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Catalyst for preparing chlorine by oxidation of hydrogen chloride and preparation thereof

a hydrogen chloride and catalyst technology, applied in the direction of chloride preparation, physical/chemical process catalysts, metal/metal-oxide/metal-hydroxide catalysts, etc., can solve the problem of low added value of produced hydrochloric acid, difficult to find hydrogen chloride outlets, and oversupply of sodium hydroxide, etc. problems, to achieve the effect of improving stability, reducing price and being easy to prepar

Inactive Publication Date: 2013-10-31
WANHUA CHEM GRP CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

The invention provides a new catalyst for making chlorine by oxidizing hydrogen chloride. This new catalyst overcomes the problems of current copper-based catalysts. It is easy to prepare and has good activity and stability. Compared to other noble metals like gold and ruthenium, the new catalyst is more affordable and environmentally friendly. It also has better stability than other copper-based catalysts. The new catalyst achieves a higher yield of chlorine under high space velocity of hydrogen chloride. Compared to existing copper-based catalysts, it can improve the yield of chlorine by 1%-4% and even by 4%-5%.

Problems solved by technology

This process has two big problems.
While when sodium hydroxide requirements do not coincide with the demand for chlorine which increases greatly due to the rapid development of chlorine-consuming industries, oversupply of sodium hydroxide occurs.
As the rapid development of chlorine-consuming industries, it is increasingly difficult to find outlets for hydrogen chloride.
The resulting by-produced hydrochloric acid has low added value, needs high cost for transport and storage and the sale is difficult.
Also, 20-50 times of waste water produced in subsequent applications generates a great deal of pressure on the environment.
In the case of co-production of PVC, the domestic capacity of PVC is much excessive, and the export amount, price and utilization of capacity are always unsatisfied.
Thus, under the current conditions, the outlet of hydrogen chloride has become a bottleneck restricting further development of the chlorine-consuming industries.
Thus, its equipment investment and operational cost are high, and its operation is complex and lack of flexibility.
However, it still has an electricity consumption level of above 1700 kWh per ton chlorine, and thereby the status of high electricity-consumption in the production of chlorine is not substantially improved.
Furthermore, in comparison to ion-membrane electrolysis, the method of oxidative electrolysis of hydrochloric acid requires more complex equipments and has no advantages in economical efficiency and operability.
Objectively, the method of catalytic oxidation of hydrogen chloride also requires relatively large equipment investment, and in general, the cost for production of chlorine is estimated to be slightly higher than that of the method of ion membrane electrolysis according to the present technique of Sumitomo (Japan).
Among them, gold and ruthenium-based catalysts are expensive and have poor performance in sulfur-tolerance.
Chromium-based catalysts pollute the environment due to their higher toxicity.
Thus, the above two kinds of catalysts have such problems of high economic cost or environmental pollution or the like in use.
However, this catalyst has a relatively low activity, and the loss of the cupric chloride ingredient under a higher temperature impairs the use life of the catalyst.
With 25 g of this catalyst, the hydrogen chloride conversion is 83.6% with both of hydrogen chloride and oxygen flow rates of 200 ml / min at a reaction temperature of 380° C. However, this catalyst still has the disadvantages of loss of copper ingredients and a relatively low space velocity.
The process of preparation of the catalyst needs organic solvents and thus causes great environmental pollution.
Therefore, it is still a technical challenge in the related field to develop a cheap, environment-friendly catalyst with high activity and stability for production of chlorine by catalytic oxidation of hydrogen chloride.

Method used

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  • Catalyst for preparing chlorine by oxidation of hydrogen chloride and preparation thereof

Examples

Experimental program
Comparison scheme
Effect test

example 1

[0035]In a 40 ml of aqueous solution that contains 26.3 g CuCl2.2H2O, 60 g of HY molecular sieve (rare earth HY molecular sieve, manufactured by Mingmeiyoujie Mining Co. Ltd., Mingguang City, the same below) is impregnated for 12 h, then dried at 90° C. for 16 h. The resultant solid is re-dispersed in a 50 ml of aqueous solution that contains 0.92 g H3BO3, 4.95 g KCl, 8.15 g Ce(NO3)3.6H2O and 4.05 g Nd(NO3)3.6H2O to perform impregnation for 12 h, then dried at 90° C. for 16 h. The dried solid is calcined at 500° C. for 4 h to obtain 90 g of active catalyst. It is tableted to obtain catalyst granules of 30-60 mesh. 6 g of the catalyst of 30-60 mesh is loaded in a fixed bed reactor to conduct a reaction with of the flow rates of hydrogen chloride and oxygen of 100 ml / min respectively, with the reaction temperature at 380° C. and the reaction pressure at 0.18 MPa. After 4 h of reaction, the chlorine yield is 88.6%; and after 100 h of reaction, the chlorine yield is 89.0%. The activity ...

