Catalyst for co-production of HCFO-1232xd and HCFO-1233yd by using HCC-240da

Abstract

The invention provides a catalyst for co-production of HCFO-1232xd and HCFO-1233yd by using HCC-240da, and the catalyst comprises a main catalyst, a co-catalyst and a non-metal pore forming agent, the main catalyst is selected from one or more than two of IIIA group oxides and VIB group oxides; the cocatalyst is selected from one or more than two of IIA group oxides, IIB group oxides and VIII B group oxides; the non-metal pore-forming agent is selected from one or two of silicon elementary substance and boron elementary substance.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of catalyst preparation and fluorochlorocarbon alkene synthesis, and specifically to a catalyst for co-producing HCFO-1232xd and HCFO-1233yd from HCC-240da, a preparation method therefor, and application thereof. BACKGROUND

[0002] 1,2-dichloro-3,3-difluoropropene (HCFO-1232xd) and 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd) have a low global warming potential (GWP), a short atmospheric lifetime, no flash point, and good compatibility with mineral oil, and have good application prospects in the fields of cleaning agents, solvents, fluorine-containing intermediates, and the like. More importantly, according to its chemical structure, it is speculated that these two substances will not produce trifluoroacetic acid (TFA) in the process of atmospheric degradation, and are low environmental load fluorinated substances that meet the requirements of the fifth generation of ODS substitutes.

[0003] There are mainly four synthesis routes for HCFO-1233yd: ① 1,2-dichloro-2,3,3-trifluoropropane dehydrofluorination method (WO2019JP12585); ② 1,3-dichloro-2,3,3-trifluoropropene dehydrochlorination method (WO2022255397A1, JP2021107328A); ③ 1,2-dichloro-3,3-difluoropropene fluorination method (JP2018148841A, CN112125776A, WO2021CN72972, US202117799927A, CN117247312A); and ④ 1-chloro-2,2,3,3-tetrafluoropropane dehydrofluorination method (CN114560750A, US2018044268A1, KR20177027050A, WO2016JP55267, JP2016031636A, EP16755488A). The synthesis method of HCFO-1232xd is mainly to obtain it by fluorination reaction of 1,1,2,3,3-pentachloropropane (HCC-240da) on a metal fluoride catalyst (JP2018148841A, CN112125776A, WO2021CN72972, US202117799927A, CN117247312A). Since HCFO-1232xd and HCFO-1233yd can be converted by fluorine-chlorine exchange reaction, and HCFO-1232xd can also be obtained by the same type of reaction, it is considered to realize the co-production of these two hydrogen-chlorine-fluorine alkenes by designing a new type of metal fluoride catalyst, but there is no public information reported so far. SUMMARY

[0004] The application provides a metal fluoride catalyst for co-production of HCFO-1232xd and HCFO-1233yd, and a preparation method and application thereof. The catalyst adopts a "pore-forming-fluorine coordination" regulation strategy, uses a non-metal element to react with hydrogen fluoride to generate a gas to escape and form micropores, and simultaneously accurately controls the addition amount of hydrogen fluoride, so that directional substitution of oxygen atoms in a metal oxide is realized by adjusting activation conditions, so that the number of fluorine coordination of metal elements is adjusted. The applicant finds that the catalyst can synthesize HCFO-1232xd and HCFO-1233yd simultaneously in use, and the selectivity of products can be adjusted by changing the catalyst preparation process; in addition, further research finds that the catalyst has a long service life, can greatly reduce the consumption of the catalyst in the reaction, and achieves the purpose of reducing cost.

[0005] The application provides the following technical solutions: 1. A catalyst for co-production of HCFO-1232xd and HCFO-1233yd by using HCC-240da, wherein the catalyst comprises a main catalyst, a cocatalyst and a non-metal pore-forming agent; The main catalyst is selected from one or more than two of group ⅢA oxides and group ⅥB oxides; The cocatalyst is selected from one or more than two of group ⅡA oxides, group ⅡB oxides and group ⅧB oxides; The non-metal pore-forming agent is selected from one or both of silicon and boron.

