CN109806864B - High-stability catalyst for preparing chlorine by oxidizing hydrogen chloride - Google Patents
High-stability catalyst for preparing chlorine by oxidizing hydrogen chloride Download PDFInfo
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Abstract
The invention discloses a high-stability catalyst for preparing chlorine by oxidizing hydrogen chloride, which is characterized in that a catalyst precursor comprises the following components in percentage by mass: the component A is 0.1-3%; the component B is 0.1-6%; the balance being TiO2(ii) a Wherein the component A is Ru metal salt; the component B is one or more metal salts of Ce, Sn, Zr and Sm; TiO 22Is a rutile phase carrier with high specific surface area prepared by adopting a liquid phase template method. The invention adopts the rutile phase carrier with high specific surface area, greatly improves the dispersibility of active components, delays sintering deactivation by the limited domain effect on the active phase, and solves the problem of low stability of the existing hydrogen chloride oxidation catalyst at high temperature and high airspeed.
Description
Technical Field
The invention belongs to the field of catalysts, and particularly relates to a high-stability catalyst for preparing chlorine by oxidizing hydrogen chloride.
Background
Chlorine and hydrogen chloride are important existing forms of chlorine and are also very important chemical products and raw materials. In the chlorine-related industry, the byproduct hydrogen chloride and inorganic chloride reach 4200 million tons/year (Catalysis surfaces from Asia,2010,14(3-4): 168-. In the polyurethane industry, the demand of TDI in domestic and foreign markets is increasing, and the generation of 1-molecule TDI is accompanied with the generation of 4-molecule byproduct hydrogen chloride. While HCl is an upstream raw material for the production of vinyl chloride, large amounts of hydrogen chloride are difficult to recycle due to technical deficiencies. Therefore, the recovery of a large amount of byproduct hydrogen chloride to prepare chlorine and the realization of closed cycle of chlorine resources become common knowledge of sustainable development of chlorine industry.
The traditional Deacon process has the defects of low hydrogen chloride conversion rate, serious equipment corrosion, easy loss of catalyst and the like (US 165802). The hydrogen chloride oxidation reaction is a reversible exothermic process, a low-activity catalyst which needs higher reaction temperature is used, the equilibrium conversion rate of hydrogen chloride can be greatly reduced, and the development of a high-activity catalyst is very important. DE1567788 discloses at the very first catalysts for the oxidation of hydrogen chloride with ruthenium as active component, but the supports used are alumina and silica, the catalytic activity is not ideal. DE19734412, later, describes a ruthenium-based catalyst using titanium or zirconium oxide as a carrier, which has a better activity, but the active component is easier to sinter and the catalyst stability is poorer.
Disclosure of Invention
The invention aims to solve the technical problem of low stability of a hydrogen chloride oxidation catalyst at high temperature and high space velocity in the prior art, and provides a high-stability catalyst for preparing chlorine by hydrogen chloride oxidation, which has good dispersibility and strong sintering resistance.
The invention adopts TiO with high specific surface area and hierarchical pore structure2The carrier loads Ru, and a second component is introduced to optimize the performance of the catalyst, so that the stability of the hydrogen chloride oxidation catalyst at high temperature and high space velocity is improved, and the high activity of long service life can be maintained.
