CN113788524B - Method for treating papermaking wastewater and wastewater treatment device - Google Patents
Method for treating papermaking wastewater and wastewater treatment device Download PDFInfo
- Publication number
- CN113788524B CN113788524B CN202111138309.3A CN202111138309A CN113788524B CN 113788524 B CN113788524 B CN 113788524B CN 202111138309 A CN202111138309 A CN 202111138309A CN 113788524 B CN113788524 B CN 113788524B
- Authority
- CN
- China
- Prior art keywords
- ozone
- wastewater
- hydrogen peroxide
- papermaking wastewater
- treating
- 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.)
- Active
Links
Images
Classifications
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/782—Ozone generators
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/784—Diffusers or nozzles for ozonation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
Abstract
The invention provides a method for treating papermaking wastewater and a wastewater treatment device. The method for treating the papermaking wastewater comprises the step of treating the papermaking wastewater with ozone, hydrogen peroxide and an ozone catalyst, wherein the ozone catalyst comprises a carrier and an active component, the carrier is granular alumina, the active component comprises an oxide of a first metal element and an oxide of a second metal element, the first metal element is cerium, and the second metal element is at least one of iron, manganese, copper, nickel, zinc and titanium. According to the invention, the oxidation effect of the papermaking wastewater can be effectively improved.
Description
Technical Field
The invention relates to the field of wastewater treatment, in particular to a treatment method of papermaking wastewater and a wastewater treatment device.
Background
At present, the wastewater treatment process of the large and medium-sized pulping and papermaking plants in China mainly comprises primary physicochemical treatment, secondary biochemical treatment and tertiary Fenton (Fenton) chemical oxidation treatment. In the whole production process of the paper industry, wastewater and waste liquid are generated in each working section and workshop, and meanwhile, as the water used in the paper industry is dense and the water quality of the wastewater in different working sections is different, the fluctuation of the water quality and water quantity of the wastewater and the pollution load is larger. Therefore, a proper wastewater treatment process is selected according to actual conditions, so that wastewater treatment cost is further reduced, a new technology for reducing the solid waste generation amount and energy utilization in the wastewater treatment process is developed, technical support is provided for engineering application of the subsequent reclaimed water recycling technology, and the method is a development direction in the future.
At present, fenton oxidation is mostly adopted as three-stage treatment of papermaking wastewater in a paper mill, and certain effects are achieved. However, fenton oxidation technology has many disadvantages such as long treatment reaction time, and large amount of residual metallic iron ions and SO in the treatment liquid 4 2- Causing iron mud pollution. Therefore, in order to fundamentally get rid of the problems of iron sludge pollution and disposal of Fenton water treatment, development of a more environment-friendly treatment process is needed.
Ozone can be quickly degraded into oxygen in the air, the problem of ozone residue can be avoided, and the production cost can be effectively reduced. Therefore, the method is suitable for treating the organic matters which are difficult to degrade in the wastewater after the secondary biochemical treatment by adopting ozone catalytic oxidation.
However, the paper-making wastewater has no typical characteristic pollutant, and the organic matter component is very complex. For example, as is known from the analysis of the paper mill wastewater by gas chromatography-mass spectrometry (GC-MS), the wastewater from a certain paper mill contains a large amount of several contaminants such as phenolic antioxidants, alkanoic acids, olefins, fatty amines, and anilines, and these contaminants account for only 55% in total. Therefore, the effect of treating the papermaking wastewater by the existing ozone-hydrogen peroxide process is not ideal.
Disclosure of Invention
In order to solve one or more of the above problems in the prior art, the present invention provides a method for treating papermaking wastewater and a wastewater treatment apparatus.
The invention relates to a method for treating papermaking wastewater, which is characterized in that the papermaking wastewater is treated by ozone, hydrogen peroxide and an ozone catalyst, wherein the ozone catalyst comprises a carrier and an active component, the carrier is granular alumina, the active component comprises oxide of a first metal element and oxide of a second metal element, the first metal element is cerium, and the second metal element is at least one of iron, manganese, copper, nickel, zinc and titanium. The method for treating the papermaking wastewater adopts the novel ozone catalyst to treat the papermaking wastewater, and can effectively improve the oxidation effect of the papermaking wastewater. The carrier of the ozone catalyst is in the form of particles, so that the problems that the powder carrier is easy to run off and cannot be applied in engineering can be overcome compared with the conventional powder carrier.
Wherein, the preparation method of the ozone catalyst used in the treatment method of the papermaking wastewater can comprise the following steps: step (i): preparing a solution containing an active ingredient; step (ii): spraying and dipping the solution on granular alumina; step (iii): curing the granular alumina treated in the step (ii); step (iv): impregnating the particle alumina after the health maintenance with hydrazine hydrate; step (v): and (3) drying and roasting the granular alumina treated in the step (iv) to obtain the ozone catalyst. By introducing hydrazine hydrate in the second impregnation step in the preparation method of the ozone catalyst, the grain size of the active components is reduced, so that the number of the active components is increased, the active sites are more protruded, the activity of the ozone catalyst can be greatly improved, and the oxidation effect of the treatment method of papermaking wastewater is improved.
The treatment method of the papermaking wastewater comprises the following steps: step (a): treating papermaking wastewater by ozone and hydrogen peroxide; step (b): treating the papermaking wastewater treated in the step (a) by using an ozone catalyst and ozone. The COD treatment effect of the papermaking wastewater is better and the impact resistance is stronger by firstly carrying out ozone-hydrogen peroxide treatment and then carrying out ozone catalyst-ozone treatment.
Wherein in the step (a), the molar ratio of the hydrogen peroxide to the ozone is 0.5-1.5. By setting the molar ratio of hydrogen peroxide to ozone in the step (a) within this range, the COD treatment effect of the papermaking wastewater can be further improved.
Wherein in step (b), the liquid hourly space velocity is 14h -1 The following is given. The maximum liquid hourly space velocity of the treatment method of the papermaking wastewater reaches 14h -1 The processing cost can be greatly reduced.
