CN108558146A - Process and device associated with organic matter advanced oxidation and electrolytic catalysis in a kind of high-salt wastewater - Google Patents
Process and device associated with organic matter advanced oxidation and electrolytic catalysis in a kind of high-salt wastewater Download PDFInfo
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- CN108558146A CN108558146A CN201810612639.3A CN201810612639A CN108558146A CN 108558146 A CN108558146 A CN 108558146A CN 201810612639 A CN201810612639 A CN 201810612639A CN 108558146 A CN108558146 A CN 108558146A
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- waste water
- palladium
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- oxidation
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- 239000002351 wastewater Substances 0.000 title claims abstract description 53
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 45
- 230000003647 oxidation Effects 0.000 title claims abstract description 42
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 22
- 239000005416 organic matter Substances 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 11
- 230000008569 process Effects 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 230000003197 catalytic effect Effects 0.000 claims abstract description 22
- 238000011049 filling Methods 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000005516 engineering process Methods 0.000 claims abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000000593 degrading effect Effects 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 62
- 229910052763 palladium Inorganic materials 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- 239000002041 carbon nanotube Substances 0.000 claims description 17
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 10
- 239000010936 titanium Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004115 Sodium Silicate Substances 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000000741 silica gel Substances 0.000 claims description 9
- 229910002027 silica gel Inorganic materials 0.000 claims description 9
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 9
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000003672 processing method Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 230000032683 aging Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- -1 palladium metal oxide Chemical class 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 5
- 239000013049 sediment Substances 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 235000010981 methylcellulose Nutrition 0.000 claims description 3
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000002344 surface layer Substances 0.000 claims description 2
- 238000007689 inspection Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 claims 1
- 238000010025 steaming Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 9
- 150000003839 salts Chemical class 0.000 description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-M phenolate Chemical compound [O-]C1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-M 0.000 description 1
- 229940031826 phenolate Drugs 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B01J35/56—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
- C02F1/32—Treatment of water, waste water, or sewage by irradiation with ultraviolet light
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
-
- 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
- C02F2101/34—Organic compounds containing oxygen
-
- 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/04—Flow arrangements
- C02F2301/046—Recirculation with an external loop
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2301/00—General aspects of water treatment
- C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
-
- 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
- C02F2305/10—Photocatalysts
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F3/00—Biological treatment of water, waste water, or sewage
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
The invention discloses process and devices associated with organic matter advanced oxidation in a kind of high-salt wastewater and electrolytic catalysis, include the following steps：Industrial wastewater carries out oil removing, filtering by coarse filter, removes the suspended matter and colloidal substance in waste water；Industrial wastewater after coarse filtration is re-fed into advanced oxidation device, is passed through hydrogen peroxide and ozone, carries out advanced catalytic oxidation reaction；The waste water handled by advanced oxidation is then sent into catalytic and oxidative electrolysis technology device, under the action of catalyst filling, apply 5~24V voltages, and under ultraviolet light, carry out hardly degraded organic substance in electrolytic oxidation degrading waste water, by detecting the COD contents of waste water at sample outlet, when hit the target, is discharged；Waste water after catalytic and oxidative electrolysis technology is sent into crystallizing evaporator and is evaporated condensing crystallizing and recycles to obtain the Nacl of recycling；Waste water after evaporative condenser, which continues to be fed into, carries out biochemical treatment in biochemical device, discharged or recycled after meeting discharge standard.
Description
Technical field
The invention belongs to environmental protective chemical industry technical fields, more particularly to the processing equipment containing sodium phenolate waste water difficult to degrade and processing
Method.