A high-stability catalyst for preparing chlorine by oxidizing hydrogen chloride comprises the following components in percentage by mass: the component A is 0.1-3%; the component B is 0.1-6%; the balance being TiO2(ii) a Wherein the component A is Ru metal salt; the component B is one or more metal salts of Ce, Sn, Zr and Sm; TiO 22The rutile phase carrier with high specific surface area and hierarchical pore structure is prepared by adopting a liquid phase template method. The catalyst is prepared according to the following steps:
(1) putting deionized water into ice-water bath, continuously stirring, and dropwise adding TiCl4Wherein TiCl is4The volume ratio of the deionized water to the deionized water is 1: 10-30, so that a clear transparent solution is obtained;
(2) keeping the solution obtained in the step (1) under stirring, adding a template agent and stirring for 1h, wherein TiCl4The molar ratio of the template to the template is 1: 1-40;
(3) sealing the mixture obtained in the step (2) and carrying out water bath at 50 ℃ for 12-36 h;
(4) filtering the suspension obtained in the step (3), washing with water and alcohol for 3 times respectively, drying at 50 ℃ for 12h, and then roasting at 350-450 ℃ for 4h in an air atmosphere to obtain TiO with a high specific surface area2；
(5) Adding one metal salt of Ru into deionized water, adding one or more metal salts of a second component Ce, Sn, Zr and Sm, carrying out ultrasonic dispersion for 1-4 h after complete dissolution, and adding the TiO prepared in the step (4)2And strongly stirring for 4-24 h, wherein the Ru element is TiO20.1-3% of the mass, and one or more of the elements Ce, Sn, Zr and Sm of the second component are respectively TiO20.1-6% of mass, deionized water and TiO2The mass ratio of (A) to (B) is 1-10: 1;
(6) and (4) centrifuging, washing and drying the material obtained in the step (5), granulating, forming and drying, and roasting for 4-8 hours at 250-400 ℃ in an air atmosphere to obtain the catalyst for preparing chlorine through catalytic oxidation of hydrogen chloride.
The catalyst provided by the invention is mainly applied to the reaction of catalyzing hydrogen chloride to prepare chlorine.
In the catalyst of the invention, the carrier is rutile TiO2Has needle-like geometry and hierarchical pore structure, and specific surface area greater than 100m2/g。
The catalyst of the present invention, rutile type TiO2In the preparation process of the carrier, the adopted template agent is one or a mixture of two of piperazine and derivatives thereof, triethylene diamine and derivatives thereof, piperidine and derivatives thereof, 4-aminopiperidine and alkyl ammonium sulfate in any proportion, wherein the piperazine derivatives include but are not limited to 2-methylpiperazine, 2, 3-dimethylpiperazine, 2, 5-dimethylpiperazine, 2, 6-dimethylpiperazine, N-hydroxymethylpiperazine, N-hydroxyethylpiperazine, the triethylene diamine derivatives include but are not limited to 2-methyltriethylenediamine, N-hydroxyethyltriethylene diamine and the like, the piperidine derivatives include but are not limited to 4-hydroxypiperidine, 4-aminopiperidine, and the alkyl group of the ammonium alkyl sulfate is an alkyl group having 2 to 20 carbon atoms, such as ethyl, isopropyl, N-dodecyl, N-hexadecyl.
The catalyst of the present invention, rutile type TiO2In the preparation process of the carrier, the adopted template agent is one or a mixture of two of piperazine, triethylene diamine, piperidine, 4-aminopiperidine and ammonium alkyl sulfate in any proportion, and the alkyl of the ammonium alkyl sulfate is alkyl with 2-20C atoms, such as ethyl, isopropyl, n-dodecyl and n-hexadecyl.
The catalyst of the present invention, rutile type TiO2In the preparation process of the carrier, the adopted template agent is one or a mixture of two of piperazine, triethylene diamine, piperidine, 4-aminopiperidine, n-dodecyl ammonium sulfate and n-hexadecyl ammonium sulfate in any proportion.
In the preparation process of the catalyst, Ru and metal salts in the second components Ce, Sn, Zr and Sm are nitrate or chloride metal salts of the element or a mixture of the nitrate and the chloride metal salts.
In the preparation process of the catalyst, the Ru element in the step (5) is TiO20.5 to 2% by mass, secondOne or more elements of Ce, Sn, Zr and Sm are TiO20.5-3% of mass, deionized water and TiO2The mass ratio of (A) to (B) is 3-8: 1.
In the preparation process of the catalyst, the material treated in the step (1) is subjected to centrifugal treatment, then is fully washed by deionized water, and then is dried at the temperature of 60-80 ℃; spraying a small amount of water or dilute nitric acid water solution in the granulation process of the step (2); the forming process can adopt the processes of tabletting or extruding strip forming and the like.
