CN115999607A - Preparation method and application of hydrogen chloride catalytic oxidation catalyst - Google Patents
Preparation method and application of hydrogen chloride catalytic oxidation catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 97
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 74
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910000041 hydrogen chloride Inorganic materials 0.000 title claims abstract description 68
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 title claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000460 chlorine Substances 0.000 claims abstract description 21
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 62
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- 239000004202 carbamide Substances 0.000 claims description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 32
- 239000004327 boric acid Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 26
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 10
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- 238000002156 mixing Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000002161 passivation Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 53
- 229910052582 BN Inorganic materials 0.000 abstract description 17
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 abstract description 17
- 238000005245 sintering Methods 0.000 abstract description 3
- 238000005470 impregnation Methods 0.000 abstract 1
- 239000012299 nitrogen atmosphere Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000011049 filling Methods 0.000 description 20
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 18
- 239000002245 particle Substances 0.000 description 15
- 229920000742 Cotton Polymers 0.000 description 14
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- 239000000047 product Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000007873 sieving Methods 0.000 description 7
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 7
- 235000019345 sodium thiosulphate Nutrition 0.000 description 7
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 239000002699 waste material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
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- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000007138 Deacon process reaction Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method and application of a hydrogen chloride catalytic oxidation catalyst, wherein the preparation method comprises the following steps: preparing a boron nitride carrier; ruCl supported on boron nitride support by wet impregnation 3 And drying, roasting under hydrogen atmosphere and passivating under nitrogen atmosphere to obtain the hydrogen chloride catalytic oxidation catalyst. The catalyst for preparing chlorine by hydrogen chloride oxidation has good dispersibility, strong sintering resistance, high stability and good catalytic activity in the reaction of preparing chlorine by hydrogen chloride catalytic oxidation.
Description
Technical Field
The invention relates to the technical field of preparing chlorine by hydrogen chloride oxidation, in particular to a preparation method of a catalyst for preparing chlorine by catalyzing hydrogen chloride oxidation.
Background
Chlorine is an important chemical raw material and is widely applied to the fields of textile, medicine, petrochemical industry, drinking water disinfection, environmental protection industry and the like. When chlorine is applied to chemical synthesis, most chlorine-related reactions have low utilization rate of chlorine atoms, so that a large amount of chlorine resources are lost, and the lost chlorine resources exist in the form of byproduct hydrogen chloride. According to statistics of related documents, with the development of the chemical industry of China, the production scale of products such as polyvinyl chloride, MDI, TDI, methane chloride, trichloroethylene and the like is enlarged, the total amount of byproduct hydrogen chloride is over 500 ten thousand t/a, and the problem of recycling the byproduct hydrogen chloride becomes a common problem in the development of various industries such as chlor-alkali, fluorochemical industry, polyurethane, pesticides, medicines and the like. At present, the byproduct hydrogen chloride is mainly treated in three ways:
(1) After purification, the hydrochloric acid is sold again, but most of byproduct hydrogen chloride contains more impurities, the purification difficulty is high, and the quality of the obtained hydrochloric acid is low;
(2) The purified product is used as raw material of other chemicals;
(3) As three wastes treatment, the cost is high, the reutilization value is lost, and the environmental protection pressure is high.
The three treatment modes all cause chlorine resource waste of different degrees, and if the byproduct hydrogen chloride can be converted into chlorine, on one hand, the emission of the hydrogen chloride can be reduced, and the environmental pressure is lightened; on the other hand, the recycling of chlorine resources is realized, and the economic value is higher.
The chlorine prepared by hydrogen chloride mainly comprises 3 different preparation processes of an electrolytic method, a direct oxidation method and a catalytic oxidation method.
(1) Electrolytic process
Diaphragm electrolytic processes developed by hurst, bayer and wood have been industrially produced; industrial production has also been achieved by the process of producing chlorine by electrolysis of hydrochloric acid with an oxygen cathode (ODC) developed by bayer corporation. However, the electrolytic method has the defects of high energy consumption and large investment, and limits the further development of the electrolytic method.
