Production of 1234yf by means of one-step fluorination of 240db
By using Ni, La, Cr, Co, Fe, Sb, Mo, and Cu catalysts supported on Ce-Zr composite oxide supports, a one-step fluorination reaction of HFO-1234yf was achieved, solving the problems of cumbersome process, high energy consumption, and easy catalyst deactivation in the existing technology, improving product yield and catalyst life, and reducing production costs.
Patent Information
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- ZHEJIANG QUHUA FLUOR CHEM CO LTD
- Filing Date
- 2025-11-04
- Publication Date
- 2026-07-02
AI Technical Summary
The existing industrial production route for HFO-1234yf is cumbersome, energy-intensive, and prone to catalyst deactivation, resulting in low product yield and high production costs.
Ni, La, Cr, Co, Fe, Sb, Mo, and Cu catalysts supported on Ce-Zr composite oxide supports were used for a one-step reaction with hydrogen fluoride at 240 dB to generate 1234yf. Solid solution stabilization and surface acidity regulation were used to inhibit grain growth and carbon deposition, and a fluorine oxide layer was formed to improve catalyst activity and lifetime.
The reaction process was simplified, the selectivity and yield of 1234yf were improved, the stable operating cycle of the catalyst was extended, and the production cost and equipment maintenance expenses were reduced.
Smart Images
Figure PCTCN2025132355-FTAPPB-I100001 
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Figure PCTCN2025132355-FTAPPB-I100003
Abstract
Description
240dB one-step fluorination to produce 1234yf Technical Field
[0001] This invention relates to the field of 2,3,3,3-tetrafluoropropylene (1234yf) synthesis technology, specifically to a method for one-step fluorination of 1,1,1,2,3-pentachloropropane (240db) to generate 1234yf. Background Technology
[0002] As refrigeration technology continues to evolve, the search for efficient, environmentally friendly, and economical refrigerants has become a focal point of the industry. With increasing global awareness of environmental protection, reducing greenhouse gas emissions and ozone layer depletion has become an international consensus. Against this backdrop, 2,3,3,3-tetrafluoropropylene (HFO-1234yf), with its extremely low global warming potential (GWP<1), zero ozone depletion potential (ODP=0), and short atmospheric lifetime (only 11 days), is widely recognized as an ideal alternative to traditional refrigerants such as HFC-134a, marking the fourth generation of innovation in the refrigerant industry.
[0003] However, despite the significant environmental advantages exhibited by HFO-1234yf, its current industrial production route faces numerous challenges. Existing technologies mainly rely on multi-step, energy-intensive synthetic routes, such as complex conversion processes using hexafluoropropylene, trifluoropropylene, and tetrachloropropylene as starting materials.
[0004] For example, patent CN109796300B reports a continuous preparation method for 2,3,3,3-tetrafluoropropylene. Using carbon tetrachloride and ethylene as raw materials, CCl4 and ethylene are telomerized to generate CCl3CH2CH2Cl. Then, CCl3CH2CH2Cl undergoes dehydrochlorination to form CCl2=CHCH2Cl. CCl2=CHCH2Cl is then chlorinated to obtain CCl3CHClCH2Cl. CCl3CHClCH2Cl undergoes dehydrochlorination to obtain CCl2=CClCH2Cl. CCl2=CClCH2Cl then reacts with hydrogen fluoride to generate 2-chloro-3,3,3-trifluoropropylene (CF3CCl=CH2, 1233xf). CF3CCl=CH2 undergoes fluorine-chlorine exchange to obtain the final product HFO-1234yf.
[0005] For example, patent application CN117377646A reports the formation of HFO-1234yf. CCl3CH2CH2Cl undergoes a fluorination reaction to form CF3CH=CH2, CF3CH=CH2 undergoes a chlorination reaction to form CF3CHClCH2Cl, CF3CHClCH2Cl undergoes a dehydrochlorination reaction to form CF3CCl=CH2, CF3CCl=CH2 reacts with hydrogen fluoride in the presence of a catalyst and undergoes a hydrofluorination reaction to form CF3CFClCH3, CF3CFClCH3 undergoes a dehydrochlorination reaction to finally form HFO-1234yf. This route requires a total of 6 reaction steps, which is not only lengthy but also has stringent requirements for reaction conditions, especially at high temperatures. This increases equipment investment costs and significantly raises energy consumption levels.
