CN111569853A - Preparation method of ozone catalyst - Google Patents
Preparation method of ozone catalyst Download PDFInfo
- Publication number
- CN111569853A CN111569853A CN202010435335.1A CN202010435335A CN111569853A CN 111569853 A CN111569853 A CN 111569853A CN 202010435335 A CN202010435335 A CN 202010435335A CN 111569853 A CN111569853 A CN 111569853A
- Authority
- CN
- China
- Prior art keywords
- carrier
- catalyst
- cerium
- manganese
- ozone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 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 48
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000011068 loading method Methods 0.000 claims abstract description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 69
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 48
- 229910052593 corundum Inorganic materials 0.000 claims description 41
- 238000001035 drying Methods 0.000 claims description 41
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 41
- 229910052684 Cerium Inorganic materials 0.000 claims description 37
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 37
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 35
- 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 28
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 27
- 238000005406 washing Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 19
- 238000002791 soaking Methods 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 15
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 239000011572 manganese Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 14
- 238000005470 impregnation Methods 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 238000007667 floating Methods 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 25
- 238000007254 oxidation reaction Methods 0.000 abstract description 19
- 230000003647 oxidation Effects 0.000 abstract description 18
- 230000008901 benefit Effects 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 11
- 241001599590 Trisopterus minutus Species 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 59
- 238000012360 testing method Methods 0.000 description 12
- 239000010865 sewage Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 230000007547 defect Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002352 surface water Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012702 metal oxide precursor Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
-
- B01J35/615—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention belongs to the technical field of catalytic oxidation of ozone, and particularly relates to a preparation method of a two-component ozone catalyst based on an active alumina sphere carrier. The method solves the technical problems of poor COD removal effect, difficult guarantee of catalyst loading capacity and the like in the prior art, and has the advantages of simple preparation process, good COD removal effect, long service life and the like.
Description
Technical Field
The invention belongs to the technical field of catalytic oxidation of ozone, and particularly relates to a preparation method of an ozone catalyst based on an active alumina sphere carrier.
Background
Since twenty-first century, industrial wastewater generated by rapid development of industrial technology in China is increasing, so that urban sewage pipe networks enter more and more industrial wastewater, and pollution of surface water is aggravated. Under the severe situation of continuously increasing pollution, the environmental protection situation of China is more severe, and the requirements of relevant environmental protection departments on the water quality of effluent of urban sewage treatment plants are more strict. In the conventional secondary treatment of a sewage treatment plant, the traditional biochemical treatment unit is widely applied due to the simplicity and effectiveness thereof, and can remove most of the biochemically degradable COD, but with the increasing strictness of the industrial wastewater treatment standard, the biological treatment process can not reach the discharge standard, and an advanced treatment process is required. With the comprehensive implementation of the primary A standard, the IV class of surface water environmental quality standards (GB3838-2002) is gradually implemented. The standard of effluent COD is higher and higher, and the difficulty brought about by the effluent reaching standards is larger and larger, so that more and more sewage plants are implementing upgrading and modification engineering to increase the advanced treatment unit, and how to utilize the advanced treatment unit to realize economic and stable removal of COD becomes a problem which needs to be solved urgently.
The advanced oxidation technology is one of high-efficiency processes for deeply treating sewage, and can degrade COD which is difficult to remove by a biochemical unit in the sewage. Conventional advanced oxidation techniques mainly include ozone oxidation, fenton, wet catalytic oxidation, and the like. The existing Fenton method and wet catalytic oxidation technology can improve the removal effect of the COD in the treated sewage to a certain extent, but in practical application, the addition dosage is large, so that the operation cost is high, and the defects of secondary pollution caused by reaction products, complex operation steps and the like exist. In addition, the fenton method has the defects of high labor intensity and labor waste due to the steps of adding medicine and removing mud, and has the defects of high treatment cost, more sludge, high corrosivity and the like. Especially when the concentration of COD in water is too high, advanced oxidation technologies such as Fenton method and dosing method are difficult to realize the surface IV class COD standard. The ozone oxidation method has the advantages of no need of adding a medicament, simple operation, no secondary pollution of reaction products, no sludge generation and the like, and becomes a hotspot in the field of sewage treatment, and the market demand is vigorous.
Ozone oxidation as an effective depthThe treatment technology can further remove organic matters and meet increasingly strict effluent discharge standards, but also faces some problems in practical application. Firstly, the low solubility of ozone in water leads to low utilization rate of ozone, most of ozone is discharged along with tail gas, so that the cost is greatly increased, how to improve the utilization rate of ozone and effectively dissolving ozone in water becomes a core problem in the research field; secondly, whether ozone can be used in combination with other technologies to achieve a better removal effect is achieved, so researchers are keen to develop a catalyst with good catalytic effect, long service life and high recycling rate; thirdly, because ozone generating efficiency is lower, and the power consumption is big, the ozone generating device who researches high-efficient low energy consumption also becomes one of the key problems that will solve at present, for this reason to propose the difficult problem of target transformation, more and more sewage plants increase the advanced treatment unit, and how advanced treatment unit realizes the economy of COD and stably gets rid of becomes the key technical problem that needs to solve urgently. The principle of the ozone catalyst technology is that active components of the ozone catalyst are utilized to excite ozone to generate more hydroxyl free radicals (OH), the strong oxidizing property of the hydroxyl free radicals (OH) is utilized to generate oxidation reaction with organic pollutants in sewage, the chemical bonds of long-chain organic matters are broken to become short-chain easily-degradable organic matters, and partial organic matters are directly oxidized into end products CO in the process2And H2And O, removing residual organic matters in a subsequent treatment unit, thereby realizing the standard discharge of COD. The application of advanced ozone oxidation technology and ozone catalyst as one of the key processes of advanced treatment is imperative and is the current trend of research and development in the technical field. There have been many studies on a catalyst of a metal oxide and a metal oxide supported on a carrier, and there has been a catalyst carrier mainly containing Al2O3Silica gel, activated carbon and clay-like porous materials, wherein Al2O3Has large specific surface area, high mechanical strength, strong adhesive force with active substances, difficult shedding and Al2O3The research of removing organic matters in water by catalytic ozonation as a catalyst carrier has been focused in recent years.