Wherein the pollutants in the papermaking wastewater comprise 2, 4-di-tert-butylphenol and/or 2,2' -methylenebis (4-methyl-6-tert-butylphenol).
The invention also provides a wastewater treatment device, which comprises a hydrogen peroxide introduction part, an ozone generator and an ozone reactor connected with the hydrogen peroxide introduction part and the ozone generator, and is characterized in that an ozone catalyst is arranged in the ozone reactor, the ozone catalyst comprises a carrier and an active component, the carrier is granular alumina, the active component comprises an oxide of a first metal element and an oxide of a second metal element, the first metal element is cerium, and the second metal element is at least one of iron, manganese, copper, nickel, zinc and titanium. The waste water treatment device is used for treating the papermaking waste water, and can effectively improve the oxidation effect of the papermaking waste water. The carrier of the ozone catalyst is in the form of particles, so that the problems that the powder carrier is easy to run off and cannot be applied in engineering can be overcome compared with the conventional powder carrier.
The preparation method of the ozone catalyst comprises the following steps: step (i): preparing a solution containing an active ingredient; step (ii): spraying and dipping the solution on granular alumina; step (iii): curing the granular alumina treated in the step (ii); step (iv): impregnating the particle alumina after the health maintenance with hydrazine hydrate; step (v): and (3) drying and roasting the granular alumina treated in the step (iv) to obtain the ozone catalyst. By introducing hydrazine hydrate in the second impregnation step in the preparation method of the ozone catalyst, the grain size of the active components is reduced, so that the number of the active components is increased, the active sites are more protruded, the activity of the ozone catalyst can be greatly improved, and the performance of the wastewater treatment device is improved.
The ozone reactor comprises a first-stage ozone reactor connected with the hydrogen peroxide introducing part and the ozone generator and a second-stage ozone reactor connected with a water outlet of the first-stage ozone reactor, and the ozone catalyst is arranged in the second-stage ozone reactor. Therefore, by utilizing the wastewater treatment device, the COD treatment effect of the papermaking wastewater is better and the impact resistance is stronger by firstly carrying out ozone-hydrogen peroxide treatment and then carrying out ozone catalyst-ozone treatment.
The wastewater treatment device further comprises a wastewater pretreatment part, the wastewater pretreatment part comprises a buffer tank for homogenizing the water quality of wastewater and a sand filter tank connected with a water outlet of the buffer tank and used for removing suspended matters in the wastewater, a discharge port of the hydrogen peroxide introduction part is connected to a flow path between the water outlet of the buffer tank and a water inlet of the sand filter tank, and a water outlet of the sand filter tank is connected to a water inlet of the ozone reactor. Thus, the wastewater pretreatment can improve the wastewater treatment effect.
Drawings
The above and other objects and features of the present invention will become more apparent from the following description of the embodiments taken in conjunction with the accompanying drawings in which:
fig. 1 shows a schematic configuration of a wastewater treatment apparatus of the present invention.
Fig. 2 shows a schematic structural view of still another wastewater treatment apparatus of the present invention.
Symbol description
10. A wastewater treatment device;
11. a tail gas disrupter;
12. a buffer tank;
13. a hydrogen peroxide introduction unit;
14. a sand filtration tank;
15. an ozone generator;
16. a jet device;
17. an ozone reactor;
171. a first stage ozone reactor;
172. two-stage ozone reactor
Detailed Description
The inventors of the present invention found that a novel ozone catalyst excellent in catalytic performance can be obtained by using at least one of transition metals such as iron, manganese, copper, nickel, zinc, titanium, and the like in combination as an active component of the ozone catalyst. It is inferred that this is due to the fact that the redox reaction is essentially a process of losing electrons, whereas the above transition metals exist in various valence states, such as iron oxide (Fe) 2+ /Fe 3+ ) Manganese oxide (Mn) 2+ /Mn 3+ And Mn of 3+ /Mn 4+ ) Copper oxide (Cu) + And Cu 2+ ) Nickel oxide (Ni) 2+ /Ni 3+ ) Zinc oxide (Zn) + /Zn 2+ ) Titanium oxide (Ti) 3+ /Ti 4+ ) The multivalent metal ions have different valence conversion modes in the oxidation-reduction reaction process, so that the transfer of electrons is better promoted, the transfer of electrons in the ozone catalytic oxidation process can be enhanced, and the ozone catalytic oxidation capability is enhanced. Furthermore, it was found that the novel ozone catalyst is particularly excellent in treating papermaking wastewater with very complex organic components in an ozone-hydrogen peroxide process. The present invention has been completed based on this finding.
Specifically, the treatment method of the papermaking wastewater is a method for treating the papermaking wastewater by using ozone, hydrogen peroxide and an ozone catalyst, wherein the ozone catalyst comprises a carrier and an active component, the carrier is granular alumina, the active component comprises an oxide of a first metal element and an oxide of a second metal element, the first metal element is cerium, and the second metal element is at least one of iron, manganese, copper, nickel, zinc and titanium.
The carrier of the ozone catalyst used in the method for treating papermaking wastewater of the present invention is in the form of particles. By such a design, the problems that the powdery carrier is easy to run off and cannot be applied in engineering can be overcome compared with the conventional powdery carrier. Among them, the support is preferably spherical alumina having a diameter of 3 to 6mm or bar-shaped alumina having a diameter of 3 to 5mm and a length of 5 to 20 mm. By limiting the size of the carrier to the above range, the loading efficiency of the carrier can be effectively improved to the maximum extent while meeting engineering application.
In addition, in the method for treating paper mill wastewater of the present invention, the ozone catalyst can be used in combination with the first metal element and the second metal element, thereby improving the excellent oxidation effect on paper mill wastewater. However, the inventors have further found that an ozone catalyst having particularly excellent performance can be obtained if the molar ratio of the first metal element to the second metal element is set in the range of 1:2 to 1:4.
In addition, the second metal element is preferably manganese. By using a specific combination of cerium and manganese as an active component, the performance of the ozone catalyst can be further significantly improved as compared with using a combination of cerium and other transition metals as an active component.
