Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
  • B01J29/14—Iron group metals or copper
  • B01J29/146—Y-type faujasite
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
  • B01J27/06—Halogens; Compounds thereof
  • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/024—Multiple impregnation or coating
  • B01J37/0244—Coatings comprising several layers
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B7/00—Halogens; Halogen acids
  • C01B7/01—Chlorine; Hydrogen chloride
  • C01B7/03—Preparation from chlorides
  • C01B7/04—Preparation of chlorine from hydrogen chloride
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/20—Improvements relating to chlorine production

Definitions

• the present invention relates to a catalyst for preparing chlorine by the oxidation of hydrogen chloride and a method for producing the same.
• 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, PCl 3 and the like; as well as the industries of paper manufacture, textile industries, metallurgy industries and petroleum and chemical industries, etc.
• the catalytic oxidation method the cyclic oxidation method and the oxidative electrolysis method.
• the representative cyclic oxidation method is developed by Dupont.
• sulfuric acid is used as a cyclic oxidative medium and nitric acid is used as a catalyst.
• nitric acid is used as a catalyst.
• the oxidative electrolysis method can well relief the second problem, which was describe above, in the chlor-alkali industry. 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.
• 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).
• the greatest advantage of this method is its low electricity consumption of only about 230 kWh per ton chlorine. In addition, it is an environment-friendly chemical process.
• the active ingredients mainly are metal elements such as copper, chromium, gold and ruthenium, etc.
• 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.
• the above two kinds of catalysts have such problems of high economic cost or environmental pollution or the like in use.
• copper-based catalysts have both advantages of lower cost and being environmentally friendly, thus are of great interests.
• CN200710121298.1 discloses a catalyst containing cupric chloride, potassium chloride and cerium chloride with alumina as support and treated by phosphoric acid.
• the yield of chlorine is 80.1% under the conditions that the ratio of hydrogen chloride and oxygen is 1:1, the temperature of fixed bed reactor is 400° C., the reaction pressure is 0.1 MPa and the space velocity of hydrogen chloride is 0.8 hr ⁇ 1 .
• 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.
• CN200910027312.0 discloses a catalyst containing cupric chloride, potassium chloride, manganese nitrate and cerium nitrate supported on silica gel or ReY molecular sieve. 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.
• U.S. Pat. No. 4,123,389 discloses a copper-based catalyst with silica gel, alumina or titania as a support, in which the loading amount of active ingredients is between 25% and 70%.
• the process of preparation of the catalyst needs organic solvents and thus causes great environmental pollution.
• One object of the invention is to provide a catalyst for production of chlorine by catalytic oxidation of hydrogen chloride which overcomes the disadvantages of the current copper-based catalysts and the catalyst herein has good reaction activity and stability.
• Another object of the invention is to provide a method for preparing the above catalyst for production of chlorine by catalytic oxidation of hydrogen chloride.
• the catalyst for production of chlorine by catalytic oxidation of hydrogen chloride comprises a support and active ingredients comprising 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 and titanium, the weight percent of each ingredient is based on the total weight of the catalyst.
• the method for preparing the catalyst according to the present invention comprises the steps of:
• step (3) calcining the solid obtained in step (2) at a temperature of 450-650° C. for 1-5 h to obtain the catalyst.
• the catalyst according to the present invention can be easily prepared. Meanwhile, comparing with gold and ruthenium-based catalysts, the catalyst according to the invention has a relatively lower price. Due to free of the toxic ingredients such as Cr, etc., the catalyst is relatively environment-friendly and does not cause secondary pollution. Comparing with the available copper-containing catalysts, the catalyst according to the invention has a better stability due to the addition of boron which greatly inhibits the loss of the copper ingredient.
• the copper-containing compound and the compound containing a transition metal other than copper are firstly loaded on the support by impregnation, and then the other ingredients are loaded on the support by the second impregnation, which makes the resulted catalyst has higher activity, and thereby a higher yield of chlorine can be realized under a higher space velocity of hydrogen chloride.
• the catalyst provided by the present invention can improve the yield of chlorine by about 1%-3%, and even by about 4%-5%.
• the catalyst for oxidation of hydrogen chloride and the preparation method of the catalyst according to the invention are illustrated in detail below, however the present invention is not limited by the following description in any way.
• the total weight of the catalyst refers to the weight of the final catalyst product.
• the catalyst comprises the following active ingredients: 4-15 wt %, more preferably 5-12 wt % of copper; 0.1-4 wt %, more preferably 0.15-3 wt % of boron; 2-7 wt %, more preferably 2.5-6 wt % of alkali metal element(s); 1-11 wt %, more preferably 2-9 wt % of one or more rare earth elements; 1-8wt %, more preferably 2-6 wt % of one or more elements selected from magnesium, calcium, barium, manganese, iron, nickel, cobalt, zinc, ruthenium and titanium; as well as 60-90 wt %, preferably 60-85 wt % of a support.
