Composite catalyst for removing hydrogen sulfide gas in yellow phosphorus tail gas through comprehensive catalysis

Abstract

The invention discloses a composite catalyst for removing hydrogen sulfide gas in yellow phosphorus tail gas through comprehensive catalysis. The composite catalyst is composed of a hollow porous ceramic shell, a composite particle filtering layer on the surface of an inner cavity of the shell and mixed particles which are arranged in the cavity and composed of sugar-coated activated carbon particles and photoelectrocatalysis functional particles. The device has the characteristics of high gas passing rate, good sulfur removal property, no increase of impurities, stability, controllability and easiness in maintenance.

Description

Technical Field

[0001] The present invention relates to the technical field of environmental protection related to phosphorus chemical industry, and particularly relates to a composite catalyst for comprehensively catalytically removing hydrogen sulfide gas in yellow phosphorus tail gas. Background Art

[0002] The products obtained by specifically tackling the pain points and difficulties encountered in the phosphorus chemical production process often have two relatively serious problems. One is that the catalyst is severely corroded and damaged during the treatment of sulfur compounds. The other is that various particles, especially sulfate particles, are easily generated during the phosphorus chemical production process. Therefore, in the phosphorus chemical production process, the control of sulfur-based gases and sulfate compounds is the key.

[0003] In the current existing technologies, there is no related technology that can solve the above problems. Currently, a composite catalyst for comprehensively catalytically removing hydrogen sulfide gas in yellow phosphorus tail gas is needed, which can remove solid particles, has good sulfur removal performance, does not increase impurities, is stable and controllable, and is easy to maintain. Summary of the Invention

[0004] The present invention aims to provide a composite catalyst for comprehensively catalytically removing hydrogen sulfide gas in yellow phosphorus tail gas, which can remove solid particles, has good sulfur removal performance, does not increase impurities, is stable and controllable, and is easy to maintain.

[0005] To achieve the above object, the present invention adopts the following technical solutions: A composite catalyst for comprehensively catalytically removing hydrogen sulfide gas in yellow phosphorus tail gas, and its manufacturing method includes the following stages: S1: Raw Material Preparation ① Preparation of raw materials: Prepare a porous breathable ceramic shell, xylene, γ-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, a sufficient amount of activated carbon particles with a particle size of 0.2 mm to 0.5 mm, a nitric acid aqueous solution with a solute mass fraction of 5%, a sodium hydroxide solution with a solute mass fraction of 10%, a hydrothermal reactor, deionized water, aluminum nitrate nonahydrate, boric acid, dimethylsilane, hydroxypropyl methylcellulose, C12 polysaccharide, tetrabutyl titanate, glacial acetic acid, ethanol, guanidine hydrochloride; wherein, the C12 polysaccharide is specifically any one of sucrose or maltose; S2: Modification of the Ceramic Body Particle Filtration Structure ① By weight, prepare 65 parts to 68 parts of aluminum nitrate nonahydrate, 32 parts to 35 parts of boric acid, 3.8 parts to 4.2 parts of hydroxypropyl methylcellulose, and 80 parts to 100 parts of deionized water to obtain a turbid liquid; ② Spin-coat the dimethylsilane prepared in step ① of stage S1 on the inner cavity surface of the porous breathable ceramic shell prepared in step ① of stage S1, and the coating thickness is 1 μm to 1.2 μm; ③Coat the turbid liquid obtained in step ① on the surface of the coating obtained in step ② by the dip-coating method, with a coating thickness of 3 μm to 5 μm; then place the porous breathable ceramic shell coated with two layers of coating liquid in a vacuum environment for firing, with a heating temperature of 1210 °C to 1230 °C and a heat preservation time of 15 h to 17 h. After the treatment, rinse the surface with nitrogen to obtain a porous ceramic support shell with a particle filtration structure fixed on the inner cavity surface; S3: Preparation of functional particle A ①Under normal pressure, mix activated carbon particles with a nitric acid aqueous solution with a solute mass fraction of 5% at a mass ratio of 1:(18 - 23), heat up to 75 °C to 80 °C, and react for 4 h; filter out the activated carbon particles, wash them with deionized water and then dry them; then mix the treated activated carbon particles with a sodium hydroxide solution with a solute mass fraction of 10% at a mass ratio of 1:(8 - 12), and treat them in a hydrothermal reactor, with a reaction temperature of 215 °C to 220 °C and a reaction time of 8 h to 10 h. Filter out the reacted activated carbon particles, wash them with deionized water until the pH is neutral and then dry them to obtain surface-activated activated carbon particles; ②Using the C12 polysaccharide prepared in step ① of stage S1 as the raw material, adopt the polysaccharide carbon coating process to treat the surface-activated activated carbon particles obtained in step ①. The specific parameters of the treatment are: the coating amount of C12 polysaccharide on the activated carbon particles is 15% to 18%, the carbonization temperature is 800 °C to 820 °C, and the carbonization degree is not less than 99% to obtain polysaccharide carbon-coated activated carbon particles, which are functional particle A; S4: Preparation of functional particle B ①Mix 8 g to 10 g of tetrabutyl titanate, 24 g to 30 g of glacial acetic acid prepared in step ① of stage S1 with 200 ml to 210 ml of ethanol, and gradually drop 43 ml to 46 ml of deionized water into the mixture until the dropping is complete to form a sol; ②Let the sol obtained in step ① stand at room temperature for 15 h to 16 h to obtain a pre-gel; ③Heat the pre-gel obtained in step ② to 65 °C to 70 °C and keep it warm until it is dried to obtain a dry gel, and then grind the dry gel into powder to obtain a prefabricated powder; ④Mix the prefabricated powder obtained in step ③ with the guanidine hydrochloride prepared in step ① of stage S1 and stir evenly, then ball-mill the mixture into a mixed fine powder with a particle size range of 0.1 μm to 0.12 μm. Place the mixed fine powder in a quartz crucible and then place it in a microwave oven, and perform treatment at a microwave power of 60 W to 80 W for 2.5 min to 3 min to obtain a microwave mixture; ⑤Using xylene as the solvent and γ-β-(aminoethyl)-γ-aminopropyltrimethoxysilane as the modifier, perform a modification treatment on the microwave mixture obtained in step ④ at 125 °C to 130 °C for a treatment time of 5 h to 6 h, take out the mixed particles to obtain modified mixed particles, which are functional particle B; S5: Composite Catalyst for Comprehensive Catalytic Removal of Hydrogen Sulfide Gas in Yellow Phosphorus Tail Gas ① After uniformly mixing the functional particle A obtained in step ② of S3 and the functional particle B obtained in step ⑤ of S4 according to the mass ratio of 3:(1-1.5), fill them into the hollow cavity of the porous ceramic support shell with a particle filtration structure fixed on the inner cavity surface obtained in step ③ of S2 to obtain the required composite catalyst for comprehensive catalytic removal of hydrogen sulfide gas in yellow phosphorus tail gas.

