, and introducing a mixed gas of hexafluoropropylene oxide and oxygen, wherein the gas volume ratio of the hexafluoropropylene oxide to the oxygen is 1:2, and the flow rate of the hexafluoropropylene oxide is 10ml/min (the space velocity is 60 h)-1). The reaction is carried out under normal pressure, and GC on-line detection shows that the conversion rate of hexafluoropropylene oxide is 96.1%, and the selectivity of the target product carbonyl fluoride is 99.1%.
The bimetallic oxyfluoride catalyst keeps stable catalytic performance after 30 hours, namely the conversion rate of reactants and the selectivity of a target product are basically unchanged.
Example 2
Example 2 differs from example 1 mainly in that the catalyst was a NiLa bimetallic oxyfluoride catalyst.
Namely the preparation of the catalyst, specifically comprises the following steps:
a1, dissolving, weighing 29.1g of nickel nitrate hexahydrate and 43.3g of lanthanum nitrate hexahydrate, dissolving in 1000mL of deionized water, adding 40g of sodium hydroxide after completely stirring and dissolving, continuing stirring, and then precipitating, aging, filtering, and washing to obtain a cured product.
And A2, roasting, namely taking the condensate obtained in the step A1, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ in a muffle furnace for 4 hours to obtain the NiLa bimetallic oxide.
A3, fluorination, namely carrying out two-stage fluorination on the NiLa bimetallic oxide obtained in the step A2, and specifically comprising the following process steps:
a31, first-stage fluorination, and reaction of NiLa bimetal oxide in 25% HF/N2In the mixed gas, raising the temperature to 300 ℃ at room temperature for fluorination treatment for 2h, wherein the temperature raising speed is 2 ℃/min, and obtaining a section of fluoride;
a32, secondary fluorination, further heating the system from 300 ℃ to 380 ℃ for fluorination treatment for 1h at the heating speed of 2 ℃/min to obtain secondary fluoride; and tabletting and granulating the second-stage fluoride, and taking particles with the particle size of 0.3-0.7mm to obtain the bimetallic oxyfluoride catalyst.
The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide comprises the following steps:
s1, activating the catalyst, namely, filling 20ml of the prepared NiLa bimetal oxyfluoride catalyst into a fixed bed reactor with a GC online detection system, introducing 10ml/min inert gas nitrogen, heating to 300 ℃, removing water, and activating for 2h to obtain the activated catalyst.
S2, catalytic cracking, namely heating the temperature to 450 ℃, closing nitrogen, and introducing a mixed gas of hexafluoropropylene oxide and oxygen, wherein the gas volume ratio of the hexafluoropropylene oxide to the oxygen is 1:2, and the flow rate of the hexafluoropropylene oxide is 10ml/min (the space velocity is 30 h)-1). The reaction is carried out under normal pressure, GC on-line detection shows that the conversion rate of hexafluoropropylene oxide is 99.1%, and the selectivity of the target product carbonyl fluoride is 99.3%.
The bimetallic oxyfluoride catalyst keeps stable catalytic performance after 25 hours, namely the conversion rate of reactants and the selectivity of target products are basically unchanged.
Example 3
Example 3 differs from example 1 mainly in that the catalyst is a CoSm bimetallic oxyfluoride catalyst.
Namely the preparation of the catalyst, specifically comprises the following steps:
a1, dissolving, weighing 29.1g of cobalt nitrate hexahydrate and 44.5g of samarium nitrate hexahydrate, dissolving in 1000mL of deionized water, adding 40g of sodium hydroxide after completely stirring and dissolving, continuing stirring, and then precipitating, aging, filtering, and washing to obtain a cured product.
A2, roasting, namely taking the condensate obtained in the step A1, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ in a muffle furnace for 4 hours to obtain the CoSm bimetal oxide.
A3, fluorination, namely carrying out two-stage fluorination on the CoSm bimetal oxide in the step A2, and specifically comprising the following process steps:
a31, first-stage fluorination, and reaction of CoSm double metal oxide in 25% HF/N2In the mixed gas, raising the temperature to 300 ℃ at room temperature for fluorination treatment for 2h, wherein the temperature raising speed is 2 ℃/min, and obtaining a section of fluoride;
a32, performing second-stage fluorination, and further heating the system from 300 ℃ to 380 ℃ for fluorination treatment for 1h at the heating speed of 2 ℃/min to obtain a second-stage fluoride; and tabletting and granulating the second-stage fluoride, and taking particles with the particle size of 0.3-0.7mm to obtain the bimetallic oxyfluoride catalyst.