The invention has the beneficial effects that:
(1) the catalyst obtained by the invention adopts rutile TiO with high specific surface area and hierarchical pore structure2As a carrier, and a suitable second component is introduced to optimize the active site structure of the Ru element, the active component can be effectively prevented from sintering and inactivating through the action of local confinement, the stability of the catalyst is greatly enhanced while the high hydrogen chloride conversion rate is ensured, and the problem that the ruthenium-based catalyst in the prior art is low in stability at high temperature and high space velocity is favorably solved.
(2) The catalyst is applied to the reaction of preparing chlorine by catalytic oxidation of hydrogen chloride in reaction gases (HCl and O)2Volume ratio of 1:2) space velocity of 3000 L.h-1·kgcat -1And the hydrogen chloride conversion rate can be stably kept at a high conversion rate of 95.7% for more than 10000h at the reaction temperature of 350 ℃.
Drawings
FIG. 1 is a graph of the high specific surface area TiO prepared2Transmission Electron Microscope (TEM) images of the supported ruthenium-based catalyst;
FIG. 2 is a nitrogen isothermal adsorption-desorption curve and a pore size distribution diagram of the prepared catalyst, and the catalyst has a hierarchical pore structure of 1-100 nm, wherein 2-8nm mesopores are quite rich.
Detailed Description
The present invention is further illustrated by the following examples, but is not limited thereto.
The catalyst evaluation was carried out using a fixed-bed reactor having dimensions of 700 mm. times. phi. 40 mm. times.5 mm. The reaction is carried out under normal pressure, 20mL of catalyst is filled, hydrogen chloride gas and oxygen are used as reaction gases, and the reaction gases firstly pass through a mass flow meter and then enter a fixed bed reactor after passing through a preheater. The reactor adopts an electric heating mode to heat in three sections, the reaction temperature is 350 ℃, the flow rate of the hydrogen chloride is 400ml/min, and the flow rate of the oxygen is 800 ml/min. And (3) sampling and analyzing after the reaction is stable for 1h, and titrating chlorine and incompletely reacted hydrogen chloride in the sample by an iodometry method and an acid-base titration method respectively.
The specific operation steps are as follows: after the system is stably operated, preparing a 20% KI solution at regular intervals, switching an outlet three-way valve of the oxidation reactor, introducing the mixed gas after reaction into a constant volume (300mL) potassium iodide solution, and absorbing for 1 minute. Transferring the absorption liquid into a conical flask after absorption, titrating by using 0.2mol/L sodium thiosulfate standard solution, and using starch as an indicator; then taking phenolphthalein as an indicator, and titrating unreacted HC1 by using 0.2mol/L sodium hydroxide standard solution; each sample was taken 3 times in parallel and the results of hydrogen chloride conversion averaged.
Example 1
Placing a beaker filled with 100mL of deionized water in an ice-water bath, continuously stirring by magnetic force, and dropwise adding 10mL of TiCl4A clear and transparent solution was obtained. To the resulting solution was added 1.25g of 4-hydroxypiperidine and 5.00g of ammonium hexadecyl sulfate, and stirring was continued for 1 h. Sealing the obtained mixture, water-bathing at 50 deg.C for 24 hr, filtering, water-washing, alcohol-washing each for 3 times, oven-drying at 50 deg.C for 12 hr, and calcining at 450 deg.C in air atmosphere for 4 hr to obtain 6.51g of the prepared TiO2Is denoted as TiO2-1. The target amount was obtained by multiple accumulations by the same preparation method.
2.0g of RuCl was added3·3H2O was dissolved in 400mL of deionized water and 4.5g of Ce (NO) as a second component was added3)3·6H2O、1.5g ZrOCl3·8H2O, 100g of TiO was added2-1, intensive stirring and dipping for 24 h; and then centrifuging the obtained material, fully washing the material with deionized water, drying the material at the temperature of 80 ℃, granulating, forming and drying the material, and roasting the material for 4 hours at the temperature of 380 ℃ in an air atmosphere to obtain the catalyst A for preparing chlorine by catalytic oxidation of hydrogen chloride.