[0006] Compared with the prior art, due to the adoption of the above technical solutions, the present invention has the following advantages: (1) Substantially, the present invention is the product of the applicant's targeted research and development to solve the pain points and difficulties encountered in the long-term phosphorus chemical production process. Two relatively serious problems encountered by the applicant are: first, the corrosion and damage to the catalyst during the treatment of sulfur compounds are relatively large; second, various particles, especially sulfate particles, are easily generated during the phosphorus chemical production process. Therefore, in the phosphorus chemical production process, the control of sulfur-based gases and sulfate compounds is the key, and the specially developed composite catalyst of the present invention can effectively solve this problem and help the applicant stably and efficiently remove sulfur-based impurities.

[0007] (2) In fact, the ceramic shell of the present invention is a porous structure that basically does not impede the gas, and its purpose is to provide structural support for the particle filtration structure and filling materials inside. Through various tests by the applicant, after the purified activated carbon of the present invention is subjected to polysaccharide carbonization coverage, especially the treatment of sucrose or maltose carbonization coverage, the activated carbon filling material is the material with the best water removal effect without affecting the product purity found by the applicant in various tests.

[0008] (3) The specially prepared particle filtration layer of the present invention can achieve a particle filtration ratio of 97.5% for particles with a particle size of more than 0.3 μm, and the gas passing rate is not less than 73%.

[0009] Therefore, the present invention has the characteristics of being able to remove solid particles, having good sulfur removal performance, not increasing impurities, being stable and controllable, and being easy to maintain. Specific Embodiments Examples