(2) Direct oxidation process
By means of strong oxidising agents, e.g. NO 2 、SO 3 、NaHSO 4 Or HNO (HNO) 3 /H 2 SO 4 As an oxidant pairThe hydrogen chloride is directly oxidized, typically by the Weldson method, kel-Chlor process, and the like. The direct oxidation method has the problems of high product separation difficulty, complex process equipment, relatively large energy consumption and the like, so that large-scale industrialized application cannot be realized.
(3) Catalytic oxidation process
Oxygen or air and hydrogen chloride are used as raw materials, and chlorine is prepared through catalytic oxidation, and the chemical equation is as follows.
4HCl(g)+O 2 (g)→2H 2 O(g)+2Cl 2 (g)+114.48kJ
The catalytic oxidation method has the characteristics of strong raw material adaptability, relatively simple process flow, convenient operation, relatively low investment and the like. Typical examples of the processes include the Deacon process, the MT-Chlor process, and the Shell-Chlor process. Industrial applications of the Deacon technology are realized in japanese sumitomo chemical corporation, japanese Mitsui chemical corporation, germany basf corporation, and the like.
Among them, the catalytic oxidation method with lower energy consumption and simple operation is favored by related industries, and has been found to quickly become a research hotspot for preparing chlorine from hydrogen chloride.
In the early hydrogen chloride catalytic oxidation process, a copper-based catalyst is adopted, so that the defects of low hydrogen chloride conversion rate, high reaction temperature, easy loss of the catalyst and the like are overcome. Because the hydrogen chloride oxidation reaction is a reversible exothermic process, the high-activity catalyst is used, the reaction temperature is reduced, the equilibrium conversion rate of hydrogen chloride can be improved, and the energy consumption is reduced. Thus, the improvement of the activity of the hydrogen chloride oxidation catalyst is very critical. Japanese Sumitomo disclosed a ruthenium-based catalyst in 1999, which has better catalytic activity in low temperature environment than copper-based common transition metal catalysts, but the titanium dioxide carrier used has too low thermal conductivity, so that heat cannot be dissipated in time in the reaction process, resulting in catalyst deactivation.
The subsequent patent GB1046313 discloses a method for preparing a composite material by using silica gel, pumice stone and A1 2 O 3 Supported RuCl as support 3 The catalyst is easily deactivated. Patent US5908607A discloses a method of treating a patient with RuO 2 Catalysis taking the main component asThe catalyst, however, has a catalytic activity that gradually decreases with the increase of the operating time, and is also susceptible to deactivation by irreversible poisoning caused by impurities (such as sulfur, aromatic hydrocarbon, etc.) in the hydrogen chloride raw material and errors during the process operation. Patent CN102239003a discloses a titania or zirconia catalyst containing cavities in which ruthenium is located by dissolving silicate material with an alkali solution. The structure of the catalyst cavity can avoid the growth of active component ruthenium particles, but the patent does not disclose the specific reaction performance of the catalyst, and the catalyst has the defects that the silicate is easy to damage the titanium dioxide or zirconium dioxide layer when the silicate is dissolved by strong alkali in the preparation process of the catalyst, the dissolved silicate is discarded, waste liquid is generated, the catalyst cost is increased, and the like.
Therefore, finding a material with high thermal conductivity as a carrier to realize stable operation of the catalyst and simultaneously have good hydrogen chloride oxidation catalytic activity is one of the technical difficulties to be broken through in the field.
Disclosure of Invention
Aiming at the problem of low stability of the hydrogen chloride oxidation catalyst at low temperature and high space velocity in the prior art, the invention provides a preparation method and application of the catalyst for preparing chlorine by hydrogen chloride oxidation, wherein the catalyst has good dispersibility, strong sintering resistance, high stability and good catalytic activity.
