CN116041138B - A method for co-producing R244bb and R1234yf using R134a and dichloromethane as raw materials - Google Patents
A method for co-producing R244bb and R1234yf using R134a and dichloromethane as raw materials Download PDFInfo
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- CN116041138B CN116041138B CN202210995858.0A CN202210995858A CN116041138B CN 116041138 B CN116041138 B CN 116041138B CN 202210995858 A CN202210995858 A CN 202210995858A CN 116041138 B CN116041138 B CN 116041138B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/263—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions
- C07C17/269—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by condensation reactions of only halogenated hydrocarbons
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Abstract
The invention particularly relates to a process technology method for co-producing R244bb and R1234yf by taking R134a raw material and dichloromethane raw material as raw materials, which comprises the following steps of firstly taking the R134a raw material and the dichloromethane raw material for standby, secondly placing the R134a raw material and the dichloromethane in the first step into a conventional cracking furnace for cracking reaction to generate R244bb and R1234yf products, thirdly, in the cracking reaction in the second step, when CH 2CL2 and C 2H2F4 are cracked to remove one H+ ion and one CL-ion to generate one HCL molecule, the R244bb is C 3H3CLF4, fourthly, when CH 2CL2 in the cracking process in the third step is cracked to remove two CL ‑ ions and C 2H2F4 is cracked to remove two H + ions, the R1234yf and HCL are obtained as products, and the application of the R134a serving as a new refrigerant R1234yf preparation raw material is prolonged, so that the problem of high warming potential caused by directly using the R134a is avoided.
Description
Technical Field
The invention relates to the technical field, in particular to a technical method for co-producing R244bb and R1234yf by taking R134a and methylene dichloride as raw materials.
Background
Hexafluoropropylene addition elimination method is adopted in R1234yf production enterprises in China, and 2-chloro-3, 3-trifluoro-propene fluorine-chlorine exchange method is adopted for the new fluorine material. The common defects of the process are that the upstream raw material cost is high, HF generated in the production has large corrosion to equipment, the tail gas treatment cost is high, the environment protection is difficult to reach standards, and the like.
The main products obtained using the pyrolysis of methylene chloride with 1, 2-tetrafluoroethane (R134 a) are trifluorochloropropane (R244 bb) and R1234yf, as well as HCL. The use of R134a as a refrigerant in the automotive industry has been banned in europe, and the invention is that R1234yf obtained by subjecting R134a to a pyrolysis reaction with methylene chloride is more widely used in the refrigeration industry.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provides a method for co-producing R244bb and R1234yf by taking R134a and methylene dichloride as raw materials.
The method for co-producing R244bb and R1234yf by using R134a and methylene dichloride as raw materials adopts the following steps:
step one, taking R134a raw material and dichloromethane raw material for standby;
Step two, placing the R134a raw material in the step one and dichloromethane in a conventional cracking furnace for cracking reaction to generate R244bb and R1234yf products;
In the cracking reaction in the second step, when CH 2CL2 and C 2H2F4 are cracked to separate out an H+ ion and a CL-ion to generate an HCL molecule, the product is R244bb, and R244bb is C 3H3CLF4;
And fourthly, separating two CL - ions from CH 2CL2 in the cracking process in the third step, and separating two H + ions from C 2H2F4 by cracking, wherein the products are R1234yf and HCL.
Further, the temperature of the conventional cracking furnace in the second step is 600-800 ℃.
Further, the main reaction of the cleavage reaction in step two is as follows:
further, the cleavage reaction in step two is reacted as follows:
further, the side reaction process of the cleavage reaction in the second step is as follows:
CF3·+·CL→CCLF3
The method for co-producing R244bb and R1234yf by using R134a and methylene dichloride as raw materials has the beneficial effects that the industrial chain of R134a is prolonged, the application of R134a as a new refrigerant R1234yf preparation raw material is promoted, and the problem of high Global Warming Potential (GWP) caused by directly using R134a is avoided.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate and together with the description serve to explain the application, if necessary:
FIG. 1 is a third sampled hydrogen spectrum analysis chart of the experiment in the hydrogen spectrum analysis chart of the present invention;
FIG. 2 is an analysis chart showing the analysis result of a third sampling of the experiment in the first hydrogen spectrum analysis chart of the present invention.
