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Adsorption desulfurizer for ultra-deep removal of thiophene in coke oven gas and preparation method thereof

A technology for adsorption desulfurization and coke oven gas, which is applied in chemical instruments and methods, other chemical processes, and combustible gas purification, etc., and can solve the problem of reduced industrial production efficiency, limited open-loop hydrogenation capacity, and utilization rate of active components of adsorption desulfurizers. Low problems, to achieve the effect of simple and easy preparation, low operating conditions and low requirements for the device

Active Publication Date: 2021-06-08
TAIYUAN UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0006] However, at a temperature of 180-250°C and a space velocity of 5000h -1 Under certain working conditions, the adsorption capacity of commercial copper-zinc-aluminum composite oxide adsorption desulfurizer for thiophene is about 17 mg / g, and the utilization rate of the active component copper is less than 1%.
The reason for the low utilization rate of the active components of the adsorption desulfurizer is mainly due to the insufficient dispersion of the hydrogenation active center copper in the copper-zinc-aluminum composite oxide adsorption desulfurizer prepared by the traditional co-precipitation method, and the copper is not good enough for the ring-opening of thiophene. Hydrogenation capacity is limited
[0007] Furthermore, the process of loading and reducing the adsorption desulfurizer in industrial production is extremely complicated. If the adsorption desulfurizer is replaced frequently, it will inevitably lead to a significant reduction in industrial production efficiency and cause great losses.

Method used

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  • Adsorption desulfurizer for ultra-deep removal of thiophene in coke oven gas and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035] Weigh 7.248g of copper nitrate trihydrate, 8.925g of zinc nitrate hexahydrate, 2.251g of aluminum nitrate nonahydrate, 0.233g of nickel nitrate hexahydrate and 1.717g of zirconium nitrate pentahydrate, and dissolve them together in 200mL of deionized water to prepare copper and zinc A metal salt solution with a total ion concentration of 0.30 mol / L and an atomic ratio of Cu:Zn:Al:Ni:Zr=15:15:3:0.4:2.

[0036] Weigh 9.540g of anhydrous sodium carbonate, dissolve it in 180mL deionized water, and prepare 0.50mol / L Na 2 CO 3 solution.

[0037] The above metal salt solution and Na 2 CO 3 The solution was added dropwise into a container with heating and stirring, and the temperature of the reaction system in the container was kept at 60° C. and the pH value was 7.0 during the dropwise addition.

[0038] After the dropwise addition, the temperature of the reaction solution was raised to 80° C. and continued stirring for 2 h, cooled to room temperature, and suction filtered...

Embodiment 2

[0043] Weigh 7.248g of copper nitrate trihydrate, 8.925g of zinc nitrate hexahydrate, 2.251g of aluminum nitrate nonahydrate, 0.291g of nickel nitrate hexahydrate and 0.859g of zirconium nitrate pentahydrate, and dissolve them together in 120mL of deionized water to prepare copper and zinc A metal salt solution with a total ion concentration of 0.50 mol / L and an atomic ratio of Cu:Zn:Al:Ni:Zr=15:15:3:0.5:1.

[0044] Weigh 9.540g of anhydrous sodium carbonate, dissolve it in 300mL of deionized water, and prepare 0.30mol / L Na 2 CO 3 solution.

[0045] The above metal salt solution and Na 2 CO 3 The solution was added dropwise into a container with heating and stirring, and the temperature of the reaction system in the container was kept at 70° C. and the pH value was 7.1 during the dropwise addition.

[0046] After the dropwise addition, the temperature of the reaction solution was raised to 75° C. and continued stirring for 2.5 h, cooled to room temperature, and suction fil...

Embodiment 3

[0050] Weigh 7.248g of copper nitrate trihydrate, 8.925g of zinc nitrate hexahydrate, 2.251g of aluminum nitrate nonahydrate, 0.1162g of nickel nitrate hexahydrate and 1.288g of zirconium nitrate pentahydrate, and dissolve them together in 75mL of deionized water to prepare copper and zinc A metal salt solution with a total ion concentration of 0.80 mol / L and an atomic ratio of Cu:Zn:Al:Ni:Zr=15:15:3:0.2:1.5.

[0051] Weigh 9.540g of anhydrous sodium carbonate, dissolve it in 225mL of deionized water, and prepare 0.40mol / L Na 2 CO 3 solution.

[0052] The above metal salt solution and Na 2 CO 3 The solution was added dropwise into a container with heating and stirring, and the temperature of the reaction system in the container was kept at 65° C. and the pH value was 7.2 during the dropwise addition.

[0053] After the dropwise addition, the temperature of the reaction solution was raised to 70° C. and continued stirring for 3 h, cooled to room temperature, and suction fil...

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Abstract

The invention provides an adsorption desulfurizer for ultra-deep removal of thiophene in coke oven gas, which consists of active components copper oxide and zinc oxide, carrier aluminum oxide, and metal additives nickel oxide and zirconium oxide. Including 30-50% of copper oxide, 30-50% of zinc oxide, 5-10% of aluminum oxide, 1-4% of nickel oxide and 2-15% of zirconia, and keep the atomic ratio of zirconium to nickel at 2-8 , The atomic ratio of copper to zirconium is 3-15. The adsorption desulfurizer is mainly used to realize ultra-deep removal of thiophene in coke oven gas after hydrogen reduction. The invention improves the dispersion and hydrogenation activity of the active components of the adsorption desulfurizer by regulating the ratio of nickel and zirconium in the adsorption desulfurizer, further improves the sulfur capacity of the adsorption desulfurizer, and realizes the ultra-deep concentration of thiophene in coke oven gas removal, and prolong the service life of the adsorption desulfurizer.

Description

technical field [0001] The invention belongs to the technical field of coke oven gas purification, and relates to an adsorption desulfurizer for coke oven gas, in particular to an adsorption desulfurizer for removing thiophene in coke oven gas. Background technique [0002] my country's coking industry is developing rapidly, and the output of coke oven gas is relatively high. Coke oven gas is widely used, and the synthesis of natural gas through methanation is one of its important uses. [0003] Coke oven gas methanation catalyst is the core of coke oven gas methanation process, and has the most direct impact on coke oven gas methanation. However, sulfur compounds in coke oven gas can lead to poisoning and deactivation of methanation catalysts and degradation of the quality of the synthesized natural gas products. [0004] Before methanation, the inorganic sulfur and most of the organic sulfur in the coke oven gas are relatively easy to remove, and most of the residual sul...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): B01J20/08B01J20/30B01J23/80C10K1/00C10K1/32C10K1/34
CPCB01J20/06B01J20/08B01J23/002B01J23/80C10K1/004C10K1/32C10K1/34
Inventor 廖俊杰卫藩婧王建成郭佳伟胡江亮常丽萍鲍卫仁
Owner TAIYUAN UNIV OF TECH