In order to solve the problems, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a hydrogen chloride catalytic oxidation catalyst, comprising the steps of:
(1) Uniformly mixing a certain amount of urea, boric acid and ferric nitrate at room temperature to obtain a mixture, wherein the molar ratio of the urea to the boric acid is 1:1.5-1:2.8, and the mass of the ferric nitrate is 0.5-1.5wt% of the total mass of the urea, the boric acid and the ferric nitrate;
(2) Placing the mixture obtained in the step (1) in a muffle furnace, firstly raising the temperature to 280-300 ℃ from room temperature in 5-15 ml/min of high-purity hydrogen, and then keeping constant temperature for preheating for 50-70 minutes;
(3) Then the muffle furnace temperature is raised to 800-900 ℃ for roasting for 5-9 hours;
(4) Cooling the roasting product obtained in the step (3) by nitrogen;
(5) Fully washing the product obtained in the step (4) by distilled water, and drying in an oven at 60-100 ℃ to finally obtain a BN sample;
(6) Dissolving RuCl with ethanol at room temperature 3 The reason for adding ethanol into the aqueous solution for dissolution is to reduce the surface tension of the solution and avoid RuCl 3 The solution is excessively adsorbed on the wall, then the BN sample obtained in the step (5) is added for dipping, and the mixture is kept stand for 6 to 10 hours;
(7) Placing the standing mixture in the step (6) into a baking oven at 100-150 ℃ for drying;
(8) Placing the dried product obtained in the step (7) into a muffle furnace in hydrogen atmosphere, and roasting for 4-8 hours at 400-500 ℃ to obtain a catalyst preliminarily;
(9) And (3) placing the catalyst prepared in the step (8) in high-purity nitrogen for room temperature passivation for 20-30 hours, and finally obtaining the hydrogen chloride catalytic oxidation catalyst.
Preferably, in step (1), the molar ratio of urea to boric acid is 1:2, and the mass of ferric nitrate is 1wt% of the total mass of urea, boric acid and ferric nitrate.
Preferably, in the step (2), the temperature rising rate is 2 to 3 ℃/min. As a further preferred feature, in step (2), the preheating temperature is 300 ℃ and the preheating time is 1h.
Preferably, in the step (3), the temperature rising rate is 8 to 12 ℃/min.
Preferably, in step (6), the RuCl 3 The mass ratio of the solution to BN sample is 0.8-1.3: 100 batch feeding.
Preferably, in the step (8), the baking temperature is 450 ℃ and the baking time is 5 hours.
In a second aspect, the invention provides an application of the prepared hydrogen chloride catalytic oxidation catalyst in preparing chlorine by hydrogen chloride catalytic oxidation. Before use, the hydrogen chloride catalytic oxidation catalyst is activated by oxygen.
Compared with other ruthenium-based catalysts, the catalyst provided by the invention adopts the carrier which is boron nitride with high strength, low density, corrosion resistance, strong wave permeability and high heat conductivity, has the advantages of high heat value, high heat conduction efficiency, uniform heat conduction rate, high temperature control precision, no odor, low-pressure operation, safety and convenience and the like, and can maintain the physical properties of the catalyst at a higher temperature for a long time. Meanwhile, raw materials for synthesizing the boron nitride are common substances such as urea, boric acid and the like, so that the industrial economic pressure is relieved to a certain extent. In addition, the catalyst provided by the invention is used for preparing chlorine by hydrogen chloride catalytic oxidation, and has high stability and high hydrogen chloride conversion rate.
Detailed Description
The invention is illustrated below by means of specific examples. It is to be noted that the examples are only for further explanation of the present invention and are not to be construed as limiting the scope of the present invention in any way. Such modifications and improvements are intended to be within the scope of the invention as claimed.
Example 1
(1) Taking a certain amount of urea, boric acid and ferric nitrate, uniformly mixing at room temperature, wherein the molar ratio of the urea to the boric acid is 1:2, and the ferric nitrate plays a role of a catalyst, so that the mass ratio of the urea to the boric acid is 1wt% of the urea to the ferric nitrate.
(2) The mixture obtained in (1) was placed in a muffle furnace, heated from room temperature to 300℃in 10ml/min of high purity hydrogen at a rate of 2.5℃per minute, and preheated at constant temperature for 1 hour.
(3) The muffle furnace temperature was then raised from 10deg.C/min to 850 deg.C and fired for 7 hours.
(4) And (3) cooling the roasting product in the step (3) by using nitrogen to obtain a boron nitride sample.
(5) And (3) washing the boron nitride sample obtained in the step (4) with distilled water three times, and drying in an oven at 70 ℃ for 10 hours to finally obtain a BN sample.
(6) 0.5mL RuCl was dissolved in 20mL ethanol at room temperature 3 The reason why the aqueous solution (with Ru concentration of 0.1 g/mL) is dissolved in the culture dish by adding ethanol is to lower the surface tension of the solution and avoid RuCl 3 The solution is adsorbed on the wall of the culture dish too much, and then the solution obtained in the step (5) is used for preparing5g of the final BN sample is weighed and soaked, and the BN sample is kept stand for 6 hours.
