CN114471566A - Carrier for Fenton oxidation treatment of fluidized bed containing salt wastewater and preparation and application thereof - Google Patents
Carrier for Fenton oxidation treatment of fluidized bed containing salt wastewater and preparation and application thereof Download PDFInfo
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- CN114471566A CN114471566A CN202011159402.8A CN202011159402A CN114471566A CN 114471566 A CN114471566 A CN 114471566A CN 202011159402 A CN202011159402 A CN 202011159402A CN 114471566 A CN114471566 A CN 114471566A
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- fluidized bed
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- 239000002351 wastewater Substances 0.000 title claims abstract description 88
- 150000003839 salts Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 230000003647 oxidation Effects 0.000 title claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 18
- 238000011282 treatment Methods 0.000 title claims abstract description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 79
- 229910052742 iron Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 25
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 239000006004 Quartz sand Substances 0.000 claims description 15
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- 230000032683 aging Effects 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 abstract description 14
- 230000008025 crystallization Effects 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 42
- 229910001868 water Inorganic materials 0.000 description 41
- 238000006243 chemical reaction Methods 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 239000000243 solution Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000004519 manufacturing process Methods 0.000 description 17
- 239000003822 epoxy resin Substances 0.000 description 16
- 229920000647 polyepoxide Polymers 0.000 description 16
- 230000008569 process Effects 0.000 description 10
- 238000011068 loading method Methods 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 239000004576 sand Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 239000005504 Dicamba Substances 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt(II) nitrate Inorganic materials [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- IWEDIXLBFLAXBO-UHFFFAOYSA-N dicamba Chemical compound COC1=C(Cl)C=CC(Cl)=C1C(O)=O IWEDIXLBFLAXBO-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 239000011800 void material Substances 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- 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
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- B01J23/755—Nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
The invention provides a carrier for Fenton oxidation treatment of a fluidized bed for salt-containing wastewater and a preparation method thereof. The invention also provides a fluidized bed Fenton oxidation treatment method using the supporter. The specific surface area of the carrier is 120～190m2·g‑1Surface hydroxyl group density of greater than 10DOH/nm2. The carrier is used for the fluidized bed Fenton oxidation treatment method of the salt-containing wastewater, can quickly degrade COD of the salt-containing organic wastewater, and improves the iron crystallization rate.
Description
Technical Field
The invention relates to a treatment process of salt-containing organic wastewater, in particular to a carrier for fluidized bed Fenton oxidation treatment of salt-containing organic wastewater, a fluidized bed Fenton oxidation treatment method using the carrier and a preparation method of the carrier.
Background
The salt-containing organic wastewater refers to wastewater containing organic pollutants and inorganic ionic salts, a large amount of wastewater is generated in industrial production processes of petrifaction, pharmacy, dye, leather processing, textile and the like, the wastewater contains organic pollutants with higher concentration, damages the environment and harms human health, and also contains higher inorganic ions such as chloride ions, calcium ions, sulfate ions, sodium ions and the like, the decomposition of oxidants such as hydrogen peroxide and the like can be inhibited in the wastewater treatment process, weak complexation is generated between the oxidants such as iron and the like, and the treatment difficulty is increased. Fenton (Fenton) oxidation technique by Fe2+And H2O2The method has the advantages that chain reaction is carried out to generate hydroxyl radicals with stronger oxidability to degrade pollutants in water, the process is simple, the treatment effect is good, the method is an effective advanced oxidation technology and is widely applied to various organic wastewater treatments, but because the pH response range is narrow, and a large amount of iron mud is easily generated, the further development of the technology is limited, compared with the traditional Fenton oxidation technology, the fluidized bed Fenton technology enables iron to be crystallized on the surface of a supporter through surface precipitation, the generation amount of sludge can be reduced, the pollutant removal effect is improved, and the method is green, energy-saving and environment-friendly.