[0010] A composite catalyst for comprehensive catalytic removal of hydrogen sulfide gas in yellow phosphorus tail gas, and its manufacturing method includes the following stages: S1: Raw Material Preparation ① Raw material preparation: Prepare a porous breathable ceramic shell, xylene, γ-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, sufficient activated carbon particles with a particle size of 0.2 mm to 0.5 mm, a nitric acid aqueous solution with a solute mass fraction of 5%, a sodium hydroxide solution with a solute mass fraction of 10%, a hydrothermal reactor, deionized water, aluminum nitrate nonahydrate, boric acid, dimethylsilane, hydroxypropyl methylcellulose, C12 polysaccharide, tetrabutyl titanate, glacial acetic acid, ethanol, guanidine hydrochloride; wherein, the C12 polysaccharide is specifically any one of sucrose or maltose; S2: Modification of the ceramic particle filtration structure ① By weight, prepare 65 parts to 68 parts of aluminum nitrate nonahydrate, 32 parts to 35 parts of boric acid, 3.8 parts to 4.2 parts of hydroxypropyl methylcellulose, and 80 parts to 100 parts of deionized water to obtain a turbid liquid; ② Spin-coat the dimethylsilane prepared in step ① of stage S1 on the inner cavity surface of the porous breathable ceramic shell prepared in step ① of stage S1, with a coating thickness of 1 μm to 1.2 μm; ③ Coat the turbid liquid obtained in step ① on the surface of the coating obtained in step ② by the dip-coating method, with a coating thickness of 3 μm to 5 μm; then place the porous breathable ceramic shell coated with two layers of coating liquid in a vacuum environment for firing, with a heating temperature of 1210 °C to 1230 °C and a holding time of 15 h to 17 h. After the treatment, flush the surface with nitrogen to obtain a porous ceramic support shell with a particle filtration structure fixed on the inner cavity surface; S3: Preparation of functional particle A ① Under normal pressure, mix the activated carbon particles and the nitric acid aqueous solution with a solute mass fraction of 5% evenly according to a mass ratio of 1:(18 - 23), then heat up to 75 °C to 80 °C and react for 4 h; filter out the activated carbon particles, wash them with deionized water and dry them; then mix the treated activated carbon particles and the sodium hydroxide solution with a solute mass fraction of 10% evenly according to a mass ratio of 1:(8 - 12), and treat them in a hydrothermal reactor, with a reaction temperature of 215 °C to 220 °C and a reaction time of 8 h to 10 h. Filter out the reacted activated carbon particles, wash them with deionized water until the pH is neutral and then dry them to obtain surface-activated activated carbon particles; ② Using the C12 polysaccharide prepared in step ① of stage S1 as the raw material, adopt the polysaccharide carbon coating process to treat the surface-activated activated carbon particles obtained in step ①. The specific parameters of the treatment are: the coating amount of C12 polysaccharide on the activated carbon particles is 15% to 18%, the carbonization temperature is 800 °C to 820 °C, and the carbonization degree is not less than 99% to obtain polysaccharide carbon-coated activated carbon particles, which are functional particle A; S4: Preparation of functional particle B ① Mix 8 g to 10 g of tetrabutyl titanate, 24 g to 30 g of glacial acetic acid prepared in step ① of stage S1 with 200 ml to 210 ml of ethanol evenly, and then gradually drop 43 ml to 46 ml of deionized water into the mixed solution until the dropping is completed to form a sol; ② Let the sol obtained in step ① stand at room temperature for 15 h to 16 h to obtain a pre-gel; ③ Heat the pre-gel obtained in step ② to 65 °C to 70 °C, keep it warm until it is dried to obtain a dry gel, and then grind the dry gel into powder to obtain a prefabricated powder; ④ Mix the prefabricated powder obtained in step ③ with the guanidine hydrochloride prepared in step ① of stage S1 and stir evenly, then ball-mill the mixture into a mixed fine powder with a particle size range of 0.1 μm to 0.12 μm, place the mixed fine powder in a quartz crucible, and then place it in a microwave oven, and perform treatment at a microwave power of 60 W to 80 W for 2.5 min to 3 min to obtain a microwave mixture; ⑤ Use xylene as a solvent and γ-β-(aminoethyl)-γ-aminopropyltrimethoxysilane as a modifier to perform modification treatment on the microwave mixture obtained in step ④ at 125 °C to 130 °C for a treatment time of 5 h to 6 h, take out the mixed particles to obtain modified mixed particles, which are functional particles B; S5: Composite catalyst for comprehensively catalytically removing hydrogen sulfide gas from yellow phosphorus tail gas ① After mixing the functional particles A obtained in step ② of S3 and the functional particles B obtained in step ⑤ of S4 evenly according to the mass ratio of 3:(1 to 1.5), fill them into the hollow cavity of the porous ceramic support shell with a particle filtration structure fixed on the inner cavity surface obtained in step ③ of S2 to obtain the required composite catalyst for comprehensively catalytically removing hydrogen sulfide gas from yellow phosphorus tail gas. The above description of the disclosed embodiments is only to enable those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be obvious to those skilled in the art. The