(7) The mixture was left to stand in (6) and dried in an oven at 120℃for 8 hours.
(8) And (3) placing the product obtained in the step (7) into a muffle furnace in a hydrogen atmosphere, and roasting at 450 ℃ for 5 hours to obtain the catalyst preliminarily.
(9) And (3) putting the catalyst prepared in the step (8) in high-purity nitrogen for passivation at room temperature for 24 hours to finally obtain the target catalyst.
Firstly tabletting the catalyst by using a tablet press, sieving particles with 60 meshes, filling quartz sand and quartz cotton into the bottom of a fixed bed reactor reaction tube, filling 0.1g of catalyst particles with 60 meshes, recharging quartz sand and quartz cotton, installing the catalyst, and then filling O 2 Activating for half an hour, and then introducing HCl gas, wherein the reaction conditions are as follows: whsv=1000h -1 ，V(HCl):V(O 2 ) Reaction temperature t=350℃=1:1. Then, the tail gas was absorbed by potassium iodide solution, chlorine gas was titrated by sodium thiosulfate, and the residual hydrogen chloride amount was titrated by sodium hydroxide solution, so that the conversion rate was calculated, and after 1000 hours of reaction, the hydrogen chloride conversion rate was 98.12%.
Example 2
(1) Taking a certain amount of urea, boric acid and ferric nitrate, uniformly mixing at room temperature, wherein the molar ratio of the urea to the boric acid is 1:2, and the ferric nitrate plays a role of a catalyst, so that the mass ratio of the urea to the boric acid is 1wt% of the urea to the ferric nitrate.
(2) The mixture obtained in (1) was placed in a muffle furnace, heated from room temperature to 300℃in 10ml/min of high purity hydrogen at a rate of 2.5℃per minute, and preheated at constant temperature for 1 hour.
(3) The muffle furnace temperature was then raised from 10deg.C/min to 850 deg.C and fired for 7 hours.
(4) And (3) cooling the roasting product in the step (3) by using nitrogen to obtain a boron nitride sample.
(5) And (3) washing the boron nitride sample obtained in the step (4) with distilled water three times, and drying in an oven at 70 ℃ for 10 hours to finally obtain a BN sample.
(6) 0.5mL RuCl was dissolved in 20mL ethanol at room temperature 3 Aqueous solution(wherein the concentration of Ru is 0.1 g/mL) in a culture dish, the reason for dissolving by adding ethanol is to reduce the surface tension of the solution and avoid RuCl 3 The solution was excessively adsorbed on the wall of the dish, and then 5g of the final BN sample obtained in (5) was weighed and immersed, and left to stand for 6 hours.
(7) The mixture was left to stand in (6) and dried in an oven at 120℃for 8 hours.
(8) And (3) placing the catalyst obtained in the step (7) into a muffle furnace in a hydrogen atmosphere, and roasting at 350 ℃ for 5 hours to obtain the catalyst.
(9) And (3) placing the catalyst prepared in the step (8) in high-purity nitrogen for room temperature passivation for 24 hours to finally obtain the target catalyst.
Firstly tabletting the catalyst by using a tablet press, sieving to obtain particles with 60 meshes, filling quartz sand and quartz cotton into the bottom of a fixed bed reactor reaction tube, filling 0.1g of catalyst particles with 60 meshes, recharging the quartz sand and the quartz cotton, installing the catalyst, and then introducing O 2 Activating for half an hour, and then introducing HCl gas, wherein the reaction conditions are as follows: whsv=1000h -1 ，V(HCl):V(O 2 ) Reaction temperature t=350℃=1:1. Then, the tail gas was absorbed by potassium iodide solution, chlorine gas was titrated by sodium thiosulfate, and the residual hydrogen chloride amount was titrated by sodium hydroxide solution, so that the conversion rate was calculated, and after 1000 hours of reaction, the hydrogen chloride conversion rate was 83.73%.
Example 3
(1) Taking a certain amount of urea, boric acid and ferric nitrate, uniformly mixing at room temperature, wherein the molar ratio of the urea to the boric acid is 1:2, and the ferric nitrate plays a role of a catalyst, so that the mass ratio of the urea to the boric acid is 1wt% of the urea to the ferric nitrate.
