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Method for co-production of 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene

一种四氟丙烯、六氟丙烯的技术，应用在含氟烯烃的制备领域，能够解决产品成本高、工艺路线长、反应器腐蚀等问题，达到投资小、简化工艺流程、转化率高的效果

Active Publication Date: 2015-09-30
ZHEJIANG QUHUA FLUOR CHEM
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The raw material 3,3,3-trifluoropropene of 3,3,3-trifluoropropene method is not easy to obtain, the process of this kind of process is long, the three wastes are much, and the product cost is high; 1,1,2,3-tetrachloropropene method The preparation of 1,1,2,3-tetrachloropropene raw materials is relatively complicated, and there are more three wastes in the process; hexafluoropropylene can be prepared from difluorochloromethane (HCFC-22), so hexafluoropropylene is used as raw material to synthesize HFO -1234yf is an ideal process route from the perspective of the industrial chain
The disadvantage is that the process route is long, liquid phase dehydrofluorination, more wastes, low yield, serious corrosion inside the reactor

Method used

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  • Method for co-production of 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] 200ml Pd / AlF 3 Catalyst (the mass percentage composition of Pd is 0.3%) loads the C section of reactor, 300ml chromium-aluminum-zinc catalyst (by mass percentage, catalyst is composed of: 5% of chromium oxide, 90% of aluminum oxide, 5% of zinc oxide ) into section B, 200mlPd / Al 2 o 3 Catalyst (0.3% by mass of Pd) is loaded into section A. 700ml of chromium-indium-nickel catalyst (by mass percentage, catalyst composition: chromium oxide 60%, indium oxide 5%, nickel oxide 35%) was loaded into the second reactor.

[0041] Then the temperature of section A of the first reactor was raised to 55°C, the temperature of section B was raised to 200°C, and the temperature of the second reactor was raised to 300°C. When the temperature of the first reactor and the second reactor is raised, the temperature rise rate is 1°C / min from normal temperature to 150°C, and the temperature rise rate is 0.5°C / min above 150°C. After the temperature rise of the first reactor and the second r...

Embodiment 2

[0045] 200ml Pd / AlF 3 Catalyst (the mass percentage composition of Pd is 0.6%) loads the C section of reactor, 300ml chromium-aluminum-zinc catalyst (by mass percentage, catalyst is composed of: chromium oxide 10%, aluminum oxide 80%, zinc oxide 10% ) into section B, 200ml Pd / Al 2 o 3 Catalyst (the mass percent content of Pd is 1%) is loaded into section A. 700ml of chromium-indium-nickel catalyst (by mass percentage, catalyst composition: 80% chromium oxide, 10% indium oxide, 10% nickel oxide) was loaded into the second reactor.

[0046] Then, the temperature of section A of the first reactor was raised to 70°C, the temperature of section B was raised to 240°C, and the temperature of the second reactor was raised to 330°C. When the temperature of the first reactor and the second reactor is raised, the temperature rise rate is 1°C / min from normal temperature to 150°C, and the temperature rise rate is 0.5°C / min above 150°C. After the temperature rise of the first reactor an...

Embodiment 3

[0050] First 200ml Pd / C catalyst (the mass percentage composition of Pd is 0.3%) is packed into reactor C section, 300ml chromium-aluminum-zinc catalyst (by mass percentage, catalyst composition is: chromium oxide 8%, aluminum oxide 85% , ZnO 7%) into section B, 200ml Pd / Al 2 o 3 Catalyst (the mass percent content of Pd is 1.5%) is loaded into section A. 700ml of chromium-indium-nickel catalyst (by mass percentage, catalyst composition: chromium oxide 66%, indium oxide 7%, nickel oxide 27%) was loaded into the second reactor.

[0051]Then, the temperature of section A of the first reactor is raised to 65°C, the temperature of section B is raised to 250°C, and the temperature of the second reactor is raised to 350°C. When the first reactor and the second reactor are heated up, the temperature rise rate is 1°C / min, 150°C at a heating rate of 0.5°C / min. After the temperature rise of the first reactor and the second reactor was completed, nitrogen was passed into the reactor f...

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Abstract

The invention discloses a method for co-production of 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene. The method includes the following steps: the raw materials, namely hexafluoropropene and hydrogen, enter a first reactor after preheating, wherein the first reactor is divided into three sections A, B and C, and the three sections are filled with different catalysts; different reaction conditions are controlled for the reaction, so that a mixture of 1,1,1,2,3-pentafluoropropane, 1,1,1,2,3,3-hexafluoropropane and hydrogen fluoride is obtained; after separation, 1,1,1,2,3,3-hexafluoropropane returns to the lower part of the section A of the reactor, 1,1,1,2,3-pentafluoropropane and a small amount of hydrogen fluoride enter a second reactor and react under the action of a catalyst, so that a mixture of 2,3,3,3-tetrafluoropropene, 1,3,3,3-tetrafluoropropene, hydrogen fluoride and unreacted 1,1,1,2,3-pentafluoropropane is obtained; the products are washed with water and then with alkali, dried, and distilled to obtain 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene products. The method provided by the invention is simple in process, small in investment, low in energy consumption and high in conversion rate.

Description

technical field [0001] The invention relates to a preparation method of fluorine-containing olefins, in particular to a method for co-producing 2,3,3,3-tetrafluoropropene and 1,3,3,3-tetrafluoropropene. Background technique [0002] Hydrofluoroolefins (HFO), such as 2,3,3,3-tetrafluoropropene (HFO-1234yf) and 1,3,3,3-tetrafluoropropene (HFO-1234ze), the boiling point of HFO-1234yf is - 29.5°C, GWP value of 4, atmospheric life of 10 days, can be used as refrigerant, fire extinguishing agent, propellant, foaming agent, foaming agent, carrier fluid, polishing abrasive, power cycle working fluid. The more promising use of HFO-1234yf is in the field of refrigerants, as a fourth-generation refrigerant to replace 1,1,1,2-tetrafluoroethane (HFC-134a). There are two types of HFO-1234ze, type Z and type E. The boiling point of type Z is 9°C, the boiling point of type E is -19°C, and the GWP value is 6. Type Z can be used as a foaming agent, and type E can be mixed with other substanc...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C21/18C07C17/25C07C17/383
CPCC07C17/383C07C17/25C07C21/18C07C17/354C07C17/38C07C19/08
Inventor 雷俊王爱国杨波张彦周华东赵阳刘国安朱意苏刚
Owner ZHEJIANG QUHUA FLUOR CHEM
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