CN104923239A - Copper-based catalyst for preparing chlorine gas by catalyzing and oxidizing hydrogen chloride as well as preparation method and application thereof - Google Patents

Copper-based catalyst for preparing chlorine gas by catalyzing and oxidizing hydrogen chloride as well as preparation method and application thereof Download PDF

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CN104923239A
CN104923239A CN201510285017.0A CN201510285017A CN104923239A CN 104923239 A CN104923239 A CN 104923239A CN 201510285017 A CN201510285017 A CN 201510285017A CN 104923239 A CN104923239 A CN 104923239A
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hydrogen chloride
copper
chloride
catalyst
chlorine gas
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郭杨龙
孙宇
卢冠忠
詹望成
郭耘
王筠松
王丽
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East China University of Science and Technology
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East China University of Science and Technology
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Abstract

The invention discloses a copper-based catalyst for preparing chlorine gas by catalyzing and oxidizing hydrogen chloride as well as a preparation method and application thereof. The copper-based catalyst is prepared by loading copper chloride, potassium chloride, samarium chloride or samarium chloride and lanthanum chloride on the surface of an activated aluminium oxide carrier by using an impregnation method. The copper-based catalyst comprises the following components in percentage by weight: 3-20 percent of CuCl2, 1-7 percent of KCl, 2-25 percent of SmCl3, 0-15 percent of LaCl3 and 50-90 percent of Al2O3. The catalyst is an environment-friendly, high-performance and low-cost copper-based catalyst and is free of poisonous components including Cr element or high-cost ruthenium compounds; through the addition of samarium chloride, the catalysis performance of the loaded copper-based catalyst is greatly improved. The preparation method of the catalyst is the impregnation method; the preparation method is simple and is liable to operate; the industrialization is liable to implement; the catalyst is high in activity and excellent in stability.

Description

For the copper-based catalysts and its preparation method and application of catalytic oxidation of hydrogen chloride for preparing chlorine gas
Technical field
The present invention relates to the copper-based catalysts and its preparation method and application for catalytic oxidation of hydrogen chloride for preparing chlorine gas, specifically, adopt infusion process copper chloride, potassium chloride, samarium trichloride and lanthanum chloride load to be made on active aluminum oxide carrier surface.
Background technology
China's industrial by-product hydrogen chloride total amount nearly 4,000,000 tons/year, along with MDI, TDI, methane chloride etc. relate to the development of expanding production on a large scale of chlorine products and chlor-alkali industry, estimate that in the coming years, by-product hydrogen chloride total amount will reach 5,000,000 tons/year, the problem that recycles of a large amount of by-product hydrogen chloride has become a general character difficult problem for numerous industry developments such as restriction polyurethane, chlor-alkali, Organic fluoride industry, agricultural chemicals, medication chemistry.In isocyanate production processes, chlorine is the carrier of phosgene reaction process, and target approach product, is not finally converted into hydrogen chloride completely, the hydrogen chloride of this process by-product accounts for more than 50% of national by-product hydrogen chloride total amount, seriously restricts the fast development of isocyanates industry.If more than 300 ten thousand of China's by-product tons/year of hydrogen chloride are made chlorine recycle, 72.78 hundred million kilowatt hours of can economizing on electricity every year (2,550,000 tons/year, signature coal), indirectly reduce discharging 6,000 ten thousand tons all kinds of containing organic impurities waste water, economic benefit and social benefit huge.Be that chlorine produced by raw material with hydrogen chloride, realize chlorine resource circulation utilization, can effectively solve by-product hydrogen chloride problem, promote the sound development of new industry and the optimization and upgrading of chlor-alkali industry.Exploitation has the chlorine resource circulation utilization technology of China's independent intellectual property right, breaks foreign technology monopolization, is recycled by the chlorine for chemical processes such as China's polyurethane, chlor-alkali, Organic fluoride, pharmacy and provide important support with energy-saving and emission-reduction.
