Fluorinated chrome base fluorination catalyst and application thereof

A technology of chromium fluoride-based fluorination catalyst and chromium-based fluorination catalyst, which is used in physical/chemical process catalysts, organic chemistry, dehalogenation preparation, etc., can solve the problem of low catalytic activity, short catalytic life, easy carbon deposition, etc. question

Active Publication Date: 2012-06-27
XIAN MODERN CHEM RES INST
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] At present, chromium-based fluorination catalysts are mainly used in the synthesis of hydrofluorocarbons (HFCs), and can also be used in the fluorination reactions of a series of hydrofluoroolefins (HFOs) and hydrofluorochloroole...

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Implementation with reference to the mass percent composition of the following chromium-based fluorination catalyst precursor:

[0024] Chromium Oxide: 80.0%; Rare Earth Metal Oxide CeO 2 : 7.0%, La 2 o 3 : 5.0%, Nd 2 o 3 : 2.0%, Y 2 o 3 : 2.0%, ZrO 2 : 2.0%, Yb 2 o 3 : 2.0%.

[0025] Catalyst preparation:

[0026] Chromium chloride, Ce(NO 3 ) 4 , La(NO 3 ) 3 , Nd(NO 3 ) 3 , Y(NO 3 ) 3 , Zr(NO 3 ) 4 and Yb(NO 3 ) 3 Add ammonia water under stirring at a temperature of 20°C to 90°C, adjust the pH value of the above aqueous solution to 7.5 to 8.5, let it stand still, filter, wash the obtained filter cake with water, and dry the obtained filter cake at a temperature of 100°C to 200°C After the filter cake is formed, it is pressed into tablets and baked at 300°C to 400°C for 8 hours to obtain a catalyst precursor. The resulting precursor is granulated, shaped, and fluorinated with hydrogen fluoride gas at 350°C to 450°C for 12 hours , to obtain chromiu...

Embodiment 2

[0030] Implementation with reference to the mass percent composition of the following chromium-based fluorination catalyst precursor:

[0031] Chromium Oxide: 80.0%; Rare Earth Metal Oxide CeO 2 : 20.0%.

[0032] Catalyst preparation:

[0033] The catalyst preparation steps are basically the same as in Example 1, except that the mass percentage of the chromium-based fluorination catalyst precursor is different.

[0034] Catalyst application:

[0035]In a nickel tube fixed bed tubular reactor with an inner diameter of 38 mm, 60 ml of the above-mentioned prepared fluorination catalyst are charged, and HF and HCC-240fa are introduced to react, and the molar ratio of HF / HCC-240fa is controlled to be 10: 1. The contact time is 5.5 seconds, the reaction temperature is 200°C, the reaction product is washed with water and alkali to remove HCl and HF, and reacted for 20 hours. The conversion rate of HCC-240fa is 100% and the selectivity of HCFO-1233zd is 94.0% according to gas chrom...

Embodiment 3

[0037] Implementation with reference to the mass percent composition of the following chromium-based fluorination catalyst precursor:

[0038] Chromium Oxide: 99.0%; Rare Earth Metal Oxide La 2 o 3 : 1.0%.

[0039] Catalyst preparation:

[0040] The catalyst preparation steps are basically the same as in Example 1, except that the mass percentage of the chromium-based fluorination catalyst precursor is different.

[0041] Catalyst application:

[0042] In a nickel tube fixed bed tubular reactor with an internal diameter of 38 mm, 60 ml of the above-mentioned prepared fluorination catalyst are charged, and HF and 1,1,1,2,2-pentachloropropane (HCC-240ab) are introduced to react , the molar ratio of HF / HCC-240ab is controlled to be 15:1, the contact time is 10.9 seconds, and the reaction temperature is 260°C. After the reaction product was washed with water and alkali to remove HCl and HF, it was reacted for 20 hours, and the conversion rate of HCC-240ab was 100% by gas chro...

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PUM

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Abstract

The invention discloses a fluorinated chrome base fluorination catalyst and application thereof. The weight percentage composition of a precursor of the catalyst is that chromic oxide 80.0%-99.0% and rare-earth metal oxide 1.0%-20.0%, wherein the rare-earth metal oxide is selected from one or more of CeO2, La2O3, Nd2O3, Y2O3, ZrO2 and Yb2O3. The precursor of the catalyst is roasted at 300 DEG C-400 DEG C, and the fluorinated chrome base fluorination catalyst is obtained by fluorating the precursor of the catalyst by utilizing hydrogen fluoride gas at 350-450 centidegree. The obtained fluorination catalyst has the advantages of being good in carbon deposit resistance performance and activation and the like. The catalyst is mainly used for preparation of hydrofluoroolefin and hydrogen fluorine chlorine olefins.

Description

technical field [0001] The invention relates to a chromium fluoride-based fluorination catalyst for synthesizing hydrofluoroolefins and its application. In particular, it relates to a fluorination catalyst for the vapor phase fluorination of halocarbons to produce hydrofluoroolefins (HFOs) or hydrofluorochloroolefins (HCFOs). Background technique [0002] In recent years, due to global warming, hydrofluoroolefins (HFOs) and hydrofluorochloroolefins (HCFOs) have been largely used to replace hydrofluorocarbons (HFCs) with high greenhouse potentials (GWPs). [0003] In the fluorine chemical industry, HFOs and HCFOs are often prepared by gas-phase fluorinated halogenated hydrocarbons. This method has the advantages of simple equipment, easy continuous large-scale production, and safety. The fluorination catalyst plays a central role in the gas-phase fluorination of halogenated hydrocarbons. At present, the gas-phase fluorination catalysts used in industry are chromium-containi...

Claims

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Application Information

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IPC IPC(8): B01J27/132C07C21/18C07C17/20C07C17/25C07C17/10C07C17/23
Inventor 王博吕剑寇联岗李凤仙杜咏梅张伟毛伟秦越韩升刘波
Owner XIAN MODERN CHEM RES INST
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