[0006] 2. The catalyst according to item 1, wherein, The group ⅢA oxide is selected from one or more than two of diboron trioxide (B2O3), aluminum oxide (Al2O3), gallium oxide (Ga2O3) and indium oxide (In2O3); The group ⅥB oxide is selected from one or more than two of chromium oxide (Cr2O3), molybdenum trioxide (MoO3) and tungsten trioxide (WO3); The group ⅡA oxide is selected from one or more than two of magnesium oxide, barium oxide and calcium oxide; The group ⅡB oxide is selected from one or both of zinc oxide (ZnO) and cadmium oxide (CdO); The group ⅧB oxide is selected from one or more than two of diiron trioxide (Fe2O3), cobalt oxide (CoO), nickel oxide (NiO) and palladium oxide (PdO).

[0007] 3. The catalyst according to item 1, wherein, The main catalyst is one or both of chromium oxide (Cr2O3) and aluminum oxide (Al2O3); preferably, the main catalyst is chromium oxide (Cr2O3); The co-catalyst is one or more of magnesium oxide, zinc oxide (ZnO), barium oxide, calcium oxide, cobalt oxide (CoO); preferably magnesium oxide.

[0008] 4. The catalyst according to item 1, wherein the co-catalyst is 2-10 parts by mass and the non-metallic pore-forming agent is 0.1-3 parts by mass, relative to 100 parts by mass of the main catalyst.

[0009] 5. A method for preparing the catalyst according to any one of items 1-4, comprising: pressing, drying, calcining the main catalyst, the co-catalyst and the non-metallic pore-forming agent, and obtaining after activation by a mixed gas of anhydrous hydrogen fluoride and air.

[0010] 6. The method for preparing according to item 5, wherein the drying temperature is 100-200°C.

[0011] 7. The method for preparing according to item 5, wherein the calcining temperature is 300-400°C.

[0012] 8. The method for preparing according to item 5, wherein the activation temperature is 200-400°C; preferably 250-400°C.

[0013] 9. The method for preparing according to item 5, wherein the volume concentration of anhydrous hydrogen fluoride in the mixed gas of anhydrous hydrogen fluoride and air is 5-50%; preferably 5-15%.

[0014] 10. The method for preparing according to item 5, wherein the residence time of the mixed gas of anhydrous hydrogen fluoride and air is 3-40 s.

[0015] 11. A method for synthesizing HCFO-1232xd and HCFO-1233yd, comprising using the catalyst according to any one of items 1-4 or prepared by the method according to any one of items 4-10.

[0016] 12. The method for preparing according to item 11, wherein HCC-240da is converted into HCFO-1232xd and HCFO-1233yd by a gas phase catalytic method, specifically as follows: The catalyst is fixed and heated to the reaction temperature under a nitrogen atmosphere; HCC-240da and anhydrous hydrogen fluoride are introduced, and after mixing, a gas phase fluorine-chlorine exchange reaction is carried out to obtain HCFO-1232xd and HCFO-1233yd.

[0017] 13. The method for preparing according to item 12, wherein, the temperature of the gas phase fluorine-chlorine exchange reaction is 150-500°C; The molar ratio of anhydrous hydrogen fluoride to HCC-240da is (5-20):1; The time for the gas-phase fluorine-chlorine exchange reaction is 1~120s.

[0018] Compared with the prior art, the beneficial effects of this application are as follows: 1. This application uses any one or more of Group IIIA and Group VIB oxides as the main catalyst, and any one or more of Group IIA, Group IIB and Group VIIIB oxides as the co-catalyst, with elemental silicon and boron as non-metallic pore-forming agents. A porous metal fluoride catalyst is prepared by pressing, drying, calcining and activation. This catalyst is used in the synthesis reaction of HCFO-1232xd and HCFO-1233yd. The conversion rate of this catalyst for HCC-240da is in the range of 90-99%, the selectivity for HCFO-1232xd is about 30-70%, the selectivity for HCFO-1233yd is about 20-60%, and the impurity content is not higher than 10%.

[0019] 2. This application further selects appropriate main catalyst, co-catalyst and non-metallic pore-forming agent, and further optimizes the mass ratio of the three to obtain a catalyst with better performance (conversion rate of HCC-240da, selectivity of HCFO-1232xd, selectivity of HCFO-1233yd and impurity content when it is used for catalytic reaction).