The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide comprises the following steps:
s1, activating the catalyst, namely, filling 20ml of the prepared CoSm bimetal oxyfluoride catalyst into a fixed bed reactor with a GC (gas chromatography) online detection system, introducing 10ml/min inert gas nitrogen, heating to 300 ℃, and performing water removal and activation treatment for 2h to obtain the activated catalyst.
S2, catalytic cracking, namely heating the temperature to 350 ℃, closing nitrogen and introducing a mixed gas of hexafluoropropylene oxide and oxygen, wherein the gas volume ratio of hexafluoropropylene oxide to oxygen is 1:2, and the flow rate of hexafluoropropylene oxide is 10ml/min (the space velocity is 30 h)-1). The reaction is carried out under normal pressure, GC on-line detection shows that the conversion rate of hexafluoropropylene oxide is 98.9%, and the selectivity of the target product carbonyl fluoride is 99.4%.
The bimetallic oxyfluoride catalyst keeps stable catalytic performance after 38 hours, namely the conversion rate of reactants and the selectivity of target products are basically unchanged.
Example 4
Example 4 differs from example 1 mainly in that the catalyst is a FeLa bimetallic oxyfluoride catalyst.
Namely the preparation of the catalyst, specifically comprises the following steps:
a1, dissolving, weighing 40.4g of ferric nitrate nonahydrate and 21.6g of lanthanum nitrate hexahydrate, dissolving in 1000mL of deionized water, adding 40g of sodium hydroxide after completely stirring and dissolving, continuing stirring, and then precipitating, aging, filtering, and washing to obtain a cured product.
And A2, roasting, namely taking the condensate obtained in the step A1, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ in a muffle furnace for 4 hours to obtain the FeLa bimetallic oxide.
A3, fluorination, namely, carrying out two-stage fluorination on the FeLa bimetal oxide in the step A2, and specifically comprising the following process steps:
a31, first-stage fluorination, namely, putting FeLa bimetallic oxide in 25 percent of HF/N2In the mixed gas, raising the temperature to 300 ℃ at room temperature for fluorination treatment for 2h, wherein the temperature raising speed is 2 ℃/min, and obtaining a section of fluoride;
a32, secondary fluorination, further heating the system from 300 ℃ to 380 ℃ for fluorination treatment for 1h at the heating speed of 2 ℃/min to obtain secondary fluoride; and tabletting and granulating the second-stage fluoride, and taking particles with the particle size of 0.3-0.7mm to obtain the bimetallic oxyfluoride catalyst.
The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide comprises the following steps:
s1, activating the catalyst, namely, filling 5ml of the prepared FeLa bimetal oxyfluoride catalyst into a fixed bed reactor with a GC online detection system, introducing 10ml/min inert gas nitrogen, heating to 300 ℃, removing water, and activating for 2h to obtain the activated catalyst.
S2, catalytic cracking, keeping the temperature at 300 ℃, closing nitrogen, and introducing a mixed gas of hexafluoropropylene oxide and oxygen, wherein the gas volume ratio of hexafluoropropylene oxide to oxygen is 1:5, and the hexafluoropropylene oxide isThe flow rate of propane was 10ml/min (space velocity 120 h)-1). The reaction is carried out under normal pressure, GC on-line detection shows that the conversion rate of hexafluoropropylene oxide is 95.7%, and the selectivity of the target product carbonyl fluoride is 99.3%.
The bimetallic oxyfluoride catalyst keeps stable catalytic performance after 20 hours, namely the conversion rate of reactants and the selectivity of target products are basically unchanged.
Example 5
Example 5 differs from example 1 mainly in that the catalyst was a NiSm bimetallic oxyfluoride catalyst.
Namely the preparation of the catalyst, specifically comprises the following steps:
a1, dissolving, weighing 29.1g of nickel nitrate hexahydrate and 22.2g of samarium nitrate hexahydrate, dissolving in 1000mL of deionized water, adding 40g of sodium hydroxide after completely stirring and dissolving, continuing stirring, and then precipitating, aging, filtering, and washing to obtain a cured product.