In addition, the mass ratio of the particulate alumina to the active component may be appropriately selected as required. However, too high an amount of particulate alumina relative to the active component can result in too small an amount of active component supported per unit area of particulate alumina, affecting the catalytic efficiency of the ozone catalyst; too low an amount of particulate alumina relative to the active component can result in unnecessary wastage of the active component and increased production costs. Therefore, it is preferable that the mass ratio of the particulate alumina to the active component is 50:1 to 5:1.
In addition, the preparation method of the ozone catalyst used in the treatment method of papermaking wastewater of the present invention preferably comprises the steps of: step (i): preparing a solution containing an active ingredient; step (ii): spraying and dipping the solution on granular alumina; step (iii): curing the granular alumina treated in the step (ii); step (iv): impregnating the particle alumina after the health maintenance with hydrazine hydrate; step (v): and (3) drying and roasting the granular alumina treated in the step (iv) to obtain the ozone catalyst. By introducing hydrazine hydrate in the second impregnation step in the preparation method of the ozone catalyst, the grain size of the active components is reduced, so that the number of the active components is increased, the active sites are more protruded, the activity of the ozone catalyst can be greatly improved, and the effect of the treatment method of papermaking wastewater is improved. In particular, the capability of oxidizing two antioxidant organic matters, namely 2, 4-di-tert-butylphenol and 2,2' -methylenebis (4-methyl-6-tert-butylphenol), which are characteristic pollutants in papermaking wastewater, is greatly improved.
In addition, the amount of hydrazine hydrate may be appropriately selected according to the need. Preferably, the molar amount of hydrazine hydrate is 1 to 10 times the molar amount of the active ingredient.
In addition, in step (i), the solution is preferably prepared by dissolving cerium nitrate and nitrate of the second metal element in water. In the case where the raw material of the active component is mainly nitrate, the nitrate generates NOx during the calcination process to pollute the environment. And the salt generated by the reaction of the hydrazine hydrate and the precursor of the active component can not generate NOx in the roasting process, so that the environmental pollution is avoided.
The curing time in step (iii) and the drying temperature, drying time, baking temperature and baking time in step (v) may be appropriately set as required. Preferably, in the step (iii), the life time is 4 to 10 hours. Preferably in step (v), after drying at 100-150℃for 3-10 hours, calcination is carried out at 300-800℃for 2-8 hours.
In addition, the treatment method of papermaking wastewater of the present invention preferably comprises the steps of: step (a): treating papermaking wastewater by ozone and hydrogen peroxide; step (b): treating the papermaking wastewater treated in the step (a) by using an ozone catalyst and ozone. The COD treatment effect of the papermaking wastewater is better and the impact resistance is stronger by firstly carrying out ozone-hydrogen peroxide treatment and then carrying out ozone catalyst-ozone treatment.
Wherein the molar ratio of hydrogen peroxide to ozone in step (a) is preferably 0.5-1.5. It is particularly preferred that the molar ratio of hydrogen peroxide to ozone in step (a) is 0.5. By setting the molar ratio of hydrogen peroxide to ozone in the step (a) within this range, the COD treatment effect of the papermaking wastewater can be further improved.
Wherein the liquid hourly space velocity in step (b) can reach up to 14h -1 In this way, the processing cost can be greatly reduced. This is because the liquid hourly space velocity is defined as the volume of the catalyst per unit volume of the treated sewage per hour, and thus the amount of treated water and the amount of ozone catalyst added determine the liquid hourly space velocity. And under the same condition, the lower the liquid hourly space velocity is, the better the treatment effect is. Setting a higher liquid hourly space velocity means that the shorter the oxidation reaction time, the less the amount of ozone catalyst used, i.e. the lower the investment cost, for the same amount of treated water, while ensuring the removal effect of COD. In the method for treating papermaking wastewater of the present invention, it is preferable that the liquid hourly space velocity in the step (b) is 2h -1 Above and 14h -1 Hereinafter, it is more preferable to use 4 hours -1 Above and 14h -1 Hereinafter, 8h is particularly preferable -1 Above and 14h -1 The following is given.
In addition, the invention also provides a wastewater treatment device, which comprises a hydrogen peroxide introduction part, an ozone generator and an ozone reactor which is connected with the hydrogen peroxide introduction part and the ozone generator and is provided with the novel ozone catalyst. The waste water treatment device is used for treating the papermaking waste water, and can effectively improve the oxidation effect of the papermaking waste water.
Wherein, the preferred ozone reactor includes the first-stage ozone reactor that is connected with hydrogen peroxide leading-in portion and ozone generator and the second-stage ozone reactor that is connected with the delivery port of first-stage ozone reactor, and ozone catalyst sets up in the second-stage ozone reactor. Therefore, by using the wastewater treatment device, the COD treatment effect of the papermaking wastewater is better and the impact resistance is stronger by firstly carrying out ozone-hydrogen peroxide treatment and then carrying out ozone catalyst-ozone treatment.
Wherein, preferably wastewater treatment device still includes waste water pretreatment unit, and waste water pretreatment unit is including being used for the buffer tank of the quality of water of even waste water and being connected and be used for getting rid of the sand filtration jar of suspended solid in the waste water with the delivery port of buffer tank, and the discharge gate of hydrogen peroxide solution leading-in unit is connected in the flow path between the delivery port of buffer tank and the water inlet of sand filtration jar, and the delivery port of sand filtration jar is connected in ozone reactor's water inlet. Thus, the wastewater pretreatment can improve the wastewater treatment effect.
The technical scheme of the present invention will be described in detail by examples, but the scope of the present invention is not limited to the examples.
First, the following ozone catalyst of the present invention is prepared for use.
1. The ozone catalyst (hereinafter also referred to as ozone catalyst a) of the present invention, which contains cerium and manganese as active components, was prepared according to the following procedure.
Step (i): 16.3kg of manganese nitrate (wherein the manganese element was 91 mol), 7.5kg of cerium nitrate (wherein the cerium element was 23 mol) and 250kg of spherical alumina having a diameter of 3 to 5mm were weighed. Manganese nitrate and cerium nitrate were dissolved in 145L deionized water to prepare solution a.
