CN116550321A - High-dispersity ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation and preparation method thereof - Google Patents

High-dispersity ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation and preparation method thereof Download PDF

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CN116550321A
CN116550321A CN202310574910.XA CN202310574910A CN116550321A CN 116550321 A CN116550321 A CN 116550321A CN 202310574910 A CN202310574910 A CN 202310574910A CN 116550321 A CN116550321 A CN 116550321A
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ruthenium
catalyst
hydrogen chloride
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improving
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宋薛
王定军
李洪花
卢奇佳
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CANAN NEW MATERIAL (HAGNZHOU) Inc
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CANAN NEW MATERIAL (HAGNZHOU) Inc
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    • 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
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a preparation method for improving the metal dispersity of a ruthenium catalyst for preparing chlorine by hydrogen chloride, which comprises the steps of preparing a composite carrier by titanium oxide and aluminum oxide, impregnating an impregnating solution pre-mixed with a surfactant, and obtaining the grain size of 1-10nm and the surface area of ruthenium metal of 120-410m through the processes of drying, calcining, cooling, washing, drying and the like 2 And (g. Ru), ruthenium catalyst in a highly dispersed state. According to the embodiment of the invention, the catalyst for preparing chlorine by hydrogen chloride oxidation is provided, the metal dispersity of the catalyst is improved, the use amount of active metal is reduced, and the catalyst has the characteristics of low temperature and high activity.

Description

High-dispersity ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation and preparation method thereof
Technical Field
The invention relates to the field of catalysts, in particular to a high-dispersity ruthenium catalyst for catalyzing and oxidizing hydrogen chloride into chlorine by oxygen and a preparation method thereof.
Background
Chlorine is an important chemical basic raw material and is widely applied to the industries of chemistry, metallurgy, papermaking, textile, petrochemical industry, drinking water disinfection, environmental protection and the like. When the organic chlorine product is industrially produced, a large amount of byproduct hydrogen chloride is produced, the atom utilization rate is 50% at most, and most of the hydrogen chloride gas is absorbed by water to prepare hydrochloric acid, but the hydrogen chloride gas contains organic impurities and has limited application. Some areas are directly neutralized by alkali and then discharged, so that not only is chlorine resource wasted, but also environmental pollution is possibly caused.
With the enhancement of environmental awareness, the requirements on transportation management, emission and the like of toxic and highly corrosive substances such as chlorine, hydrogen chloride and the like are more and more strict, and the byproduct hydrogen chloride becomes more and more difficult to treat. The method for preparing chlorine by converting hydrogen chloride can realize closed cycle utilization of chlorine resources, is the most effective method for treating and recycling byproduct hydrogen chloride, and has formed high consensus in the chlorine industry. The hydrogen oxidation to make chlorine is a good idea to solve these two problems, and in view of the development in the last decades, the catalytic oxidation method is the most effective solution, especially the catalytic oxidation method through the Deacon reaction, and has the most industrialization potential due to the characteristics of simple operation and low equipment cost.
In the process developed in 1868 by Deacon for the catalytic oxidation of hydrogen chloride, hydrogen chloride is oxidized to chlorine by exothermic equilibrium of oxygen. The conversion of hydrogen chloride to chlorine allows the chlorine production to be separated from the sodium hydroxide production by chloralkali electrolysis. The separation is very attractive because the world demand for chlorine is higher than that of sodium hydroxide.
The most central factor in the Deacon reaction is the catalyst, and after a copper-based catalyst (Deacon catalyst), a transition metal catalyst such as iron and chromium has been successively pushed out, and in recent years, a ruthenium-based (Ru), cerium-based (Ce) and composite oxide catalyst having high activity has been developed. Copper-based catalysts are attracting attention due to low cost, and "an oxychlorination catalyst and its application" of China patent application of Qinghua university (publication No. CN101125297A, publication No. 2008-02-20) uses inert carriers of copper and oxide, but copper particles are aggregated with the lapse of reaction time at high temperature, and bridges are formed among particles, so that the specific surface area of the catalyst is greatly reduced, the activity is reduced, and the deactivation is caused. The copper-containing hydrogen chloride oxidation catalyst can be loaded by adopting a carrier inert to a hydrogen chloride oxidation reaction system, such as a carrier of U.S. patent application No. 4123389A (publication No. 1978-10-31), wherein copper is used as a main active component, but the preparation process needs to be impregnated by an organic solvent, and the environmental pollution is large.
Chromium catalysts, although active, are extremely toxic and are used in large quantities with adverse environmental impact. U.S. Pat. No. 3,182,62 (publication No. 1998-02-10) reports the use of a catalyst composed of chromium oxide and rare earth cerium, a loading of 45g of catalyst, a HCl flow rate of 0.3L/min, O 2 The flow is 0.225L/min, and the conversion rate of hydrogen chloride can reach 85.2% at 380 ℃. Chromium is toxic, and chromium oxychloride with a low boiling point is easy to form with chlorine, so that the catalyst is easy to deactivate.