[0006] The patent specification with publication number CN107074697A discloses a method for producing 2,3,3,3-tetrafluoropropylene, comprising: reacting a composition comprising at least 99% by weight of 1,1,1,2,3-pentachloropropane with hydrofluoric acid in the gas phase, which may be a catalytic fluorination step, wherein the catalyst may be a supported or unsupported catalyst containing metals such as Cr, Ni, Fe, Zn, Ti, V, Zr, Mo, Ge, Sn, Pb, Mg, Sb, chromium fluoride, aluminum fluoride, or aluminum fluoride. Summary of the Invention
[0007] This invention provides a one-step fluorination method for generating 1234yf at 240dB, which simplifies the process and improves the reaction effect. It can solve the problems of cumbersome process, many intermediate substances, low yield of 1234yf final product, and easy deactivation of catalyst in the existing technology.
[0008] The specific technical solution is as follows:
[0009] A method for one-step fluorination of 240dB to generate 1234yf includes: reacting 240dB and hydrogen fluoride in the presence of a fluorinated catalyst to generate 1234yf in a next step.
[0010] The catalyst comprises a Ce-Zr composite oxide support and one or more of Ni, La, Cr, Co, Fe, Sb, Mo, and Cu supported on the support. Further, the catalyst preferably comprises one or more of Ni, Cr, Co, and Cu supported on the support, which exhibits excellent activation ability for fluorine sources (such as HF) and can effectively promote the reaction of 240 dB with fluorine to generate 1234 YF in one step.
[0011] Fluorination treatment can convert the active components of the catalyst into fluorides, while simultaneously forming a fluorine-oxygen layer on the surface of the Ce-Zr composite oxide support.
[0012] The method for generating 1234yf by one-step fluorination at 240dB preferably includes the following fluorination treatment: fluorinating the catalyst in a gas containing HF at 280-360°C (e.g., 300°C, 340°C, 350°C, etc., preferably 300-350°C).
[0013] Furthermore, the HF-containing gas may include HF and inert gases.
[0014] In this invention, the inert gas refers to a gas that does not participate in the reaction, such as nitrogen.
[0015] In some preferred embodiments, the volume fraction of HF in the HF-containing gas is 5% to 10%.
[0016] In some preferred embodiments, the fluorination reaction takes 2 to 3 hours.
[0017] The preferred method for preparing the catalyst includes: impregnating a Ce-Zr composite oxide support into a precursor solution containing one or more of Ni, La, Cr, Co, Fe, Sb, Mo, and Cu using an impregnation method; after impregnation, the solid is dried and calcined to obtain the catalyst. The calcination temperature is preferably 340–400°C, for example, 350°C or 380°C, and more preferably 350–380°C. The calcination time is preferably 3–4 hours. The precursor solution can be a salt solution, and more preferably a nitrate solution or a chloride solution.
[0018] The preferred method for preparing the Ce-Zr composite oxide support includes: using a co-precipitation-hydrothermal method, adjusting the pH of a solution containing Ce(III) and Zr(IV) to 9-10, and then carrying out a hydrothermal reaction at 160-200℃ (e.g., 180℃, 190℃, etc., preferably 180-190℃). After the hydrothermal reaction, the solid is calcined to obtain the Ce-Zr composite oxide support. The hydrothermal reaction time is preferably 12-18 hours. The calcination temperature is preferably 480-520℃, more preferably 500℃. The calcination time is preferably 4-5 hours.
[0019] In the preparation method of the Ce-Zr composite oxide support, Ce(III) is preferably derived from cerium nitrate.
[0020] In the preparation method of the Ce-Zr composite oxide support, Zr(IV) is preferably derived from zirconium nitrate.
[0021] In the preparation method of the Ce-Zr composite oxide carrier, ammonia is preferably used to adjust the pH.
[0022] In the catalyst, based on the mass of the Ce-Zr composite oxide support as 100%, the mass percentage of one or more of Ni, La, Cr, Co, Fe, Sb, Mo, and Cu is preferably 5% to 15%, for example, 10%.
[0023] In the Ce-Zr composite oxide support, the molar ratio of Ce to Zr is preferably 1:1 to 5, for example, 1:3.
[0024] In the method for one-step fluorination of 240dB to generate 1234yf, the molar ratio of 240dB to hydrogen fluoride is preferably 1:5 to 30, such as 1:10, 1:15, 1:20, 1:25, 1:30, etc.
[0025] The method for generating 1234yf by one-step fluorination at 240dB is preferably performed at a reaction temperature of 250–390°C, for example, 300°C.
[0026] The method for generating 1234yf by one-step fluorination at 240dB is preferably performed at a reaction pressure of 0.1 to 0.6 MPa, for example, 0.4 MPa.