A2, roasting, namely taking the condensate obtained in the step A1, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ in a muffle furnace for 4 hours to obtain the NiSm bimetal oxide.
A3, fluorination, namely carrying out two-stage fluorination on the NiSm bimetal oxide obtained in the step A2, and specifically comprising the following process steps:
a31, first-stage fluorination, namely, putting NiSm double metal oxide in 25 percent of HF/N2In the mixed gas, raising the temperature to 300 ℃ at room temperature for fluorination treatment for 2h, wherein the temperature raising speed is 2 ℃/min, and obtaining a section of fluoride;
a32, secondary fluorination, further heating the system from 300 ℃ to 380 ℃ for fluorination treatment for 1h at the heating speed of 2 ℃/min to obtain secondary fluoride; and tabletting and granulating the second-stage fluoride, and taking particles with the particle size of 0.3-0.7mm to obtain the bimetal oxyfluoride catalyst.
The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide comprises the following steps:
s1, activating the catalyst, namely, filling 5ml of the NiSm bimetal oxyfluoride catalyst prepared in the previous step into a fixed bed reactor with a GC online detection system, introducing 10ml/min inert gas nitrogen, heating to 300 ℃, and performing water removal and activation treatment for 2h to obtain the activated catalyst.
S2, catalytic cracking, namely heating the temperature to 350 ℃, closing nitrogen, and introducing a mixed gas of hexafluoropropylene oxide and oxygen, wherein the gas volume ratio of the hexafluoropropylene oxide to the oxygen is 1:4, and the flow rate of the hexafluoropropylene oxide is 10ml/min (the space velocity is 120 h)-1). The reaction is carried out under normal pressure, GC on-line detection shows that the conversion rate of hexafluoropropylene oxide is 98.1%, and the selectivity of the target product carbonyl fluoride is 99.6%.
The bimetallic oxyfluoride catalyst keeps stable catalytic performance after 20 hours, namely the conversion rate of reactants and the selectivity of a target product are basically unchanged.
Example 6
Example 6 differs from example 1 mainly in that the catalyst is a CoCe bimetallic oxyfluoride catalyst.
Namely the preparation of the catalyst, specifically comprises the following steps:
a1, dissolving, weighing 29.1g of cobalt nitrate hexahydrate and 21.7g of cerous nitrate hexahydrate, dissolving in 1000mL of deionized water, adding 40g of sodium hydroxide after completely stirring and dissolving, continuing stirring, and then precipitating, aging, filtering, and washing to obtain a cured product.
And A2, roasting, namely taking the condensate obtained in the step A1, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ in a muffle furnace for 4 hours to obtain the CoCe bimetal oxide.
A3, fluorination, namely, two-stage fluorination is carried out on the CoCe bimetal oxide in the step A2, and the method specifically comprises the following process steps:
a31, first-stage fluorination, and reaction of CoCe double-metal oxide in 25% HF/N2In the mixed gas, raising the temperature to 300 ℃ at room temperature for fluorination treatment for 2h, wherein the temperature raising speed is 2 ℃/min, and obtaining a section of fluoride;
a32, secondary fluorination, further heating the system from 300 ℃ to 380 ℃ for fluorination treatment for 1h at the heating speed of 2 ℃/min to obtain secondary fluoride; and tabletting and granulating the second-stage fluoride, and taking particles with the particle size of 0.3-0.7mm to obtain the bimetallic oxyfluoride catalyst.
The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide comprises the following steps:
s1, activating the catalyst, namely, filling 20ml of the prepared CoCe bimetal oxyfluoride catalyst into a fixed bed reactor with a GC (gas chromatography) online detection system, introducing 10ml/min of inert gas nitrogen, heating to 300 ℃, and performing water removal and activation treatment for 2h to obtain the activated catalyst.
