CN108927212B - Iron silver oxide zeolite catalyst for controlling bromate formation in ozone oxidation process - Google Patents
Iron silver oxide zeolite catalyst for controlling bromate formation in ozone oxidation process Download PDFInfo
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- CN108927212B CN108927212B CN201710364325.1A CN201710364325A CN108927212B CN 108927212 B CN108927212 B CN 108927212B CN 201710364325 A CN201710364325 A CN 201710364325A CN 108927212 B CN108927212 B CN 108927212B
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 39
- 239000010457 zeolite Substances 0.000 title claims abstract description 39
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 230000003647 oxidation Effects 0.000 title claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 19
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 title claims abstract description 17
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 title claims abstract description 17
- XRUZAHLMEKMYRG-UHFFFAOYSA-N iron;oxosilver Chemical compound [Fe].[Ag]=O XRUZAHLMEKMYRG-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 title claims description 6
- 239000007787 solid Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 7
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003513 alkali Substances 0.000 claims abstract description 3
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical group O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 229910001603 clinoptilolite Inorganic materials 0.000 claims description 2
- 229910052680 mordenite Inorganic materials 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 235000020188 drinking water Nutrition 0.000 abstract description 8
- 239000003651 drinking water Substances 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000005202 decontamination Methods 0.000 abstract description 2
- 230000003588 decontaminative effect Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000002131 composite material Substances 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 7
- 150000004706 metal oxides Chemical class 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 125000002084 dioxo-lambda(5)-bromanyloxy group Chemical group *OBr(=O)=O 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 235000012206 bottled water Nutrition 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000010891 toxic waste Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/20—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing iron group metals, noble metals or copper
- B01J29/24—Iron group metals or copper
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
-
- B01J35/396—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
Abstract
The present invention belongs to drinking water treatmentIn particular to an iron-silver oxide zeolite catalyst for controlling the generation of bromate in the ozone oxidation process. The preparation method of the zeolite catalyst comprises the following steps: adding zeolite to saturated FeCl3Centrifuging the solution, taking out a solid matter, and drying at low temperature to obtain zeolite A; adding Zeolite A to AgNO3Reacting in the solution for 5-20min, centrifuging, taking out solid, and drying at low temperature to obtain zeolite B; soaking zeolite B in alkali solution with pH of 10-11, reacting at 30-40 deg.C for 10-20min, taking out solid, and drying at 105-110 deg.C. The zeolite catalyst can effectively control bromate BrO in the ozone oxidation process on the premise of not reducing the ozone oxidation decontamination efficiency3 ‑Generating; and the application cost is low, the operation is simple and easy, the use is safe and reliable, and the application prospect is wide.
Description
Technical Field
The invention belongs to the field of drinking water treatment, and particularly relates to an iron-silver oxide zeolite catalyst for controlling bromate generation in an ozone oxidation process.
Background
Along with the increasing deterioration of water pollution and the development of water supply treatment technology, the application of ozone disinfection technology in drinking water is increasingly wide, and the ozone disinfection technology is particularly applied to occasions such as direct drinking water and bottled water treatment with higher control requirements on residual chlorine and bacteria number. When the raw water contains bromide, BrO harmful to human body is generated under the strong oxidation action of ozone3 -。BrO3 -Is considered as one of the compounds with higher carcinogenicity, so that all countries in the world put forward strict limits on the content, and the current 'sanitary standard for drinking water' (GB5749-2006), the 'drinking water criterion' of WHO and the limit given by the EPA in the United states are all 10 mu g.L-1. In most cases, BrO3 -The generated amount of the ozone is approximately in direct proportion to the ozone adding amount to ensure a certain sterilization effect, and the ozone adding amount is ensured to be not less than 0.5-1.5 mg.L-1Containing Br in raw water-In the case of (2), BrO is easily caused3 -The problem is more serious when underground water and mineral water with higher mineralization degree are treated and water supply treatment is carried out in coastal areas affected by salt tide. The oxidation effect of ozone and the generation of bromate are always the main contradictions of the ozone water treatment link.