Step (ii): solution a was spray-impregnated onto spherical alumina for 2 hours.
Step (iii): and preserving the health for 4 hours.
Step (iv): 8kg of hydrazine hydrate is weighed and poured into the spherical alumina, the hydrazine hydrate is diluted by deionized water until the liquid surface just drops out of the alumina, and then the mixture is stirred uniformly for 10 hours and filtered.
Step (v): after drying at 100℃for 10 hours, it was calcined at 300℃for 8 hours.
Thus, the ozone catalyst a of the present invention was obtained.
2. The ozone catalyst (hereinafter also referred to as ozone catalyst b) of the present invention, which contains cerium and iron as active components, was prepared according to the following procedure.
Step (i): 180kg of iron nitrate (wherein the iron element 744 mol), 74.5kg of cerium nitrate (wherein the cerium element 228 mol) and 250kg of 3-5mm spherical alumina were weighed. Ferric nitrate and cerium nitrate were dissolved in 145L deionized water to prepare solution a.
Step (ii): solution a was spray-impregnated onto spherical alumina for 2 hours.
Step (iii): and preserving the health for 10 hours.
Step (iv): weighing 80kg of hydrazine hydrate, pouring the hydrazine hydrate into the spherical alumina, diluting the hydrazine hydrate by deionized water until the liquid level just drops out of the spherical alumina, uniformly stirring the mixture, and filtering the mixture after 10 hours.
Step (v): after drying at 150℃for 2 hours, it was calcined at 800℃for 2 hours.
Thus, the ozone catalyst b of the present invention was obtained.
3. The ozone catalyst (hereinafter also referred to as ozone catalyst c) of the present invention, which uses cerium and copper as active components, was prepared according to the following procedure.
Step (i): 18.9kg of copper nitrate (wherein copper element 101 mol), 14.9kg of cerium nitrate (wherein cerium element 46 mol) and 250kg of spherical alumina of 3 to 5mm were weighed. Copper nitrate and cerium nitrate were dissolved in 145L deionized water to prepare solution a.
Step (ii): solution a was spray-impregnated onto spherical alumina for 2 hours.
Step (iii): and preserving the health for 6 hours.
Step (iv): weighing 31.8kg of hydrazine hydrate, pouring the hydrazine hydrate into the spherical alumina, diluting the hydrazine hydrate by deionized water until the liquid level just drops out of the spherical alumina, uniformly stirring, and filtering after 10 hours.
Step (v): after drying at 120℃for 4 hours, it was calcined at 500℃for 4 hours.
Thus, the ozone catalyst c of the present invention was obtained.
4. The ozone catalyst (hereinafter also referred to as ozone catalyst d) of the present invention, which uses cerium and nickel as active components, was prepared according to the following procedure.
Step (i): 50kg of nickel nitrate (wherein the nickel element 274 mol), 30kg of cerium nitrate (wherein the cerium element 92 mol) and 300kg of spherical alumina of 3 to 5mm were weighed. Nickel nitrate and cerium nitrate were dissolved in 145L deionized water to prepare solution A.
Step (ii): solution a was spray-impregnated onto spherical alumina for 2 hours.
Step (iii): and preserving the health for 5 hours.
Step (iv): weighing 50kg of hydrazine hydrate, pouring the hydrazine hydrate into the spherical alumina, diluting the hydrazine hydrate by deionized water until the liquid level just drops out of the spherical alumina, uniformly stirring, and filtering after 10 hours.
Step (v): after drying at 120℃for 6 hours, it was calcined at 600℃for 3 hours.
Thus, the ozone catalyst d of the present invention is obtained.
Example 1
Fig. 1 shows the structure of a wastewater treatment apparatus 10 according to example 1 of the present invention. As shown in fig. 1, the wastewater treatment apparatus 10 includes an exhaust gas destructor 11, a buffer tank 12, a hydrogen peroxide solution introduction portion 13, a sand filter tank 14, an ozone generator 15, an ejector 16, and an ozone reactor 17 filled with 140L of the prepared ozone catalyst a. Wherein the buffer tank 12 and the sand filter tank 14 constitute a wastewater pretreatment section of the present invention. Specifically, the water outlet of the buffer tank 12 is connected to the water inlet of the sand filter tank 14, and the discharge port of the hydrogen peroxide introduction unit 13 is connected between the water outlet of the buffer tank 12 and the flow path of the water inlet of the sand filter tank 14, and is used for supplying hydrogen peroxide to the flow path. In addition, the water outlet of the sand filter tank 14 is connected with the water inlet of the ejector 16, the air outlet of the ozone generator 15 is connected with the air inlet of the ejector 16, and the water outlet of the ejector 16 is connected with the water inlet of the ozone reactor 17. The air outlet of the ozone reactor 17 is connected with the air inlet of the tail gas destructor 11.
The wastewater treatment apparatus 10 of fig. 1 is used to perform the treatment method of treating papermaking wastewater using the ozone catalyst-ozone-hydrogen peroxide process of the present invention.
Specifically, after the water quality of the papermaking wastewater to be treated is uniform in the buffer tank 12, the papermaking wastewater enters the sand filter tank 14 from the buffer tank 12, suspended Substances (SS) in the papermaking wastewater in the sand filter tank 14 are effectively removed, and then the papermaking wastewater enters the reactor 17 from the sand filter tank 14 through the ejector 16 connected with the ozone generator 15 for oxidation reaction, and the generated tail gas is introduced into the tail gas destructor 11 for treatment. In this example, the ozone reactor 17 used was a cylindrical reactor made of stainless steel having an inner diameter of 0.6m, a total height of 2m, and an effective height of 1 m. The purpose of the jet 16 is to better achieve gas-water mixing by generating microbubbles to increase the solubility of ozone. The air source of the ozone generator 15 is an oxygen steel cylinder.
Namely, the process flow of the wastewater treatment apparatus 10 is: uniform water quality in the buffer tank 12- & gtremoval of Suspended Solids (SS) in the papermaking wastewater in the sand filter tank 14- & gtthorough mixing of the papermaking wastewater with ozone by the jet device 16- & gtoxidation in the ozone reactor 17- & gtwater yielding.