(2) The mixture obtained in (1) was placed in a muffle furnace, heated from room temperature to 300℃in 10ml/min of high purity hydrogen at a rate of 2.5℃per minute, and preheated at constant temperature for 1 hour.
(3) The muffle furnace temperature was then raised from 10deg.C/min to 850 deg.C and fired for 7 hours.
(4) And (3) cooling the roasting product in the step (3) by using nitrogen to obtain a boron nitride sample.
(5) And (3) washing the boron nitride sample obtained in the step (4) with distilled water three times, and drying in an oven at 70 ℃ for 10 hours to finally obtain a BN sample.
(6) 0.5mL RuCl was dissolved in 20mL ethanol at room temperature 3 The reason why the aqueous solution (with Ru concentration of 0.1 g/mL) is dissolved in the culture dish by adding ethanol is to lower the surface tension of the solution and avoid RuCl 3 The solution was excessively adsorbed on the wall of the dish, and then 5g of the final BN sample obtained in (5) was weighed and immersed, and left to stand for 6 hours.
(7) The mixture was left to stand in (6) and dried in an oven at 120℃for 8 hours.
(8) And (3) placing the catalyst obtained in the step (7) into a muffle furnace in a hydrogen atmosphere, and roasting at 550 ℃ for 5 hours to obtain the catalyst.
(9) And (3) placing the catalyst prepared in the step (8) in high-purity nitrogen for room temperature passivation for 24 hours to finally obtain the target catalyst.
Firstly tabletting the catalyst by using a tablet press, sieving particles with 60 meshes, filling quartz sand and quartz cotton into the bottom of a fixed bed reactor reaction tube, filling 0.1g of catalyst particles with 60 meshes, recharging quartz sand and quartz cotton, installing the catalyst, and then filling O 2 Activating for half an hour, and then introducing HCl gas. The reaction conditions are as follows: whsv=1000h -1 ，V(HCl):V(O 2 ) Reaction temperature t=350℃=1:1. Then, the tail gas was absorbed by potassium iodide solution, chlorine gas was titrated by sodium thiosulfate, and the residual hydrogen chloride amount was titrated by sodium hydroxide solution, so that the conversion rate was calculated, and after 1000 hours of reaction, the hydrogen chloride conversion rate was 85.12%.
Example 4
(1) Taking a certain amount of urea, boric acid and ferric nitrate, uniformly mixing at room temperature, wherein the molar ratio of the urea to the boric acid is 1:2, and the ferric nitrate plays a role of a catalyst, so that the mass ratio of the urea to the boric acid is 1wt% of the urea to the ferric nitrate.
(2) The mixture obtained in (1) was placed in a muffle furnace, heated from room temperature to 300℃in 10ml/min of high purity hydrogen at a rate of 2.5℃per minute, and preheated at constant temperature for 1 hour.
(3) The muffle furnace temperature was then raised from 10deg.C/min to 850 deg.C and fired for 7 hours.
(4) And (3) cooling the roasting product in the step (3) by using nitrogen to obtain a boron nitride sample.
(5) And (3) washing the boron nitride sample obtained in the step (4) with distilled water three times, and drying in an oven at 70 ℃ for 10 hours to finally obtain a BN sample.
(6) 0.5mL RuCl was dissolved in 20mL ethanol at room temperature 3 The reason why the aqueous solution (with Ru concentration of 0.1 g/mL) is dissolved in the culture dish by adding ethanol is to lower the surface tension of the solution and avoid RuCl 3 The solution was excessively adsorbed on the wall of the dish, and then 5g of the final BN sample obtained in (5) was weighed and immersed, and left to stand for 6 hours.
(7) The mixture was left to stand in (6) and dried in an oven at 120℃for 8 hours.
(8) And (3) placing the catalyst obtained in the step (7) into a muffle furnace in a hydrogen atmosphere, and roasting at 250 ℃ for 5 hours to obtain the catalyst.
(9) And (3) placing the catalyst prepared in the step (8) in high-purity nitrogen for room temperature passivation for 24 hours to finally obtain the target catalyst.
