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Catalyst for preparing furan by decarbonylation of furfural, preparation method and application

A catalyst and catalyst technology for decarbonylation of furan, applied in chemical instruments and methods, physical/chemical process catalysts, metal/metal oxide/metal hydroxide catalysts, etc., can solve the problems of easy deactivation, poor stability, and environmental pollution and other problems, to avoid the formation of polymers, prolong the stable operation period, and avoid the effect of excessive loss

Active Publication Date: 2019-11-12
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the 1960s and 1970s, metal oxide catalysts such as Zn-Cr and Zn-Cr-Mn were developed. The advantages are low cost, high furan yield, and higher activity than oxidative decarboxylation catalysts. However, due to poor stability, the catalytic activity decreases rapidly. At the same time, due to harsh reaction conditions and serious environmental pollution, it was gradually eliminated by industry
The biggest disadvantage of the liquid phase decarbonylation method is that the Pd content of the catalyst is high and the stability is too poor, and it is easy to deactivate

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] ① Preparation of La(NO 3 ) 3 and CaCl containing 1gCa 2 50ml of aqueous solution, 100g of spherical carrier Al 2 o 3 Immersed in the aqueous solution, dried at 105°C, and calcined at 840°C to obtain La and Ca-modified carrier Al 2 o 3 , with a specific surface area of ​​845m 2 / g;

[0054] ②Prepare 50ml of aqueous solution of palladium acetate containing 0.32gPd, and the carrier Al modified by La and Ca 2 o 3 Immerse in the solution, dry at 105°C, and bake at 580°C to obtain Pd / Al 2 o 3 catalyst;

[0055] ③ Preparation of Ga(NO) containing 0.8gGa 3 ) 3 50ml of aqueous solution, the solution is sprayed on Pd / Al 2 o 3 On the catalyst, dry at 110°C and bake at 580°C to obtain Pd-Ga 2 o 3 / Al 2 o 3 catalyst;

[0056] ④ In an adiabatic fixed-bed reactor, use a mixed gas of methane and hydrogen containing 80% hydrogen to reduce at 550°C for 4 hours, and the temperature control range is ±2°C to obtain catalyst MC-1, wherein the Pd content is 0.32wt%. The Ga...

Embodiment 2

[0058] ① Preparation of KNO containing 1gK 3 and Co(NO with 0.5gCo 3 ) 2 45ml of ethanol solution, 100g column carrier Al 2 o 3 Immersed in the solution, dried at 90°C, and calcined at 920°C to obtain K and Co modified carrier Al 2 o 3 , with a specific surface area of ​​532m 2 / g;

[0059] ② Preparation of PdCl containing 0.09gPd 2 60ml of aqueous solution, K and Co modified carrier Al 2 o 3 Immerse in the solution, dry at 110°C, and bake at 500°C to obtain Pd / Al 2 o 3 catalyst;

[0060] ③ Preparation of GaCl containing 0.25gGa 3 45ml of ethanol solution, the solution is impregnated in Pd / Al 2 o 3 On the catalyst, dry at 95°C and bake at 500°C to obtain Pd-Ga 2 o 3 / Al 2 o 3 catalyst;

[0061] ④ In an adiabatic fixed-bed reactor, use nitrogen and hydrogen mixed gas containing 70% hydrogen to reduce at 400°C for 8 hours, and the temperature control range is ±1°C to obtain catalyst MC-2, wherein the Pd content is 0.09wt%. The Ga content is 0.25 wt%, the K co...

Embodiment 3

[0063] ① Preparation of Cu(NO 3 ) 2 and 0.1gNi of Ni(NO 3 ) 2 57ml of aqueous solution, 100g tooth carrier Al 2 o 3 Immersed in the solution, dried at 105°C, and calcined at 880°C to obtain Cu and Ni modified carrier Al 2 o 3 , with a specific surface area of ​​607m 2 / g;

[0064] ② Preparation of PdCl containing 0.18gPd 2 45ml of isopropanol solution, the Cu and Ni modified carrier Al 2 o 3 Immerse in the solution, dry at 135°C, and bake at 550°C to obtain Pd / Al 2 o 3 catalyst;

[0065] ③Prepare 57ml of an aqueous solution of gallium trifluoromethanesulfonate containing 0.6gGa, and impregnate the solution in Pd / Al 2 o 3 On the catalyst, dry at 105°C and bake at 550°C to obtain Pd-Ga 2 o 3 / Al 2 o 3 catalyst;

[0066] ④ In an adiabatic fixed-bed reactor, use a mixed gas of nitrogen and hydrogen containing 55% hydrogen to reduce at 450°C for 6 hours, and the temperature control range is ±1°C to obtain catalyst MC-3, wherein the Pd content is 0.18wt%. The Ga ...

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Abstract

The invention discloses a catalyst applied to decarbonylation of furfural for preparation of furan, and a preparation method and application thereof. The catalyst comprises an Al2O3 carrier, and a main component Pd and an auxiliary active component Ga-Ga2O3 loaded on the carrier, wherein the auxiliary active component Ga is prepared through partial reduction of Ga2O3; the reduction degree of Ga inGa2O3 is 10-70%; the content of Pd accounts for 0.05 to 0.4 wt% of the total weight of the carrier; and the total content of Ga in the auxiliary active component Ga-Ga2O3 accounts for 0.1-5.0 wt% ofthe total weight of the carrier. The catalyst provided by the invention has high activity and stability in gas-phase decarbonylation of furfural for preparation of furan and is slow in inactivation speed and long in operation period.

Description

technical field [0001] The invention relates to the field of furan preparation, and furthermore, relates to a catalyst for preparing furan by decarbonylation of furfural, a preparation method and application. Background technique [0002] Furan is one of the important intermediate substances, widely used in many important organic synthesis such as pyrrole, thiophene, tetrahydrofuran and drug synthesis. Furfural is a cheap and easy-to-obtain organic chemical raw material, which is generally produced from crop waste. my country is a large agricultural country with abundant raw materials for furfural production. At present, there are more than 200 furfural production plants with an annual output of nearly 200,000 tons of furfural. The export volume accounts for 1 / 3 of the global trade volume. my country has become the world's major Furfural producing and exporting countries. The yield of furan produced by furfural decarbonylation is relatively high, therefore, the production o...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J23/62B01J23/63B01J23/89C07D307/36
CPCB01J23/62B01J23/63B01J23/896C07D307/36
Inventor 卫国宾戚文新穆玮李前石瑞红
Owner CHINA PETROLEUM & CHEM CORP
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