CN114471622A - Ozone decomposition catalyst and preparation method thereof - Google Patents
Ozone decomposition catalyst and preparation method thereof Download PDFInfo
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- CN114471622A CN114471622A CN202111592082.XA CN202111592082A CN114471622A CN 114471622 A CN114471622 A CN 114471622A CN 202111592082 A CN202111592082 A CN 202111592082A CN 114471622 A CN114471622 A CN 114471622A
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- calcium sulfate
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- ozone
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000000354 decomposition reaction Methods 0.000 title claims description 19
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 74
- VWYPZFOWFPQMHD-UHFFFAOYSA-L [O-2].[Mn+2].S(=O)(=O)([O-])[O-].[Ca+2] Chemical group [O-2].[Mn+2].S(=O)(=O)([O-])[O-].[Ca+2] VWYPZFOWFPQMHD-UHFFFAOYSA-L 0.000 claims abstract description 21
- 238000005949 ozonolysis reaction Methods 0.000 claims abstract description 19
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000011572 manganese Substances 0.000 claims abstract description 12
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims description 45
- 229910052925 anhydrite Inorganic materials 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 23
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 150000002696 manganese Chemical class 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000011656 manganese carbonate Substances 0.000 claims description 7
- 235000006748 manganese carbonate Nutrition 0.000 claims description 7
- 229940093474 manganese carbonate Drugs 0.000 claims description 7
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 7
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 7
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 5
- 238000000975 co-precipitation Methods 0.000 claims description 4
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 229910052748 manganese Inorganic materials 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 229960001484 edetic acid Drugs 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 238000001035 drying Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 238000011068 loading method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 7
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- -1 ozone ion Chemical class 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 238000005470 impregnation Methods 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000005979 thermal decomposition reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 229910001437 manganese ion Inorganic materials 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000002468 redox effect Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- BAZFAMAVACBDQL-UHFFFAOYSA-L [O-2].[O-2].[Mn+6].S(=O)(=O)([O-])[O-] Chemical compound [O-2].[O-2].[Mn+6].S(=O)(=O)([O-])[O-] BAZFAMAVACBDQL-UHFFFAOYSA-L 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 210000003928 nasal cavity Anatomy 0.000 description 1
- 238000011328 necessary treatment Methods 0.000 description 1
- 230000001338 necrotic effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 208000023504 respiratory system disease Diseases 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- 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
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
- B01D53/8675—Ozone
-
- 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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The invention relates to the technical field of ozonolysis, in particular to an ozonolysis catalyst and a preparation method thereof. The technical key point is that the catalyst is a calcium sulfate-manganese oxide composite material, wherein the mass percentage of the calcium sulfate is 5-12% of the mass of the calcium sulfate-manganese oxide composite material. The calcium sulfate-manganese oxide catalyst provided by the invention can efficiently decompose ozone for a long time, and has the advantages of strong moisture resistance, good stability, no secondary pollution and the like; the calcium sulfate and manganese-based materials are low in price and easy to obtain, and the catalyst is simple in preparation process, easy for large-scale production and wide in application prospect.
Description
Technical Field
The invention relates to the technical field of ozonolysis, in particular to an ozonolysis catalyst and a preparation method thereof.
Background
Ozone (O)3) Is an allotrope of oxygen, a pale blue gas with a fishy smell. Ozone is a trace gas in the earth atmosphere, is formed by combining oxygen atoms with surrounding oxygen molecules after oxygen molecules in the atmosphere are decomposed into oxygen atoms by solar radiation, and contains three oxygen atoms. More than 90% of ozone in the atmosphere exists in the upper part of the atmosphere or the stratosphere, 10-50 km is away from the ground, and the atmospheric ozone layer can resist harmful ultraviolet rays from directly irradiating the earth. And a small part of ozoneWhen the child wanders near the ground, the child still can block ultraviolet rays to a certain extent. However, too high a concentration of ozone in the atmosphere near the ground can have adverse effects on animals, plants and the environment. Ozone has strong oxidizing property, and can seriously stimulate nasal cavity and throat, cause chest contraction, even cardiovascular and respiratory system disorders, accelerate aging and the like. In addition, the ozone can weaken the photosynthesis of plants, even kill cells, and lead the leaves of the plants to be necrotic and shed, thereby slowing down the growth of the plants, causing the yield reduction of various crops and influencing the economic benefit of the whole country. The adverse effect of ozone has attracted people's attention, and it is important to reduce the ozone emission value and perform necessary treatment before the exhaust gas containing ozone is discharged.