CN109201085A discloses a preparation method and application of a fluidized bed Fenton catalyst, and the specific method comprises the following steps: firstly, cleaning to obtain the building sand with easily acid-soluble substances removed; secondly, drying; thirdly, screening to obtain the building sand with the granularity of 20-30 meshes; fourthly, adding building sand into the fluidized bed Fenton reactor; fifthly, preparing feed water containing Fe2+ and feed water containing H2O 2; sixthly, adjusting Fe2+And containing H2O2The pH of the influent water; seventhly, putting the reduced iron powder and the ferric oxide into a fluidized bed Fenton reactor; eight, continuously operating the fluidized bed Fenton reactor to obtainFluidized bed fenton catalyst. The method improves the catalyst manufacturing speed and the iron content, but the concentration of the treated wastewater is low, and the COD removal rate is not ideal when the organic nitrogen wastewater with higher concentration is treated. And simultaneously, a large amount of iron mud is generated.
CN108191129A discloses a dicamba high salt waste water integrated processing system, assembles little electrolysis reaction device, MVR evaporimeter and fenton reaction device, makes waste water degradation more abundant and reduced waste water treatment time. However, the fenton device in the system generates a large amount of iron mud, and the technical application is limited to a certain extent.
Therefore, how to increase the iron crystallization rate and reduce the generation of iron mud becomes a problem to be solved urgently for the Fenton oxidation of the fluidized bed.
Disclosure of Invention
One of the technical problems to be solved by the invention is to provide a novel carrier for fluidized bed Fenton oxidation treatment of salt-containing organic wastewater and a preparation method thereof, aiming at the problems of low COD removal rate and low iron crystallization rate in the fluidized bed Fenton treatment of salt-containing organic wastewater in the prior art, so as to achieve the effects of high COD removal rate and high iron crystallization rate.
The second technical problem to be solved by the invention is to provide a fluidized bed Fenton oxidation treatment method for salt-containing organic wastewater.
In order to solve one of the above technical problems, a first aspect of the present invention provides a carrier for fluidized bed fenton oxidation treatment of salt-containing wastewater, wherein the carrier has a specific surface area of 120 to 190m2·g-1Surface hydroxyl group density of greater than 10DOH/nm2The surface hydroxyl group density is preferably 12 to 20DOH/nm2。
In the technical scheme, the supporter is one or more of quartz sand, ceramics, alumina and the like with the surface modified by modified metal.
In the above technical solution, the modified metal is selected from at least one of Cu, Co, Ni, and Fe. The content of the modified metal on the carrier is preferably more than 0 and 50g/kg or less, more preferably 1 to 20g/kg, and most preferably 1 to 5 g/kg.
The second aspect of the present invention provides a method for preparing the carrier, comprising the following steps:
1) soaking the carrier of the fluidized bed in a mixed aqueous solution of hydrochloric acid and phosphoric acid;
2) roasting the peracid-soaked fluidized bed support;
3) soaking the roasted fluidized bed carrier in a modified metal salt solution, and adjusting the pH value to 9-12;
4) aging and roasting to obtain the supporter.
In the above technical scheme, the content of hydrochloric acid in the mixed aqueous solution of hydrochloric acid and phosphoric acid in step 1) is preferably 1 wt% to 5 wt%, and the content of phosphoric acid is preferably 5 wt% to 10 wt%. The soaking time is preferably 2-4 h.
In the technical scheme, the roasting temperature in the step 2) is preferably 600-800 ℃, and the roasting time is preferably 2-4.5 hours.
In the technical scheme, the concentration of the modified metal salt solution in the step 3) is 1-50 g/L. The modified metal is at least one selected from Cu, Co, Ni and Fe. The compound of Cu may be selected from CuCl2、Cu(NO3)2And CuSO4One or more of (a). The Fe compound may be selected from FeCl3、Fe(NO3)3And Fe2(SO4)3One or more of (a). The compound of Co can be selected from CoCl2、Co(NO3)2And CoSO4One or more of (a). The Ni compound may be selected from NiCl2、Ni(NO3)2And NiSO4One or more of (a).
In the technical scheme, the aging temperature in the step 4) is 60-90 ℃, and the time is 4-8 h; the roasting temperature is preferably 400-600 ℃, and the roasting time is preferably 2-4.5 hours.
