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Catalyst for liquid-phase selective hydrogenation of alkynes and dialkenes, and preparation method and application thereof

A hydrogenation catalyst and diene liquid technology, which is applied in chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, etc., can solve the difficulty of large-scale industrialization and reduce reaction options Problems such as stability and coking degree are reduced, and the effects of prolonging the stable operation period, reducing the degree of aggregation, and improving the hydrogenation capacity are achieved.

Active Publication Date: 2018-05-01
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

CN104098427A discloses a dual active component Pd and Ni supported catalyst, its carrier alumina has a bimodal pore distribution structure, and the anti-coking component Ni is distributed in the macropores of the carrier, so that the coking degree on the surface of the catalyst is greatly reduced, However, Ni, as an important active metal in the full hydrogenation reaction, can easily cause excessive hydrogenation of propylene to generate propane, reducing the reaction selectivity
CN104415752A discloses a nano-precious metal alloy active component Pd-X supported catalyst, the metal X is one of Ag, Au and Cu, the alloy active component is loaded on the surface of the carrier in the form of nano-alloy particles, the particle composition is uniform, and the particle composition is uniform. The diameter distribution is narrow, the dispersion is good, the utilization rate of active components is effectively improved, and it has good activity and selectivity in the carbon three-liquid phase selective hydrogenation reaction. High precision, long process, difficult large-scale industrialization

Method used

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  • Catalyst for liquid-phase selective hydrogenation of alkynes and dialkenes, and preparation method and application thereof
  • Catalyst for liquid-phase selective hydrogenation of alkynes and dialkenes, and preparation method and application thereof
  • Catalyst for liquid-phase selective hydrogenation of alkynes and dialkenes, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0058] ① Preparation of Bi(NO 3 ) 3 and KNO containing 2.5gK 3 200ml of aqueous solution, 500g of spherical carrier Al 2 o 3 Immersed in the aqueous solution, dried at 105°C, and calcined at 1000°C to obtain Bi and K modified carrier Al 2 o 3 , with a specific surface area of ​​450m 2 / g;

[0059] ② Preparation of Pd(NO 3 ) 2 200ml of aqueous solution, the Bi and K modified carrier Al 2 o 3 Immerse in the solution, dry at 105°C, and bake at 500°C to obtain Pd / Al 2 o 3 catalyst;

[0060] ③ Preparation of GaCl containing 1gGa 3 200ml of aqueous solution, the solution is sprayed on Pd / Al 2 o 3 On the catalyst, dry at 105°C and bake at 350°C to obtain Pd-Ga 2 o 3 / Al 2 o 3 catalyst;

[0061] ④ In an adiabatic fixed-bed reactor, use a mixed gas of methane and hydrogen containing 90% hydrogen to reduce at 320°C for 6 hours with a temperature control range of ±1°C to obtain catalyst NC3-1, wherein the Pd content is 0.1wt%, Ga content is 0.2wt%, Bi content is 1wt%...

Embodiment 2

[0063] ① Preparation of Zn(NO 3 ) 2 and MgCl with 2.5 gMg 2 250ml of aqueous solution, 500g tooth carrier Al 2 o 3 Immersed in the aqueous solution, dried at 110°C, and calcined at 1100°C to obtain Zn and Mg modified carrier Al 2 o 3 , with a specific surface area of ​​120m 2 / g;

[0064] ② Preparation of [(NH 4 ) 2 Pd]Cl 4 250ml of aqueous solution, Zn and Mg modified carrier Al 2 o 3 Immerse in the solution, dry at 105°C, and bake at 550°C to obtain Pd / Al 2 o 3 catalyst;

[0065] ③ Preparation of Ga(NO) containing 0.5gGa 3 ) 3 278ml of ethanol solution, the solution is impregnated in Pd / Al 2 o 3 On the catalyst, dry at 90°C and bake at 430°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 70% hydrogen to reduce at 270°C for 4 hours, and the temperature control range is ±1°C to obtain catalyst NC3-2, wherein the Pd content is 0.06wt%. The Ga content is 0.1 wt%, t...

Embodiment 3

[0068] ⑤ Preparation of HAuCl containing 1gAu 4 235ml of n-butanol solution, 500g column carrier Al 2 o 3 Immersed in the solution, dried at 130°C, and calcined at 1070°C to obtain Au-modified carrier Al 2 o 3 , with a specific surface area of ​​340m 2 / g;

[0069] ⑥ Preparation of PdCl containing 0.375gPd 2 265ml of aqueous solution, the Au-modified carrier Al 2 o 3 Immerse in the solution, dry at 105°C, and bake at 520°C to obtain Pd / Al 2 o 3 catalyst;

[0070] ⑦Prepare 265ml of an aqueous solution of gallium trifluoromethanesulfonate containing 0.65gGa, and impregnate the solution in Pd / Al 2 o 3On the catalyst, dry at 120°C and bake at 370°C to obtain Pd-Ga 2 o 3 / Al 2 o 3 catalyst;

[0071] 8. In an adiabatic fixed-bed reactor, use a mixed gas of nitrogen and hydrogen containing 85% hydrogen to reduce at 300° C. for 8 hours with a temperature control range of ± 1° C. to obtain catalyst NC3-3, wherein the Pd content is 0.075 wt %, The Ga content is 0.13 wt%...

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Abstract

The invention discloses a catalyst for liquid-phase selective hydrogenation of alkynes and dialkenes, 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 Ga2O3 exists in the form of an amorphous gamma crystal phase; Ga is obtained through partial reduction of Ga2O3; the reduction degree of Ga in Ga2O3 is 10-70%; the content of Pd accounts for 0.04 to 0.20 wt% of the total mass of the carrier; and the total content of Ga accounts for 0.02-0.80 wt% of the totalmass of the carrier. The catalyst provided by the invention has high activity and stability in liquid-phase selective hydrogenation of C3 and is applicable to long-period operation.

Description

technical field [0001] The invention relates to the field of catalysts, in particular to a liquid-phase selective hydrogenation catalyst for alkynes and dienes, a preparation method and application. Background technique [0002] The cracked gas produced by the cracking of hydrocarbons on the ethylene industrial device contains 0.1-0.5% of acetylene, and 0.2-0.9% of methyl acetylene and propadiene (hereinafter referred to as MAPD). During the separation process of cracked gas, acetylene is enriched in the carbon 2 fraction, and MAPD is enriched in the carbon 3 fraction, and the MAPD in the carbon 3 fraction is about 1-5%. In order to obtain polymer grade propylene, MAPD must be removed to the required index. MAPD mainly adopts gas-phase catalytic selective hydrogenation, liquid-phase catalytic selective hydrogenation and catalytic distillation to remove MAPD in the third fraction of carbon in industrial devices. [0003] Liquid-phase catalytic selective hydrogenation proces...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/62C07C7/163C07C7/167C07C11/06C07C11/24
Inventor 卫国宾彭晖毛祖旺李前戚文新
Owner CHINA PETROLEUM & CHEM CORP
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