CN108558084B - Treatment method and device for electrolytic catalysis coupling advanced oxidation of organic matters in high-salt wastewater - Google Patents
Treatment method and device for electrolytic catalysis coupling advanced oxidation of organic matters in high-salt wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 40
- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 238000011282 treatment Methods 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000008878 coupling Effects 0.000 title claims abstract description 10
- 238000010168 coupling process Methods 0.000 title claims abstract description 10
- 238000005859 coupling reaction Methods 0.000 title claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 8
- 230000003197 catalytic effect Effects 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 16
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002425 crystallisation Methods 0.000 claims abstract description 13
- 230000008025 crystallization Effects 0.000 claims abstract description 13
- 239000005416 organic matter Substances 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010842 industrial wastewater Substances 0.000 claims abstract description 6
- 238000004064 recycling Methods 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 5
- 239000000084 colloidal system Substances 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 238000001704 evaporation Methods 0.000 claims abstract description 3
- 230000008020 evaporation Effects 0.000 claims abstract description 3
- 238000005070 sampling Methods 0.000 claims abstract description 3
- 238000007599 discharging Methods 0.000 claims abstract 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 49
- 239000003054 catalyst Substances 0.000 claims description 26
- 229910052763 palladium Inorganic materials 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000002041 carbon nanotube Substances 0.000 claims description 23
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 23
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- 239000000945 filler Substances 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 13
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal 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
- 239000011248 coating agent Substances 0.000 claims description 9
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 9
- 239000000741 silica gel Substances 0.000 claims description 9
- 229910002027 silica gel 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
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000758 substrate Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- -1 palladium metal oxide Chemical class 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 230000009471 action Effects 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 230000001680 brushing effect Effects 0.000 claims description 4
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 3
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- 238000011068 loading method Methods 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
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 claims description 3
- 238000005554 pickling Methods 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000010815 organic waste Substances 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
- 238000005303 weighing Methods 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 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
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005137 deposition process Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method 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
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
-
- 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
- C02F1/46—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
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/782—Ozone generators
Abstract
The invention discloses a method and a device for treating organic matter in high-salt wastewater by electrolytic catalysis coupling advanced oxidation, comprising the following steps: removing oil and filtering industrial wastewater through a coarse filter to remove suspended matters and colloid substances in the wastewater; feeding the industrial wastewater after coarse filtration into a tubular reactor, applying 5-24V voltage between a tube body and a negative electrode under the condition of introducing hydrogen peroxide and ozone to perform electrolytic catalytic oxidation, detecting COD content of the wastewater at an outlet end through a sampling port, and discharging water until a preset index is reached; delivering the wastewater subjected to electrolytic catalytic oxidation into a crystallization evaporator for evaporation, concentration and crystallization, centrifuging, drying and recycling the concentrated crystal to obtain industrial salt; the gas phase of the crystallization evaporator is condensed and then sent into a biochemical device for biochemical treatment, and is discharged or recycled after meeting the discharge standard. The invention effectively degrades organic matters in the wastewater by means of coupling electrolytic oxidation with advanced catalytic oxidation, and recovers industrial salt.
Description
Technical Field
The invention belongs to the technical field of environmental protection and chemical industry, and particularly relates to equipment and a method for treating wastewater containing nondegradable phenol sodium salt.