The prior documents retrieved by the applicant include:
patent document No. 201710668026.7 discloses an ozone oxidation catalyst based on gamma-alumina sphere carrier and a preparation method thereof, which has the advantages of simple preparation steps by adopting an impregnation method, lower price than that of the catalyst of mainstream manufacturers in the current market by more than 50 percent, and cost saving. However, the method has the disadvantages that only one kind of load metal is available, the single-component catalyst has poor catalytic effect and low removal rate of COD; and the loading mode adopted is equal-volume impregnation, so that enough loading capacity of the catalyst cannot be ensured.
The patent document with the application number of 201210475655.5 discloses a preparation method of a supported bi-component metal oxide ozone catalytic oxidation catalyst, which has the advantages that gamma-Al is added2O3The microspheres are soaked in hydrochloric acid for activation treatment, and the pore structure of the carrier is changed, so that the loading capacity is increased; the load is two metals, the double-component catalyst improves the removal rate of COD, and the catalytic effect is better. However, the method has the disadvantages that the metal oxide precursor solution is a mixed solution of two metals, the loading amounts and the molar ratio of the two metals cannot be strictly controlled, and the catalytic effect of the catalyst is influenced.
The patent document with the application number of 201510639519.9 discloses an ozone catalyst for wastewater difficult to biochemically generate and a preparation method thereof, which have the advantages that in the preparation method of the ozone catalyst, a catalyst carrier and a catalyst precursor are respectively modified, so that the purpose of uniformly dispersing and loading active components is achieved, and the ozone catalyst has higher removal rate for the wastewater difficult to biochemically generate with low concentration. However, the preparation method has the disadvantages of complex preparation process and complicated steps, and the preparation cost is greatly increased by adopting Au as an auxiliary agent, so the method is not suitable for wide popularization and application.
Patent document 201510107275.X discloses a preparation method for preparing an ozone catalyst by bonding an alumina mother ball and a catalytic mixture, which has the advantages of high adhesion strength of the catalytic mixture, prevention of loss of active components, guarantee of effective utilization of the active components when the formed ozone catalyst is used, and reduction of production cost of the catalyst. But the defects are that the catalytic mixture is only sintered on the outer layer of the alumina mother ball, the content of effective components is low, the loading capacity of the metal catalytic substance is not enough, the specific surface area of the finished product is small, and the strength of catalyst particles can not be accurately ensured in the balling process.
In conclusion, the market needs a method for preparing an ozone catalyst with good catalytic effect, simple preparation steps, low cost, high mechanical strength of the finished product, long service life and high recycling rate.
Disclosure of Invention
The invention aims to provide a preparation method of an ozone catalyst, which adopts a two-component catalyst loaded by an excessive impregnation method, has simple preparation method, uniform finished product loading and good catalytic effect, can improve the oxidation capability of ozone in an ozone oxidation process, improves the degradation capability on COD, and solves the problem of high operation cost caused by high ozone adding amount.
The overall technical concept of the invention is as follows:
the preparation method of the ozone catalyst comprises the following steps:
A. pretreatment of the support
A1, selecting Al with diameter of 3-6 mm and water absorption of 50-60%2O3Washing the carrier with water to remove floating powder on the surface, washing with deionized water for 2-3 times to remove cleaned Al2O3Drying the carrier, and cooling the dried carrier to 20-30 ℃;
a2, citric acid modification: soaking the carrier cooled in the step A1 in a citric acid solution for 4-6 hours, and then roasting for 4-6 hours at the temperature of 350-450 ℃;
B. preparation of precursor solution
B1, calculating the total mass of the manganese element and the cerium element according to the proportion that the total mass of the manganese element and the cerium element accounts for 0.1-2% of the mass of the carrier obtained in the step A2, wherein the total mass of the manganese element and the cerium element is calculated according to the following formula: calculating the mass of manganese nitrate and cerium nitrate according to the molar ratio of the cerium element of 10-7: 0-3;
b2, Al obtained in the step A22O3Carrier times Al2O3The water absorption of the carrier obtains the mass of the solvent in the precursor liquid;
b3, respectively dissolving the manganese nitrate and the cerium nitrate calculated in the step B1 in the solvent calculated in the step B2 to prepare a manganese nitrate solution and a cerium nitrate solution;
C. preparing ozone catalyst by adopting excess impregnation method and secondary roasting method
C1, loading of catalyst metal manganese
C1-1, slowly adding the manganese nitrate solution prepared in the step B3 into the Al pretreated in the step A2O3Soaking the carrier in the solution for 6-8 hours under stirring, removing the redundant solution, and drying the carrier;
c1-2, dried Al2O3Roasting the carrier at 500-800 deg.c for 1-4 hr, cooling to 20-30 deg.c;
c2, loading of catalyst metal cerium
C2-1, adding the Al loaded with metal manganese prepared in the step C12O3Adding the carrier into the cerium nitrate solution prepared in the step B3, dipping for 6-8 hours under a stirring state, discarding the redundant solution, and drying the carrier;
c1-2, dried Al2O3Roasting the carrier for 1-4 hours at the temperature of 500-800 ℃, taking out and cooling after roasting is finished, washing for 3-4 times by deionized water, drying and placing for no less than 24 hours to obtain the ozone catalyst.