At present realized industrialization and stable operation take hydrogen chloride as the catalytic oxidation that raw material produces electrolysis of hydrochloric acid method that the method for chlorine is Beyer Co., Ltd and SUMITOMO CHEMICAL chemistry.Although Beyer Co., Ltd, by Continual Improvement, builds up the industrial production device of oxygen depolarization negative electrode (ODC) electrolysis hydrochloric acid preparing chlorine gas, and stable operation.But electrolysis exists that operating cost is high, investment is large and to shortcomings such as the impurity in salt acid starting material are very responsive, electrolysis of hydrochloric acid method cannot be applied on a large scale.And the catalytic oxidation of hydrogen chloride method, have that hydrogen chloride adaptability to raw material is strong, energy consumption is low and the advantage such as stable operation, become the future thrust of chlorine resource circulation utilization technology.The catalyst system that it is active constituent that SUMITOMO CHEMICAL chemical industry Co., Ltd. successfully develops with ruthenium-oxide, titanium oxide is carrier and the fixed bed reactors of 120,000 tons/year of scales, successively in ground practical applications such as MIT, Bayer Shanghai company and ten thousand Huaning ripple industry parks.But because the cost of ruthenium-based catalyst is higher, calculate with the catalyst life of 16000 hours, in the production cost of ton chlorine, catalyst is about 100 yuan.
The chemical equation of catalytic oxidation of hydrogen chloride for preparing chlorine gas is:
HCl+O 2? Cl 2+H 2O+57.8kJ
This chemical reaction has following characteristics: 1. this is the reversible reaction of a strong heat release, and by the restriction of thermodynamical equilibrium, the equilibrium conversion of HCl is lower.Raise reaction temperature to be conducive to improving reaction rate, but can equilibrium conversion be reduced; Although reduce reaction temperature equilibrium conversion can be improved, be reduction of reaction rate.2. because equilibrium conversion is not high, unreacted HCl and the H that may condense 2o combines and generates hydrochloric acid, brings serious equipment corrosion problem, simultaneously coagulated H 2o makes Catalyst Viscosity increase, and reduces the fluidizing performance of catalyst.3. in high-temperature reaction process, catalyst activity component easily runs off, and causes catalysqt deactivation.Therefore, for catalytic oxidation of hydrogen chloride for preparing chlorine gas reaction, be badly in need of a kind of catalyst at a lower reaction temperature with higher catalytic activity of exploitation.
US Patent No. 5716592 discloses the catalyst adopting chromated oxide and cerium compound, catalytic oxidation hydrogen chloride at 360 ~ 380 DEG C, the conversion ratio of hydrogen chloride reaches as high as 85.2%, but because chromium has larger toxicity, and chromium and chlorine very easily form lower boiling chromium oxychloride, easily make catalysqt deactivation.
It is carrier that US Patent No. 2007292336 discloses with tin oxide, and the oxide of load ruthenium is catalyst, and the conversion per pass of hydrogen chloride is between 15 ~ 90%.The ruthenium oxide catalysts that it is carrier that Chinese patent CN1145328A discloses with titanium oxide, aluminium oxide or zirconia, selects the presoma of one or more ruthenium compounds as active component of ruthenic chloride, ruthenic chloride ammino-complex and ruthenium carbonyl complex.But because ruthenium compound cost is higher, be unfavorable for its applying industrially.
Chinese patent CN101125297A discloses with load copper chloride, potassium chloride and cerium chloride on the alumina support as catalyst, then with phosphoric acid, this catalyst is processed, be 1:1 in the mol ratio of hydrogen chloride and oxygen, reaction temperature is 400 DEG C, and the weight space velocity of hydrogen chloride charging is 0.8h -1, the yield of product chlorine is 80.1%.
It is active component that Chinese patent CN102000583A discloses with copper chloride, take molecular sieve as carrier, with the addition of boron, alkali metal, rare earth metal and alkaline-earth metal, and adopt the method for two step dippings to prepare this catalyst, be 0.1 ~ 0.6MPa in reaction pressure, reaction temperature is 320 ~ 460 DEG C, and hydrogen chloride mass space velocity is 0.1 ~ 2.5h -1time, the conversion ratio of hydrogen chloride can reach more than 85%.
The copper oxide catalyst that it is carrier that US Patent No. 4123389 discloses with silica gel, titanium oxide or aluminium oxide, the load capacity of active component between 25 ~ 70%, but is carried out in organic solvent due to catalyst soakage process need, comparatively serious to the pollution of environment.