With respect to the use of ruthenium catalysts for hydrogen chloride oxidation catalysis, the Sumitomo chemical Co., ltd., in China, patent CN1182717A (publication 1998-05-27), CN1150127C (publication 1998-03-18) and CN1272238C (publication 2000-03-01) disclose impregnation of ruthenium oxide and a catalyst based on TiO 2 、ZrO 2 The isooxides are used as carriers for calcination to prepare the ruthenium-based catalyst. Furthermore, bayer materials science (Bayer Materialscience AG) discloses a ruthenium-containing based catalytic system containing tin dioxide at 11/29 of 2007 (WO 2007/134772 A1).
Although the ruthenium-based catalyst has the characteristics of low usage and high activity at low temperature compared with other catalysts, for example, ruO is described in CN1182717A 2 And SiO 2 Loaded onto TiO 2 The ruthenium-based catalyst prepared by the method has better low-temperature catalytic performance. But due to the exothermic effect of the reaction, the active component RuO 2 The particles are easy to sinter due to insufficient heat dissipation, and the catalyst still has the problem of reduced reactivity after long-term use.
The Deacon reaction temperature is generally 280-420 ℃, and the Deacon reaction temperature is in a higher thermal environment, and the Deacon reaction belongs to an exothermic reaction, so that the Deacon catalyst not only has good heat conductivity and heat stability, but alsoHas a low specific surface area, such as 10-50m 2 And/g. Due to the influence of the heating effect of the material, the material with large specific surface area can be reduced by changing the pore structure along with the growth of crystal grains at high temperature. This is very disadvantageous for catalysts loaded with active components, and can cause a decrease in activity and accelerate deactivation.
The grain size and dispersity of the active components of the catalyst greatly influence the activity of the reaction, the smaller the metal grain diameter is, the higher the metal can be dispersed, and meanwhile, the catalyst can be well combined with a carrier, the grains are not easy to grow, and the catalyst has better thermal stability. High specific surface area materials are typically selected as supports in the preparation of catalysts, which facilitate loading of the active metals and higher dispersity. The Deacon reaction requires a carrier with good thermal stability due to the limitation of reaction conditions, and materials with smaller specific surface areas are selected as the carrier, which can lead to the difficulty in achieving high dispersion of active component ruthenium, thus not only affecting the activity of the catalyst, but also increasing the dosage of ruthenium, and being unfavorable for cost control.
Disclosure of Invention
The invention aims to provide a catalyst for preparing chlorine by hydrogen chloride oxidation, wherein active component ruthenium is in a high dispersion state, and the preparation method of the ruthenium catalyst can effectively exert the utilization rate of active metal atoms, reduce the load of the active component and have high catalytic activity at low temperature; it is a further object of the present invention to provide a ruthenium catalyst prepared by the aforementioned preparation method, which is used for the catalytic oxidation of hydrogen chloride to chlorine by oxygen.
The technical scheme is as follows: in order to achieve the above object, the preparation method of the ruthenium catalyst with high dispersity for preparing chlorine by hydrogen chloride oxidation of the invention comprises the following steps:
(1) Dispersing the ruthenium-containing active component by a surfactant to prepare an impregnating solution;
(2) A step of attaching the impregnating solution to a composite carrier containing titanium oxide and aluminum oxide in contact with each other, drying the composite carrier, and calcining the dried composite carrier;
(3) Cooling, washing and drying.
The related researches on the components of the ruthenium active component loaded carrier, the specific surface area of the carrier, parameters such as temperature, time and the like in the production and preparation process are carried out in the field, but the dispersibility of the ruthenium active component, the grain size of ruthenium or the pretreatment of the impregnating solution and the like are not explored. Wherein the surfactant is selected from any one or a combination of a plurality of hydrophilic nonionic surfactants including but not limited to polyoxyethylene nonionic surfactants, polyethylene glycol, polysorbate and the like. More specifically, the surfactant is selected from any one or a combination of more than one of T-80 (Tween-80), OP-10 (alkylphenol ethoxylate) and PEG-400 (polyethylene glycol 400); more preferably T-80 is used as surfactant. The surfactant is added to form coating isolation between active component ruthenium particles, and the ruthenium components do not generate serious agglomeration during impregnation adsorption or during drying, so that noble metal ruthenium (Ru) serving as the active component is in a high dispersion state, and agglomeration caused by growth of metal particles due to calcination is further inhibited.
Further, the amount of the surfactant is 1 to 10 times, preferably 1 to 5 times, the mass of the metal element in the ruthenium active component.
