A process for the co-production of R244bb and R1234yf using CH3CL and C2HCLF4 as starting materials

Abstract

The present application relates to a kind of method for using CH3CL and C2HCLF4 as raw material co-production R244bb and R1234yf, using the following steps: step one: take chloromethane raw material and tetrafluoro-chloroethane raw material, standby;Step two: the chloromethane raw material and tetrafluoro-chloroethane raw material in step one, in conventional cracking furnace, carry out cracking reaction, generate R244bb and R1234yf product;Step three: when CH3CL and C2HCLF4 cracking release one H+ Ion and one CL- ion, generate one HCL molecule in the cracking reaction in step two, product is R244bb, R244bb is C3H3CLF4;Step four: when R244bb continues to remove one HCl in the cracking process in step three, product is R1234yf and HCL;It avoids the problem of high global warming potential brought by directly using R124, improves environmental performance.

Description

TECHNICAL FIELD

[0001] The present application relates to a method for co-production of R244bb and R1234yf using CH3CL and C2HCLF4 as raw materials. BACKGROUND

[0002] The current market R1234yf production process mainly has: hexafluoropropylene addition elimination method, five fluoropropane dehydrofluorination method, 2-chloro-3,3,3-trifluoropropene fluorine chlorine exchange method, monochloromethane and tetrafluoroethylene high temperature cracking method, hexafluoropropane and five fluoropropane synthesis method, etc.

[0003] In China's R1234yf production enterprises, the hexafluoropropylene addition elimination method is adopted, and the 2-chloro-3,3,3-trifluoropropene fluorine chlorine exchange method is adopted. The common shortcomings of these processes are high cost of upstream raw materials, large corrosion of equipment by HF generated in production, high cost of tail gas treatment, and difficulty in meeting environmental standards. Using chloromethane and HCFC-124, tetrafluoro-chloroethane high temperature cracking method, the main products obtained are tris(tetra)fluorochloropropane (R244bb) and R1234yf and HCL.

[0004] R-124 refrigerant, also known as R124, Freon 124, F-124, HCFC-124, tetrafluoro-chloroethane, chemical formula CHClFCF3. Since R-124 belongs to HCFC (the second batch of limited ODS substances Class II Ozone-depleting Substances) - which destroys the ozone layer and has a greenhouse effect, therefore in developed countries has stopped the initial installation on new air conditioners, refrigeration equipment. SUMMARY

[0005] The purpose of the present application is to overcome the defects and deficiencies of the prior art, provide a method for co-production of R244bb and R1234yf using CH3CL and C2HCLF4 as raw materials, which is beneficial to reduce the production cost of HFO series fluorinated chemical products, prolong the industrial chain of R124, promote the use of R124 as a raw material for the preparation of new refrigerant R1234yf, and avoid the problem of high global warming potential (GWP) caused by direct use of R124.

[0006] The method for co-production of R244bb and R1234yf using CH3CL and C2HCLF4 as raw materials according to the present application adopts the following steps:

[0007] Step 1: Take chloromethane raw material and tetrafluoro-chloroethane raw material for standby;

[0008] Step two: the chloromethane raw material in step one and the tetrafluoro-chloroethane raw material are placed in a conventional cracking furnace to perform a cracking reaction to generate R244bb and R1234yf products;

[0009] Step three: when CH3CL and C2HCLF4 crack off one H+ ion and one CL- ion to generate one HCL molecule in the cracking reaction in step two, the product is R244bb, and R244bb is C3H3CLF4;

[0010] Step four: when R244bb continues to crack off one HCl in the cracking process in step three, the product is R1234yf and HCL.

[0011] Further, the temperature of the conventional cracking furnace in step two is 600-800°C.

[0012] Further, the reaction formula of the main reaction in step two is as follows:

[0013] CF3CHCLF + CH3CL 高温裂解 CF3CCLFCH3(R244bb)→CF3CF=CH2(R1234yf).

[0014] Further, the reaction process of the main reaction in step two is as follows:

[0015]

[0016]

[0017]

[0018] Further, the side reaction process of the main reaction in step two is as follows:

[0019]

[0020]

[0021]

[0022]

[0023]

[0024] The application has the beneficial effect that the method for co-production of R244bb and R1234yf by using CH3CL and C2HCLF4 as raw materials, which adopts the method for producing the fourth generation refrigerant HFO at low cost, prolongs the industrial chain of R124, promotes the use of R124 as raw material for preparing the new refrigerant R1234yf, avoids the problem of high global warming potential (GWP) caused by direct use of R124, and improves the environmental protection performance. BRIEF DESCRIPTION OF DRAWINGS

[0025] The drawings described herein are used to provide further understanding of the application, form part of the application, and do not constitute improper limitations on the application, in the drawings:

[0026] Figure 1 is the hydrogen spectrum analysis chart of the ninth sampling in experiment one in hydrogen spectrum analysis chart legend one in the application;

[0027] Figure 2 is the analysis result analysis chart of the ninth sampling in experiment one in hydrogen spectrum analysis chart legend one in the application.