Background technology
As China's industry is grown rapidly, sewage discharge increasingly increases, and is largely difficult to biodegradable chemicals with waste water
Form is discharged into environment, causes the serious pollution of water resource, has become the pain spot of social development and the hot spot of concern.Especially exist
That is discharged in the industrial processes such as coking, petrochemical industry, printing and dyeing, pharmacy, organic synthesis is anhydrous containing a large amount of toxic organic compounds and height
Concentration salt, such as sodium sulphate, sodium chloride, sodium nitrate, copper sulphate etc. so that can not be needed pair directly by biochemical treatment means
After Nacl carries out Crystallization Separation in waste water, then biochemical treatment is carried out, to generate toxic industrial waste salt, can not accomplish industry
Salt recycling treatment；Simultaneously because useless Organic substance in water contains such as formaldehyde, alcohols and difficult to degrade and high boiling phenolic material
Matter, at present Conventional catalytic oxidation can not also be handled, and for brine waste, and the salt obtained by distillation crystallization is abraum salt,
It can not recycling treatment.Oxidation means of the advanced oxidation as new development obtain extremely strong energy of oxidation by screening suitable catalyst
The macromolecular debirs of high bond energy in water body are oxidized to degradable, hypotoxicity small molecule by the free radical of power, but it is catalyzed
Agent and core process technology be all from external import, it is of high cost, be unfavorable for the development of domestic sewage disposal technology.
Invention content
Goal of the invention：For above-mentioned existing problem and shortage, the object of the present invention is to provide a kind of high-salt wastewaters
Process unit and method associated with middle organic matter advanced oxidation and electrolytic catalysis.
Technical solution：In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：Have in a kind of high-salt wastewater
Processing method associated with machine object advanced oxidation and electrolytic catalysis, includes the following steps：
Step 1：Industrial wastewater carries out oil removing, filtering by coarse filter, removes the suspended matter and colloidal substance in waste water；
Step 2：Industrial wastewater after coarse filtration is re-fed into advanced oxidation device, is passed through hydrogen peroxide and ozone, and
Under the action of catalyst filling, advanced catalytic oxidation reaction is carried out, the advanced oxidation device is the catalytic tower of plural serial stage,
Catalyst filling is mounted in every grade of catalytic tower, and tower top is formed with bottom of tower by pipeline pump and is connected by circulation, and in tower
Waste water carries out cycle catalysis oxidation；
Step 3：The waste water handled by advanced oxidation is then sent into catalytic and oxidative electrolysis technology device, in the work of catalyst filling
Under, apply 5~24V voltages, and under ultraviolet light, carries out hardly degraded organic substance in electrolytic oxidation degrading waste water, pass through
The COD contents of waste water at sample outlet are detected, when hit the target is discharged；
Step 4：Waste water after catalytic and oxidative electrolysis technology is sent into crystallizing evaporator and is evaporated condensing crystallizing and recycles
To the Nacl of recycling；Waste water after evaporative condenser, which continues to be fed into, carries out biochemical treatment in biochemical device, meet discharge standard
After discharged or recycled.
Preferably, the catalyst filling be using silica gel as carrier, carried metal palladium, iron or silver active component.
Preferably, active component is the oxide of Metal Palladium or/and iron in the catalyst.
Preferably, the load capacity of the oxide of the Metal Palladium or/and iron is 4~12%.
Preferably, the preparation method of the catalyst is as follows：
First, the sodium silicate solution of 20% mass concentration is prepared, be used in combination sodium hydroxide adjust pH value 12~13 it
Between, formation obtains weighing solution；In addition palladium bichloride is dissolved in 20~30% dilute hydrochloric acid and obtains palladium chloride solution, then stirred
It mixes down, which is slowly added to carry out hybrid reaction in sodium silicate solution, the hydroxide for obtaining silica gel and palladium is total
The sediment of doping, during being somebody's turn to do, the mass ratio of sodium metasilicate and Metal Palladium is 10:0.5~1.2.
Then, ph values are adjusted in the range of 6-8, continue to keep aging reaction at least 2h or more, then will be sunk after aging
Starch is filtered separation, and organic palladium catalyst is dried to obtain at 50~60 DEG C；
Then, by organic palladium catalyst and methyl cellulose binder according to 1:0.1~0.2 mass ratio is mixed,
Honeycomb green body, and dry 24 or more are formed under mould action, green body liquid phase component content are reduced, when avoiding high-temperature roasting
Chap and the surface layer oversintering for causing filling body, influence catalytic activity；
Finally, after carrying out 0.5~2h of roasting at a temperature of green body being placed in 400~600 DEG C, the catalysis of high-specific surface area is obtained
Agent honeycomb filling body.