[0020] 3. This application further optimizes the preparation process parameters when preparing the catalyst, such as drying temperature, calcination temperature, activation temperature, and activator residence time, in order to obtain a catalyst with better performance (conversion rate of HCC-240da, selectivity of HCFO-1232xd, selectivity of HCFO-1233yd, and impurity content when the catalyst is used for catalytic reaction).

[0021] 4. The catalyst prepared by this application using chromium oxide, magnesium oxide and silicon powder as raw materials and activated with anhydrous hydrogen fluoride has a significantly extended service life: after a service time of up to 100 hours, the catalyst still maintains good stability; for example, its conversion rate of HCC-240da is reduced by only 3%, and the impurity content is no higher than 8%.

[0022] 5. This application provides a simple and efficient method for the co-production of HCFO-1232xd and 1-chloro-2,3,3-trifluoropropene (HCFO-1233yd), comprising using 1,1,2,3,3-pentachloropropane (HCC-240da) as raw material, employing a porous metal fluoride catalyst prepared based on a "pore-forming-fluorine coordination" control strategy, and synthesizing 1,2-dichloro-3,3-difluoropropene and 1-chloro-2,3,3-trifluoropropene in a one-step gas-phase continuous reaction. This application achieves the co-production of HCFO-1232xd and HCFO-1233yd by adjusting the catalyst preparation process, with a raw material conversion rate of up to 99%, and features a stable process and a long catalyst lifespan. Detailed Implementation

[0023] The present application is further illustrated below with reference to embodiments. It should be understood that the embodiments are only used to further illustrate and explain the present application and are not intended to limit the present application.

[0024] Unless otherwise defined, technical and scientific terms used in this specification have the same meaning as commonly understood by one of ordinary skill in the art. While similar or identical methods and materials may be applied in experimental or practical applications, materials and methods are described herein. In case of conflict, the definitions included herein shall prevail. Furthermore, materials, methods, and examples are for illustrative purposes only and are not intended to be limiting. The present application is further described below with reference to specific embodiments, but is not intended to limit the scope of the application.

[0025] In this application, HCC-240da refers to the cis isomer, trans isomer, or mixture thereof of 1,1,2,3,3-pentachloropropane.

[0026] In this application, HCFO-1232xd refers to the cis isomer, trans isomer, or mixture thereof of 1,2-dichloro-3,3-difluoropropene, and HCFO-1233yd refers to the cis isomer, trans isomer, or mixture thereof of 1-chloro-2,3,3-trifluoropropene.

[0027] In this application, the process of co-producing HCFO-1232xd and HCFO-1233yd from HCC-240da mainly involves the following reactions: This application provides a catalyst for the co-production of HCFO-1232xd and HCFO-1233yd using HCC-240da, wherein the catalyst comprises a main catalyst, a co-catalyst, and a non-metallic pore-forming agent; the main catalyst is selected from one or more of Group IIIA oxides and Group VIB oxides; the co-catalyst is selected from one or more of Group IIA oxides, Group IIB oxides, and Group VIIIB oxides; and the non-metallic pore-forming agent is selected from one or two of elemental silicon and elemental boron.

[0028] In some embodiments of this application, the group IIIA oxide is selected from one or more of boron trioxide (B2O3), aluminum oxide (Al2O3), gallium oxide (Ga2O3), and indium oxide (In2O3).

[0029] In some embodiments of this application, the group VIB oxide is selected from one or more of chromium oxide (Cr2O3), molybdenum trioxide (MoO3), and tungsten trioxide (WO3).

[0030] In some embodiments of this application, the group IIA oxide is selected from one or more of magnesium oxide, barium oxide, and calcium oxide.

[0031] In some embodiments of this application, the group IIB oxide is selected from one or both of zinc oxide (ZnO) and cadmium oxide (CdO).

[0032] One or more of the following group VIII B oxides: ferric oxide (Fe2O3), cobalt oxide (CoO), nickel oxide (NiO), and palladium oxide (PdO).

[0033] In some embodiments of this application, the main catalyst is one or both of chromium oxide (Cr2O3) and aluminum oxide (Al2O3); preferably chromium oxide (Cr2O3).

[0034] In some embodiments of this application, the co-catalyst is one or more of magnesium oxide, zinc oxide (ZnO), barium oxide, calcium oxide, and cobalt oxide (CoO); preferably magnesium oxide.