The invention has the following specific technical characteristics:
to make Al2O3The carrier is better to load the catalyst, and the preferable technical proposal is that the drying in the step A1 is to wash the cleaned Al2O3The carrier is dried in an oven at 105-120 deg.c for 2-3 hr to constant weight.
In order to ensure the mechanical strength and the catalyst loading of the prepared ozone catalyst, the preferred technical implementation mode is that the non-pretreated Al used in the step A22O3The radial compressive strength of the carrier is more than 100N/cm, and the specific surface area is 180m2/g-220m2/g。
To ensure for Al2O3The preferable technical means for the modification of the carrier is that citric acid is dissolved in step A2The concentration of the solution is 0.1mol/L-0.3 mol/L.
To realize Al2O3The carrier is better to load the catalyst, and the preferred technical realization means is that the stirring condition in the steps C1-1 and C2-1 is to use a paddle stirrer to carry out intermittent stirring, and the rotating speed is 10-50 r/min.
In order to meet the water absorption of the metal carrier and make it better support the catalyst, the drying condition in the step C1-1 is at a temperature of 105-120 ℃.
The invention achieves the substantive characteristics and obvious technical progress that:
1. the invention selects the activated alumina as the carrier, has low cost, uniform sphere size (the diameter is between 3 and 6 millimeters), more than 50 percent of carrier water absorption, and the specific surface area of between 180 and 220m2A carrier with good conditions such as/g, gamma-Al with the performance parameters2O3The catalyst has better wear-resistant characteristic, and the specific surface area in the range is favorable for loading the active component, thereby ensuring the quality of the finished product of the catalyst.
2. The carrier modified by citric acid is adopted, so that the distribution of hydroxyl on the surface of the carrier is changed, and the load strength of active components is improved; the carrier with large mechanical strength (the radial compressive strength can reach 100N/cm) is selected at the early stage of preparing the catalyst, and the strength of the carrier is improved through pre-roasting, so that the wear-resisting property of the catalyst is enhanced.
3. By adopting the preparation method of secondary catalyst loading roasting, the balance of impregnation of two solutions cannot be destroyed, the metal loading and the molar ratio of the obtained bi-component catalyst are more accurate, and the active component can well play a role in concerted catalysis, so that more HO & lt- & gt with stronger oxidation capability is generated in the system, and a better catalytic effect is achieved.
4. The optimum loading capacity of the main catalytic component metal manganese is ensured, the loading capacity of the proper auxiliary agent metal cerium can be met, the auxiliary catalytic effect of cerium is effectively ensured, the consumption of cerium is saved, and the cost is reduced.
5. By adopting an excessive dipping method, redundant precursor liquid can be recycled, the cost is saved, the loading capacity of catalytic activity can be ensured, and the applicant tests show that a good COD removal effect can be realized. The finished catalyst prepared by strict load roasting has firm catalytic components, good catalytic effect, good mechanical property and stability, reusability and long service life.
Detailed Description
The present invention is further described with reference to the following examples, which are not intended to limit the scope of the present invention, and the claims are not to be interpreted as limiting the scope of the present invention.
Example 1
The preparation method of the ozone catalyst comprises the following steps:
A. pretreatment of the support
A1, selecting Al with diameter of 3 mm and water absorption of 50%2O3Washing the carrier with water to remove floating powder on the surface, washing with deionized water for 2 times, and washing with Al2O3Drying the carrier, and cooling the dried carrier to 20 ℃;
a2, citric acid modification: soaking the carrier cooled in the step A1 in a citric acid solution for 4 hours, and then roasting for 4 hours at 350 ℃;
B. preparation of precursor solution
B1, calculating the total mass of the manganese element and the cerium element according to the proportion that the total mass of the manganese element and the cerium element accounts for 0.1% of the mass of the carrier obtained in the step A2, wherein the total mass of the manganese element and the cerium element is calculated according to the following formula: calculating the mass of manganese nitrate and cerium nitrate according to the molar ratio of the cerium element of 7: 0;
b2, Al obtained in the step A22O3Carrier times Al2O3The water absorption of the carrier obtains the mass of the solvent in the precursor liquid;
b3, dissolving the manganese nitrate calculated in the step B1 in the solvent calculated in the step B2 to prepare a manganese nitrate solution;
C. preparing ozone catalyst by adopting excess impregnation method and roasting method
C1, loading of catalyst metal manganese
C1-1, slowly adding the manganese nitrate solution prepared in the step B3 into the Al pretreated in the step A2O3Soaking the carrier in the solution for 6 hours under the stirring state, and drying the carrier after removing the redundant solution;
c1-2, dried Al2O3Roasting the carrier for 1 hour at the temperature of 500 ℃, taking out the carrier after roasting is finished, and cooling the carrier to 20 ℃; washing with deionized water for 3-4 times, drying and standing for no less than 24 hours to obtain the ozone catalyst.
The step A1 of drying is to wash the cleaned Al2O3The support was dried in an oven at 105 ℃ for 2 hours to constant weight.
The non-pretreated Al used in the step A22O3The radial compressive strength of the carrier is more than 100N/cm, and the specific surface area is 180m2/g。
The concentration of the citric acid solution in the step A2 is 0.1 mol/L.
The stirring conditions in the steps C1-1 and C2-1 are that a blade stirrer is used for carrying out intermittent stirring, and the rotating speed is 10 revolutions per minute.
The drying condition in the steps C1-1 and C2-1 is 105 ℃.