Specifically, the ozone adding amount is 77 g/ton of water (77 mg/L), wherein the ozone concentration is 120mg/L, and the ozone air inflow is 1.26m 3 /h。
The calculation formula of the ozone addition amount is as follows:
the hydrogen peroxide is added to the reaction system by the hydrogen peroxide introduction part 13 in an amount of H 2 O 2 And O 3 The optimal molar ratio is 0.5. The ozone adding amount is 77 g/ton of water, namely, the ozone adding amount is 1.6 mol/ton of water. Therefore, the optimal hydrogen peroxide adding amount is 0.8 mol/ton of water, namely the optimal hydrogen peroxideThe dosage is 27 g/ton of water.
The water treatment amount was set to 47m 3 /d(1.96m 3 /h=1960l/h), i.e. liquid hourly space velocity of 14h -1 。
The results of treating papermaking wastewater by the wastewater treatment apparatus 10 are shown in table 1.
Comparative example 1
The process flow and process parameters were the same as in example 1 except that the hydrogen peroxide introduction portion 13 was not provided, i.e., hydrogen peroxide was not added to the reaction system. The results of the papermaking wastewater treated by this process are shown in table 1 as comparative example 1.
Comparative example 2
The process flow and process parameters were the same as in example 1 except that the ozone catalyst of the present invention was not charged at all into the ozone reactor 17. The results of the papermaking wastewater treated by this process are shown in table 1 as comparative example 2.
Thus, the results of the performance evaluation tests of the examples and comparative examples are shown in table 1:
table 1 comparison of papermaking wastewater treatment effects
The antioxidant 1 is 2, 4-di-tert-butylphenol (structural formula:
)
the antioxidant 2 is 2,2' -methylenebis (4-methyl-6-tert-butylphenol) (structural formula:
)
the symbol "-" before the number indicates an increase
As can be seen from Table 1, the different types of organics are oxidized catalytically to different extents, with aniline, alkanoic acid, amide and alkanol being readily oxidized, while the other types of organics are oxidized to different extents. However, the macroscopic removal rate of COD was best achieved by using example 1, and the amount of ozone added per mg of COD removed in this example was 1.4mg. In GB/T39308-2020, "technical Specification for advanced treatment of refractory organic wastewater", it is explicitly described that the ozone catalytic oxidation method "is used for treating COD per mg cr The ozone adding amount is 1mg-10mg ", namely the ozone adding amount for removing each milligram of COD is 1mg-10mg. This means that the ozone dosage of the invention is very low, i.e. the running cost is very low. Therefore, the treatment method of the papermaking wastewater and the corresponding wastewater treatment device have very excellent effect of treating the papermaking wastewater.
Example 2
Fig. 2 shows the structure of the wastewater treatment apparatus 10 according to example 2 of the present invention. As shown in fig. 2, the wastewater treatment apparatus 10 of embodiment 2 is different in that a primary ozone reactor 171 and a secondary ozone reactor 172 connected to the primary ozone reactor 171 are employed in place of the reactor 17. Specifically, the water outlet of the ejector 16 is connected with the water inlet of the primary ozone reactor 171, the water outlet of the primary ozone reactor 171 is connected with the water inlet of the secondary ozone reactor 172, and the water outlet of the secondary ozone reactor 172 is connected with the air inlet of the exhaust gas destructor 11. Then, the prepared 140L of ozone catalyst a was filled in the secondary ozone reactor 172. In the present embodiment, the primary ozone reactor 171 is a PVC cylindrical reactor having an inner diameter of 0.2m, a total height of 2.3m, and an effective height of 2m, and the secondary ozone reactor 172 is a stainless steel cylindrical reactor having an inner diameter of 0.6m, a total height of 2m, and an effective height of 1 m.
The method for treating papermaking wastewater using the combined process of ozone-hydrogen peroxide and ozone catalyst-ozone of the present invention is performed using the wastewater treatment apparatus 10 of fig. 2.
Specifically, the gas-water mixture from the ejector 16 is first subjected to ozone-hydrogen peroxide treatment in the primary ozone reactor 171, then to ozone catalyst-ozone treatment in the secondary ozone reactor 172, and finally the generated exhaust gas is introduced into the exhaust gas destructor 11 for treatment.
Wherein the treated water amount is 47m 3 /d(1.96m 3 /h=1960l/h). The ozone adding amount is 91 g/ton of water (91 mg/L), wherein the ozone concentration is 120mg/L, and the ozone air inflow is 1.49m 3 /h。
The hydrogen peroxide in the primary ozone reactor 171 is added in the following amount: h 2 O 2 And O 3 The optimal molar ratio is 0.5. The ozone adding amount is 91 g/ton of water, namely, the ozone adding amount is 1.9 mol/ton of water. Therefore, the optimal hydrogen peroxide adding amount is 0.95 mol/ton of water, namely, the optimal hydrogen peroxide adding amount is 32 g/ton of water.
The loading of the ozone catalyst in the secondary ozone reactor 172 was 140L, i.e., the liquid hourly space velocity was 14h -1 。
The removal rates for the characteristic contaminants 2, 4-di-t-butylphenol and 2,2' -methylenebis (4-methyl-6-t-butylphenol), and COD in the papermaking wastewater are shown in Table 2.