[0035] In some embodiments of this application, the co-catalyst is 2-10 parts by weight relative to 100 parts by weight of the main catalyst, and the non-metallic pore-forming agent is 0.1-3 parts by weight. For example, relative to 100 parts by weight of the main catalyst, the co-catalyst can be 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, or any range thereto; relative to 100 parts by weight of the main catalyst, the non-metallic pore-forming agent can be 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, or any other amount. The weight is 0.9 parts by weight, 1.0 parts by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, 2.0 parts by weight, 2.1 parts by weight, 2.2 parts by weight, 2.3 parts by weight, 2.4 parts by weight, 2.5 parts by weight, 2.6 parts by weight, 2.7 parts by weight, 2.8 parts by weight, 2.9 parts by weight, 3.0 parts by weight, or any range between them.

[0036] This application provides a method for preparing the above-mentioned catalyst, which includes: pressing, drying, calcining the main catalyst, the co-catalyst, and the non-metallic pore-forming agent, and then activating them with a mixture of anhydrous hydrogen fluoride and air to obtain the catalyst.

[0037] In some embodiments of this application, the drying temperature is 100~200℃. For example, the drying temperature can be 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃, 200℃ or any range therebetween.

[0038] In some embodiments of this application, the calcination temperature is 300~400℃. For example, the calcination temperature can be 300℃, 310℃, 320℃, 330℃, 340℃, 350℃, 360℃, 370℃, 380℃, 390℃, 400℃ or any range therefrom.

[0039] In some embodiments of this application, the activation temperature is 200~400℃; preferably 250~400℃. For example, the activation temperature can be any range from 200℃, 210℃, 220℃, 230℃, 240℃, 250℃, 260℃, 270℃, 280℃, 290℃, 300℃, 310℃, 320℃, 330℃, 340℃, 350℃, 360℃, 370℃, 380℃, 390℃, 400℃, or any range thereof.

[0040] In some embodiments of this application, the volume concentration of hydrogen fluoride in the mixture of anhydrous hydrogen fluoride and air is 5-50%; preferably 5-15%. For example, the volume concentration of hydrogen fluoride in the mixture of anhydrous hydrogen fluoride and air can be 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%, 31%, 32%, 33%, 34%, 35%, 36%, 37%, 38%, 39%, 40%, 41%, 42%, 43%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, or any range between these values.

[0041] In some embodiments of this application, the residence time of the mixture of anhydrous hydrogen fluoride and air is 3 to 40 s. For example, the residence time of the mixture of anhydrous hydrogen fluoride and air can be any range from 1 s, 2 s, 3 s, 4 s, 5 s, 6 s, 7 s, 8 s, 9 s, 10 s, 11 s, 12 s, 13 s, 14 s, 15 s, 16 s, 17 s, 18 s, 19 s, 20 s, 21 s, 22 s, 23 s, 24 s, 25 s, 26 s, 27 s, 28 s, 29 s, 30 s, 31 s, 32 s, 33 s, 34 s, 35 s, 36 s, 37 s, 38 s, 39 s, 40 s, or any range thereof.

[0042] This application provides a method for synthesizing HCFO-1232xd and HCFO-1233yd, which includes using the above-mentioned catalyst.

[0043] In some embodiments of this application, HCC-240da is converted into HCFO-1232xd and HCFO-1233yd using a gas-phase catalytic method, as detailed below: With the catalyst fixed, the temperature is raised to the reaction temperature under a nitrogen atmosphere; HCC-240da and anhydrous hydrogen fluoride were introduced, and after mixing HCC-240da and anhydrous hydrogen fluoride, a gas-phase fluorine-chlorine exchange reaction was carried out to obtain HCFO-1232xd and HCFO-1233yd.

[0044] In some embodiments of this application, the temperature of the gas-phase fluorine-chlorine exchange reaction is 150-500°C. For example, the temperature of the gas-phase fluorine-chlorine exchange reaction can be any range from 150°C, 160°C, 170°C, 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C, 260°C, 270°C, 280°C, 290°C, 300°C, 310°C, 320°C, 330°C, 340°C, 350°C, 360°C, 370°C, 380°C, 390°C, 400°C, 410°C, 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, 480°C, 490°C, 500°C, or any range thereof.