S2, catalytic cracking, namely heating the temperature to 400 ℃, closing nitrogen and introducing a mixed gas of hexafluoropropylene oxide and oxygen, wherein the gas volume ratio of hexafluoropropylene oxide to oxygen is 1:10, and the flow rate of hexafluoropropylene oxide is 10ml/min (the space velocity is 30 h)-1). The reaction is carried out under normal pressure, GC on-line detection shows that the conversion rate of hexafluoropropylene oxide is 99.2%, and the selectivity of the target product carbonyl fluoride is 99.1%.
The bimetallic oxyfluoride catalyst keeps stable catalytic performance after 37h, namely the conversion rate of reactants and the selectivity of target products are basically unchanged.
Example 7
Example 7 differs from example 1 mainly in that the catalyst is a NiFe bimetallic oxyfluoride catalyst.
Namely the preparation of the catalyst, specifically comprises the following steps:
a1, dissolving, weighing 29.1g of nickel nitrate hexahydrate and 8.7g of cerous nitrate hexahydrate, dissolving in 1000mL of deionized water, adding 40g of sodium hydroxide after completely stirring and dissolving, continuing stirring, and then precipitating, aging, filtering, and washing to obtain a cured product.
And A2, roasting, namely taking the condensate obtained in the step A1, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ in a muffle furnace for 4 hours to obtain the NiCo bimetal oxide.
A3, fluorination, namely, taking NiCo bimetal oxide in the step A2 for two-stage fluorination, and specifically comprising the following process steps:
a31, first-stage fluorination, and placing NiCo bimetal oxide in 25% HF/N2In the mixed gas, raising the temperature to 300 ℃ at room temperature for fluorination treatment for 2h, wherein the temperature raising speed is 2 ℃/min, and obtaining a section of fluoride;
a32, secondary fluorination, further heating the system from 300 ℃ to 380 ℃ for fluorination treatment for 1h at the heating speed of 2 ℃/min to obtain secondary fluoride; and tabletting and granulating the second-stage fluoride, and taking particles with the particle size of 0.3-0.7mm to obtain the bimetal oxyfluoride catalyst.
The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide comprises the following steps:
s1, activating the catalyst, namely, filling 30ml of the NiCo bimetallic oxyfluoride catalyst prepared in the previous step into a fixed bed reactor with a GC on-line detection system, introducing 10ml/min of inert gas nitrogen, heating to 300 ℃, and performing water removal and activation treatment for 2h to obtain the activated catalyst.
S2, catalytic cracking, namely heating the temperature to 450 ℃, closing nitrogen, and introducing a mixed gas of hexafluoropropylene oxide and oxygen, wherein the gas volume ratio of the hexafluoropropylene oxide to the oxygen is 1:10, and the flow rate of the hexafluoropropylene oxide is 10ml/min (the space velocity is 20 h)-1). The reaction is carried out under normal pressure, GC on-line detection shows that the conversion rate of hexafluoropropylene oxide is 96.7%, and the selectivity of the target product carbonyl fluoride is 99.2%.
The bimetallic oxyfluoride catalyst keeps stable catalytic performance after 35 hours, namely the conversion rate of reactants and the selectivity of a target product are basically unchanged.
Example 8
Example 8 differs from example 1 primarily in that the catalyst is a FeSm bimetallic oxyfluoride catalyst.
Namely the preparation of the catalyst, specifically comprises the following steps:
a1, dissolving, weighing 40.4g of ferric nitrate nonahydrate and 8.9g of samarium nitrate hexahydrate, dissolving in 1000mL of deionized water, adding 40g of sodium hydroxide after completely stirring and dissolving, continuing stirring, and then precipitating, aging, filtering, and washing to obtain a cured product.
And A2, roasting, namely taking the condensate obtained in the step A1, drying at 120 ℃ for 12 hours, and roasting at 400 ℃ in a muffle furnace for 4 hours to obtain the FeSm bimetal oxide.
A3, fluorination, namely carrying out two-stage fluorination on the FeSm bimetal oxide obtained in the step A2, and specifically comprising the following process steps:
a31, first-stage fluorination, namely, adding FeSm double metal oxide into 25 percent HF/N2In the mixed gas, inRaising the temperature to 300 ℃ at room temperature for fluorination treatment for 2h, wherein the temperature raising speed is 2 ℃/min, and obtaining a section of fluoride;
a32, secondary fluorination, further heating the system from 300 ℃ to 380 ℃ for fluorination treatment for 1h at the heating speed of 2 ℃/min to obtain secondary fluoride; and tabletting and granulating the second-stage fluoride, and taking particles with the particle size of 0.3-0.7mm to obtain the bimetallic oxyfluoride catalyst.