The present invention also provides process unit associated with organic matter advanced oxidation in a kind of high-salt wastewater and electrolytic catalysis, packets
Include wastewater disposal basin, and connect with wastewater disposal basin successively by pipeline pump coarse filter, advanced oxidation device, tubular reactor, buffering
Pond, evaporator, crystallization apparatus and centrifuge, the tubular reactor include inner tube, middle tube and outer tube, the middle tube
The anode of power supply is connected as electrolytic anode, the surfaces externally and internally of the middle tube is coated with carbon nanotube loaded palladium metal oxidation
Object coating, the inner tube and outer tube are separately connected power cathode, are equipped between the middle tube and inner tube and outer tube
Catalyst filling.
Preferably, the carbon nanotube loaded palladium metal oxide coating preparation process of the middle tube surfaces externally and internally is such as
Under：
Step 1：Titanium base is dried after oil removing, pickling successively spare；
Step 2：At 50~60 DEG C, carbon nanotube is immersed in chloroazotic acid carry out it is acidic activated after, with pure water to ph
Then value is dried in 6-8；
Step 3：Then after tetra-triphenylphosphine palladium being dissolved in benzole soln, by 1:0.5~1.2 mass ratio is added step 2 and obtains
To carbon nanotube, after being dispersed with stirring uniformly, brush several times in titanium-based surface, and dried at a temperature of 60~80 DEG C；
Step 4：The titanium-base of the carbon nanotube loaded palladium coating of drying is finally sintered 0.5 at 400~600 DEG C
~2h forms carbon nanotube loaded palladium oxide catalyst coatings in titanium-based plate surface.
Advantageous effect：Compared with prior art, the present invention has the following advantages：(1) by advanced oxidation to easy in waste water
The organic matters such as degradation of organic substances such as formaldehyde, ethyl alcohol carry out efficiently quickly oxidation, while to difficult to degrade as phenolate carries out level-one oxygen
Change；Into two level catalysis oxidation is continued in the light-catalysed tubular reactor of electrolytic catalysis-, organic removal rate in waste water can ensure that
And efficiency, it is often more important that the dosage of active noble metals palladium substantially reduces in catalyst filling, reduces palladium number of dropouts and technique
Catalyst cost；By honeycomb cellular silica gel load active metal oxidation catalyst, and energy under the conditions of catalytic and oxidative electrolysis technology
Enough to carry out effectively degradation removal, especially hardly degraded organic substance your such as phenol to useless Organic substance in water, removal rate is more than 98%；
It (2), effectively will be in waste water by using the catalyst filling block of honeycomb cellular active metal load silica gel as catalyst
Debirs difficult to degrade carry out catalysis oxidation, to realize the biochemical treatment of high-salt wastewater organic matter, and acquire in recycling waste water
Technical grade salt, realize industrial waste salt resource recycling utilize；(3) double-tube type catalytic and oxidative electrolysis technology is used, electrolysis is improved
Catalytic efficiency can effectively improve the release of hydroxyl radical free radical using the Ti base anodes of carbon nanotube loaded Metal Palladium oxide covering
Efficiency improves anode region oxidation operation removal efficiency.
Description of the drawings
Fig. 1 is the structure of process unit associated with organic matter advanced oxidation and electrolytic catalysis in high-salt wastewater of the present invention
Schematic diagram.
Wherein, wastewater disposal basin 1, coarse filter 2, advanced oxidation device 3, tubular reactor 4, buffer pool 5, evaporator 6, crystallization dress
Set 7, centrifuge 8.
Specific implementation mode
In the following with reference to the drawings and specific embodiments, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate
It the present invention rather than limits the scope of the invention, after having read the present invention, those skilled in the art are to of the invention each
The modification of kind equivalent form falls within the application range as defined in the appended claims.
The preparation process of silicon substrate supported active palladium catalyst is as follows：
First, the sodium silicate solution of 20% mass concentration is prepared, be used in combination sodium hydroxide adjust pH value 12~13 it
Between, formation obtains weighing solution；In addition palladium bichloride is dissolved in 20~30% dilute hydrochloric acid and obtains palladium chloride solution, then stirred
It mixes down, which is slowly added to carry out hybrid reaction in sodium silicate solution, the hydroxide for obtaining silica gel and palladium is total
The sediment of doping, during being somebody's turn to do, the mass ratio of sodium metasilicate and Metal Palladium is 10:2~2.5.
