CN114367287A - Catalytic oxidation catalyst suitable for treating high-sulfur tail gas and preparation method thereof - Google Patents
Catalytic oxidation catalyst suitable for treating high-sulfur tail gas and preparation method thereof Download PDFInfo
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- CN114367287A CN114367287A CN202210103532.2A CN202210103532A CN114367287A CN 114367287 A CN114367287 A CN 114367287A CN 202210103532 A CN202210103532 A CN 202210103532A CN 114367287 A CN114367287 A CN 114367287A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 31
- 230000003647 oxidation Effects 0.000 title claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 31
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 29
- 239000011593 sulfur Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 66
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 42
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000011248 coating agent Substances 0.000 claims abstract description 32
- 238000000576 coating method Methods 0.000 claims abstract description 32
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 21
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011777 magnesium Substances 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 21
- 239000011733 molybdenum Substances 0.000 claims abstract description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 19
- 239000000919 ceramic Substances 0.000 claims abstract description 17
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 239000002002 slurry Substances 0.000 claims description 48
- 238000000034 method Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000006255 coating slurry Substances 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 7
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 17
- 230000032683 aging Effects 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 231100000572 poisoning Toxicity 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000002912 waste gas Substances 0.000 abstract description 2
- 239000012855 volatile organic compound Substances 0.000 description 13
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 10
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 8
- MODMKKOKHKJFHJ-UHFFFAOYSA-N magnesium;dioxido(dioxo)molybdenum Chemical compound [Mg+2].[O-][Mo]([O-])(=O)=O MODMKKOKHKJFHJ-UHFFFAOYSA-N 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JTGUKKQNIJMJAQ-UHFFFAOYSA-N [Mg].[Mo] Chemical compound [Mg].[Mo] JTGUKKQNIJMJAQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000019633 pungent taste Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/56—
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- B01J35/613—
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- B01J35/615—
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- B01J35/617—
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- B01J35/618—
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
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Abstract
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalytic oxidation catalyst suitable for treating high-sulfur tail gas and a preparation method thereof. The catalyst comprises a carrier, a coating and an active component, wherein the carrier is divided into a ceramic honeycomb carrier and a metal honeycomb carrier, the coating contains a component which can efficiently convert VOC in sulfur-containing waste gas, and the adopted titanium dioxide is a porous material with high specific surface area, has good poisoning effects on sulfur and other toxic and harmful substances, and effectively improves the sulfur poisoning resistance of the catalyst. The molybdenum and magnesium modified alumina is a porous material with high specific surface area, can effectively improve the hydrothermal aging resistance of the catalyst, and improves the hydrothermal aging rate of noble metals in the catalyst at high temperature. The auxiliary agent is one or more noble metal dispersing materials, so that the dispersity of the noble metal in the catalyst can be effectively improved, the light-off temperature of the catalyst can be effectively reduced, and the conversion efficiency of the catalyst can be effectively improved.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to a catalytic oxidation catalyst suitable for treating high-sulfur tail gas and a preparation method thereof.
Background
The catalytic oxidation technology is the main technology for treating organic waste gas at present, and is particularly suitable for a phthalic anhydride production device taking naphthalene as a raw material. The catalytic oxidation technology has wide application in the industry, and has the outstanding characteristics of high safety, strong stability, high removal efficiency and the like. Naphthalene is used as a raw material of the phthalic anhydride production device, the raw material contains elemental sulfur with the highest concentration of 800ppm and other sulfur compounds, all sulfides enter a tail gas treatment system of the phthalic anhydride production device, and the sulfur and the sulfides in the raw material are deeply oxidized into sulfur dioxide or sulfur trioxide and are finally eluted by a wet desulphurization leaching tower at the tail end of the sulfur dioxide or sulfur trioxide after passing through the tail gas treatment system. Because the wet desulphurization device adopts an alkali liquor circulation method, a part of waste liquor can be circularly discharged, and the waste liquor can generate a little treatment cost for a user.