The ruthenium active component of the present invention is derived from, but not limited to, any one or a combination of the following components: ruCl 3 、RuCl 3 ·xH 2 O、RuBr 3 、RuBr 3 ·xH 2 O; chlororuthenates, e.g. K 3 RuCl 6 、(RuCl 3 ) 3- 、K 2 RuCl 6 The method comprises the steps of carrying out a first treatment on the surface of the Chlororuthenate hydrates, e.g. RuCl 5 (H 2 O) 4 ] 2- 、[RuCl 2 (H 2 O) 4 ] + The method comprises the steps of carrying out a first treatment on the surface of the Ruthenates, e.g. K 2 RuO 4 Or Na (or) 2 RuO 4 The method comprises the steps of carrying out a first treatment on the surface of the Ruthenium oxychloride, e.g. Ru 2 OCl 4 、Ru 2 OCl 5 、Ru 2 OCl 6 The method comprises the steps of carrying out a first treatment on the surface of the Ruthenium oxychloride salts, e.g. K 2 Ru 2 OCl 10 、Cs 2 Ru 2 OCl 4 The method comprises the steps of carrying out a first treatment on the surface of the Ruthenium ammonia complexes, e.g. [ Ru (NH) 3 ) 6 ] 2+ 、[Ru(NH 3 ) 6 ] 3+ 、[Ru(NH 3 ) 5 H 2 O] 2+ The method comprises the steps of carrying out a first treatment on the surface of the Ruthenium chloride amine complexes, e.g. [ R ]u(NH 3 ) 5 Cl] 2+ 、[Ru(NH 3 ) 6 ]Cl 2 、[Ru(NH 3 ) 6 ]Cl 3 The method comprises the steps of carrying out a first treatment on the surface of the Ruthenium amine bromide complexes, e.g. [ Ru (NH) 3 ) 6 ]Br 3 The method comprises the steps of carrying out a first treatment on the surface of the Ruthenium acetylacetonate; ruthenium carbonyls, e.g. Ru (CO) 5 Or Ru (CO) 12 The method comprises the steps of carrying out a first treatment on the surface of the Organic acid salts of ruthenium, e.g. [ Ru ] 3 O(OCOCH 3 ) 6 (H 2 O) 3 ]OCOCH 3 、Ru 2 (RCOO) 4 Cl (wherein R is a hydrocarbon group having 1 to 3 carbons); ruthenium nitrosylnitrate, e.g. K 2 [RuCl 6 (NO)]、[Ru(NH 3 ) 5 (NO)]Cl 3 、[Ru(OH)(NH 3 ) 4 (NO)](NO 3 ) 2 、Ru(NO)(NO 3 ) 3 The method comprises the steps of carrying out a first treatment on the surface of the Ruthenium phosphorus complexes, and the like. Preferably, the ruthenium active component is selected from ruthenium trichloride or a hydrate thereof, ruthenium tribromide or a hydrate thereof. A more preferred compound is ruthenium trichloride hydrate.
The active noble metal component ruthenium element in the present invention accounts for 0.1 to 10wt%, preferably 0.5 to 5wt%, more preferably 1 to 3wt% of the ruthenium catalyst. Lower levels of active component may result in insufficient catalyst activity and excessive levels may increase catalyst costs.
Further, the contact adhesion mode in the step (2) is any one of equal volume impregnation, excessive impregnation and spray impregnation.
Further, the drying and calcining process in the step (2) is carried out at the drying temperature of 60-200 ℃ for 1-24 hours; calcining at 150-700 deg.C for 1-24 hr.
Further, the titanium oxide is preferably rutile titanium dioxide. The alumina is selected as alpha-Al 2 O 3 And preferably has a thermal conductivity of not less than 23W/m·deg.c. By combining rutile titanium dioxide with alpha-Al having a high thermal conductivity 2 O 3 The carrier prepared after molding has high heat conducting performance and more macropores, thereby improving the heat dissipation generated in the reaction process, preventing the growth of ruthenium active component grains caused by overhigh reaction temperature and further forming caking, and simultaneously being beneficial to realizing the high-molecular of ruthenium active componentAnd (5) dispersing. Most carriers in the prior art still have certain reaction inertia, the specific surface area is not easy to improve, and the adsorption of metal ruthenium is difficult. The adsorption of the composite carrier to the metal ruthenium is obviously improved under the pretreatment of the surfactant.
The composite carrier is prepared by a molding process, and the shape of the composite carrier comprises any one or a combination of a plurality of powder, spheres, columns, abnormal shapes and honeycombs.
The catalyst prepared by soaking and shaping the carrier has a particle size of 10-50m 2 Specific surface area per g, ruthenium crystal grain of 1-10nm, ruthenium metal surface area of 120-410m 2 And (g.Ru) is in a high dispersion state, and the preparation process strengthens the thermal stability, thereby being beneficial to prolonging the service life and meeting the requirements of industrial catalysis and production.