Currently, the methods for removing ozone mainly include an activated carbon method, a thermal decomposition method, a plasma decomposition method, a chemical liquid absorption method, and a catalytic decomposition method. The activated carbon is applied to removing ozone, the method is simple, the operability is strong, and the ozone removing effect is good, but the activated carbon in the method needs to be replaced or regenerated frequently, the method is not suitable for removing high-concentration ozone, and the activated carbon method can be influenced by factors such as humidity, dust, airflow and the like in actual application. The thermal decomposition method mainly utilizes the technology that the decay of ozone is accelerated along with the temperature rise, the thermal decomposition of ozone in air is started at 30 ℃, is remarkable at 40-50 ℃, the ozone decomposition is about 70% within one minute at 200 ℃, and the decomposition reaches 100% within 1-2 s of reaction time at 300 ℃ and above. In order to achieve a high decomposition rate in the decomposition of ozone at a high concentration, it is necessary to heat the gas to 400 ℃ and cause a redox reaction by thermal decomposition or combustion to decompose ozone. The plasma decomposition of ozone means that plasma is generated in the process of high-voltage discharge, and the plasma reacts with ozone to decompose the ozone into oxygen. The chemical solution absorption method uses a chemical such as sodium thiosulfate or sodium sulfite to absorb ozone through an oxidation-reduction reaction between a chemical solution and ozone, and this method has a problem of waste liquid treatment and is rarely used in practice. The catalytic decomposition of ozone is the most studied and applied method at present, can make up for the deficiencies of the above methods, and the catalyst is more stable, has higher removal rate of ozone, meets the requirements of safety and economy, and is the more ideal method at present.
CN108212153A discloses a self-supporting noble metal modified manganese-based composite oxide catalyst, a preparation method and an application thereof, wherein the self-supporting noble metal modified manganese-based composite oxide catalyst is formed by firstly growing Al in situ on an aluminum substrate2O3The nano-sheets form a catalyst carrier, and the manganese-based composite oxide and the active noble metal are sequentially loaded on the catalyst carrier to obtain the catalyst. CN109908934A discloses a catalyst for catalytic oxidation reaction of ozone, which comprises a composite carrier and an active metal component, wherein one or more of Pt, Pd, Rh, and Ru is/are used as the active metal component, the composite carrier comprises activated carbon and basic carbonate, and the basic carbonate is distributed on the outer surface of the activated carbon. The two catalysts have good stability, but the noble metal used by the catalysts is expensive, the preparation method is complex, and the large-scale preparation is not beneficial to industrial application. CN1259398A, CN17167674A and CN1357348A all adopt oxides of copper, nickel and cobalt as active components, and are loaded on active carbon to decompose ozone, and the oxides have good effects at normal temperature, low decomposition efficiency, unstable property, short service life and poor moisture resistance.
Disclosure of Invention
The first purpose of the invention is to provide an ozonolysis catalyst, which is obtained by compounding calcium sulfate and manganese oxide and has stable property, high decomposition efficiency and strong moisture resistance.