In a third aspect of the invention, the carrier is applied to the Fenton oxidation treatment of the fluidized bed of the salt-containing organic wastewater, and in the presence of the carrier, the mixed material I of the salt-containing organic wastewater and hydrogen peroxide and the mixed material II of the salt-containing organic wastewater and iron salt enter the fluidized bed for reaction to degrade COD in the salt-containing organic wastewater.
The loading amount of the supporter is 10-60% of the volume of the fluidized bed. The expansion degree of the carrier during the operation of the fluidized bed is preferably 40-80%.
In the above technical scheme, COD and H of the wastewater in the mixed material I2O2The molar ratio is preferably 0.1 to 10, more preferably 0.2 to 2, and most preferably 0.5 to 1.
In the above technical scheme, Fe in the mixed material II2+With H in material I2O2The molar ratio is preferably 0.01 to 10, more preferably 0.05 to 5, and most preferably 0.1 to 1.
In the technical scheme, the flow ratio of the material I and the material II entering the fluidized bed is preferably 0.1-10, and more preferably 0.5-2.
In the above technical scheme, the iron salt in the material I is selected from FeCl2、Fe(NO3)2And FeSO4At least one of (1).
In the technical scheme, the pH of the material I and the material II is preferably 3-5.
In the technical scheme, the residence time of the wastewater is preferably 20-120 minutes. The reaction temperature is 10-150 ℃.
In the technical scheme, when the modified metal is Co, the method is particularly excellent in removing COD (chemical oxygen demand) of salt-containing wastewater and improving the crystallization rate of iron.
The inventor finds that the hydroxyl group density on the surface of the fluidized bed carrier is the key for influencing the heterogeneous nucleation and crystal growth of iron crystallization, too low hydroxyl group density cannot provide enough sites for iron crystallization, and too high hydroxyl group density consumes H in the solution+The carrier prepared by the technical scheme of the invention has enhanced specific surface area and hydroxyl density, avoids the surface hardening of the carrier or the crystallization with iron, can provide enough sites for the iron crystallization, does not influence the effective removal of organic matters in the salt-containing organic wastewater, and can simultaneously ensure the degradation efficiency of the wastewater and the iron crystallization rate.
By adopting the technical scheme of the invention, under the conditions that the reaction temperature is 25 ℃, the retention time of the wastewater is 30 minutes, the pH is 3 and the expansion degree of a carrier of the fluidized bed is 50%, the organic matter content in the salt-containing organic wastewater and the iron content of the effluent can be effectively reduced, by taking the epoxy resin production wastewater as an example, the COD value of the epoxy resin production wastewater is reduced to 337mg/L from 15000mg/L through Fenton oxidation treatment of the fluidized bed, the removal rate reaches 97.8%, the iron content of the effluent is 283mg/L, and the iron crystallization rate reaches 78.4%, so that better technical effects are achieved.
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention in any way.
Detailed Description
In the present invention, the specific surface area is measured by a TRISTAR II 302 specific surface area and void analyzer, available from micromeritics, USA;
the surface hydroxyl density is calculated by the following formula:
DOH/nm2＝[SBET×WT2+(WT1-WT2)/MWH2O/NA×2]/(SBET×WT1)；
wherein, WT1And WT2The mass of the sample, S, heated to 120 ℃ and 500 ℃ respectively for thermogravimetric analysisBETIs the specific surface area of the sample, MWH2OIs the molar mass of water, NAIs the Avogastron constant.
And (4) detecting the iron content of inlet and outlet water by ICP (inductively coupled plasma), and calculating the iron removal rate, namely the crystallization rate of iron on the carrier.