And the catalytic oxidation device mainly uses a catalytic oxidation type catalyst, the catalyst adopts noble metal as a main active substance, and the catalytic oxidation device has the advantages of capability of efficiently treating organic matters at a certain temperature, capability of effectively reducing energy consumption and the like. However, noble metals in the catalytic oxidation catalyst are sensitive to substances such as sulfur, halogen and the like, and are easy to be poisoned, so that the service life of the catalyst is shortened, meanwhile, the catalyst oxidizes high-content hydrogen sulfide, sulfur dioxide and the like into sulfur trioxide, and acid mist with pungent taste is easily formed by combining the sulfur trioxide with water vapor, so that aiming at catalytic oxidants in organic waste gas containing high sulfur, on one hand, the coating needs to be optimized, the sulfur adsorption and desorption capacity of the coating is increased, the contact between the noble metals and sulfur is reduced, the service life of the catalyst is prolonged, on the other hand, the oxidation capacity of the catalyst on VOC organic components is enhanced, and the removal efficiency of VOC is improved to the greatest extent, so that COD in the circulating discharge liquid of the tail end wet desulphurization device is greatly reduced, and the waste water treatment cost is reduced.
Disclosure of Invention
The invention aims at the defects of the prior art of a catalytic oxidation catalyst for sulfur-containing VOC tail gas in the current market, and particularly relates to a catalytic oxidation catalyst suitable for treating high-sulfur tail gas and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
the catalytic oxidation catalyst is covered with a coating, the loading amount of the coating is 50-150g/L, the coating contains noble metals of Pt and Pd, the content of the noble metals is 0.5-2.5%, and the coating also contains titanium dioxide, molybdenum, magnesium modified alumina and an auxiliary agent.
Further, the mass ratio of the titanium dioxide, the molybdenum, the magnesium modified alumina and the auxiliary agent in the coating is 24:75: 1-60: 35: 5.
Further, the titanium dioxide is anatase titanium dioxide.
Further, the mass ratio of molybdenum to aluminum oxide in the molybdenum-modified aluminum oxide is 1: 99-1: 9, the mass ratio of magnesium to aluminum oxide in the magnesium-modified aluminum oxide is 1: 99-1: 9, and the ratio of molybdenum to magnesium is 1: 1.
Further, the carrier is a ceramic honeycomb carrier or a metal honeycomb carrier.
A catalytic oxidation tail gas treatment device of a phthalic anhydride product production device taking naphthalene as a raw material uses any one of the catalytic oxidation catalysts suitable for treating high-sulfur tail gas.
A method for preparing a catalytic oxidation catalyst suitable for treating a high sulfur containing tail gas, comprising the steps of:
(1) preparing modified alumina: weighing 90-99 parts of alumina with a high specific area, adding into 240 parts of distilled water with a temperature of 180-;
(2) preparation of slurry: adding titanium dioxide and modified alumina into distilled water according to a certain proportion, stirring for 2-6h, dripping the auxiliary agent into the slurry, adjusting the pH to 2-5, and then ball-milling until slurry D9010-50 μm to obtain coating slurry;
(3) addition of noble metals: adding noble metal into the coating slurry, and stirring for 8-20h until the pH of the slurry is stable to 0-3 to obtain noble metal slurry;
(4) coating a carrier: taking a ceramic honeycomb carrier or a pretreated metal carrier, giving noble metal slurry with corresponding weight by adopting a quantitative slurry feeding method, uniformly loading the noble metal slurry on the carrier by adopting a negative pressure method for suction, drying at the temperature of 100-550 ℃ for 1-5 h, and finally roasting the carrier at the temperature of 450-550 ℃ for 1-5 h to obtain the catalytic oxidation catalyst.
Further, the auxiliary agent is a barium hydroxide solution prepared in advance.
Further, the pH value of the noble metal is stabilized to be 0-3 in the adding process, and dilute nitric acid is used for adjusting.
Further, in the adding process of the noble metal, the noble metal is platinum nitrate and palladium nitrate, and the weight of the noble metal accounts for 0.5-2.5% of the weight of the coating slurry.
The invention has the following advantages:
(1) the titanium dioxide adopted by the invention is a porous material with high specific surface area, the specific surface area is more than 80m2/g, the titanium dioxide has good poisoning effects on toxic and harmful substances such as sulfur and the like, and the sulfur poisoning resistance of the catalyst is effectively improved.
(2) The molybdenum and magnesium modified alumina is a porous material with high specific surface area, the specific surface area is more than 120m2/g, the hydrothermal aging resistance of the catalyst can be effectively improved, and the hydrothermal aging rate of noble metals in the catalyst at high temperature is improved.
(3) The auxiliary agent is one or more noble metal dispersing materials, so that the dispersity of the noble metal in the catalyst can be effectively improved, the light-off temperature of the catalyst can be effectively reduced, and the conversion efficiency of the catalyst can be effectively improved.