example 2

[0039]In a 41 ml of aqueous solution that contains 26.3 g CuCl2.2H2O, 60 g kaolin is impregnated for 12 h, then dried at 90° C. for 16 h. The resultant solid is re-dispersed in a 49 ml of aqueous solution that contains 1.15 g H3BO3, 4.95 g KCl, 8.15 g Ce(NO3)3.6H2O and 4.05 g La(NO3)3.6H2O to perform impregnation for 12 h, then dried at 90° C. for 16 h. After being calcined at 500° C. for 4 h, 90 g of active catalyst is obtained. It is tableted to obtain catalyst granules of 30-60 mesh. With the same reaction conditions as in Example 1, the chlorine yield is 86.1% after 4 h of reaction and is 85.8% after 100 h of reaction. The activity of the catalyst substantially remains unchanged. After 1000 h of reaction, the catalyst still keeps its activity with the chlorine yield of 85.4%.

example 3

[0040]In a 45 ml of aqueous solution that contains 17.8 g CuCl2.2H2O and 11.5 g Co(NO3)2.6H2O, 60 g HY molecular sieve is impregnated for 12 h, then dried at 90° C. for 16 h. The resultant solid is re-dispersed in a 50 ml of aqueous solution that contains 0.46 g H3BO3, 4.95 g KCl, 8.15 g Ce(NO3)3.6H2O and 4.05 g Pr(NO3)3.6H2O to perform impregnation for 12 h, then dried at 90° C. for 16 h. After being calcined at 500° C. for 4 h, 86 g of active catalyst is obtained. It is tableted to obtain catalyst granules of 30-60 mesh. With the same reaction conditions as in Example 1, the chlorine yield is 86.4% after 4 h of reaction and is 86.8% after 100 h of reaction. The catalyst keeps a stable activity. The chlorine yield is 86.0% after 1000 h of reaction.

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Abstract

The present invention relates to a catalyst for producing chlorine by oxidation of hydrogen chloride and a method for preparing the same. The catalyst comprises a support and active ingredients that comprise 1-20 wt % of copper, 0.01-5 wt % of boron, 0.1-10 wt % of alkali metal element(s), 0.1-15 wt % of one or more rare earth elements, and 0-10 wt % of one or more elements selected from magnesium, calcium, barium, manganese, iron, nickel, cobalt, zinc, ruthenium or titanium based on the total weight of the catalyst. The catalyst is prepared by a two-step impregnation method. Comparing with the available catalysts of the same type, the catalyst according to the present invention has greatly improved conversion and stability.

Description

FIELD OF THE INVENTION[0001]The present invention relates to a catalyst for preparing chlorine by the oxidation of hydrogen chloride and a method for producing the same.BACKGROUND OF THE INVENTION[0002]Chlorine is an important basic chemical material which has been widely used in the industries of novel materials such as polyurethanes, silicons, epoxy resins, chlorinated rubbers, chlorinated polymers, chlorinated hydrocarbons and the like; the new energy industries such as manufacture of polycrystalline silicon and the like; the industries of fine chemicals such as disinfectors, detergents, food additives, cosmetic additives and the like; the industries of pesticides / pharmaceuticals such as synthetic glycerin, chlorobenzenes, chloroacetic acid, benzyl chloride, PCl3 and the like; as well as the industries of paper manufacture, textile industries, metallurgy industries and petroleum and chemical industries, etc.[0003]Almost all chlorine is produced by the electrolysis of sodium chlor...

Claims

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Application Information

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IPC IPC(8): B01J29/14B01J23/83
CPCB01J29/146B01J23/83C01B7/04B01J37/0244B01J29/16Y02P20/20B01J27/138
Inventor YI, GUANGQUANLOU, YINCHUANWAN, YIWU, XUNKUNHUA, WEIQIDING, JIANSHENG
Owner WANHUA CHEM GRP CO LTD
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