The catalyst with higher ruthenium dispersity than the existing catalyst is prepared on a carrier with lower specific surface area through the improvement of the preparation process. The test shows that the catalyst with the Ru content of 1.5 percent is industrialized at present, and the surface area of the metallic ruthenium is about 130-200m 2 The catalyst prepared by the method has the surface area of 200-340m under the condition that the Ru content is equal to 1.5 percent 2 /(g.Ru). The high dispersity increases the effective utilization rate of ruthenium atoms, excellently improves the activity of the catalyst, and can realize higher activity under the condition of lower metal loading.
The invention preferably loads the ruthenium active component after the carrier forming process, and calcination after loading does not cause obvious sintering, and can effectively prevent metal grains from growing up, thereby preparing the catalyst with high dispersity.
The carrier material selected in the invention has the characteristics of acid resistance, alkali resistance and stable high-temperature performance, wherein the selection of the material with high heat conductivity coefficient is favorable for timely dissipation of reaction heat, and the proper specific surface area is favorable for dispersion of active metals. The ruthenium catalyst provided by the invention is used for preparing chlorine by hydrogen chloride oxidation. The impregnation liquid is formed by adding the ruthenium active component into the surfactant, which is beneficial to improving the adsorption of the carrier to the active metal and improving the dispersity of the metal ruthenium. Meanwhile, the migration and agglomeration of ruthenium components can be prevented in the subsequent processes of drying, calcining and the like. The high dispersity means that the effective utilization rate of metal atoms is increased, the activity is high, the metal content is reduced while the high conversion rate is maintained, and the catalyst cost is reduced.
Drawings
FIG. 1 is a TEM image of the ruthenium catalyst of example 1;
FIG. 2 is a particle size distribution of the ruthenium catalyst of example 1;
FIG. 3 is a TEM image of the ruthenium catalyst of example 2;
FIG. 4 is a particle size distribution of the ruthenium catalyst of example 2.
Detailed Description
The invention will now be described in detail with reference to the examples, to which it should be noted that the examples described below are illustrative for the skilled person and are intended to illustrate the invention, but the invention is not limited. In the examples the ruthenium metal surface area is converted into surface area per gram of metal ruthenium in m 2 /(g.Ru). The ruthenium metal surface area test method was performed under the same conditions in all examples.
Example 1
Weighing 50 g of bar-shaped composite carrier with the diameter of 3mm and the length of 5mm and the specific surface area of 30m, which consists of rutile titanium dioxide and alpha-alumina (titanium oxide accounts for 50 percent) 2 /g。
A ruthenium chloride solution containing 0.75 g of Ru is added with 1.5g of Tween-80 to prepare 25 ml for impregnation, and the impregnation is carried out at 60 ℃ for 12 hours, so as to obtain the dried catalyst.
And (3) drying and calcining the dried catalyst in air at 200 ℃ for 5 hours, washing the product with water, and drying at 80 ℃ to obtain the catalyst product.
The mass percentage of the catalyst components obtained by theoretical calculation is as follows: 1.5% Ru/(TiO) 2 :Al 2 O 3 =50:50), ruthenium metal surface area test value 306.7m 2 /(g·Ru)。
The ruthenium metal surface area test method adopts a CO pulse adsorption method to test: specific operation CO pulse, adsorption characterization analysis was performed on the catalyst samples using a Micrometric Chemisorb chemisorber. 50mg of the sampleFilling the quartz tube into a U-shaped quartz tube, and filling a certain amount of quartz cotton at the bottom of the quartz tube; introducing H-containing 2 Is heated to 350 ℃ at a heating rate of 5 ℃/min, and is pretreated for 3 hours under the temperature and atmosphere. And cooling to room temperature, and adsorbing by Ar pulse containing CO after the baseline is stabilized until the CO is saturated. After the CO adsorption capacity is obtained, the ruthenium metal surface area can be obtained by calculating according to Ru/CO=1:1 atomic ratio. At the same time, the metal particle size was observed by Transmission Electron Microscopy (TEM), as shown in fig. 1. FIG. 2 shows that the average particle size of ruthenium, the active component of the catalyst, prepared by the present method is about 1.21nm. The following examples all employ the same experimental procedure as in example 1 to determine the ruthenium metal surface area.
Example 2
Weighing 50 g of bar-shaped composite carrier with the diameter of 3mm and the length of 5mm and the specific surface area of 25m, which consists of rutile titanium dioxide and alpha-alumina (the titanium oxide accounts for 30 percent) 2 /g。
Adding 0.5g of Tween-80 into 0.5g of ruthenium nitrosylnitrate solution containing Ru to prepare 25 ml of the solution for impregnation, and drying the solution at 80 ℃ for 6 hours to obtain a dried catalyst;
drying and roasting the dried catalyst in air at 250 ℃ for 4 hours; washing the product with water, and drying at 90 ℃ to obtain the catalyst product.