(4) The preparation method is simple and convenient, is easy to operate, the prepared catalyst can stably run under the condition of sulfur-containing waste gas, has better VOC (volatile organic compounds) treatment capability and longer service life, and the preparation technology of the catalyst is mature and is easy to industrialize.
Detailed Description
The technical solution of the present invention will be further described with reference to specific examples.
Example 1
The catalyst is suitable for efficiently treating sulfur-containing volatile organic compound tail gas (VOC), the carrier is a ceramic honeycomb carrier, the volume of the ceramic honeycomb carrier is 3.375L and 400 meshes/square foot, the coating is provided with alumina and titanium dioxide modified by noble metals of Pt, molybdenum and magnesium, the total coating amount of the coating is 100g/L, and the loading amount of the noble metal of Pt is 1.06%.
The preparation method comprises the following steps:
(1) preparing molybdenum and magnesium modified alumina: weighing 950g of alumina with a high specific area, adding the alumina into 2000g of distilled water, stirring for 2.5h, taking 50g of magnesium molybdate, adding the magnesium molybdate into a mixture of the alumina and the water, continuously stirring for 3h, drying at the temperature of 180 ℃, and roasting for 2h, wherein the roasting temperature is 650 ℃;
(2) preparation of slurry: weighing 484.8g of molybdenum and magnesium modified alumina and 484.8g of titanium dioxide, adding the weighed materials into 2000g of distilled water, stirring for 2 hours, adding a certain amount of prepared barium hydroxide solution (condensate is 19.8g) as an auxiliary agent, dripping the barium hydroxide solution into the slurry, adjusting the pH to about 4, and then carrying out ball milling until the slurry D90 is 25 microns to obtain coating slurry;
(3) addition of noble metals: and adding noble metal into the prepared coating slurry, wherein the noble metal is platinum nitrate, the weight of the noble metal is that the weight of the noble metal is 10.6g of pure platinum, stirring for 20h after the noble metal is added into the slurry until the pH of the slurry is stable to 3, and if the requirement is not met, adding dilute nitric acid for adjustment.
(4) Coating a carrier: taking a ceramic honeycomb carrier with the volume of 3.375L, adding 337.5g of noble metal slurry with the dry weight by a quantitative slurry feeding method, uniformly loading the slurry on the carrier by suction by a negative pressure method, drying at 140 ℃ for 4h, and finally roasting the carrier at 550 ℃ for 2h to obtain the finished catalyst A.
Example 2
The catalyst is suitable for efficiently treating sulfur-containing volatile organic compound tail gas (VOC), the carrier is a ceramic honeycomb carrier, the volume of the ceramic honeycomb carrier is 3.375L and 400 meshes/square foot, the coating is provided with alumina and titanium dioxide modified by noble metals of Pt, molybdenum and magnesium, the total coating amount of the coating is 100g/L, and the loading amount of the noble metal of Pt is 1.06%.
The preparation method comprises the following steps:
(1) preparing molybdenum and magnesium modified alumina: weighing 990g of alumina with a high specific area, adding the alumina into 2050g of distilled water, stirring for 2.5 hours, adding 10g of magnesium molybdate into a mixture of the alumina and the water, continuously stirring for 3 hours, drying at the temperature of 180 ℃, and roasting for 2 hours, wherein the roasting temperature is 650 ℃;
(2) preparation of slurry: 237.5g of molybdenum and magnesium modified alumina and 742.0g of titanium dioxide are weighed and added into 2000g of distilled water, stirred for 2 hours, a certain amount of prepared barium hydroxide solution (condensate is 9.9g) is added as an auxiliary agent and dripped into the slurry, the pH is adjusted to about 4, and then ball milling is carried out until slurry D9025 μm to obtain a coating slurry;
(3) addition of noble metals: and adding noble metal into the prepared coating slurry, wherein the noble metal is platinum nitrate, the weight of the noble metal is that the weight of the noble metal is 10.6g of pure platinum, stirring for 20h after the noble metal is added into the slurry until the pH of the slurry is stable to 3, and if the requirement is not met, adding dilute nitric acid for adjustment.
(4) Coating a carrier: taking a ceramic honeycomb carrier with the volume of 3.375L, adding 337.5g of noble metal slurry with the dry weight by a quantitative slurry feeding method, uniformly loading the slurry on the carrier by suction by a negative pressure method, drying at 140 ℃ for 4h, and finally roasting the carrier at 550 ℃ for 2h to obtain a finished catalyst B.