[0028] Figure 3 is the hydrogen spectrum analysis chart of the tenth sampling in experiment one in hydrogen spectrum analysis chart legend two in the application;

[0029] Figure 4 is the analysis result analysis chart of the tenth sampling in experiment one in hydrogen spectrum analysis chart legend two in the application.

[0030] Figure 5 is the hydrogen spectrum analysis chart of the eleventh sampling in experiment one in hydrogen spectrum analysis chart legend three in the application;

[0031] Figure 6 is the analysis result analysis chart of the eleventh sampling in experiment one in hydrogen spectrum analysis chart legend three in the application.

[0032] Figure 7 is the hydrogen spectrum analysis chart of the eighth sampling in experiment two in hydrogen spectrum analysis chart legend four in the application;

[0033] Figure 8 is the analysis result analysis chart of the eighth sampling in experiment two in hydrogen spectrum analysis chart legend four in the application.

[0034] Figure 9 is the hydrogen spectrum analysis chart of the ninth sampling in experiment two in hydrogen spectrum analysis chart legend five in the application;

[0035] Figure 10 is the analysis result analysis chart of the ninth sampling in experiment two in hydrogen spectrum analysis chart legend five in the application.

[0036] Figure 11 is the hydrogen spectrum analysis chart of the 13th sampling of the experiment 2 in the hydrogen spectrum analysis chart legend 6 in the present application;

[0037] Figure 12 is the analysis result chart of the 13th sampling of the experiment 2 in the hydrogen spectrum analysis chart legend 6 in the present application;

[0038] Figure 13 is the hydrogen spectrum analysis chart of the 15th sampling of the experiment 2 in the hydrogen spectrum analysis chart legend 7 in the present application;

[0039] Figure 14 is the analysis result chart of the 15th sampling of the experiment 2 in the hydrogen spectrum analysis chart legend 7 in the present application.

[0040] Figure 15 is the hydrogen spectrum analysis chart of the 16th sampling of the experiment 2 in the hydrogen spectrum analysis chart legend 7 in the present application;

[0041] Figure 16 is the analysis result chart of the 16th sampling of the experiment 2 in the hydrogen spectrum analysis chart legend 7 in the present application. DETAILED DESCRIPTION

[0042] The present application will be described in detail below with reference to the accompanying drawings and specific embodiments, wherein the schematic embodiments and the description are only used to explain the present application, but not as a limitation to the present application.

[0043] The method for co-producing R244bb and R1234yf using CH3CL and C2HCLF4 as raw materials in the present embodiment adopts the following steps:

[0044] Step one: take chloromethane raw material and tetrafluoro-monochloroethane raw material for standby;

[0045] Step two: put the chloromethane raw material and tetrafluoro-monochloroethane raw material in step one into a conventional cracking furnace to perform cracking reaction to generate R244bb and R1234yf products;

[0046] Step three: when CH3CL and C2HCLF4 in the cracking reaction in step two crack off one H+ ion and one CL- ion to generate one HCL molecule, the product is R244bb, and R244bb is C3H3CLF4;

[0047] Step four: when R244bb in the cracking process in step three continues to crack off one HCl, the product is R1234yf and HCL.

[0048] Further, the temperature of the conventional cracking furnace in step two is 600-800°C.

[0049] Further, the reaction formula of the main reaction in step two is as follows:

[0050] CF3CHCLF + CH3CL 高温裂解 CF3CCLFCH3(R244) → CF3CF=CH2(R1234yf).

[0051] Further, the reaction process of the main reaction in step two is as follows:

[0052]

[0053]

[0054]

[0055] Further, the side reaction process of the main reaction in step two is as follows:

[0056]

[0057]

[0058]

[0059]

[0060]

[0061] The present application is further illustrated by practical examples as follows:

[0062] The present application carries out experiments of R124+CH3CL reaction under different conditions, and a plurality of experiments are carried out. The experiment is stopped after 6 hours, and the raw material is recharged.

[0063] I. Reaction system: tubular furnace Φ50xΦ50x1000, three-stage, heated section 900, central constant temperature zone 300, volume 0.147L.

[0064] II. Experimental process: after the tubular furnace is heated to the set temperature, R124 is started to be fed, and the set feeding amount is adjusted. The R124 heated decomposition components are analyzed, and after the R124 feeding is stable, CH3CL is started to be fed. After the set flow is adjusted, the product gas composition under different conditions is analyzed.