Chinese patent CN101862663A discloses a kind of Catalysts and its preparation method for catalytic oxidation of hydrogen chloride for preparing chlorine gas.This catalyst consists of CuCl 21 ~ 30%, KCl 1 ~ 15%, rare earth-iron-boron (lanthanum chloride, cerium chloride or praseodymium chloride) 1 ~ 25%, Al 2o 3carrier 55 ~ 95%.When reaction pressure is 0.1 ~ 0.4MPa, reaction temperature is 350 ~ 400 DEG C, and air speed is 0.3 ~ 1.5Nm 3during/(hkgCat), the conversion ratio of hydrogen chloride is 83.1 ~ 88.1%.
Though above-mentioned existing patented technology respectively has its feature, also respectively there is its weak point, such as: containing poisonous component Cr element, the shortcoming such as ruthenium compound cost is higher, the catalyst based catalytic activity of existing copper is lower, catalyst preparation process is more complicated.
Summary of the invention
The object of the invention is to improve a kind of copper-based catalysts for catalytic oxidation of hydrogen chloride for preparing chlorine gas and preparation method thereof, to overcome many weak points that existing catalyst exists.
Composition and the weight percent content thereof of the copper-based catalysts for catalytic oxidation of hydrogen chloride for preparing chlorine gas of the present invention are:
CuCl 23~20%，
KCl 1~7%，
SmCl 32~25%，
LaCl 30~15%，
Al 2O 350~90%。
The composition of preferred copper-based catalysts and weight percent content thereof are:
CuCl 210~20%，
KCl 3~7%，
SmCl 35~25%，
LaCl 30~15%，
Al 2O 350~70%。
Copper-based catalysts of the present invention adopts infusion process preparation, specifically comprises the steps:
By copper chloride, potassium chloride, samarium trichloride and lanthanum chloride with after water-soluble solution, add alumina support, then leave standstill 8 ~ 16h, at 100 ~ 120 DEG C of drying 8 ~ 16h, at 400 ~ 600 DEG C of roasting 3 ~ 8h in air atmosphere in room temperature successively.
Described copper-based catalysts is used in catalytic oxidation of hydrogen chloride for preparing chlorine gas reaction, its catalytic reaction condition is: fixed bed reactors, and reaction temperature is 300 ~ 450 DEG C, and reaction pressure is 0.1 ~ 0.5MPa, the mol ratio of hydrogen chloride and oxygen is 1:2 ~ 4:1, and air speed is 0.45 ~ 1.8Nm 3/ (hkgCat).
The remarkable advantage of catalyst of the present invention is, catalyst activity component is made up of copper chloride, potassium chloride, samarium trichloride or samarium trichloride and lanthanum chloride, not containing poisonous component Cr element or expensive ruthenium compound, and samarium trichloride add the catalytic performance substantially increasing carried copper-base catalyst, therefore, catalyst of the present invention belongs to the high performance low cost copper-based catalysts of environment-friendly type.
The remarkable advantage of method for preparing catalyst of the present invention is, adopt infusion process copper chloride, potassium chloride, samarium trichloride and lanthanum chloride load to be made on active aluminum oxide carrier surface, preparation method is simple, and catalyst activity is high, good stability.
Accompanying drawing explanation
Fig. 1 is the catalytic performance comparison diagram of carried copper-base catalyst.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in detail.
Comparative example
By 8.14g CuCl 22H 2o, 2.14g KCl and 6.39g LaCl 3nH 2o is dissolved in 18.0mL deionized water, is then impregnated on 30.0g alumina support, finally leaves standstill 12h in room temperature successively, at 120 DEG C of dry 12h, at 450 DEG C of roasting 5h in air atmosphere, obtains Cu-K-La/Al 2o 3catalyst.
By above-mentioned for 2.0g Cu-K-La/Al 2o 3catalyst loads in fixed bed reactors, and then hydrogen chloride and oxygen are introduced in fixed bed reactors with the charging rate of 15mL/min and 7.5mL/min respectively, reaction temperature is 370 DEG C, normal pressure, and reacting the hydrogen chloride conversion ratio after 4 hours is 82.9%.