[ example 1 ]
1. Preparation of the carrier
50ml of quartz sand is soaked in a mixed aqueous solution of 5 percent hydrochloric acid and 10 percent phosphoric acid for 2 hours, roasted for 4 hours at 800 ℃ and cooled for standby. 0.22g of Co (NO)3)2·6H2Dissolving O in water to prepare 25ml of solution, soaking quartz sand cooled to room temperature in the prepared cobalt solution, dropwise adding 5mol/L NaOH aqueous solution into the cobalt solution filled with the quartz sand until the pH value is 12, uniformly stirring, aging in an oven at 90 ℃ for 4h, and calcining at 600 ℃ for 4h to obtain the modified Fenton fluidized bed support. The content of the modified metal on the carrier was 2 g/kg.
The properties of the support are shown in table 1.
2. Preparation of water
Containing H2O2Wastewater inflow: 100ml of 30 percent H is added into 1L of epoxy resin production wastewater2O2And stirring uniformly. Wherein COD and H2O2The molar ratio was 0.96.
Feeding the wastewater containing Fe into water: 27g of FeSO is added into 1L of epoxy resin production wastewater4·7H2And O, stirring uniformly. Wherein Fe2+And contain H2O2H in waste water2O2The molar ratio was 0.1.
3. The fluidized bed process conditions were as follows:
volume of the fenton fluidized bed reactor: 250 ml;
loading of the carrier: 50 ml;
controlling the air flow to ensure that the expansion degree of the supporter is: 50 percent;
the water inflow of the wastewater containing Fe: 200 ml/h;
containing H2O2Wastewater inflow: 200 ml/h;
pH of inlet water: 3;
reaction temperature: 25 ℃;
the reaction results are shown in Table 2.
[ example 2 ]
1. Preparation of the carrier
50ml of quartz sand is soaked in a mixed aqueous solution of 5 percent hydrochloric acid and 10 percent phosphoric acid for 2 hours, roasted for 4 hours at 800 ℃ and cooled for standby. 0.34g of Fe (NO)3)3·9H2Dissolving O in water to prepare 25ml of solution, soaking the quartz sand cooled to room temperature in the prepared iron solution, dropwise adding 5mol/L NaOH aqueous solution into the iron solution filled with the quartz sand until the pH value is 12, uniformly stirring, aging in an oven at 90 ℃ for 4h, and calcining at 600 ℃ for 4h to obtain the modified Fenton fluidized bed support. Modified metal content on the carrier: 2 g/kg.
The properties of the support are shown in table 1.
2. Preparation of water
Containing H2O2Wastewater inflow: 100ml of 1L epoxy resin production wastewater is added 30％H2O2And stirring uniformly. Wherein COD and H2O2The molar ratio was 0.96.
Feeding the wastewater containing Fe into water: 27g of FeSO is added into 1L of epoxy resin production wastewater4·7H2And O, stirring uniformly. Wherein Fe2+And contain H2O2H in waste water2O2The molar ratio was 0.1.
3. The fluidized bed process conditions were as follows:
volume of the fenton fluidized bed reactor: 250 ml;
loading of the carrier: 50 ml;
degree of expansion of the support: 50 percent;
the water inflow of the wastewater containing Fe: 200 ml/h;
containing H2O2Wastewater inflow: 200 ml/h;
pH of inlet water: 3;
reaction temperature: 25 ℃;
the reaction results are shown in Table 2.
[ example 3 ]
1. Preparation of the carrier
50ml of alumina is soaked in a mixed aqueous solution of 3 percent hydrochloric acid and 8 percent phosphoric acid for 3 hours, roasted for 3 hours at the temperature of 600 ℃ and cooled for standby. 0.14g of Cu (NO)3)2Dissolving the mixture in water to prepare 25ml of solution, soaking the aluminum oxide cooled to room temperature in the prepared copper solution, dropwise adding 5mol/L NaOH aqueous solution into the copper solution filled with the aluminum oxide until the pH value is 10, uniformly stirring, aging in an oven at 60 ℃ for 8 hours, and calcining at 450 ℃ for 3 hours to obtain the modified Fenton fluidized bed support. Modified metal content on the carrier: 2.0 g/kg.
The formula of the carrier modification is shown in table 1.
2. Preparation of water
Containing H2O2Wastewater inflow: 100ml of 30 percent H is added into 1L of epoxy resin production wastewater2O2And stirring uniformly. Wherein COD and H2O2The molar ratio was 0.96.