The technical purpose of the invention is realized by the following technical scheme:
the catalyst is a calcium sulfate-manganese oxide composite material, wherein the mass percentage of the calcium sulfate is 5-12% of the mass of the calcium sulfate-manganese oxide composite material. According to the invention, calcium sulfate is introduced into the composite material, so that the ozone decomposition activity of the interaction between manganese oxide and calcium sulfate is greatly improved, and when the calcium sulfate adsorbs ozone, oxygen atoms are easy to store and release and migrate to the surface of the manganese oxide, thereby promoting the formation of lattice defects and oxygen vacancies on the manganese oxide and improving the ozone decomposition capability.
Further, manganese oxide in the calcium sulfate-manganese oxide composite material is alpha-Mn2O3。α-Mn2O3As a high-stability carrier with redox properties.
Further, α -Mn2O3The specific surface area of the alloy is more than or equal to 20m2/g。
Further, α -Mn2O3The particle size of (A) is 40 to 150 nm.
Further, α -Mn2O3The preparation method is that manganese carbonate precipitate obtained after coprecipitation of soluble manganese salt solution and sodium carbonate solution is calcined.
Further, α -Mn2O3The preparation method specifically comprises the following steps:
step 2, drying and calcining to obtain alpha-Mn2O3The support, which is itself a catalyst, is catalytically active.
Further, the soluble manganese salt is manganese sulfate or manganese nitrate, and the concentration is 0.1-1 mol/L. Preferably 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.5mol/L, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Further, when the soluble manganese salt and the sodium carbonate solution are blended, the coprecipitation reaction is completed when the pH reaches 8 to 9, wherein the pH is preferably 8, 8.2, 8.4, 8.6, 8.8, 9, and the like, but is not limited to the recited values, and other values not recited in the range are also applicable.
Further, the concentration of the sodium carbonate solution in step 1 is 0.2 to 2mol/L, preferably 0.2mol/L, 0.4mol/L, 0.6mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.4mol/L, 1.6mol/L, 1.8mol/L, 2mol/L, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Further, the stirring in the step 1 is uniform stirring.
Further, before the step 2, the manganese carbonate precipitate obtained in the step 1 is washed to be neutral.
Further, the drying temperature in step 2 is 90 to 150 ℃, for example, 90 ℃, 95 ℃, 100 ℃, 110 ℃, 115 ℃, 120 ℃, 130 ℃, 13 ℃, 140 ℃ or 150 ℃, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Further, the drying time is 12 to 24 hours, preferably 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours, but not limited to the recited values, and other values not recited in the range are also applicable.
Further, the calcination temperature in step 2 is 500 to 900 ℃, for example, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃ or the like, but not limited to the recited values, and other values not recited in the range are also applicable.
Further, the calcination time is 2 to 5 hours, for example, 2 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, or 5 hours, but is not limited to the recited values, and other values not recited in the range are also applicable.
The second purpose of the invention is to provide a preparation method of the ozone decomposition catalyst, which has the same technical effect.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of an ozone decomposition catalyst comprises the following specific operations: mixing alpha-Mn2O3Soaking in calcium sulfate aqueous solution, standing, taking out, and calcining to obtain calcium sulfate-manganese oxide. The calcium sulfate-manganese oxide obtained by calcination is loaded on other carriers, such as alumina, molecular sieve and activated carbon, so as to increase the ozonolysis effect.
Furthermore, the calcium sulfate aqueous solution also comprises ethylene diamine tetraacetic acid and ammonia water. The calcium sulfate is slightly soluble in water, and in order to better disperse the calcium sulfate in the water and improve the uniformity of the load of the calcium sulfate on the manganese oxide, the ammonia water and the ethylene diamine tetraacetic acid are added into the water.
Further, in order to determine the amounts of ammonia and ethylenediaminetetraacetic acid added to the aqueous solution of calcium sulfate and to ensure complete dissolution of calcium sulfate, and considering that the molar amount of ammonia monohydrate in the aqueous solution of ammonia is twice the molar amount of EDTA, their amounts were calculated using the following formula:
wherein: m-CaSO4Mass of EDTA, g;
M——CaSO4、EDTA、NH3·H2relative molecular mass of O;
ω——NH3·H2the concentration of O;
rho-NH at ambient temperature3·H2The density of O;
v is the adding amount of ammonia water.