[0027] The method for one-step fluorination to produce 1234yf at 240dB preferably uses a catalyst volume hourly space velocity (VHSV) of 500–1500 h⁻¹ for the one-step reaction to produce 1234yf. -1 For example, 1000h -1 wait.
[0028] As a general inventive concept, the present invention also provides a catalyst, its preparation method, and its application. The catalyst and its preparation method are described in the above-described method for one-step fluorination of 240 dB to generate 1234yf. The catalyst can be used to catalyze the one-step reaction of 240 dB and hydrogen fluoride to generate 1234yf. Preferably, the catalyst is fluorinated before being used to catalyze the one-step reaction of 240 dB and hydrogen fluoride to generate 1234yf. The fluorination treatment is described in the above-described method for one-step fluorination of 240 dB to generate 1234yf.
[0029] The fluorinated catalyst of this invention has the following characteristics:
[0030] 1. Anti-sintering:
[0031] Solid solution stabilization: A co-precipitation-hydrothermal-calcination method was used to stabilize Ce. 4+ Formation and cause Ce 4+ It enters the ZrO2 lattice, increases the lattice distortion energy, and inhibits grain growth at high temperatures;
[0032] Strong metal-support interaction: The active component is converted into fluoride and forms a chemical bond with the Ce-Zr composite oxide support interface with the fluorine-oxygen layer formed on the surface, which restricts the migration and aggregation of the active component. The strong metal-support interaction greatly improves the yield and selectivity of 1234yf and gives the catalyst an ultra-long lifespan.
[0033] 2. Anti-carbon buildup:
[0034] Surface acidity regulation: Carbon deposition precursors mainly polymerize through strong acid sites. The cerium oxide in the catalyst of this invention can reduce the density of strong acid sites on the support surface and reduce the adsorption of olefins.
[0035] Oxidation and scavenging effect: The oxygen storage capacity of cerium oxides can oxidize deposited carbon species into CO, CO2, etc., thus inhibiting the formation of carbon deposits.
[0036] Compared with the prior art, the beneficial effects of this invention are as follows:
[0037] (1) By constructing a reaction system for the one-step fluorination of 240dB to prepare 1234yf, the traditional multi-step reaction process was deeply integrated, which effectively shortened the reaction path, reduced the process complexity of intermediate product separation and purification, and laid a structural foundation for improving reaction efficiency.
[0038] (2) The application of specific catalysts significantly improved the selectivity of 1234yf formation and the yield of target products. At the same time, by enhancing the catalyst’s resistance to deactivation, its stable operating cycle was greatly extended, solving the technical bottlenecks of rapid activity decay and difficult product distribution control in traditional catalysis.
[0039] (3) The method of the present invention, while ensuring high selectivity and high yield, has the characteristics of stable and controllable process and long catalyst life, effectively reducing material consumption and equipment maintenance costs in industrial production, and overcoming the economic and stability problems faced by existing technologies in large-scale production. Detailed Implementation
[0040] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention.
[0041] Unless otherwise specified, the operating methods in the following examples are generally performed under conventional conditions or as recommended by the manufacturer.
[0042] Example 1:
[0043] A coprecipitation-hydrothermal method was used. The pH of a solution containing cerium nitrate and zirconium nitrate was adjusted to 9-10 with ammonia water, and then a hydrothermal reaction was carried out at 180℃ for 12 hours. After the hydrothermal reaction was completed, the solid was calcined at 500℃ for 4 hours to obtain the Ce-Zr composite oxide support. In the Ce-Zr composite oxide support, the molar ratio of Ce to Zr was 1:1.
[0044] The Ce-Zr composite oxide support obtained above was immersed in a nickel nitrate solution using an impregnation method. After impregnation, the solid was dried and calcined at 350°C for 3 hours to obtain the Ni catalyst. In this Ni catalyst, the mass percentage of Ni is 5% based on 100% of the Ce-Zr composite oxide support.
[0045] The Ni catalyst obtained above was subjected to a fluorination reaction at 340°C for 2 hours in an HF / N2 mixture containing 5 vol% HF to obtain a fluorinated Ni catalyst.
[0046] 240dB and hydrogen fluoride were reacted in the next step with the above-mentioned fluorinated Ni catalyst to produce 1234yf. The reaction parameters such as reaction pressure, reaction temperature, raw material molar ratio, and the composition of the outlet gas after 20h of reaction are shown in Table 1.