Background
With the rapid development of the industry in China, the sewage discharge is increasingly increased, a large number of chemicals which are difficult to biodegrade are discharged into the environment in the form of waste water, so that serious pollution of water resources is caused, and the chemical wastewater becomes a pain point and a focus of attention of social development. Particularly, the anhydrous discharged in the industrial production processes of coking, petrochemical, printing and dyeing, pharmacy, organic synthesis and the like contains a large amount of toxic organic matters and high-concentration salts, such as sodium sulfate, sodium chloride, sodium nitrate, copper sulfate and the like, so that the industrial salts in the wastewater cannot directly pass through biochemical treatment means, and the industrial salts in the wastewater need to be subjected to crystallization separation and then to biochemical treatment, thereby generating toxic industrial waste salts, and the industrial salt recycling treatment cannot be realized; meanwhile, as organic matters in the wastewater contain formaldehyde, alcohols and refractory and high-boiling-point phenolic matters, conventional catalytic oxidation cannot be processed at present, and salt obtained by distillation and crystallization of salt-containing wastewater is waste salt and cannot be recycled. The advanced oxidation is used as a newly developed oxidation means, free radicals with extremely strong oxidation capability are obtained by screening proper catalysts, macromolecular organic waste with high bond energy in water is oxidized into small molecules with easy degradation and low toxicity, but the catalysts and core process technology are imported from abroad, the cost is high, and the development of domestic sewage treatment technology is not facilitated.
Disclosure of Invention
The invention aims to: the invention aims to solve the problems and the defects existing in the prior art and provide a device and a method for electrolytic catalytic oxidation treatment of high-salt wastewater organic matters.
The technical scheme is as follows: in order to solve the technical problems, the invention adopts the following technical scheme: a method for treating organic matter in high-salt wastewater by electrolytic catalysis coupling advanced oxidation comprises the following steps:
step 1: removing oil and filtering industrial wastewater through a coarse filter to remove suspended matters and colloid substances in the wastewater;
step 2: feeding the industrial wastewater after coarse filtration into a tubular reactor, wherein a catalyst filler is arranged in the tubular reactor, applying 5-24V voltage between a tube body and a negative electrode under the condition of introducing hydrogen peroxide and ozone to perform electrolytic catalytic oxidation, and detecting the COD content of the wastewater at an outlet end through a sampling port to reach a preset index to perform water discharge;
step 3: delivering the wastewater subjected to electrolytic catalytic oxidation into a crystallization evaporator for evaporation, concentration and crystallization, centrifuging, drying and recycling the concentrated crystal to obtain industrial salt; the gas phase of the crystallization evaporator is condensed and then sent into a biochemical device for biochemical treatment, and is discharged or recycled after meeting the discharge standard.
Preferably, the catalyst filler is an active component which takes silica gel as a carrier and loads metal palladium, iron or silver.
Preferably, the active component in the catalyst is metallic palladium or/and iron oxide.
Preferably, the loading of the metallic palladium or/and iron oxide is 10-20%.
Preferably, the preparation method of the catalyst comprises the following steps:
firstly, preparing a sodium silicate solution with the mass concentration of 20%, and regulating the PH value to be between 12 and 13 by sodium hydroxide to form a weighing solution; in addition, palladium chloride is dissolved in 20-30% of dilute hydrochloric acid to obtain palladium chloride solution, then the palladium chloride solution is slowly added into sodium silicate solution under stirring to carry out mixing reaction, and a precipitate co-doped with silica gel and palladium hydroxide is obtained, wherein in the process, the mass ratio of sodium silicate to metal palladium is 10:2-2.5.
Then adjusting the pH value to be in the range of 6-8, continuously maintaining the aging reaction for at least more than 2 hours, filtering and separating the aged precipitate, and drying at 50-60 ℃ to obtain the organic palladium catalyst;
then, mixing an organic palladium catalyst and a methyl cellulose adhesive according to the mass ratio of 1:0.1-0.2, forming a honeycomb structure green body under the action of a die, and drying more than 24 to reduce the content of liquid phase components of the green body, so as to avoid the influence of uneven overburning of a filler body on catalytic activity during high-temperature roasting;
finally, the green body is placed at 400-600 ℃ for roasting for 0.5-2 hours, and the catalyst honeycomb filler body with high specific surface area is obtained.
The invention also provides a high-salt wastewater organic matter electrolytic catalytic oxidation treatment device, which comprises a power supply and a reactor, wherein the reactor is a tubular reactor, the tubular reactor comprises an inner layer tube, a middle layer tube and an outer layer tube, the middle layer tube is connected with the anode of the power supply to serve as an electrolytic anode, the inner surface and the outer surface of the middle layer tube are coated with carbon nano tube supported palladium metal oxide coatings, the inner layer tube and the outer layer tube are respectively connected with the cathode of the power supply, and catalyst fillers are arranged between the middle layer tube and the inner layer tube and between the middle layer tube and the outer layer tube; the inner layer tube is provided with an interface for connecting the ozone generator and hydrogen peroxide.