Example 2
The preparation method of the ozone catalyst comprises the following steps:
A. pretreatment of the support
A1, selecting Al with diameter of 6 mm and water absorption rate of 60%2O3Washing the carrier with water to remove floating powder on the surface, washing with deionized water for 3 times, and washing with Al2O3Drying the carrier, and cooling the dried carrier to 30 ℃;
a2, citric acid modification: soaking the carrier cooled in the step A1 in a citric acid solution for 6 hours, and then roasting for 6 hours at the temperature of 450 ℃;
B. preparation of precursor solution
B1, calculating the total mass of the manganese element and the cerium element according to the proportion that the total mass of the manganese element and the cerium element accounts for 2% of the mass of the carrier obtained in the step A2, wherein the total mass of the manganese element and the cerium element is calculated according to the following formula: calculating the mass of manganese nitrate and cerium nitrate according to the molar ratio of the cerium element of 10: 3;
b2, Al obtained in the step A22O3Carrier times Al2O3The water absorption of the carrier obtains the mass of the solvent in the precursor liquid;
b3, respectively dissolving the manganese nitrate and the cerium nitrate calculated in the step B1 in the solvent calculated in the step B2 to prepare a manganese nitrate solution and a cerium nitrate solution;
C. preparing ozone catalyst by adopting excess impregnation method and roasting method
C1, loading of catalyst metal manganese
C1-1, slowly adding the manganese nitrate solution prepared in the step B3 into the Al pretreated in the step A2O3Soaking the carrier in the solution for 8 hours under a stirring state, removing the redundant solution, and drying the carrier;
c1-2, dried Al2O3Roasting the carrier for 4 hours at the temperature of 800 ℃, taking out the carrier after roasting is finished, and cooling the carrier to 30 ℃;
c2, loading of catalyst metal cerium
C2-1, adding the Al loaded with metal manganese prepared in the step C12O3Adding the carrier into the cerium nitrate solution prepared in the step B3, soaking for 8 hours under a stirring state, discarding the redundant solution, and drying the carrier;
c1-2, dried Al2O3And roasting the carrier for 4 hours at the temperature of 800 ℃, taking out and cooling the roasted carrier, washing the carrier for 4 times by using deionized water, and drying and placing the washed carrier for not less than 24 hours to obtain the ozone catalyst.
The step A1 of drying is to wash the cleaned Al2O3The carrier was dried in an oven at 120 ℃ for 3 hours to constant weight.
The non-pretreated Al used in the step A22O3The radial compressive strength of the carrier is more than 100N/cm, and the specific surface area is 220m2/g。
The concentration of the citric acid solution in the step A2 is 0.3 mol/L.
The stirring conditions in the steps C1-1 and C2-1 are that a blade stirrer is used for carrying out intermittent stirring, and the rotating speed is 50 revolutions per minute.
The drying conditions in the steps C1-1 and C2-1 are at a temperature of 120 ℃.
Example 3
The preparation method of the ozone catalyst comprises the following steps:
A. pretreatment of the support
A1, selecting Al with diameter of 4 mm and water absorption of 55%2O3Washing the carrier with water to remove floating powder on the surface, washing with deionized water for 3 times, and washing with Al2O3Drying the carrier, and cooling the dried carrier to 25 ℃;
a2, citric acid modification: soaking the carrier cooled in the step A1 in a citric acid solution for 5 hours, and then roasting for 5 hours at the temperature of 400 ℃;
B. preparation of precursor solution
B1, calculating the total mass of the manganese element and the cerium element according to the proportion that the total mass of the manganese element and the cerium element accounts for 1% of the mass of the carrier obtained in the step A2, wherein the total mass of the manganese element and the cerium element is calculated according to the following formula: calculating the mass of manganese nitrate and cerium nitrate according to the molar ratio of the cerium element of 8: 1.5;
b2, Al obtained in the step A22O3Carrier times Al2O3The water absorption of the carrier obtains the mass of the solvent in the precursor liquid;
b3, respectively dissolving the manganese nitrate and the cerium nitrate calculated in the step B1 in the solvent calculated in the step B2 to prepare a manganese nitrate solution and a cerium nitrate solution;
C. preparing ozone catalyst by adopting excess impregnation method and roasting method
C1, loading of catalyst metal manganese
C1-1, slowly adding the manganese nitrate solution prepared in the step B3 into the Al pretreated in the step A2O3Soaking the carrier in the solution for 7 hours under the stirring state, and drying the carrier after removing the redundant solution;
c1-2, dried Al2O3Roasting the carrier at 650 deg.c for 2.5 hr, and taking outCooling to 25 ℃;
c2, loading of catalyst metal cerium
C2-1, adding the Al loaded with metal manganese prepared in the step C12O3Adding the carrier into the cerium nitrate solution prepared in the step B3, soaking for 7 hours under a stirring state, discarding the redundant solution, and drying the carrier;
c1-2, dried Al2O3And roasting the carrier for 2.5 hours at the temperature of 650 ℃, taking out the carrier after roasting is finished, cooling the carrier, washing the carrier for 4 times by using deionized water, and drying and placing the carrier for not less than 24 hours to obtain the ozone catalyst.
The step A1 of drying is to wash the cleaned Al2O3The carrier was dried in an oven at 110 ℃ for 2.5 hours to constant weight.
The non-pretreated Al used in the step A22O3The radial compressive strength of the carrier is more than 100N/cm, and the specific surface area is 200m2/g。
The concentration of the citric acid solution in the step A2 is 0.2 mol/L.
The stirring conditions in the steps C1-1 and C2-1 are that a blade stirrer is used for carrying out intermittent stirring, and the rotating speed is 30 revolutions per minute.
The drying conditions in the steps C1-1 and C2-1 are temperature 110 ℃.