Embodiment 1
By 10.36g CuCl 22H 2o, 2.73g KCl and 13.64g SmCl 3be dissolved in 18.0mL deionized water, be then impregnated on 30.0g alumina support, finally leave standstill 12h in room temperature successively, at 120 DEG C of dry 12h, at 450 DEG C of roasting 5h in air atmosphere, obtain Cu-K-Sm/Al 2o 3catalyst.
By above-mentioned for 2.0g Cu-K-Sm/Al 2o 3catalyst loads in fixed bed reactors, and then hydrogen chloride and oxygen are introduced in fixed bed reactors with the charging rate of 15mL/min and 7.5mL/min respectively, reaction temperature is 352 DEG C, normal pressure, and reacting the hydrogen chloride conversion ratio after 4 hours is 93.4%.
Embodiment 2
By 9.5g CuCl 22H 2o, 2.5g KCl and 10.0g SmCl 3be dissolved in 18.0mL deionized water, be then impregnated on 30.0g alumina support, finally leave standstill 12h in room temperature successively, at 120 DEG C of dry 12h, at 450 DEG C of roasting 5h in air atmosphere, obtain Cu-K-Sm/Al 2o 3catalyst.
By above-mentioned for 2.0g Cu-K-Sm/Al 2o 3catalyst loads in fixed bed reactors, and then hydrogen chloride and oxygen are introduced in fixed bed reactors with the charging rate of 15mL/min and 7.5mL/min respectively, reaction temperature is 370 DEG C, normal pressure, and reacting the hydrogen chloride conversion ratio after 4 hours is 89.8%.
Embodiment 3
By 9.5g CuCl 22H 2o, 2.5g KCl, 3.7g LaCl 3nH 2o and 7.5g SmCl 3be dissolved in 18.0mL deionized water, be then impregnated on 30.0g alumina support, finally leave standstill 12h in room temperature successively, at 120 DEG C of dry 12h, at 450 DEG C of roasting 5h in air atmosphere, obtain Cu-K-La-Sm/Al 2o 3catalyst.
By above-mentioned for 2.0g Cu-K-La-Sm/Al 2o 3catalyst loads in fixed bed reactors, then with the charging rate of 15mL/min and 7.5mL/min, hydrogen chloride and oxygen are introduced in fixed bed reactors respectively, reaction temperature is 358 DEG C, normal pressure, reacting the hydrogen chloride conversion ratio after 8 hours is 87.6%, through 120 hours, reacted hydrogen chloride conversion ratio was still 87.6%, and catalyst activity is substantially constant.
Embodiment 4
By 8.14g CuCl 22H 2o, 2.14g KCl and 4.29g SmCl 3be dissolved in 18.0mL deionized water, be then impregnated on 30.0g alumina support, finally leave standstill 12h in room temperature successively, at 120 DEG C of dry 12h, at 450 DEG C of roasting 5h in air atmosphere, obtain Cu-K-Sm/Al 2o 3catalyst.
By above-mentioned for 2.0g Cu-K-Sm/Al 2o 3catalyst loads in fixed bed reactors, and then hydrogen chloride and oxygen are introduced in fixed bed reactors with the charging rate of 15mL/min and 7.5mL/min respectively, reaction temperature is 365 DEG C, normal pressure, and reacting the hydrogen chloride conversion ratio after 4 hours is 70%.
Embodiment 5
By 8.14g CuCl 22H 2o, 2.14g KCl, 3.17g LaCl 3nH 2o and 2.14g SmCl 3be dissolved in 18.0mL deionized water, be then impregnated on 30.0g alumina support, finally leave standstill 12h in room temperature successively, at 120 DEG C of dry 12h, at 450 DEG C of roasting 5h in air atmosphere, obtain Cu-K-La-Sm/Al 2o 3catalyst.
By above-mentioned for 2.0g Cu-K-La-Sm/Al 2o 3catalyst loads in fixed bed reactors, and then hydrogen chloride and oxygen are introduced in fixed bed reactors with the charging rate of 15mL/min and 7.5mL/min respectively, reaction temperature is 370 DEG C, normal pressure, and reacting the hydrogen chloride conversion ratio after 4 hours is 83.5%.