Then, ph values are adjusted in the range of 6-8, continue to keep aging reaction at least 2h or more, it is ensured that the hydrogen of Metal Palladium
Oxide carries out being bonded load completely with silica gel during being co-deposited with silica gel, reduces Metal Palladium turnover rate.Then by aging
Sediment is filtered separation afterwards, and organic palladium catalyst is dried to obtain at 50~60 DEG C；
Then, by organic palladium catalyst and methyl cellulose binder according to 1:0.1~0.2 mass ratio is mixed,
Honeycomb green body is formed under mould action, and 24 or more drying avoids high-temperature roasting to reduce green body liquid phase component content
The uneven oversintering of Shi Zaocheng filling bodies influences catalytic activity；
Finally, after carrying out 0.5~2h of roasting at a temperature of green body being placed in 400~600 DEG C, the catalysis of high-specific surface area is obtained
Agent honeycomb filling body.
The preparation of electrolytic catalysis anode：
Step 1：Titanium base is dried after oil removing, pickling successively spare；
Step 2：At 50~60 DEG C, carbon nanotube is immersed in chloroazotic acid carry out it is acidic activated after, with pure water to ph
Value is in 6-8, then drying for standby；
Step 3：Then after tetra-triphenylphosphine palladium being dissolved in benzole soln, by 1:0.7 mass ratio addition step 2 obtains carbon and receives
Mitron after being dispersed with stirring uniformly, is uniformly brushed and is dried at a temperature of 60~80 DEG C after the pipe surface of titanium-based middle level；It repeats to brush and dry
Dry step 3 time or more；
Step 4：The titanium-base of the carbon nanotube loaded palladium coating of drying is finally sintered 0.5 at 400~600 DEG C
~2h, in titanium-based middle level, pipe surface forms carbon nanotube loaded palladium oxide catalyst coatings.
As shown in Figure 1, high-salt wastewater organic matter catalytic and oxidative electrolysis technology treatment process device, including wastewater disposal basin, and pass through
Coarse filter that pipeline pump is connect with wastewater disposal basin successively, advanced oxidation device, tubular reactor, buffer pool, evaporator, crystallization apparatus
And centrifuge, the tubular reactor include inner tube, middle tube and outer tube, the positive conduct of the middle tube connection power supply
The surfaces externally and internally of electrolytic anode, the middle tube is coated with carbon nanotube loaded palladium metal oxide coating, the inner tube
It is separately connected power cathode with outer tube, catalyst filling is equipped between the middle tube and inner tube and outer tube.
When work, waste water, which is fed in by pipeline pump in tubular reactor, to be flowed, and electrolysis generation hydroxyl is powered certainly in 5~24V
By carrying out oxidative degradation removal to useless Organic substance in water under base and catalytic filler effect.
Jiangxi petrochemical industry synthesis factory waste water is handled, waste water quality is as follows：Sodium sulphate salt content about 7%, COD contents
For 224ppm, ammonia-nitrogen content is 4~5ppm, and sodium phenolate is 2~4%, the also cyanide containing 0.1~0.2ppm, by processing
Afterwards, COD is down to 12ppm, removal rate 94% in waste water, and recycling obtains the sulfuric acid for meeting technical grade that impurity content is less than 1%
Sodium salt.
Claims (7)
1. processing method associated with organic matter advanced oxidation and electrolytic catalysis in a kind of high-salt wastewater, it is characterised in that：Including with
Lower step：
Step 1：Industrial wastewater carries out oil removing, filtering by coarse filter, removes the suspended matter and colloidal substance in waste water；
Step 2：Industrial wastewater after coarse filtration is re-fed into advanced oxidation device, is passed through hydrogen peroxide and ozone, and be catalyzed
Under the action of agent filler, carry out advanced catalytic oxidation reaction, the advanced oxidation device be plural serial stage catalytic tower, every grade
Catalyst filling is mounted in catalytic tower, and tower top is formed with bottom of tower by pipeline pump and is connected by circulation, and to waste water in tower
Carry out cycle catalysis oxidation；
Step 3：The waste water handled by advanced oxidation is then sent into catalytic and oxidative electrolysis technology device, in the effect of catalyst filling
Under, apply 5~24V voltages, and under ultraviolet light, carries out hardly degraded organic substance in electrolytic oxidation degrading waste water, pass through inspection
The COD contents of waste water at sample outlet are surveyed, when hit the target is discharged；
Step 4：Waste water after catalytic and oxidative electrolysis technology, is sent into crystallizing evaporator to be evaporated condensing crystallizing and recycle and is provided
The Nacl in source；Waste water after evaporative condenser, which continues to be fed into, carries out biochemical treatment in biochemical device, it is laggard to meet discharge standard
Row discharge recycles.