[0045] In some embodiments of this application, the molar ratio of anhydrous hydrogen fluoride to HCC-240da is (5-20):1. For example, the molar ratio of anhydrous hydrogen fluoride to HCC-240da can be 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1 or any range therefrom.

[0046] In some embodiments of this application, the time for the gas-phase fluorine-chlorine exchange reaction is 1 to 120 s. For example, the time for the gas-phase fluorine-chlorine exchange reaction can be 1 s, 2 s, 3 s, 4 s, 5 s, 6 s, 7 s, 8 s, 9 s, 10 s, 11 s, 12 s, 13 s, 14 s, 15 s, 16 s, 17 s, 18 s, 19 s, 20 s, 21 s, 22 s, 23 s, 24 s, 25 s, 26 s, 27 s, 28 s, 29 s, 30 s, 31 s, 32 s, 33 s, 34 s, 35 s, 36 s, 37 s, 38 s, or 39 s. 40s, 41s, 42s, 43s, 44s, 45s, 46s, 47s, 48s, 49s, 50s, 51s, 52s, 53s, 54s, 55s, 56s, 57s, 58s, 59s, 60s, 65s, 70s, 75s, 80s, 85s, 90s, 95s, 100s, 105s, 110s, 115s, 120s, or any range between them.

[0047] Example Catalyst performance was evaluated using a fixed-bed reactor: catalyst loading 30 mL, reaction temperature 200–450 ℃, n(HF) / n(HCC-240da) = (5–20) / 1, residence time 3–60 s. The reaction products were analyzed by gas chromatography (column: DB-VRX 30m × 0.32mm × 1.5μm, injector temperature: 150 ℃, detector temperature: 250 ℃, temperature program: column temperature 50 ℃ held for 5 min, temperature increased to 220 ℃ at 10 ℃ / min, held for 7 min).

[0048] Example 1: 100g of chromium oxide, 10g of magnesium oxide powder, and 0.5g of silicon powder were weighed, mixed evenly, and pressed into 3mm particles. The mixture was dried to constant weight at 120℃ and calcined at 300℃. A mixture of HF and nitrogen (HF volume concentration 10%) was introduced at 200℃, with the mixed gas residing in the catalyst bed for 12 s to activate the catalyst. The activation endpoint was reached when the pH of the tail gas stabilized at 4-5, yielding the composite catalyst, denoted as 100Cr-10Mg-0.5Si.

[0049] The 100Cr-10Mg-0.5Si composite catalyst was used to catalyze 1,1,2,3,3-pentachloropropane (HCC-240da) to co-produce 1,2-dichloro-3,3-difluoropropene and 1-chloro-2,3,3-trifluoropropene. The specific process is as follows: 1) The activated catalyst is loaded into the isothermal zone of the fixed-bed reactor and heated to the reaction temperature under a nitrogen atmosphere; 2) Use a peristaltic pump to send the raw material HCC-240da into the preheater at a certain flow rate, and use a mass flow meter to send anhydrous hydrogen fluoride into the preheater at a certain flow rate. After the materials are mixed evenly, they enter the reactor for gas-phase fluorine-chlorine exchange reaction. The reaction temperature is 300 ℃, the feed ratio is HF:HCC-240da 12:1, and the reaction time is 36 s. 3) After the reaction product is washed with water and alkali to remove acidic substances, the organic phase is taken and analyzed by gas chromatography. The reaction conversion rate and the selectivity of the target product are calculated based on the test results.

[0050] 100Cr-10Mg-0.5Si indicates that the catalyst is prepared from 100 parts of chromium oxide, 10 parts of magnesium oxide, and 0.5 parts of silicon. The same applies below; only the elements or their mass fractions change.

[0051] Example 2: Weigh 100g of alumina and synthesize a 100Al-10Mg-0.5Si composite catalyst according to the method in Example 1.

[0052] Example 3: Weigh 0.5g of boron powder and synthesize a 100Cr-10Mg-0.5B composite catalyst according to the method in Example 1.

[0053] Example 4: Weigh 0.5g of boron powder and synthesize a 100Al-10Mg-0.5B composite catalyst according to the method in Example 2.

[0054] Example 5: Weigh 10g of zinc oxide and synthesize a 100Cr-10Zn-0.5Si composite catalyst according to the method in Example 1.