Example 4
The preparation method of the ozone catalyst comprises the following steps:
A. pretreatment of the support
A1, selecting Al with diameter of 5 mm and water absorption of 58%2O3Washing the carrier with water to remove floating powder on the surface, washing with deionized water for 3 times, and washing with Al2O3Drying the carrier, and cooling the dried carrier to 28 ℃;
a2, citric acid modification: soaking the carrier cooled in the step A1 in a citric acid solution for 6 hours, and then roasting for 5.5 hours at the temperature of 420 ℃;
B. preparation of precursor solution
B1, calculating the total mass of the manganese element and the cerium element according to the proportion that the total mass of the manganese element and the cerium element accounts for 1.5% of the mass of the carrier obtained in the step A2, wherein the total mass of the manganese element and the cerium element is calculated according to the following formula: calculating the mass of manganese nitrate and cerium nitrate according to the molar ratio of the cerium element of 9: 2;
b2, Al obtained in the step A22O3Carrier times Al2O3The water absorption of the carrier obtains the mass of the solvent in the precursor liquid;
b3, respectively dissolving the manganese nitrate and the cerium nitrate calculated in the step B1 in the solvent calculated in the step B2 to prepare a manganese nitrate solution and a cerium nitrate solution;
C. preparing ozone catalyst by adopting excess impregnation method and roasting method
C1, loading of catalyst metal manganese
C1-1, slowly adding the manganese nitrate solution prepared in the step B3 into the Al pretreated in the step A2O3Soaking the carrier in the solution for 6 hours under the stirring state, and drying the carrier after removing the redundant solution;
c1-2, dried Al2O3Roasting the carrier for 3.5 hours at the temperature of 700 ℃, taking out the carrier after roasting is finished, and cooling the carrier to 28 ℃;
c2, loading of catalyst metal cerium
C2-1, adding the Al loaded with metal manganese prepared in the step C12O3Adding the carrier into the cerium nitrate solution prepared in the step B3, soaking for 8 hours under a stirring state, discarding the redundant solution, and drying the carrier;
c1-2, dried Al2O3And roasting the carrier for 3 hours at the temperature of 750 ℃, taking out and cooling the roasted carrier, washing the carrier for 3 times by using deionized water, and drying and placing the washed carrier for not less than 24 hours to obtain the ozone catalyst.
The step A1 of drying is to wash the cleaned Al2O3The support was dried in an oven at 115 ℃ for 2.5 hours to constant weight.
The non-pretreated Al used in the step A22O3The radial compressive strength of the carrier is more than 100N/cm, and the specific surface area is 210m2/g。
The concentration of the citric acid solution in the step A2 is 0.25 mol/L.
The stirring conditions in the steps C1-1 and C2-1 are that a blade stirrer is used for carrying out intermittent stirring, and the rotating speed is 40 revolutions per minute.
The drying conditions in the steps C1-1 and C2-1 are 115 ℃.
Example 5
The preparation method of the ozone catalyst comprises the following steps:
A. pretreatment of the support
A1, selecting Al with diameter of 3.5 mm and water absorption of 52%2O3Washing the carrier with water to remove floating powder on the surface, washing with deionized water for 2 times, and washing with Al2O3Drying the carrier, and cooling the dried carrier to 22 ℃;
a2, citric acid modification: soaking the carrier cooled in the step A1 in a citric acid solution for 4.5 hours, and then roasting at 370 ℃ for 4.5 hours;
B. preparation of precursor solution
B1, calculating the total mass of the manganese element and the cerium element according to the proportion that the total mass of the manganese element and the cerium element accounts for 0.5% of the mass of the carrier obtained in the step A2, wherein the total mass of the manganese element and the cerium element is calculated according to the following formula: calculating the mass of manganese nitrate and cerium nitrate according to the molar ratio of the cerium element of 7.5: 1;
b2, Al obtained in the step A22O3Carrier times Al2O3The water absorption of the carrier obtains the mass of the solvent in the precursor liquid;
b3, respectively dissolving the manganese nitrate and the cerium nitrate calculated in the step B1 in the solvent calculated in the step B2 to prepare a manganese nitrate solution and a cerium nitrate solution;
C. preparing ozone catalyst by adopting excess impregnation method and roasting method
C1, loading of catalyst metal manganese
C1-1, slowly adding the manganese nitrate solution prepared in the step B3 into the Al pretreated in the step A2O3Soaking the carrier in the solution for 6.5 hours under stirring, removing the redundant solution, and drying the carrier;
c1-2, dried Al2O3Roasting the carrier for 1.5 hours at the temperature of 600 ℃, taking out the carrier after roasting is finished, and cooling the carrier to 22 ℃;
c2, loading of catalyst metal cerium
C2-1, adding the Al loaded with metal manganese prepared in the step C12O3Adding the carrier into the cerium nitrate solution prepared in the step B3, soaking for 6.5 hours under a stirring state, discarding the redundant solution, and drying the carrier;
c1-2, dried Al2O3And roasting the carrier at the temperature of 550 ℃ for 1.5 hours, taking out the carrier after roasting is finished, cooling the carrier, washing the carrier for 3 times by using deionized water, drying and standing the carrier for not less than 24 hours to obtain the ozone catalyst.
The step A1 of drying is to wash the cleaned Al2O3The support was dried in an oven at 108 ℃ for 2.5 hours to constant weight.
The non-pretreated Al used in the step A22O3The radial compressive strength of the carrier is more than 100N/cm, and the specific surface area is 190m2/g。
The concentration of the citric acid solution in the step A2 is 0.15 mol/L.
The stirring conditions in the steps C1-1 and C2-1 are that a blade stirrer is used for carrying out intermittent stirring, and the rotating speed is 15 revolutions per minute.
The drying condition in the steps C1-1 and C2-1 is 108 ℃.