[0047] Example 2:
[0048] A coprecipitation-hydrothermal method was used. The pH of a solution containing cerium nitrate and zirconium nitrate was adjusted to 9-10 with ammonia water, and then a hydrothermal reaction was carried out at 180℃ for 12 hours. After the hydrothermal reaction was completed, the solid was calcined at 500℃ for 4 hours to obtain the Ce-Zr composite oxide support. In the Ce-Zr composite oxide support, the molar ratio of Ce to Zr was 1:3.
[0049] The Ce-Zr composite oxide support obtained above was immersed in a lanthanum nitrate solution using an impregnation method. After impregnation, the solid was dried and calcined at 350°C for 3 hours to obtain the La catalyst. In this La catalyst, the mass percentage of La is 10% based on 100% of the Ce-Zr composite oxide support.
[0050] The La catalyst obtained above was subjected to a fluorination reaction at 340°C for 2 hours in an HF / N2 mixture containing 5 vol% HF to obtain a fluorinated La catalyst.
[0051] 240dB and hydrogen fluoride were reacted in the next step with the above-mentioned fluorinated La catalyst to produce 1234yf. The reaction parameters such as reaction pressure, reaction temperature, raw material molar ratio, and the composition of the outlet gas after 20h of reaction are shown in Table 1.
[0052] Example 3:
[0053] A coprecipitation-hydrothermal method was used. The pH of a solution containing cerium nitrate and zirconium nitrate was adjusted to 9-10 with ammonia water, and then a hydrothermal reaction was carried out at 180℃ for 12 hours. After the hydrothermal reaction was completed, the solid was calcined at 500℃ for 4 hours to obtain the Ce-Zr composite oxide support. In the Ce-Zr composite oxide support, the molar ratio of Ce to Zr was 1:5.
[0054] The Ce-Zr composite oxide support obtained above was immersed in a chromium chloride solution using an impregnation method. After impregnation, the solid was dried and calcined at 350°C for 3 hours to obtain the Cr catalyst. In this Cr catalyst, based on the mass of the Ce-Zr composite oxide support being 100%, the mass percentage of Cr is 15%.
[0055] The Cr catalyst obtained above was subjected to a fluorination reaction at 340°C for 2 hours in an HF / N2 mixture containing 5 vol% HF to obtain a fluorinated Cr catalyst.
[0056] 240dB and hydrogen fluoride were reacted in the next step with the above-mentioned fluorinated Cr catalyst to produce 1234yf. The reaction parameters such as reaction pressure, reaction temperature, raw material molar ratio, and the composition of the outlet gas after 20h of reaction are shown in Table 1.
[0057] Table 1
[0058] Example 4:
[0059] The only difference from Example 1 is that cobalt nitrate solution is used instead of nickel nitrate solution during impregnation to obtain Co catalyst. In this Co catalyst, the mass percentage of Co is 5% based on the mass of Ce-Zr composite oxide support being 100%, and the rest are the same. The reaction parameters such as reaction pressure, reaction temperature, raw material molar ratio, and the composition of the outlet gas after 20 hours of reaction are shown in Table 2.
[0060] Example 5:
[0061] The only difference from Example 2 is that a chromium nitrate and copper nitrate solution (chromium and copper molar ratio of 1:1) is used instead of a lanthanum nitrate solution during impregnation to obtain a Cr-Cu catalyst. In this Cr-Cu catalyst, the total mass ratio of Cr and Cu is 10% based on the mass of the Ce-Zr composite oxide support being 100%, and the Cr and Cu are in equimolar ratio. All other parameters are the same. The reaction pressure, reaction temperature, raw material molar ratio, and other reaction parameters for the one-step fluorination to produce 1234yf at 240dB are shown in Table 2.
[0062] Example 6:
[0063] The only difference from Example 3 is that ferric nitrate and molybdenum nitrate solution (iron and molybdenum molar ratio of 1:1) is used instead of chromium chloride solution during impregnation to obtain Fe-Mo catalyst. In this Fe-Mo catalyst, the total mass ratio of Fe and Mo is 15% based on the mass of Ce-Zr composite oxide support of 100%, and the molar ratio of Fe and Mo is equimolar. All other parameters are the same. The reaction pressure, reaction temperature, raw material molar ratio and other reaction parameters for one-step fluorination to produce 1234yf at 240dB are shown in Table 2.
[0064] Table 2
[0065] Example 7:
[0066] Referring to Example 5, a long-term experiment was conducted to produce 1234yf by one-step fluorination at 240dB, with a total catalytic reaction time of 500 hours. The results are shown in Table 3.