Feeding the wastewater containing Fe into water: 13g of FeSO is added into 1L of epoxy resin production wastewater4·7H2O, stirring allAnd (4) homogenizing. Wherein Fe2+And contain H2O2H in waste water2O2The molar ratio was 0.05.
3. The fluidized bed process conditions were as follows:
volume of the fenton fluidized bed reactor: 250 ml;
loading of the carrier: 120 ml;
degree of expansion of the support: 40 percent;
the water inflow of the wastewater containing Fe: 300 ml/h;
containing H2O2Wastewater inflow: 150 ml/h;
pH of inlet water: 4;
reaction temperature: 25 ℃;
the reaction results are shown in Table 2.
[ example 4 ]
1. Preparation of the carrier
50ml of ceramics is soaked in a mixed aqueous solution of 5 percent hydrochloric acid and 10 percent phosphoric acid for 2 hours, roasted at 800 ℃ for 4 hours and cooled for standby. 0.14g of Ni (NO)3)2Dissolving the ceramic in water to prepare 25ml of solution, soaking the ceramic cooled to room temperature in the prepared nickel solution, dropwise adding 5mol/L NaOH aqueous solution into the nickel solution filled with the ceramic until the pH value is 12, uniformly stirring, aging in an oven at 90 ℃ for 6h, and calcining at 600 ℃ for 4h to obtain the modified Fenton fluidized bed support. Modified metal content on the carrier: 2.0g/kg
The properties of the carrier modification are shown in table 1.
2. Preparation of water
Containing H2O2Wastewater inflow: 200ml of 30 percent H is added into 1L of epoxy resin production wastewater2O2And stirring uniformly. Wherein COD and H2O2The molar ratio was 0.5.
Feeding Fe-containing wastewater into water: adding 13g of FeSO into 1L of epoxy resin production wastewater4·7H2And O, stirring uniformly.
Wherein Fe2+And contain H2O2H in waste water2O2The molar ratio is 0.05
3. The fluidized bed process conditions were as follows:
volume of the fenton fluidized bed reactor: 250 ml;
loading of the carrier: 50 ml;
degree of expansion of the support: 50 percent;
the water inflow of the wastewater containing Fe: 100 ml/h;
containing H2O2Wastewater inflow: 200 ml/h;
pH of inlet water: 3;
reaction temperature: 25 ℃;
the reaction results are shown in Table 2.
Comparative example 1
1. Preparation of carrier
50ml of quartz sand is washed by deionized water until the effluent is clear and is filled in a Fenton fluidized bed.
The properties of the support are shown in table 1.
2. Preparation of water
Containing H2O2Wastewater inflow: 100ml of 30 percent H is added into 1L of epoxy resin production wastewater2O2And stirring uniformly. Wherein COD and H2O2The molar ratio was 0.96.
Feeding the wastewater containing Fe into water: 27g of FeSO is added into 1L of epoxy resin production wastewater4·7H2And O, stirring uniformly. Wherein Fe2+And contain H2O2H in waste water2O2The molar ratio was 0.1.
3. The fluidized bed process conditions were as follows:
volume of the fenton fluidized bed reactor: 250 ml;
loading of the carrier: 50 ml;
degree of expansion of the support: 50 percent;
the water inflow of the wastewater containing Fe: 200 ml/h;
containing H2O2Wastewater inflow: 200 ml/h;
pH of inlet water: 3;
reaction temperature: 25 ℃;
the reaction results are shown in Table 2.
Comparative example 2
1. Preparation of the Carrier
50ml of quartz sand is soaked in a mixed aqueous solution of 5 percent hydrochloric acid and 10 percent phosphoric acid for 2 hours, roasted for 4 hours at 800 ℃ and cooled for standby. 0.22g of Co (NO)3)2·6H2Dissolving O in water to prepare 25ml of solution, soaking quartz sand cooled to room temperature in the prepared cobalt solution, dropwise adding 5mol/L NaOH aqueous solution into the cobalt solution filled with the quartz sand until the pH value is 12, uniformly stirring, aging in an oven at 90 ℃ for 4h, and calcining at 600 ℃ for 4h to obtain the modified Fenton fluidized bed support. The content of the modified metal on the carrier was 2 g/kg.
