Selective hydrogenation catalyst and preparation method and application thereof

A technology of selective hydrogenation and catalyst, which is applied in the preparation of the catalyst, the catalyst for selective hydrogenation of C8-C9 heavy fractions, and the field of pyrolysis gasoline C5-C9 fractions, which can solve the problems of low-temperature activity and selectivity and low-temperature activity. And other issues

Active Publication Date: 2015-09-30
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the low-temperature activity and selectivity of the catalyst need to be improved
[0006] Chinese patent application publication CN1361231A discloses a catalyst for selective hydrogenation of diolefins, the carrier is an aluminum-titanium composite oxide carrier prepared by chemical co-precipitation method, wherein the weight percentage content of alumina is 1-99%, and the carrier The pore size distribution has double peaks at 50nm and 1000nm. It supports Pd active components and optional IB and / or IA or IIA group metals. It has the advantages of high activity, high selectivity, strong resistance to sulfur and arsenic, but its low temperature Activity still needs to be improved

Method used

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  • Selective hydrogenation catalyst and preparation method and application thereof
  • Selective hydrogenation catalyst and preparation method and application thereof
  • Selective hydrogenation catalyst and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0066] step 1

[0067] (1) Using TiCl 4 Prepare 0.25mol / L TiCl with deionized water 4 aqueous solution;

[0068] (2) Using Al(NO 3 ) 3 9H 2 O crystal and deionized water prepare the aluminum nitrate aqueous solution of 1.55mol / L;

[0069] (3) use attapulgite and deionized water to prepare the attapulgite aqueous solution of 10g / L;

[0070] (4) According to Al 2 o 3 weight of TiCl 4 with TiO 2 The content of meter is 20% by weight and the attapulgite content is the amount of 1% by weight, solution A, B and C are mixed, obtain the mixed solution containing attapulgite, Ti and Al;

[0071] (5) Using the co-current co-precipitation method, in a constant temperature water bath at 40°C, 0.5mol / L (NH 4 ) 2 CO 3 Aqueous solution and prepared mixed solution containing attapulgite, Ti and Al, wherein the dropping rate of mixed solution is 60 drops / min, (NH 4 ) 2 CO 3 The dropping rate of the aqueous solution is 30 drops / min; after the dropwise addition is completed, adju...

Embodiment 2

[0079] Repeat the steps 1-3 of embodiment 1, difference is: in the sub-step (4) of step 1, according to based on aluminum nitrate with Al 2 o 3 weight of TiCl 4 with TiO 2 The content of the attapulgite is 20% by weight, and the content of attapulgite is 3% by weight. Solutions A, B and C are mixed to obtain a mixed solution containing attapulgite, Ti and Al.

[0080] As a result, in the attapulgite-titania-alumina composite oxide support obtained in Step 1, the content of attapulgite was 3% by weight based on the weight of alumina, and TiO 2 The content of is 20% by weight; and the specific surface area of ​​the carrier is 122m 2 / g, the most probable pore diameter is 17nm, and the pore volume is 0.50ml / g.

[0081] As a result, palladium-based catalyst 2 was obtained through step 3. The palladium content of the palladium-based catalyst 2 is 0.3% by weight, the cerium content is 0.3% by weight, and the crushing strength is 21 N / mm; in the carrier of the catalyst, the cont...

Embodiment 3

[0083] Steps 1-3 of Example 1 were repeated, except that the impregnation solution used in step 2 for impregnating the composite carrier was replaced with 90 ml of 0.2 mol / L lanthanum nitrate aqueous solution.

[0084] As a result, palladium-based catalyst 3 was finally obtained. Palladium-based catalyst 3 has a palladium content of 0.3% by weight, a lanthanum content of 0.3% by weight, and a crush strength of 21 N / mm; in the carrier of the catalyst, the content of attapulgite is 1% by weight based on the weight of alumina, TiO 2 The content based on the weight of alumina is 20% by weight; and the specific surface area of ​​the carrier is 128m 2 / g, the most probable pore diameter is 18nm, and the pore volume is 0.52ml / g.

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Abstract

The invention relates to a catalyst for selective hydrogenation of pyrolysis gasoline. The selective hydrogenation catalyst comprises an attapulgite-titanium oxide-aluminium oxide composite oxide as a carrier, and metal palladium active components and rare earth metal assistant metal which are loaded on the composite oxide carrier, wherein the content of metal palladium is 0.25-0.35wt%, the content of the assistant metal is 0-3wt%, and based on the content of aluminium oxide in the carrier, the content of attapulgite in the carrier is 0.1-3wt% and the content of titanium oxide in the carrier is 5-20wt%. The catalyst can be used for selective hydrogenation of pyrolysis gasoline and is high in low-temperature activity, high in selectivity, high in capacity of resisting impurities including As, S, O and N, large in glue containing amount and stable in activity under long-time running condition. In addition, the invention also relates to a preparation method of the catalyst and application of the catalyst in the selective hydrogenation of pyrolysis gasoline. Finally, the invention further relates to a composite oxide carrier preparation method by adopting a cocurrent flow coprecipitation method.

Description

technical field [0001] The invention relates to a catalyst for selective hydrogenation of petroleum hydrocarbons, especially cracked gasoline C 5 -C 9 Fractions, especially C 8 -C 9 Catalysts for hydrogenation of heavy fractions. The invention also relates to the preparation method and application of the catalyst. Background technique [0002] pyrolysis gasoline C 5 -C 9 Distillate is a by-product of the ethylene industry. Depending on the cracking raw material and cracking depth, its output accounts for more than 50% by weight of the ethylene production capacity, and the content of aromatics accounts for 40-80% by weight, so it is the main source of aromatics. Cutting C on industrial production 8 and C 9 The distillate undergoes one-stage hydrogenation to remove highly unsaturated hydrocarbons, such as chain conjugated dienes, styrene, alkynes and cyclic conjugated dienes, and then undergoes two-stage hydrodesulfurization to remove monoenes, sulfur, and nitrogen , ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/63C10G47/14
Inventor 纪玉国季静柴忠义杜周任玉梅
Owner CHINA PETROLEUM & CHEM CORP
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