Furthermore, calcium sulfate and EDTA have coordination effect, and the addition of ammonia water can further increase the solubility of EDTA, so that calcium sulfate can be completely dissolved finally. The formula can accurately calculate the adding amount of ammonia water and ethylene diamine tetraacetic acid in the calcium sulfate aqueous solution, so that the calcium sulfate aqueous solution can be completely loaded in alpha-Mn2O3On a carrier.
Further, the preparation method of the calcium sulfate-manganese oxide is obtained by adopting a precipitation method and an impregnation method, and comprises the following specific steps:
s1, preparing a calcium sulfate solution by adding Ethylene Diamine Tetraacetic Acid (EDTA) and ammonia water;
s2 preparation of alpha-Mn2O3A catalyst support;
s3, mixing alpha-Mn2O3Soaking in calcium sulfate solution, and standing;
and S4, drying and calcining to obtain the calcium sulfate-manganese oxide catalyst.
Further, in step S3, the standing time is 12 to 24 hours, preferably 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or 24 hours, but not limited to the recited values, and other values not recited in the range are also applicable.
Further, in step S4, the drying temperature is 60 to 120 ℃, preferably 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃ or 120 ℃, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Further, the drying time is 8 to 12 hours, for example, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours or 12 hours, but not limited to the recited values, and other values not recited in the range are also applicable.
Further, the calcination temperature after drying is 450 to 700 ℃, for example, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, or the like, but not limited to the recited values, and other values not recited in the range are also applicable, but the temperature higher than 700 ℃ causes the deactivation of calcium sulfate.
Further, the calcination time is 3 to 5 hours, preferably 3 hours, 3.5 hours, 4 hours, 4.5 hours, or 5 hours, etc., but not limited to the recited values, and other values not recited in the range are also applicable.
Furthermore, the calcium sulfate-manganese oxide catalyst provided by the invention can be applied to the outer surface of a building or a radiator of a motor vehicle as a coating to solve the problem of ozone pollution in the atmosphere.
Furthermore, the calcium sulfate-manganese oxide catalyst provided by the invention can be used for solving the problem of ozone pollution in high altitude on the outer surface of a high altitude aircraft.
In conclusion, the invention has the following beneficial effects:
the calcium sulfate-manganese oxide catalyst provided by the invention can efficiently decompose ozone for a long time, and has the advantages of strong moisture resistance, good stability, no secondary pollution and the like; the calcium sulfate and manganese-based materials are low in price and easy to obtain, and the catalyst is simple in preparation process, easy for large-scale production and wide in application prospect.
Drawings
FIG. 1 relates to pure CaSO4An in situ infrared plot of the adsorption characteristics of ozone;
FIG. 2 is a-Mn2O3XRD pattern of the catalyst support;
FIG. 3 is a-Mn2O3SEM and TEM images of the support;
FIG. 4 shows 10 wt% CaSO obtained in example 44/α-Mn2O3TEM images of the catalyst;
FIG. 5 shows 10 wt% CaSO obtained in example 44/α-Mn2O3XRD pattern of the catalyst;
FIG. 6 shows 10 wt% CaSO obtained in example 44/α-Mn2O3An in situ infrared plot of the adsorption characteristics of the catalyst to ozone.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the detailed description of the embodiments, features and effects of the ozonolysis catalyst and the preparation method thereof according to the present invention are as follows.
A calcium sulfate-manganese oxide catalyst for decomposing ozone is prepared through depositing to obtain alpha-Mn2O3The catalyst was used as a support and then various amounts of CaSO were impregnated by impregnation4The method comprises the following steps:
(1) dissolving soluble manganese salt in water, slowly dropwise adding a sodium carbonate solution into the water, stirring the solution until the pH value is between 8 and 9, and precipitating manganese ions to obtain a manganese carbonate precipitate;
(2) drying and calcining to obtain the alpha-Mn2O3A carrier;
(3) adding a certain amount of calcium sulfate solution prepared by EDTA and ammonia water into the solution filled with alpha-Mn2O3And standing the mixture in the beaker for 12-24 hours, drying and calcining the mixture to obtain the calcium sulfate-manganese oxide catalyst.