To verify the technical effect of the present invention, the applicant conducted the following tests:
first, COD removing effect test
The printing and dyeing wastewater was used as test water, and commercially available Al was used2O3The COD removal tests were carried out on the ozone catalysts prepared in examples 1-5 using the carriers and laboratory citric acid modified carriers as controls, and the results are shown in Table one.
Watch 1
| Examples | Raw water COD (mg/L) | COD of effluent (mg/L) | COD removal Rate (%) |
| Al2O3Carrier | 70.97 | 37.10 | 47.72％ |
| Modified support | 66.13 | 31.42 | 52.49％ |
| Example 1 | 72.48 | 22.93 | 68.36％ |
| Example 2 | 65.83 | 19.97 | 69.66％ |
| Example 3 | 171.60 | 54.18 | 68.43％ |
| Example 4 | 170.05 | 60.2 | 64.60％ |
| Example 5 | 176.10 | 50.42 | 71.37％ |
From the above experimental results, it can be concluded that: the method has the advantages that the COD removal rate of the wastewater directly obtained by adding the alumina carrier independently is low, the ozone utilization rate is low, the specific surface area and the pore volume are increased after the carrier is modified, and the improvement of the catalyst activity is facilitated. The addition of the Mn-Ce composite catalyst can obviously improve the treatment effect of ozone oxidation, the addition of the catalyst is 30 percent (by height), the addition of ozone can be reduced, the use of the catalyst can reduce the addition of ozone to 3/5 and reduce the treatment cost on the premise of achieving the same COD removal effect (less than or equal to 25 mg/L).
Second, repeatability test
In order to verify the stability of the effect of the ozone catalyst prepared by the method of the present invention, five repeated tests were performed on the finished catalysts of examples 1-5 under the same conditions, and the results are shown in table two.
Results of the two-fold test
According to the second table, the removal rate of COD of the same catalyst after repeated use is stable, the catalytic effect is stable, and the catalyst can be repeatedly used.
Third, ozone catalytic degradation test
The method is carried out in an organic glass reactor, ozone is provided by an ozone generator, the ozone generation concentration is 10g/h, the domestic wastewater is taken as test water, 1000 ml of water sample is poured into the reactor, 300 ml of catalyst is added, the adding ratio is determined to be 30% (by height), the reaction is carried out by introducing the ozone after 30 minutes of adsorption, and the reaction time is 50 minutes. In each group of test process, 10 milliliters of the sample is sampled at intervals of 10 minutes, and COD determination is carried out after sampling is finished.
According to the experimental results of the pilot plant, compared with the commercial common catalyst, the ozone catalyst prepared by the method of the invention has certain advantages in removal rate and removal rate for removing COD (see table III). The catalyst of the invention can reach 27.27-36.71% removal rate of organic pollutants after ozone is introduced for 20 minutes, and the removal rate of COD is only 14.89% compared with the removal rate of COD of the common catalyst on the market. After 50 minutes of ozone is introduced, the COD removal rate of the catalyst in the embodiments 1 to 5 can reach 38.71 to 46.81 percent, while the COD removal rate of the commercial catalyst is 27.65 percent and is lower than that of the catalyst provided by the invention. According to the experimental result, the main COD index in the two groups of photocatalytic net devices can reach IV-class surface water environmental quality standard (GB3838-2002) after the experiment is carried out for 50 minutes, namely the COD concentration is less than 30mg/L, so that the water quality can be determined to be excellent.
TABLE TRI comparison of the results for a commercial catalyst with the catalyst of the invention
| Ozone is applied for 20 minutes | Ozone is applied for 50 minutes | |
| COD removal Rate (%) | 14.89％ | 27.65％ |
| Example 1 catalyst COD removal (%) | 27.27％ | 40.35％ |
| Example 2 catalyst COD removal (%) | 34.51％ | 44.41％ |
| Example 3 catalyst COD removal (%) | 28.34％ | 43.33％ |
| Example 4 catalyst COD removal (%) | 35.48％ | 38.71％ |
| Example 5 catalyst COD removal (%) | 36.17％ | 46.81％ |
From the above experimental results, the following conclusions can be drawn:
after the ozone catalyst and a commercially available catalyst are subjected to a catalytic oxidation ozone test for 50 minutes, the COD of the effluent can reach the national surface water quality IV standard, but the ozone catalyst has certain advantages in pollutant removal efficiency compared with the commercially available catalyst. The ozone utilization rate can be improved, so that the reaction time and the ozone adding amount are shortened, the ozone treatment method has the advantages of good stability and high mechanical strength, and has the advantage of reutilization, so that the ozone treatment method is good in project prospect when being applied to relevant water body treatment in a large scale.