Example 2
TiO2-1 preparation same as example 1. Adding 3.2g of anhydrous ruthenium trichloride into 500mL of deionized water, fully dissolving, and adding a second component SnCl4·5H2O5.4 g, 150g of TiO2-1 adding and stirring vigorously, dipping for 12 h; and then centrifuging the obtained material, fully washing the material with deionized water, drying the material at the temperature of 80 ℃, granulating, forming and drying the material, and roasting the material for 6 hours at the temperature of 350 ℃ in an air atmosphere to obtain the catalyst B for preparing chlorine by catalytic oxidation of hydrogen chloride.
Example 3
Placing a beaker filled with 200mL of deionized water in an ice-water bath, continuously stirring by magnetic force, and dropwise adding 15mL of TiCl4A clear and transparent solution was obtained. To the resulting solution was added 7.20g of ammonium lauryl sulfate and 3.54g of triethylene diamine, and stirring was continued for 1 h. Sealing the obtained mixture, water-bathing at 50 deg.C for 18h, filtering, water-washing, alcohol-washing each for 3 times, oven-drying at 50 deg.C for 12h, and calcining at 400 deg.C in air atmosphere for 4h to obtain 9.85g of prepared TiO2Is denoted as TiO2-2. The target amount was obtained by multiple accumulations by the same preparation method.
1.2g of RuCl was added3·3H2O is added into 400mL of deionized water, and then a second component SmCl is added3·6H2O 2.1g、SnCl4·5H2O3.6 g, adding TiO2-2 adding the solution and stirring vigorously, and soaking for 20 h; and then centrifuging the obtained material, fully washing the material with deionized water, drying the material at the temperature of 80 ℃, granulating, forming and drying the material, and roasting the material for 4 hours at the temperature of 400 ℃ in an air atmosphere to obtain the catalyst C for preparing chlorine by catalytic oxidation of hydrogen chloride.
Example 4
TiO2-2 preparation same as example 3. 1.5g of RuCl3·3H2O to 320mL of deionized water, and adding a second component Sm (NO)3)3·6H2O 2.5g、Ce(NO3)3·6H2O4.2 g, 80g of TiO2-2, adding, stirring and dipping for 10 h; centrifuging the obtained materialFully washing with deionized water, drying at 80 ℃, granulating, molding and drying, and roasting at 380 ℃ for 6 hours in an air atmosphere to obtain the catalyst D for preparing chlorine by catalytic oxidation of hydrogen chloride.
The performance evaluation of the high-stability catalyst for preparing chlorine by oxidizing hydrogen chloride of the invention comprises the following steps:
the catalysts A, B, C, D obtained in examples 3-6 were respectively loaded into a fixed bed reactor for catalyst evaluation, and the hydrogen chloride conversion rate was stably maintained at about the average conversion rate over 10000 h. The reaction results are shown in Table 1.
TABLE 1 results of the reaction
| Catalyst and process for preparing same | 500h conversion/%) | 5000h conversion/% | 10000h conversion/%) |
| A | 97.0 | 96.9 | 95.7 |
| B | 98.3 | 97.8 | 95.5 |
| C | 97.9 | 96.8 | 94.2 |
| D | 96.6 | 95.9 | 94.0 |
And (4) conclusion: the catalyst of the invention is applied to the reaction of preparing chlorine by catalytic oxidation of hydrogen chloride, and the conversion rate of the hydrogen chloride can be in the reaction gas (HCl and O)2Volume ratio of 1:2) space velocity of 3000 L.h-1·kgcat -1And the reaction temperature is kept at 95.7 percent under the reaction condition of 350 ℃.