FIG. 3 is a diagram of hydrogen spectrum analysis of the sixth sample of experiment in the second example of hydrogen spectrum analysis map of the present invention;
FIG. 4 is a diagram showing the analysis results of the sixth sampling analysis of the experiment in the second example of the hydrogen spectrum analysis chart of the present invention;
FIG. 5 is an analysis chart of a hydrogen spectrum analysis chart of a ninth sample of experiment three in a hydrogen spectrum analysis chart illustration three in the present invention;
FIG. 6 is an analysis result analysis chart of the ninth sampling of experiment three in the hydrogen spectrum analysis chart diagram III in the present invention;
FIG. 7 is a diagram of hydrogen spectrum analysis of a tenth subsampled experiment in a fourth example of a hydrogen spectrum analysis map of the present invention;
FIG. 8 is an analysis result analysis chart of the tenth subsamples of experiment III in the hydrogen spectrum analysis chart diagram of the present invention;
FIG. 9 is a diagram showing a hydrogen spectrum analysis chart of an eleventh sample of experiment IV in a diagram of a hydrogen spectrum analysis chart in the present invention;
FIG. 10 is an analysis result analysis chart of the eleventh sample of experiment IV in the hydrogen spectrum analysis chart diagram of the present invention;
FIG. 11 is a diagram showing a hydrogen spectrum analysis chart of a seventh sample of the experiment in the sixth example of the hydrogen spectrum analysis chart of the present invention;
FIG. 12 is an analysis result analysis chart of the seventh sample of the experiment in the sixth hydrogen spectrum analysis chart of the present invention;
FIG. 13 is a diagram showing a hydrogen spectrum analysis chart of the fifth sample of the experiment in the seventh example of the hydrogen spectrum analysis chart of the present invention;
FIG. 14 is an analysis result analysis chart of the fifth sample of the experiment in the seventh hydrogen spectrum analysis chart of the present invention.
Detailed Description
The present invention will now be described in detail with reference to the drawings and the specific embodiments thereof, wherein the exemplary embodiments and the description are for the purpose of illustrating the invention only and are not to be construed as limiting the invention.
The method for co-producing R244bb and R1234yf by taking R134a and methylene dichloride as raw materials in the specific embodiment comprises the following steps:
step one, taking R134a raw material and dichloromethane raw material for standby;
Step two, placing the R134a raw material in the step one and dichloromethane in a conventional cracking furnace for cracking reaction to generate R244bb and R1234yf products;
In the cracking reaction in the second step, when CH 2CL2 and C 2H2F4 are cracked to separate out an H+ ion and a CL-ion to generate an HCL molecule, the product is R244bb, and R244bb is C 3H3CLF4;
And fourthly, separating two CL - ions from CH 2CL2 in the cracking process in the third step, and separating two H + ions from C 2H2F4 by cracking, wherein the products are R1234yf and HCL.
Further, the temperature of the conventional cracking furnace in the second step is 600-800 ℃.
Further, the main reaction of the cleavage reaction in step two is as follows:
further, the cleavage reaction in step two is reacted as follows:
further, the side reaction process of the cleavage reaction in the second step is as follows:
CF3·+·CL→CCLF3
The invention is further illustrated by taking practical test examples, namely experiments of R134a+CH 2CL2 reaction are carried out under different conditions, and the experiments are carried out for a plurality of times, the reaction is stopped for 6 hours, and the raw materials are added again.
1. The reaction system is that the tubular furnace phi 50x1000, the three-section type heating section 900 and the central constant temperature zone with the volume of 0.147L calculated by 300
2. In the experimental process, after the temperature of the tube furnace is increased to a set temperature, CH 2CL2 is started, the feeding amount is adjusted to be set, CH 2CL2 is subjected to thermal decomposition component collection analysis, after CH 2CL2 is fed stably, R134a is started, after the feeding amount is adjusted to be set, and the composition of product gas is analyzed under different conditions.
3. Experimental data:
4. analysis of experimental results:
(1) R134a and CH 2CL2 start to decompose at 400-700 ℃, the temperature is high, the decomposition proportion is high, but the product components in different temperature areas are different.
(2) The ratio of the generated R1234yf is larger than that of the generated R244bb in the reaction within the range of 400-600 ℃, and the conversion rate of the R1234yf can reach 18%;
(3) In the 600-700 degree range, the ratio of R1234yf produced is lower than that of R244bb, and the conversion of R244bb reaches about 38% calculated on methylene chloride.