general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to these embodiments shown herein, but will conform to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A composite catalyst for comprehensively catalytically removing hydrogen sulfide gas from yellow phosphorus tail gas, characterized in that Its manufacturing method It includes the following stages: S1: Raw material preparation ① Raw material preparation: Prepare a porous breathable ceramic shell, xylene, γ-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, sufficient activated carbon particles with a particle size of 0.2 mm to 0.5 mm, a nitric acid aqueous solution with a solute mass fraction of 5%, a sodium hydroxide solution with a solute mass fraction of 10%, a hydrothermal reactor, deionized water, aluminum nitrate nonahydrate, boric acid, dimethylsilane, hydroxypropyl methylcellulose, C12 polysaccharide, tetrabutyl titanate, glacial acetic acid, ethanol, guanidine hydrochloride; wherein, the C12 polysaccharide is specifically any one of sucrose or maltose; S2: Modification of the ceramic body particle filtration structure ① By weight, prepare 65 parts to 68 parts of aluminum nitrate nonahydrate, 32 parts to 35 parts of boric acid, 3.8 parts to 4.2 parts of hydroxypropyl methylcellulose, and 80 parts to 100 parts of deionized water to obtain a turbid liquid; ② Spin-coat the dimethylsilane prepared in step ① of stage S1 on the inner cavity surface of the porous breathable ceramic shell prepared in step ① of stage S1, with a coating thickness of 1 μm to 1.2 μm; ③ Coat the turbid liquid obtained in step ① on the surface of the coating obtained in step ② by the dip-coating method, with a coating thickness of 3 μm to 5 μm; then place the porous breathable ceramic shell coated with two layers of coating liquid in a vacuum environment for firing, with a heating temperature of 1210 °C to 1230 °C and a holding time of 15 h to 17 h. After the treatment is completed, flush the surface with nitrogen to obtain a porous ceramic support shell with a particle filtration structure fixed on the inner cavity surface; S3: Preparation of functional particle A ① Under normal pressure, mix the activated carbon particles and a nitric acid aqueous solution with a solute mass fraction of 5% evenly according to a mass ratio of 1:(18 - 23), then heat up to 75 °C to 80 °C and react for 4 h; filter out the activated carbon particles, wash them with deionized water and then dry them; then mix the treated activated carbon particles and a sodium hydroxide solution with a solute mass fraction of 10% evenly according to a mass ratio of 1:(8 - 12), and treat them in a hydrothermal reactor, with a reaction temperature of 215 °C to 220 °C and a reaction time of 8 h to 10 h. Filter out the reacted activated carbon particles, wash them with deionized water until the pH is neutral and then dry them to obtain surface-activated activated carbon particles; ② Using the C12 polysaccharide prepared in step ① of stage S1 as the raw material, adopt the polysaccharide carbon coating process to treat the surface-activated activated carbon particles obtained in step ①. The specific parameters of the treatment are: the coating amount of C12 polysaccharide on the activated carbon particles is 15% to 18%, the carbonization temperature is 800 °C to 820 °C, and the carbonization degree is not less than 99% to obtain polysaccharide carbon-coated activated carbon particles, which are functional particle A; S4: Preparation of functional particle B ① Mix 8 g to 10 g of tetrabutyl titanate, 24 g to 30 g of glacial acetic acid prepared in step ① of stage S1 with 200 ml to 210 ml of ethanol evenly, and then gradually drop 43 ml to 46 ml of deionized water into the mixed solution until the dropping is completed to form a sol; ② Let the sol obtained in step ① stand at room temperature for 15 h to 16 h to obtain a pre-gel; ③ Heat the pre-gel obtained in step ② to 65 °C to 70 °C and keep it warm until it is dried to obtain a dry gel, and then grind the dry gel into powder to obtain a prefabricated powder; ④Mix the prefabricated powder obtained in step ③ with the guanidine hydrochloride prepared in step ① of stage S1 and stir evenly. Then, ball-mill the mixture into a mixed fine powder with a particle size range of 0.1 μm to 0.12 μm. Place the mixed fine powder in a quartz crucible and then in a microwave oven, and perform treatment at a microwave power of 60 W to 80 W for 2.5 min to 3 min to obtain a microwave mixture. ⑤Using xylene as a solvent and γ-β-(aminoethyl)-γ-aminopropyltrimethoxysilane as a modifier, perform a modification treatment on the microwave mixture obtained in step ④ at 125 °C to 130 °C for a treatment time of 5 h to 6 h. Take out the mixed particles to obtain modified mixed particles, which are functional particles B. S5: Composite catalyst for comprehensively catalytically removing hydrogen sulfide gas from yellow phosphorus tail gas ①After mixing the functional particles A obtained in step ② of S3 and the functional particles B obtained in step ⑤ of S4 evenly according to a mass ratio of 3:(1 - 1.5), fill them into the hollow cavity of the porous ceramic support shell with a particle filtration structure fixed on the inner cavity surface obtained in step ③ of S2 to obtain the required composite catalyst for comprehensively catalytically removing hydrogen sulfide gas from yellow phosphorus tail gas.