[0065] III. Experimental data: Note: the raw material composition of R124 is R124: 95.6%, R114: 0.5%, and R123: 3.9%.

[0066]

[0067]

[0068]

[0069] Four, experimental results analysis, as follows:

[0070] (1) reaction at 600-650 degrees temperature, the main product is R244bb, 600 degrees below difficult to react, 650-700 degrees reaction equilibrium to product R1234yf move, 700 degrees above easy carbonization.

[0071] (2) the same temperature, increase the feed ratio of R124, can not improve the conversion rate of R1234yf.

[0072] (3) under the same conditions, increase the R124 and CH3CL feed amount, namely the space velocity increases, residence time decreases, R1234yf content reduces, the conversion rate reduces.

[0073] (4) under the same conditions, improve the reaction concentration of chloromethane is beneficial to the generation of R244B component, the concentration of R1234yf component reduces.

[0074] (5), by adjusting the feed ratio can make the target product R244bb selectivity increases to 78.8%

[0075] Five, hydrogen spectrum analysis spectrum legend analysis as follows:

[0076] In the present application, hydrogen spectrum analysis spectrum legend one, the first experiment 9th sampling analysis chart: hydrogen spectrum analysis spectrum, as shown in Figure 1 , the analysis results as shown in Figure 2 .

[0077] In the present application, hydrogen spectrum analysis spectrum legend two, the first experiment 10th sampling analysis chart: hydrogen spectrum analysis spectrum, as shown in Figure 3 , the analysis results as shown in Figure 4 .

[0078] In the present application, hydrogen spectrum analysis spectrum legend three, the first experiment 11th sampling analysis chart: hydrogen spectrum analysis spectrum, as shown in Figure 5 , the analysis results as shown in Figure 6 .

[0079] In the present application, hydrogen spectrum analysis spectrum legend four, the second experiment 8th sampling analysis chart: hydrogen spectrum analysis spectrum, as shown in Figure 7 , the analysis results as shown in Figure 8 .

[0080] In the present application, hydrogen spectrum analysis chart legend five, the second experiment of the 9th sampling analysis chart: hydrogen spectrum analysis chart, as shown in Figure 9 ; analysis results as shown in Figure 10 .

[0081] In the present application, hydrogen spectrum analysis chart legend six, the second experiment of the 13th sampling analysis chart: hydrogen spectrum analysis chart, as shown in Figure 11 ; analysis results as shown in Figure 12 .

[0082] In the present application, hydrogen spectrum analysis chart legend seven, the second experiment of the 15th sampling analysis chart: hydrogen spectrum analysis chart, as shown in Figure 13 ; analysis results as shown in Figure 14 .

[0083] In the present application, hydrogen spectrum analysis chart legend eight, the second experiment of the 16th sampling analysis chart: hydrogen spectrum analysis chart, as shown in Figure 15 ; analysis results as shown in Figure 16 .

[0084] The effects of the present application are as follows:

[0085] The present application is beneficial to find low-cost production of HFO series products, prolong the R124 industry chain, and promote the use of R124 as a new refrigerant R1234yf preparation raw material. In the laboratory experiment, R1234yf product can reach a conversion rate of 30% in the R124 single-pass conversion process, and in mass production, the optimized process design, raw material recycling, and full heat exchange can be used for continuous production, achieving ideal yield.

[0086] The above is only the preferred embodiment of the present application, so any equivalent changes or modifications made according to the characteristics and principles described in the present application patent application scope are included in the present application patent application scope.

Claims

1. A process for the co-production of R244bb and R1234yf using CH3CL and C2HCLF4 as starting materials, characterized in that: Adopting the following steps: Step one: take chloromethane raw material and tetrafluoro-chloroethane raw material, standby; Step two: put the chloromethane raw material and tetrafluoro-chloroethane raw material in step one into a conventional cracking furnace, the temperature of the conventional cracking furnace is 640 DEG C, 650 DEG C, carry out cracking reaction, generate CF3CCLFCH3 and R1234yf product; Step three: in the cracking reaction in step two, when CH3CL and C2HCLF4 crack off one H+ ion and one CL- ion, generate one HCL molecule, the product is R244bb, R244bb is C3H3CLF4; Step four: when R244bb in the cracking process in step three continues to crack off one HCl, the product is R1234yf and HCL. The reaction formula of the main reaction in step two is as follows:

2. The method for co-production of R244bb and R1234yf using CH3CL and C2HCLF4 as raw materials according to claim 1, characterized in that: CF3CHCLF+CH3CL→CF3CCLFCH3→CF3CF=CH2. ​

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