The properties of the support are shown in table 1.
2. Preparation of water
Containing H2O2Wastewater inflow: 100ml of 30 percent H is added into 1L of epoxy resin production wastewater2O2And stirring uniformly. Wherein COD and H2O2The molar ratio was 0.96.
Feeding the wastewater containing Fe into water: 27g of FeSO is added into 1L of epoxy resin production wastewater4·7H2And O, stirring uniformly. Wherein Fe2+And contain H2O2H in waste water2O2The molar ratio was 0.1.
3. The fluidized bed process conditions were as follows:
volume of the fenton fluidized bed reactor: 250 ml;
loading of the carrier: 50 ml;
degree of expansion of the support: 10 percent;
the water inflow of the wastewater containing Fe: 200 ml/h;
containing H2O2Wastewater inflow: 200 ml/h;
pH of inlet water: 3;
reaction temperature: 25 ℃;
the reaction results are shown in Table 2.
Comparative example 3
1. Preparation of the Carrier
50ml of quartz sand is soaked in a mixed aqueous solution of 5 percent hydrochloric acid and 10 percent phosphoric acid for 2 hours, roasted for 4 hours at 800 ℃ and cooled for standby. 0.22g of Co (NO)3)2·6H2Dissolving O in water to obtain 25ml solution, and soaking in quartz sand cooled to room temperatureAnd (3) dropwise adding a 5mol/L NaOH aqueous solution into the prepared cobalt solution filled with quartz sand until the pH value is 12, uniformly stirring, aging in an oven at 90 ℃ overnight, and calcining at 600 ℃ for 4h to obtain the modified Fenton fluidized bed support. The content of the modified metal on the carrier was 2 g/kg.
The properties of the carrier are shown in Table 1 (same as example 1).
2. Preparation of water
Containing H2O2Wastewater inflow: 100ml of 30 percent H is added into 1L of epoxy resin production wastewater2O2And stirring uniformly. Wherein COD and H2O2The molar ratio was 0.96.
Feeding the wastewater containing Fe into water: 27g of FeSO is added into 1L of epoxy resin production wastewater4·7H2And O, stirring uniformly. Wherein Fe2+And contain H2O2H in waste water2O2The molar ratio was 0.1.
3. The fluidized bed process conditions were as follows:
volume of the fenton fluidized bed reactor: 250 ml;
loading of the carrier: 50 ml;
degree of expansion of the support: 100 percent;
the water inflow of the wastewater containing Fe: 200 ml/h;
containing H2O2Wastewater inflow: 200 ml/h;
pH of inlet water: 3;
reaction temperature: 25 ℃;
the reaction results are shown in Table 2.
The supports of comparative examples 2 and 3 were prepared in the same manner as in example 1, except that the degree of support expansion was changed in the operating conditions.
TABLE 1 Carrier Properties
Referring to the data in table 1 for the examples and comparative example 1, it can be seen that: the carrier prepared by the modification method has large specific surface area and higher surface hydroxyl density.
TABLE 2 reaction results
Referring to the data of example 1 and comparative examples 2 and 3 in table 2, it can be seen that when the swelling degree of the support is within the technical condition range of the present invention, the shearing force caused by the fluidized bed can inhibit the complexation of the inorganic salt ions to iron, and can not affect the hydroxyl groups on the surface of the support and the iron crystallization, thereby avoiding the surface hardening of the support, and ensuring the degradation efficiency of the wastewater and the iron crystallization rate.
Claims (13)
1. A carrier for Fenton oxidation treatment of a fluidized bed for salt-containing wastewater, which is characterized in that the specific surface area of the carrier is 120-190 m2·g-1Surface hydroxyl group density of greater than 10DOH/nm2The surface hydroxyl group density is preferably 12 to 20DOH/nm2。
2. The carrier according to claim 1, wherein the carrier is one or more of quartz sand, ceramics, and alumina having a modified metal supported on the surface thereof.