[0055] Example 6: Weigh 10g of cobalt oxide and synthesize a 100Cr-10Co-0.5Si composite catalyst according to the method in Example 1.

[0056] Table 1. Effects of different main / co-catalysts and pore-forming agents on catalytic performance.

[0057] As shown in Table 1, the chromium-based catalyst exhibits significantly better reactivity than the aluminum-based catalyst, the catalyst prepared with silicon pore-forming agent shows better reactivity than the one prepared with boron pore-forming agent, and among the co-catalysts, magnesium has a better catalytic effect than zinc and cobalt.

[0058] The most important factors are a high conversion rate and good stability for 240da.

[0059] Both 1232xd and 1233yd are important products. The co-production process of this application can achieve flexible control over 1232xd and 1233yd. For example, the production process can be adjusted in a timely manner according to market demand, thereby meeting the user's requirements for different products.

[0060] Example 7: Weigh 5g of magnesium oxide and synthesize a 100Cr-5Mg-0.5Si composite catalyst according to the method in Example 1.

[0061] Example 8: Weigh 15g of magnesium oxide and synthesize a 100Cr-15Mg-0.5Si composite catalyst according to the method in Example 1.

[0062] Example 9: Weigh 20g of magnesium oxide and synthesize a 100Cr-20Mg-0.5Si composite catalyst according to the method in Example 1.

[0063] Table 2 Effect of different amounts of co-catalyst on catalytic effect

[0064] As shown in Table 2, increasing the magnesium oxide content helps to improve the reaction conversion rate. When the ratio of magnesium oxide to chromium oxide is 0.15, the reaction conversion rate can reach 99.2%. Further increasing the magnesium oxide ratio does not significantly improve the catalytic activity.

[0065] Example 10: Weigh 0.1g of silicon and synthesize a 100Cr-15Mg-0.1Si composite catalyst according to the method in Example 1.

[0066] Example 11: Weigh 1g of silicon and synthesize a 100Cr-15Mg-1.0Si composite catalyst according to the method in Example 1.

[0067] Example 12: Weigh 1.5g of silicon and synthesize a 100Cr-15Mg-1.5Si composite catalyst according to the method in Example 1.

[0068] Example 13: Weigh 2.0g of silicon and synthesize a 100Cr-15Mg-2.0Si composite catalyst according to the method in Example 1.

[0069] Table 3. Effect of different amounts of silica pore-forming agent on catalytic effect

[0070] As shown in Table 3, increasing the amount of silicon added can help improve the reaction conversion rate to some extent (Example 11), but a mass ratio of silicon to chromium oxide higher than 0.01 will cause the catalyst structure to collapse (Examples 12-13), affecting the reaction conversion rate and selectivity. Similarly, if the silicon content is too low, it will also affect the reaction activity (Example 10).

[0071] Example 14: The 100Cr-15Mg-1.0Si composite catalyst was synthesized at a drying temperature of 100℃ according to the method in Example 11.

[0072] Example 15: The 100Cr-15Mg-1.0Si composite catalyst was synthesized at a drying temperature of 150℃ according to the method in Example 11.

[0073] Example 16: The calcination temperature was 350℃, and the 100Cr-15Mg-1.0Si composite catalyst was synthesized according to the method in Example 11.

[0074] Example 17: The calcination temperature was 400℃, and the 100Cr-15Mg-1.0Si composite catalyst was synthesized according to the method in Example 11.

[0075] Table 4. Effect of different drying / calcination temperatures on catalytic performance

[0076] As shown in Table 4, drying and calcination temperatures have no significant effect on catalyst activity and product selectivity. Within the experimental range, the catalytic activity is basically between 91% and 93%, and the selectivity of the two target products does not change significantly.

[0077] Example 18: The 100Cr-15Mg-1.0Si composite catalyst was synthesized at an activation temperature of 250℃ according to the method in Example 15.

[0078] Example 19: The 100Cr-15Mg-1.0Si composite catalyst was synthesized at an activation temperature of 300℃ according to the method in Example 15.

[0079] Example 20: The 100Cr-15Mg-1.0Si composite catalyst was synthesized at an activation temperature of 350℃ according to the method in Example 15.