Claims (5)
1. A high-stability catalyst for preparing chlorine by oxidizing hydrogen chloride is characterized in that the mass percentage of a precursor of the catalyst is as follows: the component A is 0.1-3%; the component B is 0.1-6%; the balance being TiO2(ii) a Wherein the component A is Ru metal salt; the component B is one or more metal salts of Ce, Sn, Zr and Sm; TiO 22The carrier is a rutile phase carrier with high specific surface area and a hierarchical pore structure prepared by adopting a liquid-phase template method; the high-stability catalyst for preparing chlorine by oxidizing hydrogen chloride is prepared by the following steps:
(1) putting deionized water into ice-water bath, continuously stirring, and dropwise adding TiCl4Wherein TiCl is4The volume ratio of the deionized water to the deionized water is 1: 10-30, so that a clear transparent solution is obtained;
(2) keeping the solution obtained in the step (1) under stirring, adding a template agent and stirring for 1h, wherein TiCl4The molar ratio of the template to the template is 1: 1-40;
(3) sealing the mixture obtained in the step (2) and carrying out water bath at 50 ℃ for 12-36 h;
(4) filtering, washing with water, washing with alcohol, drying and roasting the suspension obtained in the step (3) to obtain TiO with high specific surface area2；
(5) Adding one metal salt of Ru into deionized water, adding one or more metal salts of second components Ce, Sn, Zr and Sm, and adding (4)TiO prepared in (1)2And strongly stirring for 4-24 h, wherein the Ru element is TiO20.1-3% of the mass, and one or more of the elements Ce, Sn, Zr and Sm of the second component are respectively TiO20.1-6% of mass, deionized water and TiO2The mass ratio of (A) to (B) is 1-10: 1;
(6) centrifuging, washing, drying, granulating, molding and drying the material obtained in the step (5), and then burning in an air atmosphere to obtain a catalyst for preparing chlorine gas by catalytic oxidation of hydrogen chloride;
prepared TiO2The carrier has needle-like geometry and hierarchical pore structure, and specific surface area greater than 100m2/g；
The template agent in the step (2) comprises one or a mixture of two of piperazine, triethylene diamine, piperidine, 2-methyl piperazine, 2, 3-dimethyl piperazine, 2, 5-dimethyl piperazine, 2, 6-dimethyl piperazine, N-hydroxymethyl piperazine, N-hydroxyethyl piperazine, 2-methyl triethylene diamine, N-hydroxyethyl triethylene diamine, 4-hydroxypiperidine, 4-aminopiperidine and alkyl ammonium sulfate, wherein the alkyl group of the alkyl ammonium sulfate is an alkyl group with 2-20 carbon atoms in any proportion.
2. The highly stable catalyst for hydrogen chloride oxidation to chlorine gas of claim 1, wherein the alkyl group having 2 to 20 carbon atoms is ethyl, isopropyl, n-dodecyl or n-hexadecyl.
3. The highly stable catalyst for hydrogen chloride oxidation to chlorine gas as claimed in claim 1, wherein the metal salt of Ru and the second component Ce, Sn, Zr, Sm is a nitrate or chloride metal salt of the element or a mixture of the two.
4. The catalyst according to claim 1, wherein the Ru element in step (5) is TiO20.5-2% of the mass, and one or more of elements Ce, Sn, Zr and Sm as a second component is TiO20.5-3% of mass, deionized water and TiO2The mass ratio of (A) to (B) is 3-8: 1.
5. The high-stability catalyst for preparing chlorine by oxidizing hydrogen chloride according to claim 1, wherein the material treated in step (1) is subjected to centrifugal treatment, then fully washed by deionized water, and then dried at 60-80 ℃; spraying a small amount of water or dilute nitric acid water solution in the granulation process of the step (2); the forming process can adopt a tabletting forming or extruding strip forming process.
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| KR102709295B1 (en) * | 2019-12-31 | 2024-09-23 | 한화솔루션 주식회사 | Molding catalyst for hydrogen chloride oxidation reaction and preparation method thereof |
| CN112536032A (en) * | 2020-12-04 | 2021-03-23 | 浙江师范大学 | High-temperature-resistant sintering catalyst for preparing chlorine by oxidizing hydrogen chloride and preparation method thereof |
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