Further, the preparation process of the carbon nanotube supported palladium metal oxide coating on the inner surface and the outer surface of the middle layer tube comprises the following steps:
step 1: sequentially degreasing and pickling a titanium substrate, and airing for later use;
step 2: immersing the carbon nano tube in aqua regia at 50-60 ℃ for acidic activation, washing with pure water until the pH value is 6-8, and then drying;
step 3: then, after dissolving tetraphenylphosphine palladium in a benzene solution, adding the benzene solution into the carbon nano tube obtained in the step 2 according to the mass ratio of 1:0.5-1.2, stirring and dispersing uniformly, brushing the carbon nano tube on the surface of a titanium base for multiple times, and drying the carbon nano tube at the temperature of 60-80 ℃;
step 4: and finally, sintering the dried titanium substrate with the carbon nanotube supported palladium coating at 400-600 ℃ for 0.5-2 h to form the carbon nanotube supported palladium oxide catalytic coating on the surface of the titanium substrate.
The beneficial effects are that: compared with the prior art, the invention has the following advantages: (1) The honeycomb porous silica gel is used for loading an active metal oxidation catalyst, and organic matters in the wastewater can be effectively degraded and removed under the condition of electrolytic catalytic oxidation, and particularly, the removal rate of refractory organic matters such as phenol is more than 98%; (2) The catalyst filler blocks of the honeycomb porous active metal supported silica gel are used as catalysts, so that organic wastes difficult to degrade in the wastewater are effectively subjected to catalytic oxidation, the biochemical treatment of high-salt wastewater organic matters is realized, industrial-grade salt in the wastewater is collected and recycled, and the recycling of the industrial waste salt is realized; (3) The double-layer tube type electrolytic catalytic oxidation is adopted, so that the electrolytic catalytic efficiency is improved, and the Ti-based anode with the carbon nanotube supported metal palladium oxide coating can effectively improve the release efficiency of hydroxyl radicals and improve the organic matter oxidation removal efficiency in the anode region.
Drawings
FIG. 1 is a schematic diagram of the electrolytic catalytic oxidation treatment device for high-salt wastewater organic matters.
Wherein, wastewater tank 1, coarse filter 2, tubular reactor 3, buffer tank 4, evaporator 5, crystallization device 6, centrifuge 7, biochemical device 8.
Detailed Description
The present invention is further illustrated in the accompanying drawings and detailed description which are to be understood as being merely illustrative of the invention and not limiting of its scope, and various modifications of the invention, which are equivalent to those skilled in the art upon reading the invention, will fall within the scope of the invention as defined in the appended claims.
The preparation process of the silicon-based supported active palladium catalyst comprises the following steps:
firstly, preparing a sodium silicate solution with the mass concentration of 20%, and regulating the PH value to be between 12 and 13 by sodium hydroxide to form a weighing solution; in addition, palladium chloride is dissolved in 20-30% of dilute hydrochloric acid to obtain palladium chloride solution, then the palladium chloride solution is slowly added into sodium silicate solution under stirring to carry out mixing reaction, and a precipitate co-doped with silica gel and palladium hydroxide is obtained, wherein in the process, the mass ratio of sodium silicate to metal palladium is 10:2-2.5.