Claims (6)
1. The preparation method of the ozone catalyst is characterized by comprising the following steps:
A. pretreatment of the support
A1 selectionTaking Al with the diameter of 3-6 mm and the water absorption of 50-60 percent2O3Washing the carrier with water to remove floating powder on the surface, washing with deionized water for 2-3 times to remove cleaned Al2O3Drying the carrier, and cooling the dried carrier to 20-30 ℃;
a2, citric acid modification: soaking the carrier cooled in the step A1 in a citric acid solution for 4-6 hours, and then roasting for 4-6 hours at the temperature of 350-450 ℃;
B. preparation of precursor solution
B1, calculating the total mass of the manganese element and the cerium element according to the proportion that the total mass of the manganese element and the cerium element accounts for 0.1-2% of the mass of the carrier obtained in the step A2, wherein the total mass of the manganese element and the cerium element is calculated according to the following formula: calculating the mass of manganese nitrate and cerium nitrate according to the molar ratio of the cerium element of 10-7: 0-3;
b2, Al obtained in the step A22O3Carrier times Al2O3The water absorption of the carrier obtains the mass of the solvent in the precursor liquid;
b3, respectively dissolving the manganese nitrate and the cerium nitrate calculated in the step B1 in the solvent calculated in the step B2 to prepare a manganese nitrate solution and a cerium nitrate solution;
C. preparing ozone catalyst by adopting excess impregnation method and roasting method
C1, loading of catalyst metal manganese
C1-1, slowly adding the manganese nitrate solution prepared in the step B3 into the Al pretreated in the step A2O3Soaking the carrier in the solution for 6-8 hours under stirring, removing the redundant solution, and drying the carrier;
c1-2, dried Al2O3Roasting the carrier at 500-800 deg.c for 1-4 hr, cooling to 20-30 deg.c;
c2, loading of catalyst metal cerium
C2-1, adding the Al loaded with metal manganese prepared in the step C12O3Adding the carrier into the cerium nitrate solution prepared in the step B3, dipping for 6-8 hours under a stirring state, discarding the redundant solution, and drying the carrier;
c1-2, dryingLatter Al2O3Roasting the carrier for 1-4 hours at the temperature of 500-800 ℃, taking out and cooling after roasting is finished, washing for 3-4 times by deionized water, drying and placing for no less than 24 hours to obtain the ozone catalyst.
2. The method of claim 1, wherein the drying step A1 is to wash Al2O3The carrier is dried in an oven at 105-120 deg.c for 2-3 hr to constant weight.
3. The method of claim 1, wherein said Al used in step A2 is not pretreated2O3The radial compressive strength of the carrier is more than 100N/cm, and the specific surface area is 180m2/g-220m2/g。
4. The method for preparing an ozone catalyst according to any one of claims 1 or 3, wherein the concentration of the citric acid solution in the step A2 is 0.1mol/L-0.3 mol/L.
5. The method for preparing an ozone catalyst according to claim 1, wherein the stirring conditions in the steps C1-1 and C2-1 are intermittent stirring using a paddle stirrer, and the rotation speed is 10-50 rpm.
6. The method for preparing an ozone catalyst according to claim 1, wherein the drying conditions in the steps C1-1 and C2-1 are at a temperature of 105 ℃ to 120 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010435335.1A CN111569853A (en) | 2020-05-21 | 2020-05-21 | Preparation method of ozone catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010435335.1A CN111569853A (en) | 2020-05-21 | 2020-05-21 | Preparation method of ozone catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111569853A true CN111569853A (en) | 2020-08-25 |
Family
ID=72117574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010435335.1A Pending CN111569853A (en) | 2020-05-21 | 2020-05-21 | Preparation method of ozone catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111569853A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618475A (en) * | 2022-04-06 | 2022-06-14 | 上海复荣科技(集团)有限公司 | Preparation method of flexible manganese-based catalyst for decomposing ozone |
| CN115155584A (en) * | 2022-06-22 | 2022-10-11 | 广东中膜科技有限公司 | Preparation method and application of alumina high-dispersion iron ozone catalyst |
| CN115739101A (en) * | 2022-09-07 | 2023-03-07 | 南京大学 | Controllable preparation method of bimetal supported ozone catalyst and water treatment application thereof |
| CN116808839A (en) * | 2023-07-03 | 2023-09-29 | 威海智洁环保技术有限公司 | Preparation method and application of ozone catalyst modified ceramic membrane |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6403031B1 (en) * | 1998-06-18 | 2002-06-11 | Degremont | Method for mineralization of organic pollutants in water by catalytic ozonization |
| CN102166522A (en) * | 2011-03-07 | 2011-08-31 | 山东众禾环保科技股份有限公司 | Flue gas denitration catalyst and preparation method and application thereof |
| CN102941084A (en) * | 2012-11-22 | 2013-02-27 | 大连理工大学 | Method for preparing double-component metallic oxide catalytic ozonation catalyst |
| CN106268783A (en) * | 2016-07-19 | 2017-01-04 | 中国矿业大学 | Mn Ce/Al2o3the preparation of catalyst and the method for catalytic ozonation organic wastewater with difficult degradation thereby |
| WO2017128600A1 (en) * | 2016-01-30 | 2017-08-03 | 北京纬纶华业环保科技股份有限公司 | Ozone catalytic oxidation catalyst for wastewater treatment and preparation method therefor |
| CN109382092A (en) * | 2017-08-07 | 2019-02-26 | 光大水务（深圳）有限公司 | Ozone oxidation catalyst and preparation method thereof based on the balloon borne body of active gama-alumina |
| US20190193059A1 (en) * | 2016-08-25 | 2019-06-27 | Wanhua Chemical Group Co., Ltd. | Catalyst For Catalytic Oxidation Treatment Of Organic Wastewater, Preparation Method Thereof, And Application Thereof |
| CN110538655A (en) * | 2018-05-29 | 2019-12-06 | 中国石油天然气股份有限公司 | Ozone oxidation catalyst and preparation method thereof |
-
2020
