CN112604695A - Wastewater treatment catalyst, preparation method thereof, wastewater treatment system and method - Google Patents
Wastewater treatment catalyst, preparation method thereof, wastewater treatment system and method Download PDFInfo
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- CN112604695A CN112604695A CN202011495806.4A CN202011495806A CN112604695A CN 112604695 A CN112604695 A CN 112604695A CN 202011495806 A CN202011495806 A CN 202011495806A CN 112604695 A CN112604695 A CN 112604695A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 90
- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000004065 wastewater treatment Methods 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002351 wastewater Substances 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 31
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 16
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 16
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 16
- 231100000719 pollutant Toxicity 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 12
- 239000011149 active material Substances 0.000 claims abstract description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 11
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 10
- 239000012876 carrier material Substances 0.000 claims abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004480 active ingredient Substances 0.000 claims abstract description 4
- 230000005496 eutectics Effects 0.000 claims abstract description 4
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims abstract description 4
- 230000008018 melting Effects 0.000 claims abstract description 4
- 150000002978 peroxides Chemical class 0.000 claims abstract description 4
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 4
- 239000011591 potassium Substances 0.000 claims abstract description 4
- WWTORYHTBNJMMT-UHFFFAOYSA-N potassium sodium oxygen(2-) Chemical class [K+].[O-2].[Na+] WWTORYHTBNJMMT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 19
- 238000005273 aeration Methods 0.000 claims description 16
- 239000003814 drug Substances 0.000 claims description 11
- 239000004575 stone Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
- 238000011282 treatment Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 230000009471 action Effects 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000012668 chain scission Methods 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000011630 iodine Substances 0.000 claims description 4
- 229910052740 iodine Inorganic materials 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000007142 ring opening reaction Methods 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 claims description 3
- 238000011221 initial treatment Methods 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 2
- SJLOMQIUPFZJAN-UHFFFAOYSA-N oxorhodium Chemical compound [Rh]=O SJLOMQIUPFZJAN-UHFFFAOYSA-N 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910003450 rhodium oxide Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 25
- 238000003795 desorption Methods 0.000 abstract description 6
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000011010 flushing procedure Methods 0.000 description 3
- 239000002920 hazardous waste Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000003570 air Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000003181 co-melting Methods 0.000 description 2
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- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 1
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- -1 hydroxyl ferric oxide Chemical compound 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
Images
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
- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
-
- B01J35/31—
-
- B01J35/40—
-
- B01J35/50—
-
- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/002—Construction details of the apparatus
-
- 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 discloses a wastewater treatment catalyst, a preparation method thereof, a wastewater treatment system and a method, wherein the preparation method of the catalyst comprises the following steps: mixing a catalyst carrier material, an alkali metal catalytic assistant, a noble metal catalytic material and an active material in proportion, grinding into powder, and sintering at high temperature for eutectic melting to obtain a catalyst material; the active ingredients in the alkali metal catalytic promoter are sodium, potassium and sodium-potassium oxides; the active material is hydroxyl ferric peroxide, iron or ferroferric oxide. The carbon-based material is used as a main material, the purpose is to adsorb the characteristic pollutants in the wastewater to the periphery of the catalyst by utilizing the adsorption capacity of the carbon-based material, and the target pollutants are decomposed by utilizing the content of hydroxyl free radicals generated on the surface of the catalyst by utilizing hydrogen peroxide, and the desorption process of the carbon-based material is completed at the same time, so that the cyclic process of adsorption-desorption-reabsorption-desorption is completed.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a wastewater treatment catalyst, a preparation method thereof, a wastewater treatment system and a wastewater treatment method.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
In the field of pharmaceutical chemical industry, due to the characteristics of raw and auxiliary materials and products used in the production process, the produced process wastewater has the remarkable characteristics of complex components, poor biochemical degradability, high salinity, high COD concentration and the like. At present, the combination of electrochemistry, micro-electrolysis, Fenton process and the like is often adopted as a pretreatment process, and a biochemical system is combined for treatment. The inventor finds that the operation cost of the mode is high, and the mode is difficult to bear by an owner; meanwhile, the COD removal of the process is obvious, but the toxicity is poor, so that the treatment efficiency of a biochemical system is low, and in addition, when the Fenton process is used as a pretreatment process for pretreating wastewater, more salt is introduced into the wastewater, so that the microbial activity of a subsequent biochemical system can be influenced, and the treatment efficiency of the biochemical system is further reduced. In order to ensure the stable standard discharge of the wastewater, Fenton is reserved at the rear section as an advanced treatment process, and the whole process chain has large occupied area, high operation cost and large hazardous waste disposal cost.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a wastewater treatment catalyst, a preparation method thereof, a wastewater treatment system and a wastewater treatment method.