Example 3
The catalyst is suitable for efficiently treating sulfur-containing volatile organic compound tail gas (VOC), the carrier is a ceramic honeycomb carrier, the volume of the ceramic honeycomb carrier is 3.375L and 400 meshes/square foot, the coating is provided with alumina and titanium dioxide modified by noble metals of Pt, molybdenum and magnesium, the total coating amount of the coating is 100g/L, and the loading amount of the noble metal of Pt is 1.06%.
The preparation method comprises the following steps:
(1) preparing molybdenum and magnesium modified alumina: weighing 900g of alumina with a high specific area, adding the alumina into 1950g of distilled water, stirring for 2.5 hours, taking 100g of magnesium molybdate, adding the magnesium molybdate into a mixture of the alumina and the water, continuously stirring for 3 hours, drying at the temperature of 180 ℃, and roasting for 2 hours, wherein the roasting temperature is 650 ℃;
(2) preparation of slurry: weighing 5936g of molybdenum-magnesium modified alumina and 346.3g of titanium dioxide are added into 2000g of distilled water, stirred for 2 hours, added with a certain amount of prepared barium hydroxide solution (49.5 g of solidified material) as an auxiliary agent and dripped into the slurry, the pH value is adjusted to about 4, and then ball-milled until slurry D9025 μm to obtain a coating slurry;
(3) addition of noble metals: and adding noble metal into the prepared coating slurry, wherein the noble metal is platinum nitrate, the weight of the noble metal is that the weight of the noble metal is 10.6g of pure platinum, stirring for 20h after the noble metal is added into the slurry until the pH of the slurry is stable to 3, and if the requirement is not met, adding dilute nitric acid for adjustment.
(4) Coating a carrier: taking a ceramic honeycomb carrier with the volume of 3.375L, adding 337.5g of noble metal slurry with the dry weight by a quantitative slurry feeding method, uniformly loading the slurry on the carrier by suction by a negative pressure method, drying at 140 ℃ for 4h, and finally roasting the carrier at 550 ℃ for 2h to obtain the finished catalyst C.
Example 4
The catalyst is suitable for efficiently treating sulfur-containing volatile organic compound tail gas (VOC), the carrier is a ceramic honeycomb carrier, the volume of the ceramic honeycomb carrier is 3.375L and 400 meshes/square foot, the coating is provided with alumina and titanium dioxide modified by noble metals of Pt, molybdenum and magnesium, the total coating amount of the coating is 100g/L, and the loading amount of the noble metal of Pt is 1.06%.
The preparation method comprises the following steps:
(1) preparing molybdenum and magnesium modified alumina: weighing 950g of alumina with a high specific area, adding the alumina into 2000g of distilled water, stirring for 2.5h, taking 50g of magnesium molybdate, adding the magnesium molybdate into a mixture of the alumina and the water, continuously stirring for 3h, drying at the temperature of 180 ℃, and roasting for 2h, wherein the roasting temperature is 650 ℃;
(2) preparation of slurry: 477.4g of molybdenum and magnesium modified alumina and 477.4g of titanium dioxide are weighed and added into 2000g of distilled water, stirred for 2 hours, a certain amount of prepared barium hydroxide solution (34.6 g of condensate) is added as an auxiliary agent and dripped into the slurry, the pH is adjusted to about 4, and then ball milling is carried out until the slurry D9025 μm to obtain a coating slurry;
(3) addition of noble metals: and adding noble metal into the prepared coating slurry, wherein the noble metal is platinum nitrate, the weight of the noble metal is that the weight of the noble metal is 10.6g of pure platinum, stirring for 20h after the noble metal is added into the slurry until the pH of the slurry is stable to 3, and if the requirement is not met, adding dilute nitric acid for adjustment.
(4) Coating a carrier: taking a ceramic honeycomb carrier with the volume of 3.375L, adding 337.5g of noble metal slurry with the dry weight by a quantitative slurry feeding method, uniformly loading the slurry on the carrier by suction by a negative pressure method, drying at 140 ℃ for 4h, and finally roasting the carrier at 550 ℃ for 2h to obtain the finished catalyst D.