[0080] Example 21: The 100Cr-15Mg-1.0Si composite catalyst was synthesized at an activation temperature of 400℃ according to the method in Example 15.

[0081] Example 22: The HF concentration in the mixed gas was 5%, and the 100Cr-15Mg-1.0Si composite catalyst was synthesized according to the method in Example 15.

[0082] Example 23: The HF concentration in the mixed gas was 15%, and the 100Cr-15Mg-1.0Si composite catalyst was synthesized according to the method in Example 15.

[0083] Example 24: The HF concentration in the mixed gas was 20%, and the 100Cr-15Mg-1.0Si composite catalyst was synthesized according to the method in Example 15.

[0084] Example 25: The HF concentration in the mixed gas was 40%, and the 100Cr-15Mg-1.0Si composite catalyst was synthesized according to the method in Example 15.

[0085] Example 26: The residence time of the mixed gas in the catalyst bed was 36 s, and the 100Cr-15Mg-1.0Si composite catalyst was synthesized according to the method of Example 15.

[0086] Example 27: The residence time of the mixed gas in the catalyst bed was 18 s, and the 100Cr-15Mg-1.0Si composite catalyst was synthesized according to the method of Example 15.

[0087] Example 28: The residence time of the mixed gas in the catalyst bed was 9 s, and the 100Cr-15Mg-1.0Si composite catalyst was synthesized according to the method of Example 15.

[0088] Example 29: The residence time of the mixed gas in the catalyst bed was 7.2 s, and the 100Cr-15Mg-1.0Si composite catalyst was synthesized according to the method of Example 15.

[0089] Example 30: The residence time of the mixed gas in the catalyst bed was 6 s, and the 100Cr-15Mg-1.0Si composite catalyst was synthesized according to the method of Example 15.

[0090] Table 5. Effect of different activation temperatures on catalytic performance

[0091] As shown in Table 5, the activation temperature has a more significant effect on the product selectivity. When the activation temperature is below 250 °C, the selectivity of other impurities in the product is 6-7%, while after increasing the activation temperature, the selectivity of other impurities increases significantly to 20-21%, and the corresponding reaction conversion rate decreases slightly.

[0092] Table 6. Structural parameters of catalysts prepared at different activation temperatures

[0093] Table 6 shows that the activation temperature affects the physical structure and surface properties of the catalyst. At an activation temperature of 250 °C, the specific surface area of ​​the catalyst can reach 88.7 m². 2 The surface area is 0.7 nm, with a surface acidity of 6.18 mmol / g. Upon increasing the activation temperature, the specific surface area and surface acidity decrease, while the pore size gradually increases.

[0094] Table 7. Effect of different gas mixture concentrations on catalytic performance

[0095] Table 7 shows that when the HF concentration in the mixed gas is below 15%, the reaction conversion rate of the prepared catalyst is relatively high, while the impurity selectivity of the product is also the lowest. Increasing the HF concentration will decrease the selectivity of HCFO-1233yd, while increasing the selectivity of impurities.

[0096] Table 8. Structural parameters of catalysts prepared with different gas mixture concentrations

[0097] Table 8 shows that the concentration of the mixed gas affects the specific surface area and surface acidity of the catalyst. The catalyst prepared with an HF concentration of 15% has a significantly higher specific surface area and surface acidity than other catalysts. This is mainly because an excessively high HF concentration will cause the oxygen / silicon elements in the catalyst to react violently with HF, which is not conducive to the formation of rich pore structures and affects the fluorine coordination unsaturation of chromium.

[0098] Table 9. Effect of gas-mixture residence time on catalytic effect

[0099] As shown in Table 9, extending the residence time slightly decreased the reaction conversion rate, while increasing the selectivity for impurities. Reducing the residence time had a significant impact on the selectivity for impurities; in Example 29, the selectivity for impurities was only 4.1%, while the selectivity for HCFO-1233yd increased to 44.3%.

[0100] Comparative Example 1 A commercially available chromium-based catalyst (from Condis Chemical (Hubei) Co., Ltd., chromium fluoride) was used in a 100-h continuous fluorination reaction under the same reaction conditions as in Example 29.