To solve the above technical problem, one or more of the following embodiments of the present invention provide the following technical solutions:
in a first aspect, the present invention provides a method for preparing a wastewater treatment catalyst, comprising the steps of:
mixing a catalyst carrier material, an alkali metal catalytic assistant, a noble metal catalytic material and an active material in proportion, grinding into powder, and sintering at high temperature for eutectic melting to obtain a catalyst material;
the active ingredients in the alkali metal catalytic promoter are sodium, potassium and sodium-potassium oxides;
the active material is hydroxyl ferric peroxide, iron or ferroferric oxide.
In a second aspect, the invention provides a wastewater treatment catalyst prepared by the preparation method of the wastewater treatment catalyst.
In a third aspect, the present invention provides a heterogeneous catalytic reaction column comprising: the device comprises a reaction tower body, wherein a hydrogen peroxide adding device, an aeration layer, a supporting layer, a catalytic reaction zone, an expansion zone and a clear water zone are sequentially arranged in the reaction tower body from bottom to top, wherein a catalyst is filled in the catalytic reaction zone;
the supporting layer is a cobblestone layer, and the catalyst is arranged above the cobblestone layer;
the waste water inlet is positioned below the aeration layer, and the clear water outlet is positioned above the clear water area.
In a fourth aspect, the present invention provides a wastewater treatment system comprising:
the waste water inlet of the heterogeneous catalytic reaction tower is connected with a waste water source through a pump;
the fan is communicated with the aeration layer;
and the medicine storage container is communicated with the bottom of the heterogeneous catalytic reaction tower through a medicine feeding pump.
In a fifth aspect, the present invention provides a wastewater treatment method, comprising the steps of:
the wastewater is introduced from the bottom of the heterogeneous catalytic reaction tower, and when the wastewater flows through the catalyst layer from bottom to top, pollutants in the wastewater are adsorbed by the carbon-based catalyst, and the pollutants are oxidized and decomposed by hydroxyl radicals under the action of the catalyst; and the wastewater after primary treatment flows to an expansion region to carry out ring-opening chain scission reaction, the cyclic carbon chain is decomposed into long chain or short chain, the long chain substance is further decomposed into short chain substance, and the treated clean water is discharged outside or enters a post-stage treatment system.
Compared with the prior art, one or more technical schemes of the invention have the following beneficial effects:
the carbon-based material is used as a main material, the characteristic pollutants in the wastewater are adsorbed to the periphery of the catalyst by utilizing the adsorption capacity of the carbon-based material, and the target pollutants are decomposed by utilizing the maximum content of hydroxyl radicals generated on the surface of the catalyst by utilizing hydrogen peroxide, and the desorption process of the carbon-based material is completed at the same time, so that the cyclic process of adsorption-desorption-reabsorption-desorption is completed. The ratio of the catalyst material to the liquid medium after the whole material absorbs water is 1.05-1.1, and under the aeration action of the fan, the contact and collision frequency of the wastewater and the catalyst can be increased, which is beneficial to further decomposition of pollutants.
The catalyst is attached with different states of iron agent elements (ferrous iron, hydroxyl ferric oxide, iron and the like) and sodium potassium and other in-situ regenerants, and simultaneously replaces the reaction mechanism of single iron element in Fenton reaction, and on the basis, the metal ions in the wastewater are further utilized to accelerate the capability of obtaining electrons so as to slow down the overall consumption rate
The construction period and the occupied area are shortened, and the integrated equipment can be made and directly butted on a project site;
ferrous ions do not need to be added all the time, the yield of the iron mud is greatly reduced, and the cost for disposing hazardous waste is reduced;
the applicable pH value range is wider, and the acid-base adjusting cost is saved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is a schematic view of the overall structure of the embodiment of the present invention.