Firstly tabletting the catalyst by using a tablet press, sieving particles with 60 meshes, filling quartz sand and quartz cotton into the bottom of a fixed bed reactor reaction tube, filling 0.1g of catalyst particles with 60 meshes, recharging quartz sand and quartz cotton, installing the catalyst, and then filling O 2 Activating for half an hour, and then introducing HCl gas. The reaction conditions are as follows: whsv=1000h -1 ，V(HCl):V(O 2 ) Reaction temperature t=350℃=1:1. Then, the tail gas was absorbed by potassium iodide solution, chlorine gas was titrated by sodium thiosulfate, and the residual hydrogen chloride amount was titrated by sodium hydroxide solution, so that the conversion rate was calculated, and after 1000 hours of reaction, the hydrogen chloride conversion rate was 53.79%.
Example 5
(1) Taking a certain amount of urea, boric acid and ferric nitrate, uniformly mixing at room temperature, wherein the molar ratio of the urea to the boric acid is 1:2, and the ferric nitrate plays a role of a catalyst, so that the mass ratio of the urea to the boric acid is 1wt% of the urea to the ferric nitrate.
(2) The mixture obtained in (1) was placed in a muffle furnace, heated from room temperature to 300℃in 10ml/min of high purity hydrogen at a rate of 2.5℃per minute, and preheated at constant temperature for 1 hour.
(3) The muffle furnace temperature was then raised from 10deg.C/min to 850 deg.C and fired for 7 hours.
(4) And (3) cooling the roasting product in the step (3) by using nitrogen to obtain a boron nitride sample.
(5) And (3) washing the boron nitride sample obtained in the step (4) with distilled water three times, and drying in an oven at 70 ℃ for 10 hours to finally obtain a BN sample.
(6) 0.5mL RuCl was dissolved in 20mL ethanol at room temperature 3 The reason why the aqueous solution (with Ru concentration of 0.1 g/mL) is dissolved in the culture dish by adding ethanol is to lower the surface tension of the solution and avoid RuCl 3 The solution was excessively adsorbed on the wall of the dish, and then 5g of the final BN sample obtained in (5) was weighed and immersed, and left to stand for 6 hours.
(7) The mixture was left to stand in (6) and dried in an oven at 120℃for 8 hours.
(8) And (3) placing the catalyst obtained in the step (7) into a muffle furnace in a hydrogen atmosphere, and roasting for 5 hours at 650 ℃ to obtain the catalyst.
(9) And (3) placing the catalyst prepared in the step (8) in high-purity nitrogen for room temperature passivation for 24 hours to finally obtain the target catalyst.
Firstly tabletting the catalyst by using a tablet press, sieving to obtain particles with 60 meshes, filling quartz sand and quartz cotton into the bottom of a fixed bed reactor reaction tube, filling catalyst particles with 0.1g and 80 meshes, recharging quartz sand and quartz cotton, installing the catalyst, and then filling O 2 Activated for half an hour and then HCl is introduced. The reaction conditions are as follows: whsv=1000h -1 ，V(HCl):V(O 2 ) Reaction temperature t=350℃=1:1. Then, the tail gas was absorbed by potassium iodide solution, chlorine gas was titrated by sodium thiosulfate, and the residual hydrogen chloride amount was titrated by sodium hydroxide solution, so that the conversion rate was calculated, and after 1000 hours of reaction, the hydrogen chloride conversion rate was 48.68%.
Comparative example 1
Comparative example 1 shows, by comparison with example 1, that the final step of passivating the catalyst with nitrogen enhances the interaction of Ru with the support surface, slows down the sintering rate of Ru and improves the stability of the catalyst.
(1) Taking a certain amount of urea, boric acid and ferric nitrate, uniformly mixing at room temperature, wherein the molar ratio of the urea to the boric acid is 1:2, and the ferric nitrate plays a role of a catalyst, so that the mass ratio of the urea to the boric acid is 1wt% of the urea to the ferric nitrate.
(2) The mixture obtained in (1) was placed in a muffle furnace, heated from room temperature to 300℃in 10ml/min of high purity hydrogen at a rate of 2.5℃per minute, and preheated at constant temperature for 1 hour.
(3) The muffle furnace temperature was then raised from 10deg.C/min to 850 deg.C and fired for 7 hours.