The mass percentage of the catalyst components obtained by theoretical calculation is as follows: 1.0% Ru/(TiO) 2 :Al 2 O 3 =30:70), ruthenium metal surface area test value 281.0m 2 /(g·Ru)。
Example 3
Weighing 50 g of bar-shaped composite carrier with the diameter of 3mm and the length of 5mm and the specific surface area of 30m, which consists of rutile titanium dioxide and alpha-alumina (titanium oxide accounts for 70 percent) 2 /g。
3.8g of OP-10 was added to 25 ml of a ruthenium chloride solution containing Ru1.5 g to prepare a solution, which was impregnated, and dried at 80℃for 10 hours to obtain a dried catalyst.
Drying and calcining the dried catalyst in air at 350 ℃ for 3 hours; washing the product with water, and drying at 100 ℃ to obtain the catalyst product.
Theory ofThe mass percentage of the catalyst components is calculated as follows: 3.0% Ru/(TiO) 2 :Al 2 O 3 =70:30), ruthenium metal surface area test value 260.0m 2 /(g·Ru)。
Example 4
Weighing 50 g of bar-shaped composite carrier with the diameter of 3mm and the length of 5mm and the specific surface area of 50m, which consists of rutile titanium dioxide and alpha-alumina (titanium oxide accounts for 34 percent) 2 /g。
30 ml of Tween-80 was added to a ruthenium chloride solution containing 1.0 g of Ru to prepare a solution, followed by immersing the solution in the solution, and drying the solution at 80℃for 10 hours, thereby obtaining a dried catalyst.
Drying and calcining the dried catalyst in air at 350 ℃ for 3 hours; washing the product with water, and drying at 110 ℃ to obtain the catalyst product.
The mass percentage of the catalyst components obtained by theoretical calculation is as follows: 2.0% Ru/(TiO) 2 :Al 2 O 3 =34:66), ruthenium metal surface area test value 325.0m 2 /(g·Ru)。
Example 5
Weighing 50 g of bar-shaped composite carrier with the diameter of 3mm and the length of 5mm and the specific surface area of 29m, which consists of rutile titanium dioxide and alpha-alumina (titanium oxide accounts for 34 percent) 2 /g。
50 g of the roasted carrier is taken, 4.0g of PEG-400 is added into 0.75 g of ruthenium nitrosylnitrate solution containing Ru to prepare 30 ml for impregnation, and the impregnation is carried out, and the drying is carried out at 100 ℃ for 7 hours, thus obtaining the dried catalyst.
Drying and calcining the dried catalyst in air at 400 ℃ for 3 hours; washing the product with water, and drying at 120 ℃ to obtain the catalyst product.
The mass percentage of the catalyst components obtained by theoretical calculation is as follows: 1.5% Ru/(TiO) 2 :Al 2 O 3 =34:66), ruthenium metal surface area test value 326.7m 2 /(g·Ru)。
Example 6
Weighing 50 g of bar-shaped composite carrier with the diameter of 3mm and the length of 5mm and consisting of rutile type titanium dioxide and alpha-alumina (titanium oxide accounts for 80 percent), the strength of 150N/cm,specific surface area of 18m 2 /g。
50 g of the roasted carrier is taken, 5.0g of PEG-400 is added into 0.4 g of ruthenium nitrosylnitrate solution containing Ru to prepare 30 ml for impregnation, and the impregnation is carried out, and the drying is carried out at 110 ℃ for 6 hours, thus obtaining the dried catalyst.
Drying and calcining the dried catalyst in air at 500 ℃ for 3 hours; washing the product with water, and drying at 120 ℃ to obtain the catalyst product.
Theoretical calculation shows that the mass percentage of the catalyst component is 0.8 percent Ru/(TiO) 2 :Al 2 O 3 =80:20), ruthenium metal surface area test value 297.5m 2 /(g·Ru)。
Example 7
Weighing 50 g of bar-shaped composite carrier with the diameter of 3mm and the length of 5mm and the specific surface area of 18m, which consists of rutile titanium dioxide and alpha-alumina (titanium oxide accounts for 50 percent) 2 /g。
50 g of the roasted carrier is taken, 30 ml of Tween-80 with the concentration of 0.5g of Ru is added into the carrier to prepare 30 ml of the carrier for impregnation, and the carrier is dried at 110 ℃ for 6 hours to obtain the dried catalyst.
Drying and calcining the dried catalyst in air at 400 ℃ for 3 hours; washing the product with water, and drying at 120 ℃ to obtain the catalyst product.