Wherein, 1, a water collecting well; 2. a lift pump; 3. an aeration head; 4. a support layer; 5. inspecting the hole; 6. a catalytic reaction zone; 7. a viewing port; 8. an expansion reaction zone; 9. a retention net; 10. a water outlet pipe; 11. a back flushing pump; 12. a dosing pump; 13. a sedimentation tank; 14. a medicine storage barrel; 15. a fan.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Aiming at solving the problems of large occupied area of a wastewater treatment process chain, high operation cost, high treatment cost of hazardous waste and the like in the prior art, the invention firstly aims at the improvement of a catalyst, the generation of hydroxyl free radicals by advanced oxidation processes such as a Fenton process, a micro-electrolysis process and the like, meanwhile, a series of process products with weak oxidizability are generated, but the existence life of hydroxyl radicals in water is only 10 < -9 > s, aiming at the problem, the carbon-based material is used as a main material, the purpose is to adsorb the characteristic pollutants in the wastewater to the periphery of the catalyst by utilizing the adsorption capacity of the carbon-based material, and the target pollutants are decomposed by utilizing the content of hydroxyl free radicals generated on the surface of the catalyst by utilizing hydrogen peroxide, and the desorption process of the carbon-based material is completed at the same time, so that the cyclic process of adsorption-desorption-reabsorption-desorption is completed.
The ratio of the catalyst material to the liquid medium after the whole material absorbs water is 1.05-1.1, and under the aeration action of the fan, the contact and collision frequency of the wastewater and the catalyst can be increased, which is beneficial to further decomposition of pollutants. In addition, the operation requirement can be met by controlling the amount of the dosing pump, so that the dosing cost is saved; aiming at the acidic reaction working conditions (generally the pH value is 3-4) required by the processes of Fenton, electrolysis and the like, a small amount of noble metal and alkaline metal catalysts are blended into a carbon-based catalyst to widen the pH (which can be at pH 3-9) of the reaction so as to save the acid-base adjusting cost and reduce the adverse factors to the system caused by the introduction of salt; furthermore, in order to prevent the catalyst from falling off from the surface, the preparation process adopts high-temperature co-melting at 500-1100 ℃ to ensure the components to be homogeneous; ferrous ions are not added in the reaction process, so that the iron sludge amount and the operation cost are reduced, the core composition of the Fenton process is a Fenton reagent (ferrous ions and hydrogen peroxide), iron elements (ferrous ions, iron oxyhydroxide, iron and the like) in different states and in-situ regenerants such as sodium potassium and the like are attached to the catalyst, and meanwhile, the reaction mechanism of a single iron element of the Fenton reaction is replaced, so that the metal ions in the wastewater are further utilized, the electron obtaining capability of the metal ions is accelerated, and the integral consumption rate is reduced; further, the shape and particle size of the catalyst were optimized to give the appropriate size (4-10mm long, cylinder of diameter about 4 mm). On the basis, the catalyst product is optimized and processed into integrated equipment by combining with engineering parameters.
In order to achieve the above object, the present invention adopts the following technical solutions:
in a first aspect, the present invention provides a method for preparing a wastewater treatment catalyst, comprising the steps of:
mixing a catalyst carrier material, an alkali metal catalytic assistant, a noble metal catalytic material and an active material in proportion, grinding into powder, and sintering at high temperature for eutectic melting to obtain a catalyst material;
the active ingredients in the alkali metal catalytic promoter are sodium, potassium and sodium-potassium oxides;
the active material is hydroxyl ferric peroxide, iron or ferroferric oxide.
In some embodiments, the catalyst support material is a carbon-based material.
Further, the carbon-based material is carbon-based material with an iodine value of more than 550mg/g and a particle size of 2-10 mm. The iodine value represents the material performance of the activated carbon, the higher the value, the better the performance of the activated carbon, and the better the strength, the surface area and the toughness.
In some embodiments, the noble metal catalytic material is a noble metal oxide added in a mass percentage of 0.5-1%.
Further, the noble metal catalytic material is platinum dioxide or rhodium oxide. Contains a noble metal catalytic component for accelerating the production of hydroxyl radicals.
In some embodiments, the mass ratio of the catalyst support material, the alkali metal promoter, the noble metal catalytic material, and the active material is from 40-90:2-15:0.1-2: 3-30.
In some embodiments, the temperature of the high temperature sintering is 500-.
Furthermore, the oxygen content in the reaction system during high-temperature sintering is 5-20%.
In a second aspect, the invention provides a wastewater treatment catalyst prepared by the preparation method of the wastewater treatment catalyst.
In some embodiments, the catalyst is in the form of a cylinder 4-10mm long and 2-5mm in diameter.
In some embodiments, the catalyst has a dry matter density of 0.3 to 0.7g/cm3And the density of the material after water absorption is greater than that of water.
The material preferably has a dry matter density of 0.3-0.7g/cm3The density of the catalyst wet material is verified to be 1.1g/cm3And the left and right parts are higher than the water density, so that the catalyst is not easy to float upwards and run off, and can play a better catalytic effect.
In a third aspect, the present invention provides a heterogeneous catalytic reaction column comprising: the device comprises a reaction tower body, wherein a hydrogen peroxide adding device, an aeration layer, a supporting layer, a catalytic reaction zone, an expansion zone and a clear water zone are sequentially arranged in the reaction tower body from bottom to top, wherein the catalyst is filled in the catalytic reaction zone;
the catalyst is arranged above the supporting layer;
the waste water inlet is positioned below the aeration layer, and the clear water outlet is positioned above the clear water area.
In some embodiments, the expansion zone volume is 30-200% of the catalyst volume.
In some embodiments, the catalyst is a cylinder having a particle size of 2 to 8mm and a height of 4 to 10 mm.
In some embodiments, the support layer is divided into an upper, middle and lower stone layer, the lower stone layer has a particle size in the range of 10-20mm, the middle stone layer has a particle size in the range of 6-8mm, and the upper stone layer has a particle size in the range of 1-3 mm.
In some embodiments, the support layer is an apertured stainless steel or glass plate.
Furthermore, the diameter of the opening of the stainless steel plate or the glass plate is less than 1.8 mm.
In a fourth aspect, the present invention provides a wastewater treatment system comprising:
the waste water inlet of the heterogeneous catalytic reaction tower is connected with a waste water source through a pump;
the fan is communicated with the aeration layer;
and the medicine storage container is communicated with the bottom of the heterogeneous catalytic reaction tower through a medicine feeding pump.
In a fifth aspect, the present invention provides a wastewater treatment method, comprising the steps of:
the wastewater is introduced from the bottom of the heterogeneous catalytic reaction tower, and when the wastewater flows through the catalyst layer from bottom to top, pollutants in the wastewater are adsorbed by the carbon-based catalyst, and the pollutants are oxidized and decomposed by hydroxyl radicals under the action of the catalyst; and the wastewater after primary treatment flows to an expansion region to carry out ring-opening chain scission reaction, the cyclic carbon chain is decomposed into long chain or short chain, the long chain substance is further decomposed into short chain substance, and the treated clean water is discharged outside or enters a post-stage treatment system.
In some embodiments, the residence time of the wastewater in the catalyst layer is 20-120 min.
Examples
A heterogeneous catalytic reaction column comprising: the device comprises a reaction tower body, wherein a hydrogen peroxide adding device, an aeration layer, a supporting layer, a catalytic reaction zone, an expansion zone and a clear water zone are sequentially arranged in the reaction tower body from bottom to top, wherein the catalyst is filled in the catalytic reaction zone;
the catalyst is arranged above the supporting layer; the waste water inlet is positioned below the aeration layer, and the clear water outlet is positioned above the clear water area. The volume of the expansion area is 30-200% of the volume of the catalyst, the catalyst is a cylinder with the particle size of 2-8mm and the height of 4-10mm, the supporting layer is divided into an upper layer, a middle layer and a lower layer, the particle size range of the lower layer is 10-20mm, the particle size range of the middle layer is 6-8mm, and the particle size range of the upper layer is 1-3 mm.
A wastewater treatment system comprising: the waste water inlet of the heterogeneous catalytic reaction tower is connected with a waste water source through a pump; the fan is communicated with the aeration layer; and the medicine storage container is communicated with the bottom of the heterogeneous catalytic reaction tower through a medicine feeding pump.
The preparation method of the catalyst comprises the following steps:
mixing a catalyst carrier material (a carbon material with an iodine value larger than 550), an alkali metal catalytic assistant, a noble metal catalytic material (platinum dioxide) and active material (ferroferric oxide) powder according to a ratio of 60:8:0.2:20, and sintering and co-melting at high temperature to prepare a catalyst material; the high-temperature sintering temperature is 900 ℃, the high-temperature sintering time is 5h, and the oxygen content in the reaction system during high-temperature sintering is 10%.
The wastewater in the water collecting well 1 is pumped into the heterogeneous catalytic reaction tower by a lifting pump, an aeration head 3 is arranged in the heterogeneous catalytic reaction tower, air is blown in by a fan 15, the purpose is to increase the contact decomposition times of the wastewater, hydrogen peroxide and a catalyst, and simultaneously provide trace oxygen, a supporting layer 4 mainly plays a role of supporting the catalyst and distributing water, the supporting layer is composed of stones with different particle sizes, is divided into a lower part, a middle part and an upper part, the lower part is 10-20mm in particle size, the middle part is 6-8mm in particle size, the upper part is 1-3mm in particle size, hydrogen peroxide is pumped in from a medicine storage barrel 14 by a medicine adding pump 12, in order to prevent the catalyst from being polluted and blocked and reducing the efficiency, back flushing is carried out from a sedimentation tank 13 by a back flushing pump 11, an inspection hole 5 is arranged, the wastewater, air and hydrogen peroxide enter a catalytic reaction zone 6, a reserved expansion, in order to prevent a small amount of catalyst from losing, a retaining net 9 with a pore diameter of 1mm is arranged.
The wastewater is introduced from the bottom of the heterogeneous catalytic reaction tower, and when the wastewater flows through the catalyst layer from bottom to top, pollutants in the wastewater are adsorbed by the carbon-based catalyst, and the pollutants are oxidized and decomposed by hydroxyl radicals under the action of the catalyst; and (3) allowing the primarily treated wastewater to flow to an expansion region for ring-opening chain scission reaction, decomposing a cyclic carbon chain into a long chain or a short chain, further decomposing a long chain substance into a short chain substance, discharging the treated clear water outside or entering a rear-section treatment system, and allowing the wastewater to stay in a catalyst layer for 100 min.
Taking a certain chemical wastewater as an example, the original process adopts a process route of Fenton, hydrolysis, anaerobism, aerobism and Fenton, the dosing cost is about 120 yuan/(t.d), after the former Fenton is changed into the heterogeneous catalytic reaction tower of the embodiment, the later Fenton is changed into the guarantee that the process is not opened at ordinary times, the dosing cost is about 38 yuan/(t.d), the effluent can be stabilized and reach the standard, the iron sludge yield is greatly reduced, and the part of saving cost is not counted;
secondly, the COD of the inlet water is reduced from 10000mg/L to 3000mg/L by adopting a Fenton + electrolysis process, the heterogeneous catalytic reaction tower in the embodiment is adopted for wastewater treatment, the COD of the inlet water is reduced from 10000mg/L to 6000mg/L, but the B/C is improved from 0.17 to 0.43, the treatment efficiency of a biochemical system is greatly improved and stably reaches the standard, the operating cost is reduced from 40 yuan/(t.d) to 15 yuan/(t.d), and the toxicity of the process is also reduced from the side.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a wastewater treatment catalyst is characterized by comprising the following steps: the method comprises the following steps:
mixing a catalyst carrier material, an alkali metal catalytic assistant, a noble metal catalytic material and an active material in proportion, grinding into powder, and sintering at high temperature for eutectic melting to obtain a catalyst material;
the active ingredients in the alkali metal catalytic promoter are sodium, potassium and sodium-potassium oxides;
the active material is hydroxyl ferric peroxide, iron or ferroferric oxide.
2. The method for producing a wastewater treatment catalyst according to claim 1, characterized in that: the catalyst carrier material is a carbon-based material;
further, the carbon-based material is carbon-based material with an iodine value of more than 550mg/g and a particle size of 2-10 mm;
further, the noble metal catalytic material is noble metal oxide, and the mass percent of the noble metal oxide added is 0.5-1%;
further, the noble metal catalytic material is platinum dioxide or rhodium oxide;
furthermore, the mass ratio of the catalyst carrier material, the alkali metal catalytic promoter, the noble metal catalytic material and the active material is 40-90:2-15:0.1-2: 3-30.
3. The method for producing a wastewater treatment catalyst according to claim 1, characterized in that: the temperature of high-temperature sintering is 500-1100 ℃;
furthermore, the oxygen content in the reaction system during high-temperature sintering is 5-20%.
4. A wastewater treatment catalyst produced by the method for producing a wastewater treatment catalyst according to any one of claims 1 to 3.
5. The wastewater treatment catalyst according to claim 4, characterized in that: the catalyst is a cylinder with the length of 4-10mm and the diameter of 2-5 mm;
further, the dry matter density of the catalyst is 0.3-0.7g/cm3And the density of the material after water absorption is greater than that of water.
6. A heterogeneous catalytic reaction column, characterized in that: the method comprises the following steps: the device comprises a reaction tower body, wherein a hydrogen peroxide adding device, an aeration layer, a supporting layer, a catalytic reaction zone, an expansion zone and a clear water zone are sequentially arranged in the reaction tower body from bottom to top, wherein the catalyst is filled in the catalytic reaction zone;
the catalyst is arranged above the supporting layer;
the waste water inlet is positioned below the aeration layer, and the clear water outlet is positioned above the clear water area.
7. The heterogeneous catalytic reaction column of claim 6, wherein: the volume of the expansion zone is 30-200% of the volume of the catalyst;
further, the catalyst is a cylinder with the particle size of 2-8mm and the height of 4-10 mm;
further, the supporting layer is divided into an upper stone layer, a middle stone layer and a lower stone layer, the particle size range of the lower stone layer is 10-20mm, the particle size range of the middle stone layer is 6-8mm, and the particle size range of the upper stone layer is 1-3 mm;
further, the supporting layer is an open-pore stainless steel plate or a glass plate;
furthermore, the diameter of the opening of the stainless steel plate or the glass plate is less than 1.8 mm.
8. A wastewater treatment system, characterized by: the method comprises the following steps:
the waste water inlet of the heterogeneous catalytic reaction tower is connected with a waste water source through a pump;
the fan is communicated with the aeration layer;
and the medicine storage container is communicated with the bottom of the heterogeneous catalytic reaction tower through a medicine feeding pump.
9. A method for treating wastewater, which is characterized in that: the method comprises the following steps:
the wastewater is introduced from the bottom of the heterogeneous catalytic reaction tower, and when the wastewater flows through the catalyst layer from bottom to top, pollutants in the wastewater are adsorbed by the carbon-based catalyst, and the pollutants are oxidized and decomposed by hydroxyl radicals under the action of the catalyst; and the wastewater after primary treatment flows to an expansion region to carry out ring-opening chain scission reaction, the cyclic carbon chain is decomposed into long chain or short chain, the long chain substance is further decomposed into short chain substance, and the treated clean water is discharged outside or enters a post-stage treatment system.
10. The wastewater treatment method according to claim 9, characterized in that: the residence time of the wastewater in the catalyst layer is 20-120 min.
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| CN102020350A (en) * | 2011-01-04 | 2011-04-20 | 华中师范大学 | Processing method of heterocatalysis persulfate Fenton oxidation water |
| CN107459124A (en) * | 2017-09-04 | 2017-12-12 | 济南大学 | COD method and device in a kind of hydrogen peroxide heterocatalysis oxidized waste water |
| CN107585852A (en) * | 2017-09-04 | 2018-01-16 | 济南大学 | COD method and device in a kind of ozone heterocatalysis oxidized waste water |
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