And then, adjusting the pH value to be in the range of 6-8, continuously maintaining the aging reaction for at least more than 2 hours, ensuring that the hydroxide of the metal palladium and the silica gel are completely bonded and loaded in the co-deposition process with the silica gel, and reducing the loss rate of the metal palladium. Filtering and separating the aged precipitate, and drying at 50-60 ℃ to obtain an organic palladium catalyst;
then, mixing an organic palladium catalyst and a methyl cellulose adhesive according to the mass ratio of 1:0.1-0.2, forming a honeycomb structure green body under the action of a die, and drying more than 24 to reduce the content of liquid phase components of the green body, so as to avoid the influence of uneven overburning of a filler body on catalytic activity during high-temperature roasting;
finally, the green body is placed at 400-600 ℃ for roasting for 0.5-2 hours, and the catalyst honeycomb filler body with high specific surface area is obtained.
Preparation of an electrolytic catalytic anode:
step 1: sequentially degreasing and pickling a titanium substrate, and airing for later use;
step 2: immersing the carbon nano tube in aqua regia at 50-60 ℃ for acidic activation, washing with pure water until the pH value is 6-8, and then drying for later use;
step 3: then, after dissolving tetraphenylphosphine palladium in a benzene solution, adding the benzene solution into the carbon nano tube obtained in the step 2 according to the mass ratio of 1:0.7, uniformly stirring and dispersing, uniformly brushing the carbon nano tube on the surface of the titanium-based middle layer tube, and drying at the temperature of 60-80 ℃; repeating the steps of brushing and drying for more than 3 times;
step 4: and finally, sintering the dried titanium substrate with the carbon nano tube supported palladium coating at 400-600 ℃ for 0.5-2 h to form the carbon nano tube supported palladium oxide catalytic coating on the surface of the middle layer tube in the titanium base.
As shown in figure 1, the high-salt wastewater organic matter electrolytic catalytic oxidation treatment process device mainly comprises a coarse filter 2, a tubular reactor 3, a buffer tank 4, an evaporator 5, a crystallization device 6, a centrifugal machine 7 and a biochemical device 8, wherein the tubular reactor can be used in multistage parallel or in series, and the efficiency is improved. The tubular reactor mainly comprises an inner layer tube, a middle layer tube and an outer layer tube, wherein the middle layer tube is connected with the positive electrode of a power supply to serve as an electrolytic anode, the inner surface and the outer surface of the middle layer tube are both coated with carbon nano tube loaded palladium metal oxide coatings, the inner layer tube and the outer layer tube are respectively connected with the negative electrode of the power supply, and an insulating layer is arranged on the outer wall of the outer layer tube. Catalyst filler is arranged between the middle layer pipe and the inner layer pipe as well as between the middle layer pipe and the outer layer pipe; the inner pipe is provided with an interface for connecting the ozone generator and the hydrogen peroxide, waste water is pumped by a pipeline to flow in the pipe reactor during working, hydroxyl free radicals are generated by electrifying and electrolyzing at 5-24V, and meanwhile, under the action of the common coupling of the ozone and the hydrogen peroxide, organic matters in the waste water, especially refractory organic matters such as phenol, are removed by oxidative degradation under the action of catalytic filler.
The wastewater of a petrochemical synthesis plant in Jiangxi is treated, and the water quality of the wastewater is as follows: the sodium sulfate has a salt content of about 7%, a COD content of 224ppm, an ammonia nitrogen content of 4-5 ppm, a sodium phenolate content of 2-4% and cyanide content of 0.1-0.2 ppm, and after treatment, the COD in the wastewater is reduced to 12ppm, the removal rate is 94%, and the sodium sulfate which has an impurity content of less than 1% and meets the industrial grade is recovered.