The resulting catalyst was named awt% CaSO depending on the loading4/α-Mn2O3Wherein a is more than or equal to 5 and less than or equal to 12.
The following are typical but non-limiting examples of the invention:
example 1: calcium sulfate-manganese oxide catalyst for decomposing ozone and preparation method thereof
The present embodiment providesCalcium sulfate-manganese dioxide catalyst for decomposing ozone, prepared from alpha-Mn2O3And CaSO loaded thereon4Comprises CaSO (calcium sulfate-manganese oxide) catalyst with the total mass of 100 percent4The mass percentage content (i.e., the loading amount) of (C) is 5%, and is recorded as 5 wt% CaSO4/α-Mn2O3The preparation method comprises the following steps:
(1) preparation of alpha-Mn2O3Catalyst as carrier
Dissolving a certain amount of manganese sulfate powder in a proper amount of deionized water (the concentration is 0.25mol/L), adding a sodium carbonate solution (the concentration is 0.58mol/L) with a proper concentration into the manganese sulfate solution until the pH value of the mixed solution is 8.5, completely precipitating manganese ions, simultaneously keeping uniform stirring in the whole process to obtain manganese carbonate precipitate, then carrying out suction filtration and washing on the manganese carbonate to be neutral, drying at 90 ℃ for 12h, calcining at 600 ℃ for 3h to obtain alpha-Mn2O3。
(2) Preparation of CaSO4Solutions of
Considering that calcium sulfate is slightly soluble in water, the calcium sulfate solution is prepared by adding ethylenediamine tetraacetic acid (EDTA) and ammonia water, and the dosage of the EDTA and the ammonia water is according to a formula
Wherein: m-CaSO4Mass of EDTA, g;
M——CaSO4、EDTA、NH3·H2relative molecular mass of O;
ω——NH3·H2the concentration of O;
rho-NH at ambient temperature3·H2The density of O;
v is the adding amount of ammonia water;
adding a certain amount of calcium sulfate (calculated by the total mass of the catalyst) into a mixed solution of EDTA and ammonia water, adding 8mL of deionized water, and performing ultrasonic treatment for 30min to obtain CaSO4Impregnating the solution to make CaSO4The loading of (B) was 5 wt%.
FIG. 1 relates to pure CaSO4The in-situ infrared spectrum of the adsorption characteristic of ozone can be seen in CaSO4The surface of the sample showed a peak of ozone ion (745 cm)-1) And peak of physical adsorption of ozone molecules (1024 cm)-1) Indicating CaSO4Can adsorb ozone, and is found at 1068cm-1A peak inversion appears, which indicates CaSO4Can react with ozone to decompose the ozone.
(3) Preparation of 5 wt% CaSO4/α-Mn2O3Catalyst and process for preparing same
The prepared alpha-Mn2O3Adding to CaSO4And (3) uniformly stirring the impregnation solution, standing for 18h, drying at 90 ℃ for 8h, and calcining at 500 ℃ for 3h to obtain the catalyst.
Example 2
Except for adjusting CaSO4Except for the amount of catalyst used to give a final product having a loading of 6 wt%, the preparation and conditions were the same as in example 1, and the catalyst was recorded as 6 wt% CaSO4/α-Mn2O3。
Example 3
Adjusting CaSO4Except for the amount of the catalyst used to give a final product having a loading of 8 wt%, the preparation and conditions were the same as in example 1, and the catalyst was recorded as 8 wt% CaSO4/α-Mn2O3。
Example 4
Adjusting CaSO4Except that the loading of the final product was 10 wt%, the preparation method and conditions were the same as in example 1, and the catalyst was noted as 10 wt% CaSO4/α-Mn2O3。
FIG. 2 shows a-Mn2O3XRD pattern of carrier, pure alpha-Mn prepared2O3The carrier completely corresponds to 41-1442 cards in an XRD standard card library, and the pure alpha-Mn is shown2O3The vector was successfully prepared.