(4) Increasing the feed ratio of R134a at the same temperature advantageously increases the conversion of R244bb and decreases the conversion of R1234 yf.
(5) At about 680 degrees, the feed amount of R134a and CH2CL2 is increased, namely the airspeed is increased, the residence time is reduced, the contents of R1234yf and R244bb are increased, and the conversion rate is increased.
(6) Under the same conditions, when the ratio of R134a to CH 2CL2 is larger than the theoretical ratio, the generation of R244 products is favored, and when the ratio is smaller than the theoretical ratio, the generation of R1234yf is favored.
(7) In the experimental process, the highest selectivity of the R244bb target product is 84.4 percent and the highest selectivity of the R1234yf target product is 69.09 percent is obtained by adjusting the feeding ratio of R134a and CH 2CL2
5. The hydrogen spectrum analysis pattern is analyzed as follows:
In the invention, a hydrogen spectrum analysis chart is shown in a figure 1, and an experiment shows that the analysis result is shown in a figure 2, namely a3 rd sampling analysis chart is shown in the figure.
In the invention, a hydrogen spectrum analysis chart is shown in a second diagram, a6 th sampling analysis chart of an experiment is shown in a figure 3, and an analysis result is shown in a figure 4.
In the invention, the hydrogen spectrum analysis chart is shown in a third diagram, the 9 th sampling analysis chart of the experiment is shown in fig. 5, and the analysis result is shown in fig. 6.
In the invention, the hydrogen spectrum analysis chart is shown in a fourth diagram, the 12 th sampling analysis chart of the experiment is shown in fig. 7, and the analysis result is shown in fig. 8.
In the invention, the hydrogen spectrum analysis chart is shown in a fifth sample analysis chart of experiment four 11, the hydrogen spectrum analysis chart is shown in fig. 9, and the analysis result is shown in fig. 10.
In the invention, the hydrogen spectrum analysis chart is shown in a figure 11, and the analysis result is shown in a figure 12.
In the invention, the hydrogen spectrum analysis chart is shown in a seventh sample analysis chart of experiment five and 6 times, the hydrogen spectrum analysis chart is shown in fig. 13, and the analysis result is shown in fig. 14.
The invention is beneficial to searching for low-cost HFO series products, prolonging the industrial chain of R134a and popularizing the application of R134a as a raw material for preparing a new refrigerant R1234 yf. In laboratory experiments, the conversion rate of a product R244bb can reach about 40% as calculated by CH 2CL2, the conversion rate of R1234yf reaches 16%, the problem of low single conversion rate can be solved by adopting an optimized process design in mass production, and the conversion rate of reactants is improved by the principle of low-temperature separation and recycling of single unreacted raw materials.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the features and concepts described herein are therefore intended to be embraced therein.
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| CN109111339A (en) * | 2018-10-29 | 2019-01-01 | 中国科学院上海有机化学研究所 | A kind of preparation method and device of 2,3,3,3- tetrafluoropropene |
| CN111925274A (en) * | 2020-09-17 | 2020-11-13 | 北京宇极科技发展有限公司 | Preparation method of Z-1-chloro-3, 3, 3-trifluoropropene |
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| GB9311742D0 (en) * | 1992-06-10 | 1993-07-21 | Ici Plc | Production of hydrofluoroalkanes |
| JP5713016B2 (en) * | 2010-06-23 | 2015-05-07 | 旭硝子株式会社 | Process for producing 1,1-dichloro-2,3,3,3-tetrafluoropropene and 2,3,3,3-tetrafluoropropene |
| ES2752461T3 (en) * | 2011-11-04 | 2020-04-06 | Honeywell Int Inc | Process to produce 2,3,3,3-tetrafluoropropene |
| CN113527040B (en) * | 2020-04-22 | 2023-09-01 | 浙江省化工研究院有限公司 | A kind of preparation method of halopropene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109111339A (en) * | 2018-10-29 | 2019-01-01 | 中国科学院上海有机化学研究所 | A kind of preparation method and device of 2,3,3,3- tetrafluoropropene |
| CN111925274A (en) * | 2020-09-17 | 2020-11-13 | 北京宇极科技发展有限公司 | Preparation method of Z-1-chloro-3, 3, 3-trifluoropropene |
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