Theoretical calculation shows that the mass percentage of the catalyst component is 1.0 percent Ru/(TiO) 2 :Al 2 O 3 =50:50), ruthenium metal surface area test value 300.0m 2 /(g·Ru)。
Example 8
Weighing 50 g of bar-shaped composite carrier with the diameter of 3mm and the length of 5mm and the specific surface area of 29m, which consists of rutile titanium dioxide and alpha-alumina (titanium oxide accounts for 34 percent) 2 /g。
50 g of the calcined carrier is taken, 30 ml of Tween-80 with the concentration of 3.0g is added into a potassium chlororuthenate solution containing 0.75 g of Ru for impregnation, and the catalyst is dried at 110 ℃ for 6 hours, thus obtaining the dried catalyst.
Dry calcining the dried catalyst in air at 450 ℃ for 3 hours; washing the product with water, and drying at 120 ℃ to obtain the catalyst product.
Theoretical calculation shows that the mass percentage of the catalyst component is 1.5 percent Ru/(TiO) 2 :Al 2 O 3 =34:66), ruthenium metal surface area test value 286.7m 2 /(g·Ru)。
Example 9
Weighing 50 g of bar-shaped composite carrier with the diameter of 3mm and the length of 5mm and the specific surface area of 29m, which consists of rutile titanium dioxide and alpha-alumina (titanium oxide accounts for 34 percent) 2 /g。
50 g of the calcined carrier is taken, 3.0g of OP-10 is added into 1.0 g of ruthenium ammonia complex solution containing Ru to prepare 30 ml for impregnation, and the catalyst is dried at 110 ℃ for 6 hours to obtain the dried catalyst.
Drying and calcining the dried catalyst in air at 350 ℃ for 3 hours; washing the product with water, and drying at 120 ℃ to obtain the catalyst product.
Theoretical calculation shows that the mass percentage of the catalyst component is 2 percent Ru/(TiO) 2 :Al 2 O 3 =50:50), ruthenium metal surface area test value 305.0m 2 /(g·Ru)。
Example 10
Weighing 50 g of bar-shaped composite carrier with the diameter of 3mm and the length of 5mm and the specific surface area of 27m, which consists of rutile titanium dioxide and alpha-alumina (titanium oxide accounts for 34 percent) 2 /g。
50 g of the calcined carrier is taken, 1.5g of OP-10 is added into 0.5g of ruthenium ammonia complex solution containing Ru to prepare 30 ml for impregnation, and the catalyst is dried at 110 ℃ for 6 hours to obtain the dried catalyst.
Drying and calcining the dried catalyst in air at 300 ℃ for 3 hours; washing the product with water, and drying at 120 ℃ to obtain the catalyst product.
Theoretical calculation shows that the mass percentage of the catalyst component is 1 percent Ru/(TiO) 2 :Al 2 O 3 =50:50), ruthenium metal surface area test value 410.0m 2 /(g·Ru)。
Comparative example 1
Preparation according to Chinese invention patent CN1245773A, example 4 publicationThe ruthenium catalyst was prepared as a control group 1 by the method, and the specific steps were as follows: commercially available ruthenium oxide hydrate (RuCl) 3 ·nH 2 3.23 g of O, ru content 37.3%) was dissolved in 21.9g of pure water, and stirred to obtain an aqueous ruthenium chloride solution. The resulting aqueous solution was added dropwise to 40.0 g of a titanium oxide support, and ruthenium chloride was impregnated. The supported material was dried in air at 60℃for 2 hours to obtain titanium oxide-supported ruthenium chloride. The resulting solid was then warmed from room temperature to 350 ℃ in air over about l hours and calcined at that temperature for 3 hours to give a spherical solid. To the obtained solid, 0.5L of pure water was added, followed by stirring, standing for 30 minutes and washing with water by filtration. This operation was repeated 10 times. The water wash time was about 7 hours. The water-washed material was dried in air at 60℃for 4 hours to obtain 41.1 g of a gray-black supported ruthenium oxide catalyst.
The calculated value of the metal ruthenium content of the control group 1 is 2.9 percent Ru/TiO 2 Ruthenium metal surface area test value 162.0m 2 /(g·Ru)。
Comparative example 2
Ruthenium catalyst was prepared according to the preparation method disclosed in example 18 of chinese patent No. CN1245773a as control group 2, and the specific steps are as follows: commercially available ruthenium oxide hydrate (RuCl) 3 ·nH 2 2.03 g of O, ru content 37.3%) was dissolved in 14.6g of pure water, and stirred to obtain an aqueous ruthenium chloride solution. The resulting aqueous solution was dropped onto 50.0 g of a bar-shaped composite carrier composed of titanium oxide- α -alumina (titanium oxide: 50%) to impregnate ruthenium chloride. The supported material was dried in air at 60℃for 2 hours to obtain titania- α -alumina supported ruthenium chloride. The resulting solid was then warmed from room temperature to 350 ℃ in air over about l hours and calcined at that temperature for 3 hours to give a spherical solid. To the obtained solid, 0.5L of pure water was added, followed by stirring, standing for 30 minutes and washing with water by filtration. This operation was repeated 5 times. The water wash time was about 4 hours. The water-washed material was dried in air at 60℃for 4 hours to obtain 50.0 g of a gray black supported ruthenium oxide catalyst.