The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide comprises the following steps:
s1, activating the catalyst, namely filling 10ml of the prepared FeSm bimetal oxyfluoride catalyst into a fixed bed reactor with a GC (gas chromatography) online detection system, introducing 10ml/min inert gas nitrogen, heating to 300 ℃, and performing water removal and activation treatment for 2h to obtain the activated catalyst.
S2, catalytic cracking, namely heating the temperature to 400 ℃, closing nitrogen, and introducing a mixed gas of hexafluoropropylene oxide and oxygen, wherein the gas volume ratio of the hexafluoropropylene oxide to the oxygen is 1:8, and the flow rate of the hexafluoropropylene oxide is 10ml/min (the space velocity is 60 h)-1). The reaction is carried out under normal pressure, GC on-line detection shows that the conversion rate of hexafluoropropylene oxide is 98.3%, and the selectivity of the target product carbonyl fluoride is 99.7%.
The bimetallic oxyfluoride catalyst keeps stable catalytic performance after 32 hours, namely the conversion rate of reactants and the selectivity of target products are basically unchanged.
The above embodiments are preferred embodiments of the present application, and the protection scope of the present application is not limited by the above embodiments, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (10)
1. A method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide is characterized by comprising the following steps: the method comprises the following steps:
s1, activating the catalyst, and dehydrating and activating the catalyst by using inert gas to obtain an activated catalyst;
and S2, catalytic cracking, namely introducing hexafluoropropylene oxide and oxygen into a reaction container, and performing cracking reaction under the catalysis of the activated catalyst obtained in the step S1 to obtain carbonyl fluoride.
2. The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide according to claim 1, wherein: in the step S1, the temperature for water removal activation is 280-320 ℃; and/or in the step S1, the water removal activation time is 1.5-2.5 h.
3. The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide according to claim 1, wherein: in the step S2, the feeding volume ratio of hexafluoropropylene oxide to oxygen is 1 (2-10); and/or in the step S2, the space velocity of the hexafluoropropylene oxide is 20h-1～120h-1。
4. The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide according to claim 3, wherein: in the step S2, the temperature of the cracking reaction is 300-450 ℃.
5. The process for producing high purity carbonyl fluoride from hexafluoropropylene oxide according to any one of claims 1-4, wherein: the catalyst is bimetal oxyfluoride, and the first metal of the catalyst is one of Fe, Co and Ni in VIII subgroup metals; the second metal of the catalyst is one of La, Sm and Ce in rare earth metals.
6. The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide according to claim 5, wherein: in the catalyst, the molar ratio of the first metal to the second metal is 1: (0.2-1).
7. The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide according to claim 6, wherein: precursors of the first metal and the second metal in the catalyst are nitrates; and/or the fluorine source used in the preparation of the catalyst is 25% HF/N2And (4) mixing the gases.
8. The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide according to claim 7, wherein: the preparation process of the catalyst comprises the following steps:
a1, dissolving, namely dissolving a first metal nitrate and a second metal nitrate in water, then adding sodium hydroxide, and obtaining a cured product through precipitation, aging, suction filtration and water washing;
a2, roasting, namely roasting the condensate obtained in the step A1 to obtain a bimetallic oxide;
and A3, fluorination, namely placing the bimetal oxide obtained in the step A2 in a fluorine source for fluorination treatment to obtain the bimetal oxyfluoride catalyst.
9. The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide according to claim 8, wherein: the step a3 specifically includes the following steps:
a31, primary fluorination, heating the system to the temperature of 280-320 ℃, and carrying out fluorination treatment for 110-130min to obtain primary fluoride;
a32, two-stage fluorination, further heating the system to 360-400 ℃, and carrying out fluorination treatment for 50-70min to obtain the bimetallic oxyfluoride catalyst.
10. The method for preparing high-purity carbonyl fluoride from hexafluoropropylene oxide according to claim 9, wherein: the temperature rising speed in the step A31 and the temperature rising speed in the step A32 are both 1.8-2.2 ℃/min.
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