3. The carrier according to claim 1, wherein the modifying metal is at least one selected from the group consisting of Cu, Co, Ni and Fe; the mass content of the modified metal on the carrier is more than 0 and less than 50g/kg, preferably 1-20 g/kg, and more preferably 1-5 g/kg.
4. A method for preparing a support according to any one of claims 1 to 3, comprising the steps of:
1) soaking the carrier of the fluidized bed in a mixed aqueous solution of hydrochloric acid and phosphoric acid;
2) roasting the peracid-soaked fluidized bed support;
3) soaking the roasted fluidized bed carrier in a modified metal salt solution, and adjusting the pH value to 9-12;
4) aging and roasting to obtain the modified supporter.
5. The preparation method according to claim 4, wherein the mixed aqueous solution of hydrochloric acid and phosphoric acid in step 1) has a hydrochloric acid content of 1 wt% to 5 wt%, a phosphoric acid content of 5 wt% to 10 wt%, and a soaking time of 2 to 4 hours.
6. The preparation method of claim 4, wherein the roasting temperature in the step 2) is 600-800 ℃, and the roasting time is 2-4.5 hours.
7. The preparation method according to claim 4, wherein the aging temperature in step 4) is 60-90 ℃ for 4-8 h; the roasting temperature is 400-600 ℃, and the roasting time is 2-4.5 hours.
8. Use of a support according to any one of claims 1 to 3 or a support prepared by a method according to any one of claims 4 to 7 in the fluidized bed Fenton oxidation treatment of salt-containing wastewater, wherein a mixed material I of the salt-containing organic wastewater and hydrogen peroxide and a mixed material II of the salt-containing organic wastewater and iron salt enter a fluidized bed to react in the presence of the support, so that COD in the salt-containing organic wastewater is degraded.
9. The use according to claim 8, wherein the support is loaded at a level of from 10% to 60% by volume of the fluidized bed.
10. The use according to claim 8, wherein the degree of expansion of the support in the fluidised bed is 40 to 80%.
11. The use according to claim 8, wherein the COD and H of the wastewater in the mixed material I2O2The molar ratio is 0.1-10, preferably 0.2-2, and most preferably 0.5-1.
12. The method of claim 8Characterized in that Fe is contained in the mixed material II2+With H in material I2O2The molar ratio is 0.01 to 10, preferably 0.05 to 5, and more preferably 0.1 to 1.
13. The use according to claim 8, wherein the ratio of the flow rates of the material I and the material II entering the fluidized bed is 0.1-10, preferably 0.5-2.
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| CA2330320A1 (en) * | 1998-05-14 | 1999-11-18 | U.S. Environmental Protection Agency | Contaminant adsorption and oxidation via the fenton reaction |
| US6143182A (en) * | 1998-05-01 | 2000-11-07 | Industrial Technology Research Institute | Process for chemically oxidizing wastewater with reduced sludge production |
| CN103007937A (en) * | 2012-12-14 | 2013-04-03 | 天津市联合环保工程设计有限公司 | Catalytical ozonization catalyst utilizing multi-source sludge to prepare and application thereof |
| CN109894115A (en) * | 2017-12-11 | 2019-06-18 | 中国科学院大连化学物理研究所 | A kind of preparation method of the modified active carbon catalyst for the processing of class Fenton |
| CN110668548A (en) * | 2019-09-17 | 2020-01-10 | 上海中耀环保实业有限公司 | Heterogeneous Fenton catalytic oxidation reactor and application thereof |
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2020
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| US6143182A (en) * | 1998-05-01 | 2000-11-07 | Industrial Technology Research Institute | Process for chemically oxidizing wastewater with reduced sludge production |
| CA2330320A1 (en) * | 1998-05-14 | 1999-11-18 | U.S. Environmental Protection Agency | Contaminant adsorption and oxidation via the fenton reaction |
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