To solve this contradiction, the current practice mainly includes the following: miningPretreating raw water by reverse osmosis or ion exchange, adding inhibitor (NH)4 +/H2O2) (Li Shang Dynasty, preliminary study on bromate generation and inhibition method in ozone oxidation process of bromine-containing water) and nano TiO2Adjusting reaction pH (research on ozone oxidation efficiency and bromate generation and control in Zhuqi drinking water treatment), catalysis of cerium oxide, iron oxyhydroxide, magnesium oxide, aluminum oxide, high-silicon zeolite and the like (research on organic matter in ozone oxidation water and bromate control by Wangguang cerium oxide), Fe-Al/Al2O3Catalyst (a heterogeneous ozonization catalyst for controlling bromate formation Fe-Al/Al2O3The preparation method of (1), adding permanganate (such as wuqingping, the formation, detection and control of bromate in ozone disinfection), and the like. The addition of the inhibitor can reduce BrO3 -But at the same time the ozone oxidation capacity is also greatly affected; nano TiO 22And cerium oxide, Fe-Al/Al2O3The physical property of the catalyst is powdery, so that the catalyst is not easy to precipitate and separate from water, is difficult to use in practice, and is easy to leak to a subsequent treatment link to cause secondary pollution; the pH is adjusted within a limited range, and a lower pH can inhibit BrO3 -But also causes serious corrosion to management systems and equipment, and the pH of the drinking water treatment is not lower than 6.5. The addition of permanganate is a comparatively method, but can only reduce BrO by less than 20 percent3 -The amount of production. The development of a catalyst with low cost, safety, reliability and good control effect becomes a key problem for restricting the ozone water treatment technology.
Disclosure of Invention
In order to solve the defects and shortcomings of the prior art, the invention aims at providing a modified zeolite catalyst loaded with AgO-FeO composite metal oxide, which can effectively control bromate BrO in the ozone oxidation process on the premise of not reducing the ozone oxidation decontamination efficiency3 -And (4) generating. The catalyst has the advantages of low application cost, simple and easy operation, safe and reliable use and wide application prospect.
The invention also aims to provide a preparation method of the modified zeolite catalyst loaded with AgO-FeO composite metal oxide.
The purpose of the invention is realized by the following technical scheme:
a method of preparing an iron silver oxide zeolite catalyst for controlling bromate formation in an ozone oxidation process comprising the steps of:
(1) adding zeolite to saturated FeCl3Solution, zeolite and saturated FeCl3The mass-volume ratio of the solution is 30-150 g.L-1Soaking for 10-30min, centrifuging, taking out solid, and oven drying at low temperature to obtain zeolite A;
(2) adding zeolite A to 0.1-0.5 mol.L-1AgNO of3In solution, zeolite A and AgNO3The mass-volume ratio of the solution is 20-50 g.L-1After reacting for 5-20min, centrifugally separating and taking out solid matters, and drying at low temperature to obtain zeolite B;
(3) and (2) soaking the zeolite B into an alkali solution (preferably a sodium hydroxide solution) with the pH value of 10-11, reacting at the temperature of 30-40 ℃ for 10-20min, taking out the solid matter, and drying at the temperature of 105-110 ℃ to obtain the modified zeolite catalyst loaded with the AgO-FeO composite metal oxide (namely the iron-silver oxide zeolite catalyst for controlling bromate generation in the ozone oxidation process).
The zeolite in the step (1) is clinoptilolite or mordenite which is subjected to mechanical crushing, 30-50-mesh sieving and acid-base pretreatment.
The low-temperature drying temperature in the steps (1) and (2) is 20-40 ℃.