The calculated value of the metal ruthenium content of the control group 2 is 1.5% Ru/(TiO) 2 :Al 2 O 3 =50:50), ruthenium metal surface area test value 166.7m 2 /(g·Ru)。
The activities of all example and control catalysts were performed on a fixed bed catalytic reactor; reactor type: a quartz tube reactor with an inner diameter of 25mm; the granularity of the catalyst is particle, and the dosage is 10g; the main reaction conditions are as follows: HCl at 0.76L/min, O 2 Passes through the catalyst bed at 0.64L/min. Conversion at different temperatures is shown in tables 1 and 2, and the inventive examples and controls were carried out under the same conditions:
TABLE 1 dispersity of different catalysts and Hydrogen chloride conversion at different temperatures
TABLE 2 Hydrogen chloride conversion after 500h of operation of the different catalysts
Catalyst Conversion (%)
Example 1 93
Example 2 90
Example 3 96
Example 4 94
Example 5 92
Example 6 88
Example 7 89
Example 8 93
Example 9 93
Example 10 91
Control group 1 88
Control group 2 87
As can be seen from tables 1 and 2, the overall activity of the catalyst prepared by the invention in preparing chlorine by catalyzing hydrogen chloride oxidation is obviously superior to that of a catalyst of a control group, and particularly, the dispersity of active components is far greater than that of a comparative example, which shows that the catalyst prepared by the invention has high dispersity of active components, thus the catalyst has more excellent activity, and meanwhile, the low-content metal load has important significance for cost reduction.
The foregoing is only a preferred embodiment of the invention, it being noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the present invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.

Claims (11)

1. The preparation method for improving the metal dispersity of the ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation is characterized by comprising the following steps of:
(1) Dispersing the ruthenium-containing active component by a surfactant to prepare an impregnating solution;
(2) A step of attaching the impregnating solution to a composite carrier containing titanium oxide and aluminum oxide in contact with each other, drying the composite carrier, and calcining the dried composite carrier;
(3) Cooling, cleaning and drying.
2. The method for improving the metal dispersity of the ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation according to claim 1, which is characterized by comprising the following steps: the surfactant is selected from any one or a combination of a plurality of hydrophilic nonionic surfactants such as polyoxyethylene nonionic surfactant, polyethylene glycol, polysorbate and the like.
3. The preparation method for improving the metal dispersity of the ruthenium catalyst for preparing chlorine by oxidizing hydrogen chloride according to claim 1 or 2, which is characterized by comprising the following steps of: the dosage of the surfactant is 1-10 times of the mass of the metal element in the ruthenium-containing active component.
4. The method for improving the metal dispersity of the ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation according to claim 3, which is characterized by comprising the following steps: the active component containing ruthenium is selected from precursor solution formed by any one or a plurality of combination of ruthenium trichloride or hydrate thereof, ruthenium tribromide or hydrate thereof, ruthenate chloride or hydrate thereof, ruthenate, ruthenium oxychloride salt, ruthenium ammonia complex, ruthenium chloride amine complex, ruthenium bromide amine complex, ruthenium acetylacetonate, ruthenium carbonyl, organic acid salt of ruthenium, ruthenium nitrosyl nitrate and ruthenium phosphorus complex.
5. The method for improving the metal dispersity of the ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation according to claim 4, which is characterized by comprising the following steps: the contact adhesion mode in the step (2) is any one of equal volume impregnation, excessive impregnation and spray impregnation.
6. The method for improving the metal dispersity of the ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation according to claim 4, which is characterized by comprising the following steps: the contact in step (2) is carried out at a temperature of 30-60 ℃.
7. The method for improving the metal dispersity of the ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation according to claim 4, which is characterized by comprising the following steps: the calcination temperature in the step (2) is 150-700 ℃ and the time is 1-24 hours.
8. The method for improving the metal dispersity of the ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation according to claim 1, which is characterized by comprising the following steps: the titanium oxide is rutile type titanium dioxide, and the aluminum oxide is alpha-Al 2 O 3 。
9. The method for improving the metal dispersity of the ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation according to claim 1, which is characterized by comprising the following steps: the shape of the composite carrier prepared by the molding process comprises any one or a combination of a plurality of powder, sphere, column, special shape and honeycomb shape.
10. A ruthenium catalyst obtainable by the process according to any one of claims 1 to 2,4 to 9, wherein: the ruthenium catalyst has a specific surface area of 10-50m 2 Per gram, the grain size of ruthenium is 1-10nm, and the surface area of metallic ruthenium is 120-410m 2 /(g·Ru)。
11. The ruthenium catalyst according to claim 10, wherein: the ruthenium element accounts for 0.1-10wt% of the ruthenium catalyst.
