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Chromium-free environmentally-friendly catalyst used for gas phase fluorination synthesis of 3,3,3-trifluoropropene

A technology of trifluoropropene and catalyst, which is applied in physical/chemical process catalyst, organic chemistry, dehydrohalogenation preparation, etc., can solve the problems of ecological environment pollution, human health threat, etc., and achieves good high temperature anti-sintering ability and anti-sintering performance Superior, the effect of inhibiting carbon deposition

Active Publication Date: 2019-05-07
XIAN MODERN CHEM RES INST
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] The catalysts for gas-phase fluorination reactions reported above all use chromium as the core component. However, as a heavy metal element, chromium, a large amount of discharge will cause serious pollution to the ecological environment; especially hexavalent chromium is a highly toxic substance that is harmful to animals and humans. health poses a serious threat

Method used

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  • Chromium-free environmentally-friendly catalyst used for gas phase fluorination synthesis of 3,3,3-trifluoropropene
  • Chromium-free environmentally-friendly catalyst used for gas phase fluorination synthesis of 3,3,3-trifluoropropene
  • Chromium-free environmentally-friendly catalyst used for gas phase fluorination synthesis of 3,3,3-trifluoropropene

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Experimental program
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Effect test

Embodiment 1

[0027] Embodiment 1: prepare M / MgF 2 catalyst

[0028] Dissolve 1.0M magnesium source and 0.01-0.1M modified metal ions in 50mL polyol solvent, and add the fluorinating reagent dropwise to the above solution under stirring at 150-240°C for 15 minutes. Stir again for 6-12h to obtain M / MgF 2 Dry gel; then calcined in an air or hydrogen atmosphere at 300-500°C for more than 5 hours, and finally fluorinated the calcined material at a temperature of 150-400°C to obtain a catalyst. The fluorine reagents are gaseous hydrogen fluoride and dichlorodifluoromethane , one chlorodifluoromethane, one chlorotrifluoromethane any one. The textural properties of magnesium fluoride prepared under different magnesium sources, polyol solvents, coagulants, fluorinating reagents, and calcination temperatures are shown in Table 1.

[0029] The physicochemical property result of the magnesium fluoride-based catalyst of table 1 embodiment 1

[0030]

[0031]

Embodiment 2

[0033] Adopt the same method to prepare M / MgF in embodiment 1 2 Catalyst, apply it to the gas-phase fluorination of 1,1,1,3-tetrachloropropane to synthesize HFO-1243f. After running for 12 hours, the reaction results are as follows:

[0034] The reaction evaluation result of the magnesium fluoride-based catalyst of table 2 embodiment 2

[0035]

Embodiment 3

[0037] Adopt the same method to prepare M / MgF in embodiment 1 2 Catalyst, apply it to the gas-phase fluorination of 1,1,1,3-tetrachloropropane to synthesize HFO-1243f. After running for 12 hours, the reaction results are as follows:

[0038] The reaction evaluation result of the magnesium fluoride-based catalyst of table 3 embodiment 3

[0039]

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Abstract

The invention discloses a chromium-free environmentally-friendly catalyst used for gas phase catalysis synthesis of 3,3,3-trifluoropropene by reacting 1,1,1,3-tetrachloropropane with hydrogen fluorideand a preparation method of the catalyst. The invention aims to solve the problems that a traditional chromium-based fluorination catalyst has environmental problems, and a series of serious pollution and health problems caused by a large use amount of heavy metal chromium. The catalyst composition disclosed by the invention is M / MgF2, wherein the substrate MgF2 is a high-stability MgF2 having arutile phase, a nano spherical structure, a specific surface area of more than 120 m<2> / g, and excellent anti-sintering properties at 500 DEG C, and the active component M is one or more selected fromthe group consisting of Co<3+>, Ni<2+>, Fe<3+>, Zn<2+>, La<3+>, Al<3+>, Ga<3+>, Mn<4+> and Cu<2+>. The preparation of the catalyst comprises the following steps: (1) preparing a metal ion doped polyol solution containing a magnesium source, and adding a fluorinating reagent dropwise at 150-240 DEG C to obtain a catalyst dry gel; and (2) performing calcination on the dry gel at 300-500 DEG C, andfinally performing fluorination treatment at 150-400 DEG C to prepare the chromium-free high-performance catalyst.

Description

technical field [0001] The invention relates to a catalyst, in particular to a chromium-free and environment-friendly catalyst for synthesizing 3,3,3-trifluoropropene by gas-phase catalyzing the reaction of 1,1,1,3-tetrachloropropane and hydrogen fluoride. Background technique [0002] 3,3,3-Trifluoropropene, referred to as HFO-1243zf or TFP, has an ozone depletion value (ODP) of 0 and a greenhouse effect potential (GWP) of only 0.29, which can be used as a synthetic and environmentally friendly refrigerant2,3,3,3 - The basic raw material of tetrafluoropropene (HFO-1234yf), which can also be used to prepare mixed refrigerants to replace R22, R134a and R410A, and can also be used as a monomer to synthesize polymer materials such as fluorosilicone rubber and fluorosilicone oil. [0003] So far, among the many known synthesis methods of HFO-1243zf, the one-step gas-phase fluorination synthesis using 1,1,1,3-tetrachloropropane and anhydrous hydrogen fluoride as raw materials has...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J27/128B01J27/138B01J27/125B01J27/12B01J27/122B01J35/10B01J35/08C07C17/25C07C21/18B82Y30/00B82Y40/00
Inventor 毛伟吕剑贾兆华白彦波秦越韩升王博郝志军石磊
Owner XIAN MODERN CHEM RES INST
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