The modified zeolite catalyst loaded with the AgO-FeO composite metal oxide prepared by the method can be used for controlling the generation of bromate in the ozone oxidation process of water treatment.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the catalyst prepared by the method has the particle size of about 0.5-1mm, and AgO-FeO doped composite oxide is wrapped outside the zeolite core. The preparation conditions adopted by the method are mild, and no toxic waste is generated; the carrier has low cost and larger particle size, and is convenient for practical application; the experimental results show that the same conditions (Br)-Concentration and odorOxygen dosage, pH, etc.), the catalyst prepared by the invention can reduce BrO3 -The production amount is about 20-50%, and the permanganate index and the COD removal rate are not negatively influenced.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
The preparation method of the modified zeolite catalyst loaded with AgO-FeO composite metal oxide comprises the following steps:
(1) adding zeolite to saturated FeCl3Solution, zeolite and saturated FeCl3The mass volume ratio of the solution is 50 g.L-1Soaking for 20min for reaction, centrifuging, taking out solid matter, and drying at low temperature to obtain zeolite A;
(2) mixing zeolite A at a ratio of 30 g.L-1Adding 0.4 mol. L-1AgNO of3Reacting in the solution for 5-20min, centrifuging, taking out the solid, and drying at low temperature to obtain zeolite B;
(3) and (3) soaking the zeolite B into a NaOH solution with the pH value of 11, reacting for 15min at 40 ℃, taking out solid matters, and drying at 110 ℃ to obtain the modified zeolite catalyst loaded with the AgO-FeO composite metal oxide. The catalyst has a particle size of about 0.5-1 mm.
Water source water Br of certain water plant in northeast region-At 1-15. mu.g.L-1Treating by adopting an ozone-activated carbon process; wherein the ozone reaction unit adopts a contact reaction tank. Considering that the raw water contains phenols and has a high humic acid content, the ozone dosage is 1.5 mg.L-1But thereby resulting in BrO of the treated water3 -The overproof phenomenon is serious, and about 10-20% of monitored water samples are overproof; after the modified zeolite catalyst loaded with AgO-FeO composite metal oxide prepared by the invention is used for catalytic oxidation, BrO3 -The average production amount is reduced by 40 percent, and the maximum value reaches 8 mug.L-1Meanwhile, the water quality is not affected by any adverse effect, and the removal rate of organic matters, ammonia nitrogen and the like is the same as that of the ozone oxidation alone.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (1)
1. An iron silver oxide zeolite catalyst for controlling bromate formation in an ozone oxidation process, wherein the iron silver oxide zeolite catalyst is prepared by:
(1) adding zeolite to saturated FeCl3Solution, zeolite and saturated FeCl3The mass volume ratio of the solution is 30-150 g.L-1Soaking for 10-30min, centrifuging, separating solid, and oven drying at 20-40 deg.C to obtain zeolite A; the zeolite is clinoptilolite or mordenite which is subjected to mechanical crushing, 30-50 mesh sieving and acid-base pretreatment;
(2) adding zeolite A to 0.1-0.5mol-1AgNO of3In solution, zeolite A and AgNO3The mass-volume ratio of the solution is 20-50 g.L-1After reacting for 5-20min, centrifugally separating to take out solid matter, and drying at 20-40 ℃ to obtain zeolite B;
(3) and (2) soaking the zeolite B into an alkali solution with the pH value of 10-11, reacting at the temperature of 30-40 ℃ for 10-20min, taking out solid, and drying at the temperature of 105-110 ℃ to obtain the iron-silver oxide zeolite catalyst for controlling the generation of bromate in the ozone oxidation process.
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| CN201710364325.1A CN108927212B (en) | 2017-05-22 | 2017-05-22 | Iron silver oxide zeolite catalyst for controlling bromate formation in ozone oxidation process |
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| CN201710364325.1A CN108927212B (en) | 2017-05-22 | 2017-05-22 | Iron silver oxide zeolite catalyst for controlling bromate formation in ozone oxidation process |
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| US5019263A (en) * | 1990-06-05 | 1991-05-28 | Mobil Oil Corp. | Membrane composed of a pure molecular sieve |
| CN101327985A (en) * | 2008-07-31 | 2008-12-24 | 哈尔滨工业大学 | Method for removing organic pollutant in water by catalysis ozonation |
| CN106000380A (en) * | 2016-05-19 | 2016-10-12 | 天津大拇指环境工程有限公司 | Activated carbon-loaded nano-zinc oxide ozonation catalyst and preparation and use thereof |
| CN106268924B (en) * | 2016-07-13 | 2019-02-01 | 华电煤业集团有限公司 | A kind of synthesis gas directly prepares catalyst and its preparation and the application of aromatic hydrocarbons |
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