FIG. 3 is a-Mn2O3SEM image and TEM image of the support, from which it can be seen that pure α -Mn was produced2O3The carrier has non-uniform particle structure and large particle diameterThe size is 20-100 nm.
FIG. 4 shows 10 wt% CaSO obtained in example 44/α-Mn2O3TEM images of the catalyst; as can be seen from the figure, at 10 wt% CaSO4/α-Mn2O3Calcium sulfate particles are uniformly distributed on the catalyst.
FIG. 5 is 10 wt% CaSO obtained in example 44/α-Mn2O3XRD pattern of catalyst with CaSO appearing therein4Shows CaSO4Is well impregnated in alpha-Mn2O3On a carrier.
FIG. 6 shows 10 wt% CaSO obtained in example 44/α-Mn2O3An in situ infrared plot of the adsorption characteristics of the catalyst to ozone. As can be seen from the figure, after ozone is introduced, a plurality of characteristic peaks regarding ozone appear on the surface of the catalyst, and physical adsorption peaks (1054 and 2122 cm) of ozone exist-1) Peak of superoxide ion (1113 cm)-1) Peak of peroxygen ion (934 cm)-1) And the peak of ozone radical ion (745 cm)-1) Indicating that ozone can be adsorbed at 10 wt% CaSO4/α-Mn2O3The surface of the catalyst is, wherein, the depth is 1068cm-1The peak due to the catalyst after adsorption of ozone calcium sulfate internal release oxygen atoms (1311 cm)-1) Oxygen atoms can be transferred to alpha-Mn2O3The surface thereby accelerates the decomposition of ozone.
Example 5
Adjusting CaSO4Except for the amount of the catalyst used to obtain a final product having a loading of 12 wt%, the preparation method and conditions were the same as in example 1, and the catalyst was designated as 12 wt% CaSO4/α-Mn2O3。
Comparative example 1
Except that commercial α -Mn is used2O3(Alfa Aesar) instead of α -Mn as prepared in example 42O3Otherwise, the other preparation methods and conditions were the same as in example 1.
Comparative example 2
Using CaSO alone4The properties of the ozonolysis comparison with the other examples are specified in Table 1.
Comparative example 3
Using separately prepared alpha-Mn2O3The properties of the ozonolysis comparison with the other examples are specified in Table 1.
Comparative example 4
The only difference from example 4 is that the support is replaced by nano gamma-Al2O3The resulting catalyst and properties are detailed in table 1.
Comparative example 5
The only difference from example 4 is that the support is replaced by Fe2O3The catalyst and properties are detailed in table 1.
Comparative example 6
The only difference from example 4 is that the support is replaced by TiO2The resulting catalyst and properties are detailed in table 1.
Comparative example 7
The only difference from example 4 is that the support is replaced by SiO2The catalyst and properties are detailed in table 1.
Comparative example 8
The only difference from example 4 is that the carrier was replaced with CeO2The resulting catalyst and properties are detailed in table 1.
Comparative example 9
The only difference from example 4 is that the calcination temperature was increased to 700 ℃ and the resulting catalyst and properties are detailed in table 1.
Comparative example 10
Adjusting CaSO4Except for the amount of catalyst used to give a final product loading of 2 wt%, the other preparation methods and conditions were the same as in example 1, and the catalyst was noted as 2 wt% CaSO4/α-Mn2O3。
And (3) detection: the catalysts of the respective examples and comparative examples were subjected to an ozonolysis performance test under the specific test conditions shown in table 1.
TABLE 1
As can be seen from examples 1-5 and comparative example 10, when CaSO4When the loading amount is too low, the ozone decomposition efficiency is somewhat reduced, but the ozone still has good catalytic performance, however, when the CaSO4To a certain impregnation amount, CaSO4Is active enough to completely decompose ozone, and excessive impregnation causes certain side effects.
As can be seen from the comparison of example 4 with comparative example 1, due to the commercial α -Mn2O3The carrier has smaller specific surface area, weaker oxidation-reduction performance and is in contact with CaSO4The synergistic effect is not good, so 10 wt% CaSO4/α-Mn2O3The performance of the (commercial) catalyst is even worse.
As can be seen from the comparison of examples 1-5 with comparative examples 2 and 3, the α -Mn alone2O3And CaSO alone4The performance of ozone decomposition is worse due to the lack of activating synergy of the active species.
As can be seen from example 4 and comparative examples 4 to 8, γ -Al2O3、Fe2O3、TiO2、SiO2And CeO2Carrier and Supported CaSO4The interaction between them is different and their redox properties are poor, resulting in low ozone decomposition properties.
As can be seen from the comparison of example 4 with comparative example 9, during the preparation of the catalyst, the active component CaSO of the catalyst is caused by the excessive calcination temperature4And thus, the ozone decomposing performance thereof is low.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. The ozone decomposition catalyst is characterized by being a calcium sulfate-manganese oxide composite material, wherein the mass percent of calcium sulfate is 5-12% of the mass of the calcium sulfate-manganese oxide composite material.
2. The ozonolysis catalyst of claim 1, wherein the manganese oxide in the calcium sulfate-manganese oxide composite is α -Mn2O3。
3. The ozonolysis catalyst according to claim 2, characterized in that the α -Mn is2O3The preparation method is that manganese carbonate precipitate obtained after coprecipitation of soluble manganese salt solution and sodium carbonate solution is calcined.
4. The ozonolysis catalyst according to claim 2, characterized in that the α -Mn is2O3The specific surface area of the alloy is more than or equal to 20m2/g。
5. The ozonolysis catalyst according to claim 2, characterized in that the α -Mn is2O3The particle size of (A) is 40 to 150 nm.
6. The ozonolysis catalyst according to claim 3, wherein the soluble manganese salt is manganese sulfate or manganese nitrate, at a concentration of 0.1 to 1 mol/L.
7. The ozonolysis catalyst according to claim 3, wherein the co-precipitation reaction is terminated when the pH reaches 8-9 during the blending of the soluble manganese salt and the sodium carbonate solution.
8. The method for preparing the ozonolysis catalyst according to any one of claims 1 to 7, characterized by specifically operating as follows: mixing alpha-Mn2O3Soaking in calcium sulfate aqueous solution, standing, taking out, and calcining to obtain calcium sulfate-manganese oxide.
9. The method for preparing an ozonolysis catalyst according to claim 8, wherein said aqueous calcium sulfate solution further contains ethylenediaminetetraacetic acid and aqueous ammonia.
10. The method for producing an ozonolysis catalyst according to claim 9, wherein the amount of ammonia and ethylenediaminetetraacetic acid added to the aqueous calcium sulfate solution is calculated by the following formula:
wherein: m-CaSO4Mass of EDTA, g;
M——CaSO4、EDTA、NH3·H2relative molecular mass of O;
ω——NH3·H2the concentration of O;
rho-NH at ambient temperature3·H2The density of O;
v is the adding amount of ammonia water.
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| JPH0538494A (en) * | 1991-08-06 | 1993-02-19 | Matsushita Electric Ind Co Ltd | Device for decomposing ozone dissolved in water |
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| US20210016255A1 (en) * | 2018-03-21 | 2021-01-21 | Research Center For Eco-Environmental Sciences, Chinese Academy Of Sciences | Cerium manganese catalyst, preparation method therefor and use thereof |
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