CN202310574910.XA 2023-05-22 2023-05-22 High-dispersity ruthenium catalyst for preparing chlorine by hydrogen chloride oxidation and preparation method thereof Pending CN116550321A (en)

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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1176223A (en) * 1996-08-08 1998-03-18 住友化学工业株式会社 Process for producing chlorine
CN1245773A (en) * 1998-02-16 2000-03-01 住友化学工业株式会社 Preparation method of chlorine
CN1915800A (en) * 1998-02-16 2007-02-21 住友化学株式会社 Process for producing chlorine
CN1970143A (en) * 2006-09-06 2007-05-30 大连理工大学 Method for preparing high-activity hydrogenation catalyst nano Ru/C
CN101272852A (en) * 2005-08-25 2008-09-24 巴斯夫欧洲公司 Mechanically stable catalyst based on alpha-alumina
CN101316656A (en) * 2005-11-30 2008-12-03 住友化学株式会社 Method for production of supported ruthenium and method for production of chlorine
CN101862674A (en) * 2010-05-24 2010-10-20 清华大学 Monolithic catalyst for use in preparation of chloride by using hydrogen chloride and preparation method thereof
CN102711986A (en) * 2009-07-25 2012-10-03 拜尔材料科学股份公司 Method for producing chlorine by gas phase oxidation on nanostructured ruthenium supported catalysts
CN102803130A (en) * 2009-06-10 2012-11-28 巴斯夫欧洲公司 Method for hydrogen chloride oxidation at a catalyst having low surface roughness
CN102923797A (en) * 2012-11-06 2013-02-13 上海奥威科技开发有限公司 Method for preparing high-dispersion high-activity hydration ruthenium dioxide electrode material
CN107537480A (en) * 2016-06-29 2018-01-05 中国石油化工股份有限公司 Complex catalyst and its application method
CN109453764A (en) * 2018-11-16 2019-03-12 西安元创化工科技股份有限公司 Ruthenic oxide catalyst and preparation method thereof for preparing chlorine by oxidizing hydrogen chloride
CN112574781A (en) * 2019-09-30 2021-03-30 中国科学院宁波材料技术与工程研究所 Processing method for treating inferior heavy oil, hydrogenation protection catalyst and application

Patent Citations (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1475434A (en) * 1996-08-08 2004-02-18 ס�ѻ�ѧ��ҵ��ʽ���� Method for producing chlorine
CN1176223A (en) * 1996-08-08 1998-03-18 住友化学工业株式会社 Process for producing chlorine
CN1245773A (en) * 1998-02-16 2000-03-01 住友化学工业株式会社 Preparation method of chlorine
CN1915800A (en) * 1998-02-16 2007-02-21 住友化学株式会社 Process for producing chlorine
CN101272852A (en) * 2005-08-25 2008-09-24 巴斯夫欧洲公司 Mechanically stable catalyst based on alpha-alumina
CN101316656A (en) * 2005-11-30 2008-12-03 住友化学株式会社 Method for production of supported ruthenium and method for production of chlorine
CN1970143A (en) * 2006-09-06 2007-05-30 大连理工大学 Method for preparing high-activity hydrogenation catalyst nano Ru/C
CN102803130A (en) * 2009-06-10 2012-11-28 巴斯夫欧洲公司 Method for hydrogen chloride oxidation at a catalyst having low surface roughness
CN102711986A (en) * 2009-07-25 2012-10-03 拜尔材料科学股份公司 Method for producing chlorine by gas phase oxidation on nanostructured ruthenium supported catalysts
CN101862674A (en) * 2010-05-24 2010-10-20 清华大学 Monolithic catalyst for use in preparation of chloride by using hydrogen chloride and preparation method thereof
CN102923797A (en) * 2012-11-06 2013-02-13 上海奥威科技开发有限公司 Method for preparing high-dispersion high-activity hydration ruthenium dioxide electrode material
CN107537480A (en) * 2016-06-29 2018-01-05 中国石油化工股份有限公司 Complex catalyst and its application method
CN109453764A (en) * 2018-11-16 2019-03-12 西安元创化工科技股份有限公司 Ruthenic oxide catalyst and preparation method thereof for preparing chlorine by oxidizing hydrogen chloride
CN112574781A (en) * 2019-09-30 2021-03-30 中国科学院宁波材料技术与工程研究所 Processing method for treating inferior heavy oil, hydrogenation protection catalyst and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
曹声春: "《催化原理及其工业应用技术》", 湖南大学出版社, pages: 326 *
荣成: "载体和催化剂的制备方法对活性炭负载钌基氨合成催化剂性能的影响", 《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》, no. 01 *

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