- 2020-05-21 CN CN202010435335.1A patent/CN111569853A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6403031B1 (en) * | 1998-06-18 | 2002-06-11 | Degremont | Method for mineralization of organic pollutants in water by catalytic ozonization |
| CN102166522A (en) * | 2011-03-07 | 2011-08-31 | 山东众禾环保科技股份有限公司 | Flue gas denitration catalyst and preparation method and application thereof |
| CN102941084A (en) * | 2012-11-22 | 2013-02-27 | 大连理工大学 | Method for preparing double-component metallic oxide catalytic ozonation catalyst |
| WO2017128600A1 (en) * | 2016-01-30 | 2017-08-03 | 北京纬纶华业环保科技股份有限公司 | Ozone catalytic oxidation catalyst for wastewater treatment and preparation method therefor |
| CN106268783A (en) * | 2016-07-19 | 2017-01-04 | 中国矿业大学 | Mn Ce/Al2o3the preparation of catalyst and the method for catalytic ozonation organic wastewater with difficult degradation thereby |
| US20190193059A1 (en) * | 2016-08-25 | 2019-06-27 | Wanhua Chemical Group Co., Ltd. | Catalyst For Catalytic Oxidation Treatment Of Organic Wastewater, Preparation Method Thereof, And Application Thereof |
| CN109382092A (en) * | 2017-08-07 | 2019-02-26 | 光大水务（深圳）有限公司 | Ozone oxidation catalyst and preparation method thereof based on the balloon borne body of active gama-alumina |
| CN110538655A (en) * | 2018-05-29 | 2019-12-06 | 中国石油天然气股份有限公司 | Ozone oxidation catalyst and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张蕾等编著: "《烟气脱硝脱硫技术及催化剂的研究进展》", 31 July 2016, 徐州：中国矿业大学出版社 * |
| 王蕴: ""活性炭载锰催化剂制备及其催化臭氧氧化处理废水"", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114618475A (en) * | 2022-04-06 | 2022-06-14 | 上海复荣科技(集团)有限公司 | Preparation method of flexible manganese-based catalyst for decomposing ozone |
| CN114618475B (en) * | 2022-04-06 | 2024-04-12 | 上海复荣科技(集团)有限公司 | Preparation method of flexible manganese-based catalyst for decomposing ozone |
| CN115155584A (en) * | 2022-06-22 | 2022-10-11 | 广东中膜科技有限公司 | Preparation method and application of alumina high-dispersion iron ozone catalyst |
| CN115739101A (en) * | 2022-09-07 | 2023-03-07 | 南京大学 | Controllable preparation method of bimetal supported ozone catalyst and water treatment application thereof |
| CN116808839A (en) * | 2023-07-03 | 2023-09-29 | 威海智洁环保技术有限公司 | Preparation method and application of ozone catalyst modified ceramic membrane |
| CN116808839B (en) * | 2023-07-03 | 2024-03-19 | 威海智洁环保技术有限公司 | Preparation method and application of ozone catalyst modified ceramic membrane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111569853A (en) | Preparation method of ozone catalyst | |
| CN108993491B (en) | Activated persulfate catalyst prepared from modified carbon nano tube, and preparation and application thereof | |
| CN109647431B (en) | Catalyst for catalytic oxidation treatment of refractory wastewater by ozone, preparation method and application thereof | |
| WO2021196522A1 (en) | Supported two-component metal oxide catalyst for advanced treatment of petrochemical wastewater and preparation method therefor | |
| CN110433821A (en) | A kind of preparation method of ferrimanganic double-metal composite catalyst and its application in industrial waste water purifying | |
| CN111635025B (en) | Method for treating dye wastewater by using patina/glucose-glucose oxidase catalytic oxidation system | |
| CN113042082A (en) | Preparation method and application of monatomic catalyst | |
| CN108380214A (en) | A kind of preparation of modified meerschaum and the method applied to wastewater treatment | |
| CN107824196A (en) | A kind of organic wastewater ozone oxidation catalyst and its preparation and application | |
| CN111389435A (en) | Iron-carbon micro-electrolysis-Fenton-like catalytic system and application | |
| CN102489290A (en) | Preparation method of nano bismuth vanadate photocatalyst loaded on active carbon fiber | |
| CN106345486A (en) | High-efficiency solid-phase ozone oxidation catalyst, and preparation method and application thereof | |
| CN106064962A (en) | Utilize mud and coal ash for manufacturing for the method for catalyst particle electrode and application | |
| CN106552644B (en) | Ozone catalyst for difficult biochemical wastewater and preparation method thereof | |
| CN106964333B (en) | Rare earth supported catalyst for treating sewage, preparation method and application thereof, and method for treating sewage by catalytic oxidation of ozone | |
| CN102513091A (en) | Preparation method for graphene self-assembled nanometer bismuth vanadate photocatalyst | |
| CN102489291B (en) | Method for preparing expanded graphite load nanometer bismuth vanadate photochemical catalyst | |
| CN108314151A (en) | The method and apparatus of total nitrogen and total organic carbon in a kind of removal rolling effluent | |
| CN115501884B (en) | Silicon-aluminum-based ozone oxidation catalyst and preparation method thereof | |
| CN108558084B (en) | Treatment method and device for electrolytic catalysis coupling advanced oxidation of organic matters in high-salt wastewater | |
| CN112206827B (en) | Polyvinyl alcohol supported palladium nano-flower water treatment catalyst and preparation method thereof | |
| CN114832838A (en) | Metal/sulfur-persulfate-loaded biochar composite material and preparation and application thereof | |
| CN106964361A (en) | A kind of integral catalyzer and preparation method thereof, with and application thereof | |
| CN110652978B (en) | Preparation method and application of nonmetal modified carbon fiber | |
| CN114653369A (en) | Biochar-based redox mediator and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 050031 4th floor, Taihong building, 162 Huai'an East Road, Yuhua District, Shijiazhuang City, Hebei Province Applicant after: Hebei Yuehai Water Group Co.,Ltd. Address before: 050031 Jiacheng environmental protection Co., Ltd., 4th floor, control room of property department, 1st floor, Taihong building, 162 Huaian East Road, Yuhua District, Shijiazhuang City, Hebei Province Applicant before: JIACHENG ENVIRONMENTAL PROTECTION ENGINEERING Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200825 |
|
| RJ01 | Rejection of invention patent application after publication |