Claims (4)
1. A method for treating organic matter in high-salt wastewater by electrolytic catalysis coupling advanced oxidation is characterized by comprising the following steps:
step 1: removing oil and filtering industrial wastewater through a coarse filter to remove suspended matters and colloid substances in the wastewater;
step 2: feeding the industrial wastewater after coarse filtration into a tubular reactor, wherein a catalyst filler is arranged in the tubular reactor, applying 5-24V voltage between a tube body and a negative electrode under the condition of introducing hydrogen peroxide and ozone to perform electrolytic catalytic oxidation, and detecting the COD content of the wastewater at an outlet end through a sampling port to reach a preset index to perform water discharge;
step 3: delivering the wastewater subjected to electrolytic catalytic oxidation into a crystallization evaporator for evaporation, concentration and crystallization, centrifuging, drying and recycling the concentrated crystal to obtain industrial salt; condensing the gas phase of the crystallization evaporator, sending the condensed gas phase into a biochemical device for biochemical treatment, and discharging or recycling the condensed gas phase after meeting the discharge standard;
the catalyst filler is an active component which takes silica gel as a carrier and loads metal palladium, iron or silver;
the high-salt wastewater organic matter electrolytic catalytic oxidation treatment device comprises a power supply and a reactor, wherein the reactor is a tubular reactor, the tubular reactor comprises an inner layer tube, a middle layer tube and an outer layer tube, the middle layer tube is connected with the anode of the power supply and is used as an electrolytic anode, the inner surface and the outer surface of the middle layer tube are coated with carbon nano tube supported palladium metal oxide coatings, the inner layer tube and the outer layer tube are respectively connected with the cathode of the power supply, and catalyst fillers are arranged between the middle layer tube and the inner layer tube and between the middle layer tube and the outer layer tube; the inner layer tube is provided with an interface for connecting an ozone generator and hydrogen peroxide;
the preparation process of the carbon nanotube supported palladium metal oxide coating on the inner surface and the outer surface of the middle layer pipe comprises the following steps:
step 1: sequentially degreasing and pickling a titanium substrate, and airing for later use;
step 2: immersing the carbon nano tube in aqua regia at 50-60 ℃ for acidic activation, washing with pure water until the pH value is 6-8, and then drying;
step 3: then, after dissolving tetraphenylphosphine palladium in a benzene solution, adding the benzene solution into the carbon nano tube obtained in the step 2 according to the mass ratio of 1:0.5-1.2, stirring and dispersing uniformly, brushing the carbon nano tube on the surface of a titanium base for multiple times, and drying the carbon nano tube at the temperature of 60-80 ℃;
step 4: and finally, sintering the dried titanium substrate with the carbon nanotube supported palladium coating at 400-600 ℃ for 0.5-2 h to form the carbon nanotube supported palladium oxide catalytic coating on the surface of the titanium substrate.
2. The method for treating the organic matter in the high-salt wastewater by electrolytic catalysis coupling advanced oxidation according to claim 1, which is characterized by comprising the following steps of: the active component in the catalyst is metallic palladium or/and iron oxide.
3. The method for treating the organic matter in the high-salt wastewater by electrolytic catalysis coupling advanced oxidation according to claim 2, which is characterized by comprising the following steps of: the loading of the metallic palladium or/and the iron oxide is 10-20%.
4. The method for treating the organic matter in the high-salt wastewater by electrolytic catalysis coupling advanced oxidation according to claim 3, which is characterized in that: the preparation method of the catalyst comprises the following steps:
firstly, preparing a sodium silicate solution with the mass concentration of 20%, and regulating the pH value to be between 12 and 13 by using sodium hydroxide; in addition, palladium chloride is dissolved in 20-30% of dilute hydrochloric acid to obtain a palladium chloride solution, then the palladium chloride solution is slowly added into a sodium silicate solution under stirring to carry out a mixing reaction, and a precipitate co-doped with silica gel and palladium hydroxide is obtained, wherein the mass ratio of the sodium silicate to the metal palladium is 10:2-2.5;
then, regulating the pH value to be in the range of 6-8, continuously maintaining the aging reaction for at least more than 2 hours, filtering and separating the aged precipitate, and drying at 50-60 ℃ to obtain the organic palladium catalyst;
then, mixing an organic palladium catalyst and a methyl cellulose adhesive according to the mass ratio of 1:0.1-0.2, forming a honeycomb structure green body under the action of a die, and drying for more than 24 hours to reduce the content of liquid phase components of the green body;
finally, the green body is placed at 400-600 ℃ for roasting for 0.5-2 hours, and the catalyst honeycomb filler body with high specific surface area is obtained.
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