[0067] Table 3
[0068] As can be seen, the catalyst of this invention has strong resistance to deactivation, and its activity does not decrease after 500 hours of continuous catalytic reaction, which has very good industrial application value.
[0069] Furthermore, it should be understood that after reading the above description of the present invention, those skilled in the art can make various alterations or modifications to the present invention, and these equivalent forms also fall within the scope defined by the appended claims.
Claims
1. A method for one-step fluorination to generate 1234yf at 240dB, characterized in that, include: 240dB and hydrogen fluoride react in the next step with a fluorinated catalyst to produce 1234yf; The catalyst comprises a Ce-Zr composite oxide support and one or more of Ni, La, Cr, Co, Fe, Sb, Mo, and Cu supported on the support.
2. The method for one-step fluorination to generate 1234yf at 240dB according to claim 1, characterized in that, The fluorination treatment includes: fluorinating the catalyst in an HF-containing gas at 280–360°C.
3. The method for one-step fluorination to generate 1234yf at 240dB according to claim 2, characterized in that, The fluorination treatment includes: fluorinating the catalyst in an HF-containing gas at 300–350°C.
4. The method for one-step fluorination to generate 1234yf at 240dB according to claim 2 or 3, characterized in that, The HF-containing gas includes HF and inert gases.
5. The method for one-step fluorination to generate 1234yf at 240dB according to claim 2 or 3, characterized in that, The volume fraction of HF in the HF-containing gas is 5% to 10%.
6. The method for one-step fluorination to generate 1234yf at 240dB according to claim 2 or 3, characterized in that, The fluorination reaction takes 2 to 3 hours.
7. The method for one-step fluorination to generate 1234yf at 240dB according to claim 1, characterized in that, The catalyst preparation method includes: using an impregnation method, immersing a Ce-Zr composite oxide support in a precursor solution containing one or more of Ni, La, Cr, Co, Fe, Sb, Mo, and Cu; after impregnation, taking the solid, drying, and calcining to obtain the catalyst.
8. The method for one-step fluorination to generate 1234yf at 240dB according to claim 7, characterized in that, The calcination temperature is 340–400°C.
9. The method for one-step fluorination to generate 1234yf at 240dB according to claim 8, characterized in that, The calcination temperature is 350–380°C.
10. The method for one-step fluorination to generate 1234yf at 240dB according to any one of claims 7 to 9, characterized in that, The calcination time is 3 to 4 hours.
11. The method for one-step fluorination to generate 1234yf at 240dB according to claim 1, characterized in that, The preparation method of the Ce-Zr composite oxide support includes: using a coprecipitation-hydrothermal method, adjusting the pH of a solution containing Ce(III) and Zr(IV) to 9-10, then carrying out a hydrothermal reaction at 160-200℃, and after the hydrothermal reaction is completed, taking the solid and calcining it to obtain the Ce-Zr composite oxide support.
12. The method for one-step fluorination to generate 1234yf at 240dB according to claim 11, characterized in that, The hydrothermal reaction is carried out at 180–190℃.
13. The method for one-step fluorination to generate 1234yf at 240dB according to claim 11 or 12, characterized in that, The hydrothermal reaction takes 12 to 18 hours.
14. The method for one-step fluorination to generate 1234yf at 240dB according to claim 11, characterized in that, The roasting temperature is 480–520°C, and the roasting time is 4–5 hours.
15. The method for one-step fluorination to generate 1234yf at 240dB according to claim 1, characterized in that, In the catalyst, based on the mass of the Ce-Zr composite oxide support as 100%, one or more of Ni, La, Cr, Co, Fe, Sb, Mo, and Cu account for 5% to 15% of the mass.
16. The method for one-step fluorination to generate 1234yf at 240dB according to claim 1 or 15, characterized in that, In the Ce-Zr composite oxide support, the molar ratio of Ce to Zr is 1:1 to 5.
17. The method for one-step fluorination to generate 1234yf at 240dB according to claim 1, characterized in that, The molar ratio of 240dB to hydrogen fluoride is 1:5 to 30.
18. The method for one-step fluorination to generate 1234yf at 240dB according to claim 1, characterized in that, The reaction temperature for the one-step formation of 1234yf is 250–390 °C.
19. The method for one-step fluorination to generate 1234yf at 240dB according to claim 1, characterized in that, The reaction pressure for the one-step reaction to produce 1234yf is 0.1–0.6 MPa.
20. The method for one-step fluorination to generate 1234yf at 240dB according to claim 1, characterized in that, The catalyst volume hourly space velocity (VHSV) for the one-step reaction to produce 1234yf is 500–1500 h⁻¹. -1 .