(4) And (3) cooling the roasting product in the step (3) by using nitrogen to obtain a boron nitride sample.
(5) And (3) washing the boron nitride sample obtained in the step (4) with distilled water three times, and drying in an oven at 70 ℃ for 10 hours to finally obtain a BN sample.
(6) 0.5mL RuCl was dissolved in 20mL ethanol at room temperature 3 The reason why the aqueous solution (with Ru concentration of 0.1 g/mL) is dissolved in the culture dish by adding ethanol is to lower the surface tension of the solution and avoid RuCl 3 The solution was excessively adsorbed on the wall of the dish, and then 5g of the final BN sample obtained in (5) was weighed and immersed, and left to stand for 6 hours.
(7) The mixture was left to stand in (6) and dried in an oven at 120℃for 8 hours.
(8) And (3) roasting the catalyst obtained in the step (7) in a muffle furnace in a hydrogen atmosphere at 450 ℃ for 5 hours, and cooling to obtain the catalyst.
Firstly tabletting the catalyst by using a tablet press, sieving particles with 60 meshes, filling quartz sand and quartz cotton into the bottom of a fixed bed reactor reaction tube, filling 0.1g of catalyst particles with 60 meshes, recharging quartz sand and quartz cotton, installing the catalyst, and then filling O 2 Activated for half an hour and then HCl is introduced. The reaction conditions are as follows: whsv=1000h -1 ，V(HCl):V(O 2 ) Reaction temperature t=350℃=1:1. Then absorbing tail gas with potassium iodide solution, titrating chlorine gas with sodium thiosulfate, titrating residual hydrogen chloride with sodium hydroxide solution to calculate conversion rate, and reacting for 500 hours70.27% and after 1000 hours of reaction the hydrogen chloride conversion was 51.34%.
Comparative example 2
Comparative example 2 shows that preheating can make the catalyst baked more fully, so that Ru is oxidized more thoroughly, the stability of the catalyst is improved, and the catalytic reaction is operated better.
(1) Taking a certain amount of urea, boric acid and ferric nitrate, uniformly mixing at room temperature, wherein the molar ratio of the urea to the boric acid is 1:2, and the ferric nitrate plays a role of a catalyst, so that the mass ratio of the urea to the boric acid is 1wt% of the urea to the ferric nitrate.
(2) The mixture obtained in (1) was placed in a muffle furnace, heated from room temperature to 850℃at a rate of 10℃per minute in 10ml/min of high-purity hydrogen, and calcined for 7 hours.
(3) And (3) cooling the nitrogen obtained by roasting in the step (2) to obtain a boron nitride sample.
(4) Washing the sample obtained in the step (3) with distilled water three times, and drying in an oven at 70 ℃ for 10 hours to finally obtain a BN sample.
(5) 0.5mL RuCl was dissolved in 20mL ethanol solution at room temperature 3 The solution (0.1 g/mL) was then immersed by weighing 5g of the final BN sample obtained in (4), and allowed to stand for 6 hours.
(6) The mixture was left to stand in (5) and dried in an oven at 120℃for 8 hours.
(7) And (3) placing the catalyst obtained in the step (6) into a muffle furnace in a hydrogen atmosphere, and roasting at 450 ℃ for 5 hours to obtain the catalyst.
(8) And (3) putting the catalyst prepared in the step (7) in high-purity nitrogen room temperature for passivation for 24 hours to finally obtain the target catalyst.