2. processing method associated with organic matter advanced oxidation and electrolytic catalysis in high-salt wastewater according to claim 1, special
Sign is：The catalyst filling be using silica gel as carrier, carried metal palladium, iron or silver active component.
3. processing method associated with organic matter advanced oxidation and electrolytic catalysis in high-salt wastewater according to claim 2, special
Sign is：Active component is the oxide of Metal Palladium or/and iron in the catalyst.
4. processing method associated with organic matter advanced oxidation and electrolytic catalysis in high-salt wastewater according to claim 3, special
Sign is：The load capacity of the oxide of the Metal Palladium or/and iron is 4~12%.
5. processing method associated with organic matter advanced oxidation and electrolytic catalysis in high-salt wastewater according to claim 4, special
Sign is：The preparation method of the catalyst is as follows：
First, the sodium silicate solution of 20% mass concentration is prepared, is used in combination sodium hydroxide to adjust pH value between 12~13, shape
At obtaining weighing solution；In addition palladium bichloride is dissolved in 20~30% dilute hydrochloric acid and obtains palladium chloride solution, then under stiring,
The palladium chloride solution is slowly added to carry out hybrid reaction in sodium silicate solution, obtains the hydroxide codope of silica gel and palladium
Sediment, during being somebody's turn to do, the mass ratio of sodium metasilicate and Metal Palladium is 10:0.5~1.2.
Then, ph values are adjusted in the range of 6-8, continue to keep aging reaction at least 2h or more, then by sediment after aging
It is filtered separation, and is dried to obtain organic palladium catalyst at 50~60 DEG C；
Then, by organic palladium catalyst and methyl cellulose binder according to 1:0.1~0.2 mass ratio is mixed, in mould
Honeycomb green body, and dry 24 or more are formed under tool effect, are reduced green body liquid phase component content, are avoided causing when high-temperature roasting
The chap of filling body and surface layer oversintering, influence catalytic activity；
Finally, after carrying out 0.5~2h of roasting at a temperature of green body being placed in 400~600 DEG C, the catalyst bee of high-specific surface area is obtained
Nest filling body.
6. process unit associated with organic matter advanced oxidation and electrolytic catalysis in a kind of high-salt wastewater, it is characterised in that：Including useless
Pond, and connect with wastewater disposal basin successively by pipeline pump coarse filter, advanced oxidation device, tubular reactor, buffer pool, steaming
Device, crystallization apparatus and centrifuge are sent out, the tubular reactor includes inner tube, middle tube and outer tube, the middle tube connection
The anode of power supply is coated with carbon nanotube loaded palladium metal oxide and applies as electrolytic anode, the surfaces externally and internally of the middle tube
Layer, the inner tube and outer tube are separately connected power cathode, and catalysis is equipped between the middle tube and inner tube and outer tube
Agent filler.
7. high-salt wastewater organic matter electrolytic catalysis couples advanced oxidation processing unit according to claim 6, it is characterised in that：
The carbon nanotube loaded palladium metal oxide coating preparation process of the middle tube surfaces externally and internally is as follows：
Step 1：Titanium base is dried after oil removing, pickling successively spare；
Step 2：At 50~60 DEG C, carbon nanotube is immersed in chloroazotic acid carry out it is acidic activated after, existed with pure water to ph values
Then 6-8 is dried；
Step 3：Then after tetra-triphenylphosphine palladium being dissolved in benzole soln, by 1:0.5~1.2 mass ratio is added step 2 and obtains carbon
Nanotube is brushed in titanium-based surface, and dried at a temperature of 60~80 DEG C several times after being dispersed with stirring uniformly；
Step 4：The titanium-base of the carbon nanotube loaded palladium coating of drying is finally sintered 0.5 at 400~600 DEG C~
2h forms carbon nanotube loaded palladium oxide catalyst coatings in titanium-based plate surface.
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