Table 2 comparison of treatment effects of papermaking wastewater in different processes
The antioxidant 1 is 2, 4-di-tert-butylphenol (structural formula:
)
the antioxidant 2 is 2,2' -methylenebis (4-methyl-6-tert-butylphenol) (structural formula:
)/>
the symbol "-" before the number indicates an increase
The symbol "-" alone in the table indicates that no detection is made
As can be seen from Table 1, the characteristic contaminants in the papermaking wastewater are fatty amine, aniline, 2, 4-di-t-butylphenol, alkanoic acid and 2,2' -methylenebis (4-methyl-6-t-butylphenol)Wherein fatty amines, anilines and alkanoic acids are readily oxidized. In the three treatment processes of the ozone catalyst-ozone-hydrogen peroxide (example 1), the ozone catalyst-ozone (comparative example 1) and the ozone-hydrogen peroxide (comparative example 2), most of 2, 4-di-tert-butylphenol is subjected to dimerization reaction to generate 2,2' -methylenebis (4-methyl-6-tert-butylphenol) in the treatment process, although the macroscopic COD removal rate of the ozone catalyst-ozone-hydrogen peroxide process is the highest (55%). However, the ozone catalyst-ozone process has a good removal effect on both antioxidants. And at O 3 -H 2 O 2 In the process treatment, although a small amount of 2, 4-di-tert-butylphenol is subjected to dimerization reaction to generate 2,2' -methylenebis (4-methyl-6-tert-butylphenol), the ozone-hydrogen peroxide process treatment of 2, 4-di-tert-butylphenol has the best effect and the macroscopic COD removal rate is better. To sum up, preliminary judgment: the two processes of ozone-hydrogen peroxide and ozone catalyst-ozone are combined, so that the COD removal effect is best, and most of 2, 4-di-tert-butylphenol is oxidized in the first stage process ozone-hydrogen peroxide treatment process; in the second stage process ozone catalyst-ozone treatment process, a considerable part of two antioxidants can be oxidized, so that the COD removal rate of the combined process is obviously improved. And the ozone addition amount for removing each milligram of COD in the combined process is 1.4mg. In GB/T39308-2020, "technical Specification for advanced treatment of refractory organic wastewater", it is explicitly described that the ozone catalytic oxidation method "is used for treating COD per mg cr The ozone adding amount is 1mg-10mg ", namely the ozone adding amount for removing each milligram of COD is 1mg-10mg. This means that the ozone dosage of the present application is very low, i.e. the running cost is very low.
As is clear from Table 2 above, 2, 4-di-t-butylphenol and 2,2' -methylenebis (4-methyl-6-t-butylphenol), which are characteristic contaminants in paper-making wastewater, are generally difficult to oxidize. However, when the ozone catalyst is used in the combined process of ozone-hydrogen peroxide and ozone catalyst-ozone, the capability of oxidizing the characteristic pollutants 2, 4-di-tert-butylphenol and 2,2' -methylenebis (4-methyl-6-tert-butylphenol) in papermaking wastewater is greatly improved. This is because the ozone catalyst used in the present application reduces the grain size of the active component by introducing hydrazine hydrate in the second impregnation step during the preparation process, thereby increasing the number of active components and also making the active sites more protruded, thus greatly improving the activity of the ozone catalyst, thereby improving the ability to oxidize both antioxidant organics of 2, 4-di-t-butylphenol and 2,2' -methylenebis (4-methyl-6-t-butylphenol).
Effect comparison with respect to different ozone catalysts
With the wastewater treatment apparatus 10 of example 1, the treatment effect of the ozone catalysts a to d on the papermaking wastewater was compared by filling 140L of the prepared 140L ozone catalysts a to d in the ozone reactor 17, respectively, using the same process flow and process parameters as in example 1. The results are shown in Table 3.
TABLE 3 COD removal Rate of ozone catalysts
As is clear from table 3, the ozone catalyst containing a combination of cerium and manganese as an active ingredient has the highest average COD removal rate and the best effect, as compared with the ozone catalyst containing a combination of cerium and another transition metal as an active ingredient.
Effect contrast with respect to different molar ratios of Hydrogen peroxide to ozone
With the wastewater treatment apparatus 10 of example 2, the treatment effect of the papermaking wastewater with hydrogen peroxide and ozone using different molar ratios was compared according to the same process flow and process parameters as in example 2, except that the molar ratio of hydrogen peroxide to ozone in the primary ozone reactor 171 was changed. The results are shown in Table 4.
TABLE 4 COD removal Rate at different Hydrogen peroxide to ozone molar ratios
| Molar ratio of hydrogen peroxide to ozone | COD removal Rate (%) |
| 0.5 | 65 |
| 1.5 | 58 |
| 1.0 | 60 |
| 0.75 | 63 |
As is clear from table 4, the COD treatment effect of the papermaking wastewater can be further improved by setting the molar ratio of hydrogen peroxide to ozone in the primary ozone reactor 171 to be in the range of 1.5 to 0.5. Wherein, the effect is best when the mole ratio of hydrogen peroxide to ozone is 0.5.
The papermaking wastewater used in the above test was obtained from the secondary sedimentation tank effluent of a sewage treatment plant in a paper mill in Dongguan city of Guangdong, and its COD content was 100mg/L.
In summary, the ozone catalyst and the preparation method of the ozone catalyst provided by the invention have the following beneficial effects:
(1) The novel ozone catalyst which takes the combination of cerium and transition metal as the active components is applied to the ozone-hydrogen peroxide process, and has particularly excellent oxidation effect on papermaking wastewater. In addition, by setting the carrier of the ozone catalyst to be granular, the problems that the powdery carrier is easy to run off and cannot be applied in engineering can be overcome compared with the conventional powdery carrier. In addition, by limiting the size of the carrier to the above range, the loading efficiency of the carrier can be effectively improved to the maximum extent while meeting the engineering application.
(2) Aiming at the defect that the effect of treating the papermaking wastewater by adopting an ozone-hydrogen peroxide process is not ideal in the prior art, a customized ozone catalytic oxidation technology is provided according to the characteristic pollutants in the papermaking wastewater, and the COD treatment effect is better and the impact resistance is stronger by combining the ozone-hydrogen peroxide process and the ozone catalyst-ozone process.
(3) The maximum liquid hourly space velocity of the invention can reach 14h -1 . The relationship between the liquid hourly space velocity and the oxidation reaction time is as follows:
when the liquid hourly space velocity is 14h -1 In the time-course of which the first and second contact surfaces,
thus, the oxidation reaction time of the present application can be reduced to 4.3min. The shorter the oxidation reaction time, the less catalyst is used, i.e. the lower the investment costs, for the same amount of treated water.