Firstly tabletting the catalyst by using a tablet press, sieving particles with 60 meshes, filling quartz sand and quartz cotton into the bottom of a fixed bed reactor reaction tube, filling 0.1g of catalyst particles with 60 meshes, recharging quartz sand and quartz cotton, installing the catalyst, and then filling O 2 Activated for half an hour and then HCl is introduced. The reaction conditions are as follows: whsv=1000h -1 ，V(HCl):V(O 2 ) Reaction temperature t=350℃=1:1. After which iodination is carried outThe potassium solution absorbed tail gas titrated chlorine with sodium thiosulfate and the sodium hydroxide solution titrated the residual hydrogen chloride to calculate the conversion rate, the conversion rate of hydrogen chloride was 81.94% after 500 hours of reaction, and the conversion rate of hydrogen chloride was 74.36% after 1000 hours of reaction.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (8)
1. A preparation method of a hydrogen chloride catalytic oxidation catalyst is characterized by comprising the following steps of: the preparation method comprises the following steps:
(1) Uniformly mixing a certain amount of urea, boric acid and ferric nitrate at room temperature to obtain a mixture, wherein the molar ratio of the urea to the boric acid is 1:1.5-1:2.8, and the mass of the ferric nitrate is 0.5-1.5wt% of the total mass of the urea, the boric acid and the ferric nitrate;
(2) Placing the mixture obtained in the step (1) in a muffle furnace, firstly raising the temperature to 280-300 ℃ from room temperature in 5-15 ml/min of high-purity hydrogen, and then keeping constant temperature for preheating for 50-70 minutes;
(3) Then the muffle furnace temperature is raised to 800-900 ℃ for roasting for 5-9 hours;
(4) Cooling the roasting product obtained in the step (3) by nitrogen;
(5) Fully washing the product obtained in the step (4) by distilled water, and drying in an oven at 60-100 ℃ to finally obtain a BN sample;
(6) Dissolving RuCl with ethanol at room temperature 3 The reason for adding ethanol into the aqueous solution for dissolution is to reduce the surface tension of the solution and avoid RuCl 3 The solution is excessively adsorbed on the wall, then the BN sample obtained in the step (5) is added for dipping, and the mixture is kept stand for 6 to 10 hours;
(7) Placing the standing mixture in the step (6) into a baking oven at 100-150 ℃ for drying;
(8) Placing the dried product obtained in the step (7) into a muffle furnace in hydrogen atmosphere, and roasting for 4-8 hours at 400-500 ℃ to obtain a catalyst preliminarily;
(9) And (3) placing the catalyst prepared in the step (8) in high-purity nitrogen for room temperature passivation for 20-30 hours, and finally obtaining the hydrogen chloride catalytic oxidation catalyst.
2. The method of manufacturing according to claim 1, wherein: in the step (1), the molar ratio of urea to boric acid is 1:2, and the mass of ferric nitrate accounts for 1wt% of the total mass of urea, boric acid and ferric nitrate.
3. The method of manufacturing according to claim 1, wherein: in the step (2), the temperature rising rate is 2-3 ℃/min.
4. A method of preparation as claimed in claim 3, wherein: in the step (2), the preheating temperature is 300 ℃, and the preheating time is 1h.
5. The method of manufacturing according to claim 1, wherein: in the step (3), the temperature rising rate is 8-12 ℃/min.
6. The method of manufacturing according to claim 1, wherein: in step (6), the RuCl 3 The mass ratio of the solution to BN sample is 0.8-1.3: 100 batch feeding.
7. The method of manufacturing according to claim 1, wherein: in the step (8), the roasting temperature is 450 ℃ and the roasting time is 5 hours.
8. The use of the hydrogen chloride catalytic oxidation catalyst prepared by the preparation method according to claim 1 in the preparation of chlorine by hydrogen chloride catalytic oxidation.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20190291087A1 (en) * | 2016-08-03 | 2019-09-26 | Wanhua Chemical Group Co., Ltd. | Catalyst For Preparing Chlorine Gas By Hydrogen Chloride Oxidation, And Preparation Method And Application Thereof |
| CN115155632A (en) * | 2022-06-24 | 2022-10-11 | 西安近代化学研究所 | Preparation method of hydrogen chloride oxidation catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20190291087A1 (en) * | 2016-08-03 | 2019-09-26 | Wanhua Chemical Group Co., Ltd. | Catalyst For Preparing Chlorine Gas By Hydrogen Chloride Oxidation, And Preparation Method And Application Thereof |
| CN115155632A (en) * | 2022-06-24 | 2022-10-11 | 西安近代化学研究所 | Preparation method of hydrogen chloride oxidation catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 赵学军;柳军;杨振军;: "副产氯化氢制氯气发展现状", 中国氯碱, no. 09, 20 September 2015 (2015-09-20) * |
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|---|---|---|---|---|
| CN116899558A (en) * | 2023-05-22 | 2023-10-20 | 康纳新型材料(杭州)有限公司 | High-heat-conductivity ruthenium catalyst with thermal stability and preparation method thereof |
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