• the alkali metal element is any one selected from lithium, sodium, potassium and cesium, preferably is sodium or potassium.
• the rare earth element is at least one selected from lanthanide elements, preferably is one or more selected from cerium, lanthanum, praseodymium and neodymium.
• the support according to the invention is at least one selected from molecular sieve, kaolin, diatomite, silica, alumina, titania and zirconia, preferably is molecular sieve or kaolin, and more preferably is type Y molecular sieve (Y-zeolite).
• the impregnation time preferably lasts 8-16 h and then dried at a temperature of 70-110 ° C. for 12-24 h.
• the used copper-containing compound is a soluble salt of copper, preferably one or more selected from cupric nitrate, cupric chloride and cupric acetate.
• the used copper-containing compounds are cupric nitrate and cupric chloride.
• the compound containing a transition metal other than copper is selected from soluble salts of manganese, iron, nickel, cobalt, zinc, ruthenium and titanium, preferably one or more selected from corresponding nitrates, chlorides and acetates of manganese, iron, nickel, cobalt, zinc and titanium, and more preferably one or more of corresponding nitrates, chlorides and acetates of manganese, iron, cobalt and zinc.
• the boron-containing compound is one or two or three of boric acid, sodium borate and potassium borate.
• the alkali metal compound is one or more selected from chlorides, nitrates, acetates, carbonates and borates of lithium, sodium, potassium, preferably one or more selected from chloride, nitrate, acetate, carbonate and borate of sodium or potassium.
• the alkaline earth metal compound is one or more selected from chlorides, nitrates, acetates, carbonates and borates of magnesium, calcium and barium, and preferably one or more selected from chlorides, nitrates, acetates, carbonates and borates of magnesium and calcium.
• the rare earth metal compound is one or more selected from nitrates and chlorides of cerium, lanthanum, praseodymium and neodymium, preferably one or more selected from the nitrates.
• the catalyst of the invention is useful in the reaction for producing chlorine by catalytic oxidation of hydrogen chloride, which may be carried out in a fixed bed reactor or in other reactors suitable for such reactions.
• the reaction conditions for producing chlorine by the oxidation of hydrogen chloride are that: the reaction temperature is 320-460° C., preferably 360-400° C.; the reaction pressure is 0.1-0.6 MPa, preferably 0.1-0.35 MPa; the mole ratio between hydrogen chloride and oxygen is 0.5-9:1, preferably 1-4:1; and the mass space velocity of hydrogen chloride is 0.1-2.5 h ⁇ 1 , preferably 0.5-2 ⁇ 1 .
• the present invention provides the catalyst for producing chlorine by the oxidation of hydrogen chloride, which comprises a support and the metal salts or metal oxides applied thereon.
• the metal salts or metal oxides are loaded onto the support such that the catalyst comprises: 1-20 wt % of copper, 0.01-5 wt % of boron, 0.1-10 wt % of alkali metal element, 0.1-15 wt % of one or two or more of rare earth elements, ⁇ 0-10 wt % of one or two or more of magnesium, calcium, barium, manganese, iron, nickel, cobalt, zinc, ruthenium or titanium, each based on the total weight of the catalyst.
• the following Examples and Comparative Examples are carried out in a fixed bed reactor.
• the general reaction procedure is as follows: hydrogen chloride and oxygen are fed into the top of a quartz tube reactor with their pressures respectively controlled by pressure stabilization valves and their flow rates respectively controlled by mass flow controllers, and the gas flows pass the catalyst bed to conduct the reaction after preheated with quartz sands.
• the reaction product is absorbed by an excess potassium iodide solution, and the amount of resultant chlorine is measured by the iodometric method and the amount of unreacted hydrogen chloride is measured by acid-base titration for calculating the yield of chlorine.
• the aqueous solution containing active ingredients is slight excess in impregnation steps, and the solid is directly dried after impregnation, thus there is no loss of the active ingredients.
• HY molecular sieve In a 40 ml of aqueous solution that contains 26.3 g CuCl 2 .2H 2 O, 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 H 3 BO 3 , 4.95 g KCl, 8.15 g Ce(NO 3 ) 3 .6H 2 O and 4.05 g Nd(NO 3 ) 3 .6H 2 O 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.
• Example 4 In a fixed bed reactor, 6 g of the catalyst prepared in Example 4 is loaded to conduct a reaction with the flow rates of hydrogen chloride and oxygen of 150 ml/min respectively, with the reaction temperature at 383° C. and the reaction pressure at 0.18 MPa. After 4 h of reaction, the chlorine yield is 85.7%, and after 100 h of reaction, is 85.2%. The activity of the catalyst substantially keeps activity. After 1000 h of reaction, the chlorine yield is 85.1%.
• Example 4 It can be concluded from the comparison between Example 4 and Comparative Example 2 that the catalyst obtained through the two-step impregnation process has a significantly higher activity than that of the catalyst prepared by the one-step impregnation process has.
• Use of the inventive catalyst in a reaction for production of chlorine by oxidation of hydrogen chloride can increase the chlorine yield by about 3 percent.

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• 2010
  • 2010-11-18 CN CN2010105670389A patent/CN102000583B/zh active Active
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