Embodiment 6
By 9.5g CuCl 22H 2o, 2.5g KCl, 7.46g LaCl 3nH 2o and 5.0g SmCl 3be dissolved in 18.0mL deionized water, be then impregnated on 30.0g alumina support, finally leave standstill 12h in room temperature successively, at 120 DEG C of dry 12h, at 450 DEG C of roasting 5h in air atmosphere, obtain Cu-K-La-Sm/Al 2o 3catalyst.
By above-mentioned for 2.0g Cu-K-La-Sm/Al 2o 3catalyst loads in fixed bed reactors, and then hydrogen chloride and oxygen are introduced in fixed bed reactors with the charging rate of 15mL/min and 7.5mL/min respectively, reaction temperature is 372 DEG C, normal pressure, and reacting the hydrogen chloride conversion ratio after 4 hours is 90.3%.
Embodiment 7
By 9.5g CuCl 22H 2o, 2.5g KCl, 11.2g LaCl 3nH 2o and 2.5g SmCl 3be dissolved in 18.0mL deionized water, be then impregnated on 30.0g alumina support, finally leave standstill 12h in room temperature successively, at 120 DEG C of dry 12h, at 450 DEG C of roasting 5h in air atmosphere, obtain Cu-K-La-Sm/Al 2o 3catalyst.
By above-mentioned for 2.0g Cu-K-La-Sm/Al 2o 3catalyst loads in fixed bed reactors, and then hydrogen chloride and oxygen are introduced in fixed bed reactors with the charging rate of 15mL/min and 7.5mL/min respectively, reaction temperature is 374 DEG C, normal pressure, and reacting the hydrogen chloride conversion ratio after 4 hours is 88.6%.
Fig. 1 is the carried copper-base catalyst prepared of embodiment 1 ~ 7 and the Cu-K-La/Al for preparing of comparative example 2o 3the catalytic performance of catalyst compares, as can be seen from Figure 1, and SmCl 3add the catalytic performance substantially increasing carried copper-base catalyst.
Embodiment 8
By 1.58g CuCl 22H 2o, 0.42g KCl, 1.26g LaCl 3nH 2o and 0.83g SmCl 3be dissolved in 18.0mL deionized water, be then impregnated on 30.0g alumina support, finally leave standstill 8h in room temperature successively, at 100 DEG C of dry 8h, at 400 DEG C of roasting 3h in air atmosphere, obtain Cu-K-La-Sm/Al 2o 3catalyst.
By above-mentioned for 2.0g Cu-K-La-Sm/Al 2o 3catalyst loads in fixed bed reactors, then with the charging rate of 15mL/min and 7.5mL/min, hydrogen chloride and oxygen are introduced in fixed bed reactors respectively, reaction temperature is 300 DEG C, and reaction pressure is 0.2MPa, and reacting the hydrogen chloride conversion ratio after 4 hours is 88.1%.
Embodiment 9
By 14.26g CuCl 22H 2o, 3.75g KCl, 11.35g LaCl 3nH 2o and 7.5g SmCl 3be dissolved in 18.0mL deionized water, be then impregnated on 30.0g alumina support, finally leave standstill 16h in room temperature successively, at 120 DEG C of dry 16h, at 600 DEG C of roasting 8h in air atmosphere, obtain Cu-K-La-Sm/Al 2o 3catalyst.
By above-mentioned for 2.0g Cu-K-La-Sm/Al 2o 3catalyst loads in fixed bed reactors, then with the charging rate of 15mL/min and 7.5mL/min, hydrogen chloride and oxygen are introduced in fixed bed reactors respectively, reaction temperature is 447 DEG C, and reaction pressure is 0.5MPa, and reacting the hydrogen chloride conversion ratio after 4 hours is 85.1%.
Embodiment 10
By Cu-K-La-Sm/Al prepared by 2.0g embodiment 3 2o 3catalyst loads in fixed bed reactors, and then hydrogen chloride and oxygen are introduced in fixed bed reactors with the charging rate of 7.5mL/min and 15mL/min respectively, reaction temperature is 351 DEG C, normal pressure, and reacting the hydrogen chloride conversion ratio after 4 hours is 93.3%.
Embodiment 11
By Cu-K-La-Sm/Al prepared by 2.0g embodiment 3 2o 3catalyst loads in fixed bed reactors, and then hydrogen chloride and oxygen are introduced in fixed bed reactors with the charging rate of 11.25mL/min and 11.25mL/min respectively, reaction temperature is 352 DEG C, normal pressure, and reacting the hydrogen chloride conversion ratio after 4 hours is 92.0%.
Embodiment 12
By Cu-K-La-Sm/Al prepared by 2.0g embodiment 3 2o 3catalyst loads in fixed bed reactors, then with the charging rate of 18.0mL/min and 4.5mL/min, hydrogen chloride and oxygen are introduced in fixed bed reactors respectively, reaction temperature is 400 DEG C, and reaction pressure is 0.3MPa, and reacting the hydrogen chloride conversion ratio after 4 hours is 65.3%.
Embodiment 13
By Cu-K-La-Sm/Al prepared by 2.0g embodiment 3 2o 3catalyst loads in fixed bed reactors, and then hydrogen chloride and oxygen are introduced in fixed bed reactors with the charging rate of 10.0mL/min and 5.0mL/min respectively, reaction temperature is 351 DEG C, normal pressure, and reacting the hydrogen chloride conversion ratio after 4 hours is 92.6%.
Embodiment 14
By Cu-K-La-Sm/Al prepared by 2.0g embodiment 3 2o 3catalyst loads in fixed bed reactors, and then hydrogen chloride and oxygen are introduced in fixed bed reactors with the charging rate of 20mL/min and 10mL/min respectively, reaction temperature is 374 DEG C, normal pressure, and reacting the hydrogen chloride conversion ratio after 4 hours is 89.2%.
Embodiment 15
By Cu-K-La-Sm/Al prepared by 2.0g embodiment 3 2o 3catalyst loads in fixed bed reactors, and then hydrogen chloride and oxygen are introduced in fixed bed reactors with the charging rate of 30mL/min and 15mL/min respectively, reaction temperature is 365 DEG C, normal pressure, and reacting the hydrogen chloride conversion ratio after 4 hours is 86.2%.
Embodiment 16
By Cu-K-La-Sm/Al prepared by 2.0g embodiment 3 2o 3catalyst loads in fixed bed reactors, and then hydrogen chloride gas and oxygen are introduced in fixed bed reactors with the charging rate of 40mL/min and 20mL/min respectively, reaction temperature is 365 DEG C, normal pressure, and reacting the hydrogen chloride conversion ratio after 4 hours is 85.4%.

Claims (4)

1. for the copper-based catalysts of catalytic oxidation of hydrogen chloride for preparing chlorine gas, it is characterized in that, the composition of described catalyst and weight percent content thereof are:
CuCl 23~20%，
KCl 1~7%，
SmCl 32~25%，
LaCl 30~15%，
Al 2O 350~90%。
2. the copper-based catalysts for catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 1, is characterized in that, the composition of described catalyst and weight percent content thereof are preferably:
CuCl 210~20%，
KCl 3~7%，
SmCl 35~25%，
LaCl 30~15%，
Al 2O 350~70%。
3. prepare the method for the copper-based catalysts for catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 1 or claim 2, it is characterized in that, this preparation method is infusion process, specifically comprise the steps: copper chloride, potassium chloride, samarium trichloride and lanthanum chloride with after water-soluble solution, add alumina support, then 8 ~ 16h is left standstill, at 100 ~ 120 DEG C of drying 8 ~ 16h, at 400 ~ 600 DEG C of roasting 3 ~ 8h in air atmosphere in room temperature successively.
4. the application of the copper-based catalysts for catalytic oxidation of hydrogen chloride for preparing chlorine gas according to claim 1 or claim 2, it is characterized in that, described copper-based catalysts is used in catalytic oxidation of hydrogen chloride for preparing chlorine gas reaction, catalytic oxidation of hydrogen chloride for preparing chlorine gas reaction is carried out in fixed bed reactors, its catalytic reaction condition is: reaction temperature is 300 ~ 450 DEG C, reaction pressure is 0.1 ~ 0.5MPa, and the mol ratio of hydrogen chloride and oxygen is 1:2 ~ 4:1, and air speed is 0.45 ~ 1.8Nm 3/ (hkgCat).
