Nickel-based catalyst and preparation method therefor

A catalyst and nickel-based technology, applied in the field of nickel-based catalysts and their preparation, can solve the problems of poor hydrogenation stability and achieve good hydrogenation effect, long regeneration cycle and strong activity

Active Publication Date: 2015-11-25
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Chinese patent CN1218822A has reported a kind of Ni / Al 2 o 3 A selective hydrogenation catalyst suitable for pyrolysis gasoline fractions, the catalyst is nickel supported on Al containing lithium or alkaline earth metal 2 o 3 Made on the carrier, using this catalyst, it can only be carried out at a low feed space velocity, and the hydrogenation stability is not good

Method used

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  • Nickel-based catalyst and preparation method therefor

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028] Preparation of vector

[0029] Take the specific surface area as 176m 2 / g , the pore volume is 0.7ml / g Bar Aluminum Oxide 100 g , impregnated with 50ml of titanium sulfate in a 0.6g / ml dilute sulfuric acid solution, stirred for 20 minutes, and dried at 110oC for 10 hours to obtain alumina-titanium oxide.

[0030] Then mix the prepared alumina-titanium oxide and ZSM-5 powder, add a certain amount of 2% dilute nitric acid solution, knead and extrude, dry at 110oC for 12 hours, and roast at 500oC for 6 hours. Alumina-titania, ZSM-5 composite carrier 1 was prepared.

[0031] Catalyst preparation

[0032] Add 5.02g of nickel nitrate to 5ml of water and stir to dissolve, add 0.45g of chromium nitrate while stirring, adjust the pH value to 5, impregnate on 10g of alumina-titanium oxide, ZSM-5 composite carrier 1, and dry at 120oC for 6 Hours later, it was calcined at 600°C for 5 hours to prepare catalyst A.

Embodiment 2-6

[0034] Preparation of vector

[0035] Choose 100g of alumina with different specific surfaces and different pore volumes respectively, which are respectively B: the specific surface is 140m 2 / g , the pore volume is 0.9ml / g ; C: Specific surface is 160m 2 / g , the pore volume is 0.9ml / g ; D: Specific surface is 170m 2 / g ,

[0036] The pore volume is 1.0ml / g ; E: Specific surface is 220m 2 / g , the pore volume is 0.9ml / g ; F: Specific surface is 190m 2 / g , the pore volume is 1.1ml / g; with the method of embodiment 1, change the ratio of alumina-titanium oxide and ZSM-5 powder and the content of active component nickel oxide to prepare catalyst B, C, D, E, F. Catalyst composition is as shown in table 1:

[0037] Table 1. Catalyst composition

[0038] Example 1 2 3 4 5 6 Catalyst number A B C D E F ZSM-5 content (weight%) 70 60 50 40 30 65 TiO 2 / Al 2 o 3 Content (weight%) 30 40 50 60 70 35 Nickel ...

Embodiment 7-10

[0040] Use embodiment catalyst B, E to C respectively 6 -C 9 The distillate was subjected to selective hydrogenation, and the reaction evaluation was in 100ml

[0041] It is carried out on the isothermal bed hydrogenation reaction device, the catalyst is first reduced under 450oC hydrogen medium for 10 hours,

[0042] Then, the reaction pressure is 2.0MPa and the reaction temperature is 50oC, and the constant feedstock oil space velocity of 2.0h- 1 , Evaluation of 100 hours, every 8 hours sampling analysis bromine value, diene, bromine value analyzed in the catalyst 100 hour evaluation, the average data of diene are shown in Table 3.

[0043] Table 2, raw material properties

[0044] project analysis results color yellow density 0.8659 Bromine value (g bromine / 100g oil) 31.85 Diene (g iodine / 100 g oil) 15.02

[0045] Table 3, embodiment catalyst 100 hours evaluation average data

[0046]

[0047] Note: The bromine value and diene ...

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Abstract

The present invention relates to a nickel-based catalyst. The catalyst is prepared by loading metallic nickel active components on a composite carrier which consists of an aluminum oxide-titanium oxide complex and ZSM-5, wherein in the catalyst, a weight ratio of aluminum oxide and titanium oxide is 4:1; a content of nickel oxide is 12%-20% by weight; the aluminum oxide-titanium oxide takes 30%-70% of the entire composite carrier by weight, the ZSM-5 takes 30%-70% of the entire composite carrier by weight; the surface area of the catalyst is 90-260 m 2/g; and the pore volume is 0.5-1.5 ml/g. The catalyst has characteristics of good low-temperature hydrogenation activity, strong anti-impurity ability and sol ability, a long regeneration cycle, and good stability. Applying the catalyst to a process in which diene is converted to monoolefins through selective hydrogenation can maintain a good hydrogenation effect.

Description

technical field [0001] The invention belongs to the technical field of diolefin selective hydrogenation catalysts, and relates to a nickel-based catalyst, a preparation method thereof and the application of the catalyst in the process of diolefin selective hydrogenation conversion into monoolefin. Background technique [0002] The by-products of ethylene cracking contain a large amount of highly unsaturated hydrocarbons, such as: diolefins, styrene, etc., which are converted into corresponding monoolefins through selective hydrogenation. With the continuous enhancement of my country's ethylene production capacity, the selective hydrogenation of dienes has been developed in the direction of nickel-based catalysts. Precious metal catalysts are easy to occupy the empty orbitals of Pd due to impurity arsenic, and the Pd content is only a few thousandths, located on the surface of the catalyst, its anti-arsenic and anti-colloid ability is poor, and non-noble metal catalysts have ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J29/46C10G45/36
Inventor 季静柴忠义纪玉国张富春任玉梅杜周
Owner CHINA PETROLEUM & CHEM CORP
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