(4) By introducing hydrazine hydrate in the second step of impregnation in the preparation process of the ozone catalyst, the grain size of the active component is reduced, so that the quantity of the active component is increased, and the active site is more convex, thereby greatly improving the activity of the ozone catalyst, and particularly improving the capability of oxidizing two antioxidant organic matters, namely 2, 4-di-tert-butylphenol and 2,2' -methylenebis (4-methyl-6-tert-butylphenol), which are characteristic pollutants in papermaking wastewater. In addition, in the case where the raw material of the active component is mainly nitrate, the nitrate generates NOx during the firing process to pollute the environment. And the salt generated by the reaction of the hydrazine hydrate and the precursor of the active component can not generate NOx in the roasting process, so that the environmental pollution is avoided.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the invention; modifications and equivalent substitutions are intended to be included in the scope of the claims without departing from the spirit and scope of the present invention.
Claims (7)
1. A method for treating papermaking wastewater is characterized in that the papermaking wastewater is treated by ozone, hydrogen peroxide and an ozone catalyst, the ozone catalyst comprises a carrier and an active component, the carrier is granular alumina, the active component comprises an oxide of a first metal element and an oxide of a second metal element, the first metal element is cerium, the second metal element is at least one of iron, manganese, copper, nickel, zinc and titanium,
the preparation method of the ozone catalyst comprises the following steps:
step (i): preparing a solution containing a nitrate of the first metal element and a nitrate of the second metal element;
step (ii): spraying the solution on the granular alumina;
step (iii): curing the particulate alumina treated in step (ii);
step (iv): impregnating the granular alumina after the health maintenance with hydrazine hydrate; and
step (v): drying and roasting the granular alumina treated in the step (iv) to obtain the ozone catalyst,
the contaminants in the papermaking wastewater include 2, 4-di-tert-butylphenol and/or 2,2' -methylenebis (4-methyl-6-tert-butylphenol).
2. The method for treating papermaking wastewater according to claim 1, characterized in that the method for treating papermaking wastewater comprises the steps of:
step (a): treating the papermaking wastewater with ozone and hydrogen peroxide; and
step (b): treating the papermaking wastewater treated in the step (a) with the ozone catalyst and ozone.
3. The method for treating papermaking wastewater according to claim 2, wherein in the step (a), the molar ratio of hydrogen peroxide to ozone is 0.5 to 1.5.
4. The method for treating papermaking wastewater according to claim 2, wherein in said step (b), the liquid hourly space velocity is 14h -1 The following is given.
5. The method for treating papermaking wastewater according to claim 1, wherein the method for treating papermaking wastewater employs a wastewater treatment apparatus (10),
the wastewater treatment device (10) comprises a hydrogen peroxide introduction part (13), an ozone generator (15) and an ozone reactor (17) connected with the hydrogen peroxide introduction part (13) and the ozone generator (15), wherein the ozone catalyst is arranged in the ozone reactor (17).
6. The method according to claim 5, wherein the ozone reactor (17) comprises a primary ozone reactor (171) connected to the hydrogen peroxide introduction portion (13) and the ozone generator (15) and a secondary ozone reactor (172) connected to a water outlet of the primary ozone reactor (171), and the ozone catalyst is disposed in the secondary ozone reactor (172).
7. The method for treating papermaking wastewater according to claim 5, wherein the wastewater treatment device (10) further comprises a wastewater pretreatment part comprising a buffer tank (12) for homogenizing the water quality of wastewater and a sand filter tank (14) connected to a water outlet of the buffer tank (12) and for removing suspended matters in wastewater,
the discharge port of the hydrogen peroxide solution introducing part (13) is connected to a flow path between the water outlet of the buffer tank (12) and the water inlet of the sand filter tank (14), and the water outlet of the sand filter tank (14) is connected to the water inlet of the ozone reactor (17).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111138309.3A CN113788524B (en) | 2021-09-27 | 2021-09-27 | Method for treating papermaking wastewater and wastewater treatment device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111138309.3A CN113788524B (en) | 2021-09-27 | 2021-09-27 | Method for treating papermaking wastewater and wastewater treatment device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113788524A CN113788524A (en) | 2021-12-14 |
| CN113788524B true CN113788524B (en) | 2023-06-02 |
Family
ID=79184646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111138309.3A Active CN113788524B (en) | 2021-09-27 | 2021-09-27 | Method for treating papermaking wastewater and wastewater treatment device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113788524B (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5034828A (en) * | 1973-08-01 | 1975-04-03 | ||
| US4160757A (en) * | 1976-02-28 | 1979-07-10 | Bridgestone Tire Co., Ltd. | Adhesive composition |
| US6294140B1 (en) * | 1999-04-23 | 2001-09-25 | Degussa Ag | Layered noble metal-containing exhaust gas catalyst and its preparation |
| JP2011152512A (en) * | 2010-01-27 | 2011-08-11 | Toyota Central R&D Labs Inc | Catalyst for decomposing and removing ozone, method for manufacturing thereof, and method for decomposing and removing ozone using the catalyst |
| CN102441405A (en) * | 2011-10-31 | 2012-05-09 | 河南煤业化工集团研究院有限责任公司 | Catalyst used for gas-phase synthesis of oxalate ester and its preparation method |
| CN105026459A (en) * | 2012-12-20 | 2015-11-04 | 沙特基础全球技术有限公司 | Cross-linked polycarbonate resin with improved chemical and flame resistance |
| CN106040259A (en) * | 2016-06-24 | 2016-10-26 | 浙江恒荣环保科技有限公司 | Catalyst for catalytic combustion of VOCs and preparation method of 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 |