CN201510285017.0A 2015-05-29 2015-05-29 Copper-based catalyst for preparing chlorine gas by catalyzing and oxidizing hydrogen chloride as well as preparation method and application thereof Pending CN104923239A (en)

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CN107952436A (en) * 2016-10-14 2018-04-24 中国石油化工股份有限公司 A kind of preparing chlorine by oxidizing hydrogen chloride copper-zirconium based catalyst and its preparation method and application
CN109675582A (en) * 2018-12-25 2019-04-26 西安近代化学研究所 A kind of preparing chlorine by oxidizing hydrogen chloride catalyst and preparation method thereof
CN110801842A (en) * 2019-11-26 2020-02-18 上海氯碱化工股份有限公司 Catalyst for preparing chlorine gas by catalytic oxidation of hydrogen chloride and preparation method and application thereof
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CN112044440A (en) * 2019-06-06 2020-12-08 中南大学 Catalyst for preparing chlorine gas by catalytic oxidation of hydrogen chloride and preparation method and application thereof
CN115814815A (en) * 2022-12-19 2023-03-21 浙江工业大学 Preparation method of hydrogen chloride catalytic oxidation catalyst based on alloy carrier
CN116618069A (en) * 2023-07-24 2023-08-22 山东东岳氟硅材料有限公司 Preparation method and application of catalyst for catalytic oxidation of fluorine-containing hydrogen chloride
CN117019127A (en) * 2023-10-10 2023-11-10 山东东岳高分子材料有限公司 Catalyst carrier, catalyst for preparing chlorine by hydrogen chloride oxidation and preparation method of catalyst

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CN105289631B (en) * 2015-11-25 2020-10-30 上海氯碱化工股份有限公司 Catalyst for preparing chlorine by catalytic oxidation of hydrogen chloride and preparation method and application thereof
CN105289631A (en) * 2015-11-25 2016-02-03 上海氯碱化工股份有限公司 Catalyst for chlorine gas preparation through catalytic oxidation of hydrogen chloride, preparation method and applications thereof
CN107952436A (en) * 2016-10-14 2018-04-24 中国石油化工股份有限公司 A kind of preparing chlorine by oxidizing hydrogen chloride copper-zirconium based catalyst and its preparation method and application
CN107952436B (en) * 2016-10-14 2019-12-10 中国石油化工股份有限公司 Copper-zirconium-based catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method and application thereof
CN109675582A (en) * 2018-12-25 2019-04-26 西安近代化学研究所 A kind of preparing chlorine by oxidizing hydrogen chloride catalyst and preparation method thereof
CN112044440B (en) * 2019-06-06 2021-09-10 中南大学 Catalyst for preparing chlorine gas by catalytic oxidation of hydrogen chloride and preparation method and application thereof
CN112044440A (en) * 2019-06-06 2020-12-08 中南大学 Catalyst for preparing chlorine gas by catalytic oxidation of hydrogen chloride and preparation method and application thereof
CN110801842A (en) * 2019-11-26 2020-02-18 上海氯碱化工股份有限公司 Catalyst for preparing chlorine gas by catalytic oxidation of hydrogen chloride and preparation method and application thereof
CN112044445A (en) * 2020-08-25 2020-12-08 上海氯碱化工股份有限公司 Catalyst for preparing chlorine by catalytic oxidation of hydrogen chloride and preparation method and application thereof
CN115814815A (en) * 2022-12-19 2023-03-21 浙江工业大学 Preparation method of hydrogen chloride catalytic oxidation catalyst based on alloy carrier
CN116618069A (en) * 2023-07-24 2023-08-22 山东东岳氟硅材料有限公司 Preparation method and application of catalyst for catalytic oxidation of fluorine-containing hydrogen chloride
CN116618069B (en) * 2023-07-24 2023-11-14 山东东岳氟硅材料有限公司 Preparation method and application of catalyst for catalytic oxidation of fluorine-containing hydrogen chloride
CN117019127A (en) * 2023-10-10 2023-11-10 山东东岳高分子材料有限公司 Catalyst carrier, catalyst for preparing chlorine by hydrogen chloride oxidation and preparation method of catalyst
CN117019127B (en) * 2023-10-10 2024-01-02 山东东岳高分子材料有限公司 Catalyst carrier, catalyst for preparing chlorine by hydrogen chloride oxidation and preparation method of catalyst

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Application publication date: 20150923