Evaluation of Performance
The performance evaluation was carried out on the catalyst samples A-D of examples 1-4: the prepared catalysts a to D were subjected to activity evaluation of catalytic oxidation of organic matter (taking maleic acid as an example), and at the same time, efficiency of catalytic oxidation of organic matter after aging for 100 hours in a sulfur dioxide atmosphere was evaluated. The test conditions were as follows: 2000ppm maleic acid, 10% O2，5％H2O, using N as balance gas2The reaction temperature is 200 ℃ and 500 ℃, and the space velocity is 30000h-1. The aging conditions were as follows: 300ppm SO2，5％H2O, aging time 100h, and the results are shown in Table 1.
Table 1 examples 1-4 performance data
As can be seen from Table 1, T of catalysts A to D prepared in examples 1 to 450All below 250 ℃ and T100All at the temperature below 300 ℃, has good maleic acid catalytic oxidation capability, has no obvious aging after 100 hours of sulfur dioxide and water vapor atmosphere conditions, and has T50Increase 10-20 ℃ and T100The increase is 15-20 ℃, but the maleic acid can be completely converted below 300 ℃.
The above description is a preferred embodiment of the present invention and should not be taken as limiting the invention. Any simple modification, change and equivalent changes of the above embodiments according to the principles of the present invention are still within the protection scope of the technical solution of the present invention.
Claims (10)
1. The catalytic oxidation catalyst is characterized in that the catalytic oxidation catalyst covers a coating, the loading capacity of the coating is 50-150g/L, the coating contains noble metals Pt and Pd, the content of the noble metals is 0.5-2.5%, and the coating also contains titanium dioxide, molybdenum, magnesium modified alumina and an auxiliary agent.
2. The catalytic oxidation catalyst suitable for treating the high-sulfur tail gas as claimed in claim 1, wherein the mass ratio of the titanium dioxide, the molybdenum, the magnesium modified alumina and the auxiliary agent in the coating is 24:75: 1-60: 35: 5.
3. A catalytic oxidation catalyst suitable for treating high sulfur containing tail gas in accordance with claim 1 wherein the titanium dioxide is anatase titanium dioxide.
4. The catalytic oxidation catalyst for treating the high-sulfur tail gas according to claim 1, wherein the mass ratio of molybdenum to alumina in the molybdenum-modified alumina is 1:99 to 1:9, the mass ratio of magnesium to alumina in the magnesium-modified alumina is 1:99 to 1:9, and the ratio of molybdenum to magnesium is 1: 1.
5. The catalytic oxidation catalyst suitable for treating high sulfur containing tail gas according to claim 1, wherein the carrier is a ceramic honeycomb carrier or a metal honeycomb carrier.
6. A catalytic oxidation tail gas treatment device of a phthalic anhydride product production device taking naphthalene as a raw material is characterized in that any one of the catalytic oxidation catalysts which are suitable for treating high-sulfur tail gas in claims 1 to 5 is used.
7. A method for preparing a catalytic oxidation catalyst suitable for treating a high sulfur containing tail gas according to any one of claims 1 to 5, comprising the steps of:
(1) preparing modified alumina: weighing 90-99 parts of alumina with a high specific area, adding into 240 parts of distilled water with a temperature of 180-;
(2) preparation of slurry: adding titanium dioxide and modified alumina into distilled water according to a certain proportion, stirring for 2-6h, dripping the auxiliary agent into the slurry, adjusting the pH to 2-5, and then ball-milling until slurry D9010-50 μm to obtain coating slurry;
(3) addition of noble metals: adding noble metal into the coating slurry, and stirring for 8-20h until the pH of the slurry is stable to 0-3 to obtain noble metal slurry;
(4) coating a carrier: taking a ceramic honeycomb carrier or a pretreated metal carrier, giving noble metal slurry with corresponding weight by adopting a quantitative slurry feeding method, uniformly loading the noble metal slurry on the carrier by adopting a negative pressure method for suction, drying at the temperature of 100-550 ℃ for 1-5 h, and finally roasting the carrier at the temperature of 450-550 ℃ for 1-5 h to obtain the catalytic oxidation catalyst.
8. The method of claim 7, wherein the auxiliary agent is a pre-prepared barium hydroxide solution.
9. The method of claim 7, wherein the noble metal is added at a stable pH of 0-3 and adjusted with dilute nitric acid.
10. The method of claim 7, wherein the noble metals are platinum nitrate and palladium nitrate, and the weight of the noble metals is 0.5-2.5% of the weight of the coating slurry.
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| CN115869944A (en) * | 2022-11-29 | 2023-03-31 | 江苏优尚环境工程有限公司 | Catalytic oxidation catalyst applied to high-moisture environment and preparation method thereof |
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