| CN107298494A (en) * | 2017-07-04 | 2017-10-27 | 聊城鲁西聚碳酸酯有限公司 | A kind of system and method for handling the waste water produced in makrolon technique |
| CN111298803A (en) * | 2018-12-12 | 2020-06-19 | 金风环保有限公司 | Ozone catalytic oxidation catalyst for treating wastewater and preparation method thereof |
| CN111298804A (en) * | 2018-12-12 | 2020-06-19 | 金风环保有限公司 | Ozone catalytic oxidation catalyst for treating wastewater and preparation method thereof |
| CN111569877A (en) * | 2020-05-18 | 2020-08-25 | 金风环保有限公司 | Catalyst and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104014360B (en) * | 2014-06-12 | 2016-08-03 | 东南大学 | Multi-metal oxygen race catalyst for uns-dimethylhydrazine degraded and preparation method and application |
| CN105013504A (en) * | 2015-07-20 | 2015-11-04 | 华南理工大学 | Loaded binary composite metal oxide catalytic ozonation catalyst and preparation method thereof |
| CN106115975A (en) * | 2016-07-27 | 2016-11-16 | 广西博世科环保科技股份有限公司 | Ozone hydrogen peroxide combined apparatus and process technique for paper waste |
| CN106345485B (en) * | 2016-08-25 | 2018-12-07 | 万华化学集团股份有限公司 | A kind of catalyst and its preparation method and application for catalytic oxidation treatment organic wastewater |
| CN110116007A (en) * | 2018-02-06 | 2019-08-13 | 浙江中凯瑞普环境工程股份有限公司 | A kind of wastewater from chemical industry catalytic ozonation catalysts for treating and preparation method |
| CN111003863A (en) * | 2019-12-27 | 2020-04-14 | 浙江奇彩环境科技股份有限公司 | Method for efficiently and cooperatively treating high-concentration chemical organic wastewater and sludge |
-
2021
- 2021-09-27 CN CN202111138309.3A patent/CN113788524B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5034828A (en) * | 1973-08-01 | 1975-04-03 | ||
| US4160757A (en) * | 1976-02-28 | 1979-07-10 | Bridgestone Tire Co., Ltd. | Adhesive composition |
| US6294140B1 (en) * | 1999-04-23 | 2001-09-25 | Degussa Ag | Layered noble metal-containing exhaust gas catalyst and its preparation |
| JP2011152512A (en) * | 2010-01-27 | 2011-08-11 | Toyota Central R&D Labs Inc | Catalyst for decomposing and removing ozone, method for manufacturing thereof, and method for decomposing and removing ozone using the catalyst |
| CN102441405A (en) * | 2011-10-31 | 2012-05-09 | 河南煤业化工集团研究院有限责任公司 | Catalyst used for gas-phase synthesis of oxalate ester and its preparation method |
| CN105026459A (en) * | 2012-12-20 | 2015-11-04 | 沙特基础全球技术有限公司 | Cross-linked polycarbonate resin with improved chemical and flame resistance |
| 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 |
| CN106040259A (en) * | 2016-06-24 | 2016-10-26 | 浙江恒荣环保科技有限公司 | Catalyst for catalytic combustion of VOCs and preparation method of catalyst |
| CN107298494A (en) * | 2017-07-04 | 2017-10-27 | 聊城鲁西聚碳酸酯有限公司 | A kind of system and method for handling the waste water produced in makrolon technique |
| CN111298803A (en) * | 2018-12-12 | 2020-06-19 | 金风环保有限公司 | Ozone catalytic oxidation catalyst for treating wastewater and preparation method thereof |
| CN111298804A (en) * | 2018-12-12 | 2020-06-19 | 金风环保有限公司 | Ozone catalytic oxidation catalyst for treating wastewater and preparation method thereof |
| CN111569877A (en) * | 2020-05-18 | 2020-08-25 | 金风环保有限公司 | Catalyst and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113788524A (en) | 2021-12-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107473435B (en) | Catalytic oxidation method for treating low-concentration hardly biodegradable industrial organic wastewater | |
| CN105753133A (en) | Ozone catalytic ozonation tower and gasified waste water treatment method utilizing same | |
| Lv et al. | Denitrification of coking wastewater with micro-electrolysis | |
| CN102897960B (en) | Industrial sewage treatment device | |
| CN101386439B (en) | Technique for processing organic wastewater by atmospheric catalytic oxidation at low-temperature | |
| CN216946374U (en) | Ozone and hydrogen peroxide high-efficiency combined catalytic oxidation wastewater treatment device | |
| CN109020070A (en) | The processing method of anti-oxidant agent production waste water | |
| CN109967087B (en) | Immobilized heterogeneous Fenton catalyst and preparation method and application thereof | |
| CN109876822B (en) | Copper-manganese bimetallic ozone catalyst, preparation method and application thereof | |
| CN112939352B (en) | Treatment method of comprehensive sewage of industrial park | |
| CN112374663B (en) | System and method for treating organic wastewater by three-dimensional electrocatalytic oxidation of liquid-solid fluidized bed | |
| CN103373757A (en) | Method for treating nondegradable organic wastewater by oxidation by transition metal catalyst | |
| CN113788524B (en) | Method for treating papermaking wastewater and wastewater treatment device | |
| CN109364926A (en) | The preparation method of catalyst for desulfurization wastewater class Fenton's reaction removal ammonia nitrogen | |
| CN113856691A (en) | Ozone catalyst and preparation method thereof | |
| CN111233218A (en) | Catalytic FENTON wastewater treatment process | |
| CN209583892U (en) | A kind for the treatment of of Perfume Wastewater processing system | |
| CN114835201B (en) | Three-dimensional electrocatalytic reaction equipment system based on multifunctional catalytic particle electrode | |
| CN106006926A (en) | Efficient catalytic ozone water treatment technology based on composite oxide | |
| CN114345386B (en) | Catalyst loading device for degrading high molecular organic compound by electron beam irradiation | |
| CN113105028B (en) | System and method for realizing organic wastewater recycling by three-dimensional electrolytic removal of organic matters through liquid-solid fluidized bed | |
| CN206232465U (en) | A kind of device for catalyzing and oxidating ozone for being applied to organic wastewater with difficult degradation thereby treatment | |
| CN109876816A (en) | A kind of micro ware auxiliary catalysis wet oxidation nanocatalyst and its application | |
| CN114380364A (en) | Electric flocculation coupling ozone catalytic oxidation reactor | |
| CN115215492A (en) | Electric flocculation-ozone catalytic oxidation-ceramic membrane coupling water treatment technology for removing residual drugs in pharmaceutical wastewater |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |