CN115532261B - Heterogeneous Fenton catalyst and preparation method and application thereof - Google Patents
Heterogeneous Fenton catalyst and preparation method and application thereof Download PDFInfo
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- CN115532261B CN115532261B CN202110723528.1A CN202110723528A CN115532261B CN 115532261 B CN115532261 B CN 115532261B CN 202110723528 A CN202110723528 A CN 202110723528A CN 115532261 B CN115532261 B CN 115532261B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 79
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 40
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 40
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 claims abstract description 40
- 239000002184 metal Substances 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 229910052742 iron Inorganic materials 0.000 claims abstract description 12
- 238000004140 cleaning Methods 0.000 claims abstract description 9
- 230000008929 regeneration Effects 0.000 claims abstract description 5
- 238000011069 regeneration method Methods 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 238000001704 evaporation Methods 0.000 claims description 27
- 239000002002 slurry Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 239000010865 sewage Substances 0.000 claims description 17
- 239000000725 suspension Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 9
- 238000004537 pulping Methods 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 8
- 230000008020 evaporation Effects 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 238000010009 beating Methods 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000005299 abrasion Methods 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000009740 moulding (composite fabrication) Methods 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000012530 fluid Substances 0.000 claims 1
- 239000010842 industrial wastewater Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 17
- 229920002472 Starch Polymers 0.000 description 15
- 235000019698 starch Nutrition 0.000 description 15
- 239000008107 starch Substances 0.000 description 15
- 238000003756 stirring Methods 0.000 description 15
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 11
- 239000008103 glucose Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000001223 reverse osmosis Methods 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 239000003245 coal Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000009303 advanced oxidation process reaction Methods 0.000 description 2
- -1 iron ions Chemical class 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- GFNGCDBZVSLSFT-UHFFFAOYSA-N titanium vanadium Chemical compound [Ti].[V] GFNGCDBZVSLSFT-UHFFFAOYSA-N 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/30—
-
- B01J35/615—
-
- 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
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention discloses a heterogeneous Fenton catalyst and a preparation method and application thereof. The catalyst comprises active carbon, kaolin and an active metal component; the active metal component includes iron. The catalyst is used for treating industrial wastewater in a moving bed Fenton reactor, does not need additional cleaning and regeneration treatment, and has the characteristics of high COD removal rate, wear resistance, good stability and long service life.
Description
Technical Field
The invention belongs to the field of water pollution control, and particularly relates to a heterogeneous Fenton catalyst, a preparation method thereof and application of the catalyst in advanced treatment of catalytic oxidation sewage.
Background
The Fenton oxidation method is used as an advanced oxidation technology (Advanced Oxidation Process, AOPs) which has the advantages of high organic pollutant removal efficiency, easy implementation, convenient operation and the like, and is widely used for treating the organic wastewater difficult to degrade.
The conventional homogeneous Fenton method uses free Fe 2+ As a catalyst, a large amount of iron sludge precipitate is generated in the implementation process. Unlike homogeneous Fenton reaction, heterogeneous Fenton reaction is carried out by reacting H with the surface of a solid catalyst 2 O 2 The reaction generates a species with strong oxidability, and then organic pollutant molecules are oxidatively degraded on the surface of the catalyst. Most heterogeneous Fenton catalysts can be separated from a reaction system and recycled after being used,the problem that a large amount of iron mud is generated in the homogeneous Fenton reaction process is partially solved, so that the research is widely focused by researchers. The fluidized bed Fenton is a main technology of industrialized heterogeneous Fenton, iron ions are attached to the surface of quartz sand to form hydroxyl ferric oxide through a crystallization process, the generation amount of iron mud is reduced to a certain extent, and meanwhile, the oxidation process is strengthened through heterogeneous catalysis, dissolution and reduction, but the technology has a series of problems of high fluidization energy consumption, difficult flow state stabilization, high operation difficulty, carrier abrasion and the like.
CN201710045198.9 discloses a continuous moving bed catalytic oxidation method, which realizes the circulation and cleaning of the packing by arranging a gas stripping pipe at the bottom of the reactor to lift the natural vanadium-titanium magnetite particle packing to a separation chamber and a material cleaning pipe at the top of the reactor. However, the method adopts natural ore as a catalyst, has low reaction efficiency, and contains heavy metals such as cobalt, nickel, alum and the like, thereby causing secondary pollution.
At present, when the heterogeneous Fenton catalyst is used for treating industrial wastewater by a Fenton oxidation method, the problems of easy blockage of a reactor, poor operation continuity, low catalytic efficiency, easy inactivation, short service life, poor stability and the like of the existing catalyst are caused by the need of externally discharging and cleaning the wastewater, and the heterogeneous Fenton catalyst is a key problem for a researcher in the field to break through.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a heterogeneous Fenton catalyst and a preparation method and application thereof. The catalyst is used for treating industrial wastewater in a moving bed Fenton reactor, does not need additional cleaning and regeneration treatment, and has the characteristics of high COD removal rate, wear resistance and good stability.
The first aspect of the invention provides a heterogeneous Fenton catalyst comprising active carbon, kaolin and an active metal component; the active metal component includes iron.
According to the invention, the active carbon accounts for 10% -45% of the total weight of the catalyst, preferably 27% -40% based on the total weight of the catalyst; the kaolin accounts for 45-80% of the total weight of the catalyst, and is preferably 50-70%; the active metal component accounts for 1% -10% of the total weight of the catalyst, and preferably 3% -10% of the total weight of the catalyst.
According to the invention, the mass ratio of the activated carbon to the kaolin is 1:1-1:3.
According to the invention, the activated carbon is powdery activated carbon with the particle size of 200-500 meshes; the activated carbon comprises at least one of coal-based, coconut shell or wood.
According to the invention, the particle size of the kaolin is 200-500 meshes.
According to the present invention, preferably, the active metal component includes both iron and rare earth elements; the iron and the rare earth elements have synergistic effect, and the catalytic oxidation efficiency of the Fenton reaction is improved.
According to the invention, the mass ratio of iron to rare earth elements in the active metal component is 20:1-50:1.
According to the invention, the rare earth element comprises one or more of cerium, lanthanum and neodymium.
According to the invention, the specific surface area of the catalyst is 100-400 m 2 /g; the radial crushing resistance of the catalyst is 50-150N/cm, and the abrasion rate is below 3wt%, preferably below 1 wt%.
The second aspect of the invention provides a preparation method of the heterogeneous Fenton catalyst, which comprises the following steps: (1) Impregnating active carbon with an impregnation liquid containing active metal to obtain a suspension;
(2) Pulping kaolin;
(3) Introducing the suspension in the step (1) into the slurry obtained in the step (2), and then evaporating, forming and drying;
(4) And (3) roasting the product obtained in the step (3) in an oxygen-free atmosphere to obtain the catalyst.
According to the invention, the impregnating solution in the step (1) is prepared by dissolving an active metal source in water to obtain an impregnating solution; in the impregnating solution, the mass content of the active metal source is 5% -30%.
According to the invention, the active metal source is a nitrate of an active metal.
According to the invention, the pulping time in the step (2) is 10-60 min. The beating is to mix kaolin and one or more selected from water and low-carbon sugar for beating. The low-carbon sugar is one or more of carbon atoms of 1-6, preferably glucose.
According to the present invention, preferably, the beating is beating by mixing kaolin, water and low carbon sugar.
According to the present invention, it is further preferable that the mass ratio of kaolin, water, low carbon sugar is 1: 0-5: 0 to 0.6, preferably 1: 1-5: 0.01 to 0.6.
According to the invention, the evaporation in the step (3) is carried out under stirring; the evaporation is to evaporate excessive water so that the water content of the product meets the molding requirement; preferably, the evaporation temperature is 40-110 ℃ and the evaporation time is 30-60 min.
According to the invention, the shaping in step (3) can be carried out according to the need, preferably in the shape of a cylinder, the diameter of which can be determined according to the need, generally 0.5-5.0 mm, preferably the diameter of which is the same as the height. The molding can be added with a binder according to the need, wherein the binder is one or more of starch or polyacrylamide.
According to the invention, the drying conditions described in step (3) are as follows: and drying at 80-150 ℃ for 1-5 h.
According to the invention, the roasting conditions in step (4) are as follows: the roasting temperature is 600-1400 ℃, and the roasting time is 1-10 h.
According to the invention, the oxygen-free atmosphere in the step (4) can be obtained by selecting nitrogen or inert gas (such as argon) as a protective gas, and also can be obtained by burning carbon powder or charcoal and the like under the condition of isolating air.
The third aspect of the invention provides the application of the heterogeneous Fenton catalyst in the catalytic oxidation of sewage.
According to the invention, the application employs a moving bed Fenton reactor. The reactor is provided with a bottom water distributor, and the sewage is fully contacted with the catalyst in the upward flow process. Meanwhile, a gas stripping pipe is arranged at the outlet of the bottom of the reactor, and the catalyst is conveyed to a distributor at the upper part of the reactor through the catalyst gas pipe under the gas stripping action for redistribution, so that the catalyst can be unauthorised moved and circulated. Compared with the conventional heterogeneous Fenton catalyst, the catalyst does not need additional cleaning and regeneration.
According to the invention, the amount of catalyst circulated and moved back to the distributor every hour in the moving bed Fenton reactor accounts for 5% -50%, preferably 20% -40% of the total volume of the catalyst bed of the reactor.
According to the invention, the reaction conditions used are: the pH value is 3.0-4.5; the volume space velocity of the sewage is 0.25-4 h -1 ；H 2 O 2 Ratio to sewage COD (chemical oxygen demand), namely H 2 O 2 (mg/L): COD (mg/L) is 1:1-2:1.
Compared with the prior art, the invention has remarkable advantages and outstanding effects, and is concretely as follows:
(1) In the invention, the catalyst comprises active carbon, kaolin and an active metal component; the active metal component includes iron. The kaolin as an inert component provides good support and strength, improving the mechanical strength and attrition resistance of the catalyst. The good dispersion of the activated carbon in the kaolin effectively improves the utilization rate of the activated carbon, and also enables the large specific surface area and developed pores of the activated carbon to be fully developed. The active carbon, the kaolin and the active metal have synergistic effect, so that the oxidation efficiency of Fenton reaction is improved, the service life of the catalyst is prolonged, and the catalyst has good stability.
(2) In the preparation process of the catalyst, activated carbon is introduced into the slurry of the kaolin, so that the activated carbon is fully dispersed in the slurry to form a compound which is mutually supported by the activated carbon and the kaolin, the advantages of rich pores, large specific surface area and strong adsorption force of the activated carbon are utilized, the enrichment and contact probability of organic pollutants and free radicals on the surface and in the pores of the activated carbon can be realized, and the COD of sewage is effectively reduced.
(3) According to the invention, the heterogeneous Fenton reactor combined with the moving bed is matched with the catalyst to deeply treat industrial sewage, so that the synergistic effect of catalyst adsorption and catalytic oxidation is exerted on one hand, and on the other hand, a catalyst with a specific composition is selected, and the catalyst is completely regenerated in the air stripping circulation process by utilizing the friction process, so that the surface of the catalyst is promoted to be updated, no additional cleaning is needed, the Fenton oxidation efficiency is obviously improved, the service life of the catalyst is prolonged, and the catalyst has good stability.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
In the invention, the specific surface area is measured by adopting a low-temperature liquid nitrogen physical adsorption method.
In the invention, the catalyst attrition rate is measured by a rotary drum type attrition instrument, and the specific description of the catalyst carrier preparation and application technology (oil industry Press, month 5 of 2002, zhu Hongfa, section 4.5.4) is provided.
In the present invention, the radial crush resistance of the catalyst was measured according to standard G/T2782-2011.
In the present invention, COD in water was measured according to HJ828-2017 dichromate method.
Example 1
(1) The active metal source Fe (NO) 3 ) 3 And Ce (NO) 3 ) 3 Adding into distilled water and stirring until the active metal source is dissolved to obtain a solution (a) with the mass percent of 10%, wherein Fe: the mass ratio of Ce is 40:1. Adding 400-mesh powdered coal-based activated carbon into the solution (a) according to the metering ratio to obtain slurry (b); the slurry (b) was mechanically stirred at a rotation speed of 60r/min for 10min, and then thoroughly mixed and adsorbed to obtain a suspension (c).
(2) Adding kaolin with the particle size of 400 meshes into a glucose aqueous solution, and pulping for 30min, wherein the mass ratio of the kaolin to the water to the glucose is 1:2:0.06.
(3) Adding the suspension (c) of the step (1) into the slurry of the step (2), wherein the mass ratio of the active carbon to the active metal to the kaolin in the obtained mixed material is 35:5:60. heating and evaporating under stirring to reduce water content, wherein the evaporating temperature is 105 ℃ and the evaporating time is 60min; and adding binder starch to form paste, wherein the mass of the starch is 5% of that of the activated carbon. The extruded strip was formed into a cylindrical mass (d) of diameter 3mm and length 3 mm. Drying at 105℃for 5h.
(4) And (3) roasting the product obtained in the step (3) at 600 ℃ for 5 hours under the protection of nitrogen to obtain the catalyst A.
The properties of catalyst A are shown in Table 1. The prepared catalyst A is used for a moving bed heterogeneous Fenton reactor, the catalyst is not additionally cleaned, reverse osmosis concentrated water with the average COD concentration of 128mg/L is treated, and the treatment effect is shown in Table 2. The Fenton reaction conditions are as follows: the catalyst filling amount accounts for 1/2 of the total volume of the reactor, the pH value is 3.5, and the sewage volume space velocity is 2h -1 ，H 2 O 2 Ratio to sewage COD (chemical oxygen demand), namely H 2 O 2 (mg/L): COD (mg/L) was 1:1. The amount of catalyst circulated and moved back to the distributor every hour in the moving bed Fenton reactor was 25% of the total volume of the catalyst bed in the reactor.
Example 2
(1) The active metal source Fe (NO) 3 ) 3 、Nd(NO 3 ) 3 Adding the mixture into distilled water and stirring the mixture until the mixture is dissolved to obtain a solution (a) with the mass fraction of an active metal source of 20%, wherein Fe: the mass ratio of Nd is 40:1; adding 400-mesh powdered coconut shell activated carbon into the solution (a) according to the metering ratio to obtain slurry (b); the slurry (b) was mechanically stirred at a rotation speed of 60r/min for 30min, and then thoroughly mixed and adsorbed to obtain a suspension (c).
(2) Adding kaolin with the particle size of 400 meshes into a glucose aqueous solution, and pulping for 30min, wherein the mass ratio of the kaolin to the water to the glucose is 1:2:0.06.
(3) Adding a suspension (c) into the slurry obtained in the step (2), and controlling the mass ratio of the active carbon to the active metal to the kaolin to be 30:6:64. heating and evaporating under stirring to reduce water content, wherein the evaporating temperature is 105 ℃ and the evaporating time is 60min; then adding binder starch to form paste, wherein the mass of the starch is 5% of that of the activated carbon, extruding into cylindrical material (d) with diameter of 4 mm and length of 4 mm, and drying at 105 ℃ for 5h.
(4) And (3) roasting the product obtained in the step (3) at 600 ℃ for 5 hours under the protection of nitrogen to obtain the catalyst B.
The composition of catalyst B is shown in Table 1. The prepared catalyst B is used for treating reverse osmosis concentrated water with the average COD concentration of 128mg/L in a moving bed heterogeneous Fenton reactor, and the treatment effect is shown in Table 2.Fenton reaction conditions were the same as in example 1.
Example 3
(1) Fe (NO) 3 ) 3 Adding into distilled water and stirring until the solution is dissolved to obtain a solution (a) with the mass fraction of 10%; adding 400-mesh powdered coal-based activated carbon into Fe (NO) 3 ) 3 Obtaining slurry (b) in the solution; the slurry (b) was mechanically stirred at a rotation speed of 60r/min for 10min, and then thoroughly mixed and adsorbed to obtain a suspension (c).
(2) Adding 400-mesh kaolin into glucose aqueous solution, pulping for 30min, wherein the mass ratio of the kaolin to the water to the glucose is 1:2:0.06.
(3) Adding a suspension (c) into the slurry obtained in the step (2), and controlling the mass ratio of the active carbon to the active metal to the kaolin to be 35:5:60. heating and evaporating under stirring to reduce water content, wherein the evaporating temperature is 105 ℃ and the evaporating time is 60min; then adding adhesive starch to form paste, wherein the starch is 5% of the mass of the activated carbon, extruding the paste into a cylindrical material (d) with the diameter of 3mm and the length of 3 mm. Drying at 105 ℃ for 5 hours;
(4) And (3) roasting the product obtained in the step (3) for 5 hours at 600 ℃ under the protection of nitrogen to obtain the catalyst C.
The composition of catalyst C is shown in Table 1. The prepared catalyst C is used for treating reverse osmosis concentrated water with the average COD concentration of 128mg/L in a moving bed heterogeneous Fenton reactor, and the treatment effect is shown in Table 2.Fenton reaction conditions were the same as in example 1.
Example 4
(1) The active metal source Fe (NO) 3 ) 3 、Ce(NO 3 ) 3 Adding the mixture into distilled water and stirring the mixture until the mixture is dissolved to obtain a solution (a) with the mass fraction of an active metal source of 10%, wherein Fe: the mass ratio of Ce is 40:1; adding 400-mesh powdered coal-based activated carbon into the solution (a) according to the metering ratio to obtain slurry (b); the slurry (b) was mechanically stirred at a rotation speed of 60r/min for 10min, and then thoroughly mixed and adsorbed to obtain a suspension (c).
(2) Adding 400-mesh kaolin into water, pulping for 30min, wherein the mass ratio of the kaolin to the water is 1:2.06.
(3) Adding a suspension (c) into the slurry obtained in the step (2), and controlling the mass ratio of the active carbon to the active metal to the kaolin to be 35:5:60. heating and evaporating under stirring to reduce water content, wherein the evaporating temperature is 105 ℃ and the evaporating time is 60min; then adding binder starch to form paste, wherein the mass of the starch is 5% of that of the activated carbon, extruding into cylindrical material (d) with diameter of 3mm and length of 3mm, and drying at 105 ℃ for 5h.
(4) And (3) roasting the product obtained in the step (3) for 5 hours at 600 ℃ under the protection of nitrogen to obtain the catalyst D.
The composition of catalyst D is shown in Table 1. The prepared catalyst D is used for treating reverse osmosis concentrated water with the average COD concentration of 128mg/L in a moving bed heterogeneous Fenton reactor, and the treatment effect is shown in Table 2.Fenton reaction conditions were the same as in example 1.
Example 5
(1) The active metal source Fe (NO) 3 ) 3 And La (NO) 3 ) 3 Adding into distilled water and stirring until the active metal source is dissolved to obtain a solution (a) with the mass percent of 8%, wherein Fe: the mass ratio of La is 20:1. Adding 200-mesh wood powder coal-based activated carbon into the solution (a) according to the metering ratio to obtain slurry (b); the slurry (b) was mechanically stirred at a rotation speed of 60r/min for 10min, and then thoroughly mixed and adsorbed to obtain a suspension (c).
(2) Adding kaolin with the particle size of 200 meshes into a glucose aqueous solution, pulping for 40min, wherein the mass ratio of the kaolin to the water to the glucose is 1:4:0.3.
(3) Adding the suspension (c) of the step (1) into the slurry of the step (2), wherein the mass ratio of the active carbon to the active metal to the kaolin in the obtained mixed material is 46:4:50. heating and evaporating under stirring to reduce water content, wherein the evaporating temperature is 90 ℃ and the evaporating time is 50min; and adding binder starch to form paste, wherein the mass of the starch is 5% of that of the activated carbon. The extruded strip was formed into a cylindrical mass (d) of diameter 3mm and length 3 mm. Drying at 130℃for 3h.
(4) And (3) roasting the product obtained in the step (3) at 1000 ℃ for 7 hours under the protection of nitrogen to obtain the catalyst E.
The properties of catalyst E are shown in Table 1.The prepared catalyst E is used for a moving bed heterogeneous Fenton reactor, the catalyst is not additionally cleaned, reverse osmosis concentrated water with the average COD concentration of 128mg/L is treated, and the treatment effect is shown in Table 2. The Fenton reaction conditions are as follows: the catalyst filling amount accounts for 1/2 of the total volume of the reactor, the pH value is 4, and the sewage volume space velocity is 3h -1 ，H 2 O 2 Ratio to sewage COD (chemical oxygen demand), namely H 2 O 2 (mg/L): COD (mg/L) was 2:1. The procedure is as in example 1.
Comparative example 1
(1) Fe (NO) 3 ) 3 Adding into distilled water and stirring until the iron nitrate is dissolved to obtain a solution (a) with the iron nitrate weight fraction of 10%; adding 400-mesh coal-based activated carbon into Fe (NO) 3 ) 3 Obtaining slurry (b) in the solution; the slurry (b) was mechanically stirred at a rotation speed of 60r/min for 10min, and then fully mixed and adsorbed to obtain a metal-impregnated activated carbon suspension (c).
(2) The mass ratio of the active carbon to the active metal is controlled to be 95:5. Heating and evaporating under stirring to reduce water content, adding binder starch to form paste, wherein the starch accounts for 5% of the active carbon mass, extruding into cylindrical material (d) with diameter of 3mm and length of 3 mm. Drying at 105℃for 5h.
(3) And (3) roasting the product obtained in the step (2) at 600 ℃ for 5 hours under the protection of nitrogen to obtain the catalyst DA.
The comparative catalyst DA was used in a moving bed heterogeneous Fenton reactor for treating reverse osmosis concentrated water with an average COD concentration of 128mg/L, and the treatment effect is shown in Table 2. The properties are shown in Table 1.Fenton reaction conditions were the same as in example 1.
Comparative example 2
A commercially available columnar activated carbon (DB) with the diameter of 5mm and the length of 5mm is selected, the property is shown in table 1, and the columnar activated carbon is used for treating reverse osmosis concentrated water with the COD average concentration of 128mg/L in a moving bed heterogeneous Fenton reactor, and the treatment effect is shown in table 2.
The Fenton reaction conditions are as follows: the catalyst filling amount accounts for 1/2 of the total volume of the reactor, the pH value is 3.5, and the sewage volume space velocity is 2h -1 ，H 2 O 2 Ratio to sewage COD (chemical oxygen demand), namely H 2 O 2 (mg/L): COD (mg/L) was 1:1. Ferrous sulfate as Fe 2+ Source, sewage COD and Fe 2+ The ratio of (2) is COD (mg/L): fe (Fe) 2+ (mg/L) was 5:1. The other conditions were the same as in example 1.
Comparative example 3
(1) The active metal source Fe (NO) 3 ) 3 And Ce (NO) 3 ) 3 Adding into distilled water and stirring until the active metal source is dissolved to obtain a solution (a) with the mass percent of 10%, wherein Fe: the mass ratio of Ce is 40:1. Uniformly mixing to obtain slurry (b); the slurry (b) was mechanically stirred at a rotation speed of 60r/min for 10min, and then thoroughly mixed and adsorbed to obtain a suspension (c).
(2) Adding kaolin with the particle size of 400 meshes into a glucose aqueous solution, pulping for 30min, wherein the mass ratio of the kaolin to the water to the glucose is 1:2:0.06.
(3) Adding the suspension (c) of the step (1) into the slurry of the step (2), wherein the mass ratio of active metal to kaolin in the obtained mixed material is 5:95. heating and evaporating under stirring to reduce water content, wherein the evaporating temperature is 105 ℃ and the evaporating time is 60min; the binder starch was then added to form a paste, the starch being added in the same amount as in example 1. The extruded strip was formed into a cylindrical mass (d) of diameter 3mm and length 3 mm. Drying at 105℃for 5h.
(4) And (3) roasting the product obtained in the step (3) at 600 ℃ for 5 hours under the protection of nitrogen to obtain the catalyst DC.
The properties of catalyst DC are shown in Table 1. The prepared catalyst DC is used for a moving bed heterogeneous Fenton reactor to treat reverse osmosis concentrated water with average COD concentration of 128mg/L, and the treatment effect is shown in Table 2.Fenton reaction conditions were the same as in example 1.
Table 1 properties of the catalysts obtained in each example
| Catalyst numbering | A | B | C | D | E | DA | DB | DC |
| Specific surface area, m 2 /g | 223 | 218 | 236 | 216 | 207 | 686 | 758 | 36 |
| Abrasion rate, wt% | 0.65 | 0.62 | 0.66 | 2.54 | 0.66 | 6.4 | 7.3 | 0.43 |
| Radial crushing resistance, N/cm | 80.2 | 78.7 | 82.1 | 60.5 | 82.2 | 46.2 | 47.8 | 108.4 |
The catalysts of the invention described above are compared with the prior art. The materials are respectively used for treating reverse osmosis concentrated water with the average COD concentration of 128mg/L by a moving bed Fenton reactor, sampling is carried out after 24-h running and sampling is carried out after 30d long-term running, and the COD concentration of the effluent is shown in Table 2.
Table 2 evaluation results
| Catalyst numbering | A | B | C | D | E | DA | DB | DC |
| COD, mg/L (24 h of operation) of effluent | 38 | 40 | 48 | 47 | 40 | 48 | 82 | 108 |
| COD, mg/L (long term operation 30 d) | 38 | 41 | 50 | 53 | 45 | 88 | 83 | 106 |
As can be seen from the results of Table 2, the COD removal rate of the examples of the present invention was higher than that of the comparative examples. In particular, examples 1, 2 and 5 have significantly higher COD removal rate than example 3, compared with the catalytic effect of the rare earth element-containing catalyst.
As can be seen from the results of tables 1 and 2, the catalyst obtained by the low-carbon sugar treatment in examples 1, 2 and 5 is significantly reduced in attrition rate and significantly increased in radial crushing resistance, compared with the catalyst obtained by the low-carbon sugar treatment in example 4, and is advantageous for long-period operation of the reaction and prolonged in catalyst life.
From the long-term operation effect of table 2, the catalyst of the invention maintains good stability and has higher COD removal rate under the condition of no need of additional cleaning, pollution and regeneration.
Claims (12)
1. An application of a heterogeneous Fenton catalyst in catalytic oxidation of sewage, wherein a moving bed Fenton reactor is adopted in the application; the catalyst does not need additional cleaning and regeneration; the heterogeneous Fenton catalyst comprises active carbon, kaolin and an active metal component; the active metal component comprises iron and rare earth elements at the same time, the rare earth elements comprise one or more of cerium, lanthanum and neodymium,
the mass ratio of the activated carbon to the kaolin is 1: 1-1: 3 and not 1:1,
the preparation method of the heterogeneous Fenton catalyst comprises the following steps:
(1) Impregnating active carbon with an impregnation liquid containing active metal to obtain a suspension;
(2) Mixing kaolin, water and low-carbon sugar for pulping;
(3) Introducing the suspension in the step (1) into the slurry obtained in the step (2), and then evaporating, forming and drying;
(4) And (3) roasting the product obtained in the step (3) in an oxygen-free atmosphere to obtain the catalyst.
2. The use according to claim 1, wherein the catalyst comprises 10% -45% of active carbon, 45% -80% of kaolin, and 1% -10% of active metal component, based on the total weight of the catalyst.
3. The use according to claim 1, wherein the catalyst is 27% -40% of the total weight of the activated carbon based on the total weight of the catalyst; the kaolin accounts for 50% -70% of the total weight; the active metal component accounts for 3% -10% of the total weight based on metal elements.
4. The use according to claim 1, wherein in the catalyst, the activated carbon is powdered activated carbon with a particle size of 200-500 mesh; and/or the particle size of the kaolin is 200-500 meshes.
5. The use according to any one of claims 1 to 4, wherein the mass ratio of iron to rare earth elements in the catalyst is 20:1 to 50:1.
6. The use according to claim 1, wherein the specific surface area of the catalyst is 100-400 m 2 /g; the radial crushing resistance of the catalyst is 50-150N/cm, and the abrasion rate is below 3 wt%.
7. The use according to claim 6, wherein the attrition rate of the catalyst is less than 1 wt%.
8. The use according to claim 1, wherein in the preparation of the catalyst, the impregnation fluid in step (1) is obtained by dissolving an active metal source in water; in the impregnating solution, the mass content of the active metal source is 5% -30%.
9. The use according to claim 1, wherein in the method for preparing the catalyst, the beating time in step (2) is 10-60 min; the low-carbon sugar is one or more of 1-6 carbon atoms; the mass ratio of the kaolin to the water to the low-carbon sugar is 1: 1-5: 0.01 to 0.6.
10. The use according to claim 1, wherein in the preparation method of the catalyst, the evaporation temperature in the step (3) is 40-110 ℃ and the evaporation time is 30-60 min;
and/or, the drying conditions in step (3) are as follows: and drying at 80-150 ℃ for 1-5 h.
11. The use according to claim 1, wherein in the preparation of the catalyst, the calcination conditions of step (4) are as follows: the roasting temperature is 600-1400 ℃, and the roasting time is 1-10 h.
12. The use according to claim 1, characterized in that the reaction conditions of the use are: the pH value is 3.0-4.5; the volume space velocity of the sewage is 0.25-4 h -1 ；H 2 O 2 Ratio to sewage COD (chemical oxygen demand), namely H 2 O 2 In mg/L: COD is 1:1-2:1 in mg/L.
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