[0101] Table 10 Catalyst lifetime evaluation experiment

[0102] As shown in Table 10, the activity of commercially available chromium-based catalysts decreased rapidly within a 100-hour reaction time, with HCFO-1232xd being the main product and HCFO-1233yd having a selectivity of less than 0.5%. In contrast, the catalyst prepared in this application maintained relatively stable activity within 100 hours, and the selectivity of HCFO-1232xd and HCFO-1233yd in the product did not change significantly, with impurity content not exceeding 6%.

[0103] Although the present invention has been disclosed above with reference to embodiments, it is not intended to limit the present invention. Anyone skilled in the art may make some modifications and refinements without departing from the spirit and scope of the present invention. Therefore, the scope of protection of the present invention shall be determined by the scope of the appended patent application.

Claims

1. A catalyst for the co-production of HCFO-1232xd and HCFO-1233yd using HCC-240da, wherein, The catalyst includes a main catalyst, a co-catalyst, and a non-metallic pore-forming agent; The main catalyst is selected from one or more of Group IIIA oxides and Group VIB oxides; The co-catalyst is selected from one or more of Group IIA oxides, Group IIB oxides, and Group VIIIB oxides; The non-metallic pore-forming agent is selected from one or two of elemental silicon and elemental boron.

2. The catalyst according to claim 1, wherein, Group IIIA oxides are selected from one or more of boron trioxide (B2O3), aluminum oxide (Al2O3), gallium oxide (Ga2O3), and indium oxide (In2O3); Group VIB oxides are selected from one or more of chromium oxide (Cr2O3), molybdenum trioxide (MoO3), and tungsten trioxide (WO3); The Group IIA oxides are selected from one or more of magnesium oxide, barium oxide, and calcium oxide; The group IIB oxides are selected from one or both of zinc oxide (ZnO) and cadmium oxide (CdO); One or more of the following group VIII B oxides: ferric oxide (Fe2O3), cobalt oxide (CoO), nickel oxide (NiO), and palladium oxide (PdO).

3. The catalyst according to claim 1, wherein, The main catalyst is one or both of chromium oxide (Cr2O3) and aluminum oxide (Al2O3); preferably chromium oxide (Cr2O3). The co-catalyst is one or more of magnesium oxide, zinc oxide (ZnO), barium oxide, calcium oxide, and cobalt oxide (CoO); preferably magnesium oxide.

4. The catalyst according to claim 1, wherein, The co-catalyst is 2-10 parts by mass relative to 100 parts by mass of the main catalyst, and the non-metallic pore-forming agent is 0.1-3 parts by mass.

5. A method for preparing the catalyst according to any one of claims 1-4, comprising: The main catalyst, the co-catalyst, and the non-metallic pore-forming agent are pressed, dried, calcined, and then activated by a mixture of anhydrous hydrogen fluoride and air to obtain the final product.

6. The preparation method according to claim 5, wherein, The drying temperature is 100~200℃, or, The roasting temperature is 300~400℃.

7. The preparation method according to claim 5, wherein, The activation temperature is 200~400℃; preferably 250~400℃.

8. The preparation method according to claim 5, wherein, The volume concentration of hydrogen fluoride in the mixture of anhydrous hydrogen fluoride and air is 5-50%; preferably 5-15%.

9. The preparation method according to claim 5, wherein, The residence time of the mixture of anhydrous hydrogen fluoride and air is 3~40 s.

10. A method for synthesizing HCFO-1232xd and HCFO-1233yd, comprising using the catalyst according to any one of claims 1-4 or the catalyst prepared by the preparation method according to any one of claims 4-9; Preferably, HCC-240da was converted into HCFO-1232xd and HCFO-1233yd using a gas-phase catalytic method, as detailed below: With the catalyst fixed, the temperature is raised to the reaction temperature under a nitrogen atmosphere; HCC-240da and anhydrous hydrogen fluoride were introduced, and after mixing HCC-240da and anhydrous hydrogen fluoride, a gas-phase fluorine-chlorine exchange reaction was carried out to obtain HCFO-1232xd and HCFO-1233yd. More preferably, The temperature range for gas-phase fluorine-chlorine exchange reactions is 150-500℃; The molar ratio of anhydrous hydrogen fluoride to HCC-240da is (5-20):1; The time for the gas-phase fluorine-chlorine exchange reaction is 1~120s.

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