CN115400802B - Preparation method of hydrogen peroxide remover in electronic waste liquid and method for treating hydrogen peroxide - Google Patents
Preparation method of hydrogen peroxide remover in electronic waste liquid and method for treating hydrogen peroxide Download PDFInfo
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- CN115400802B CN115400802B CN202211063530.1A CN202211063530A CN115400802B CN 115400802 B CN115400802 B CN 115400802B CN 202211063530 A CN202211063530 A CN 202211063530A CN 115400802 B CN115400802 B CN 115400802B
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 180
- 239000007788 liquid Substances 0.000 title claims abstract description 167
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000010793 electronic waste Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 39
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000010936 titanium Substances 0.000 claims abstract description 30
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 30
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims abstract description 26
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 13
- 239000008346 aqueous phase Substances 0.000 claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 11
- 238000000518 rheometry Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 229920005591 polysilicon Polymers 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 239000011863 silicon-based powder Substances 0.000 claims abstract description 7
- 238000002791 soaking Methods 0.000 claims abstract description 6
- 229910001338 liquidmetal Inorganic materials 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000011068 loading method Methods 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 7
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 7
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 7
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical compound CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 claims description 5
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 5
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims description 4
- 230000008961 swelling Effects 0.000 claims description 4
- 239000002562 thickening agent Substances 0.000 claims description 4
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 2
- 229920001214 Polysorbate 60 Polymers 0.000 claims description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 2
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 2
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 239000000230 xanthan gum Substances 0.000 claims description 2
- 229920001285 xanthan gum Polymers 0.000 claims description 2
- 235000010493 xanthan gum Nutrition 0.000 claims description 2
- 229940082509 xanthan gum Drugs 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 3
- 230000000996 additive effect Effects 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- 235000000380 Nyssa aquatica Nutrition 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 51
- 239000002699 waste material Substances 0.000 abstract description 44
- 239000002253 acid Substances 0.000 abstract description 39
- 238000010438 heat treatment Methods 0.000 abstract description 27
- 229910052751 metal Inorganic materials 0.000 abstract description 23
- 239000002184 metal Substances 0.000 abstract description 23
- 238000001816 cooling Methods 0.000 abstract description 19
- 238000007254 oxidation reaction Methods 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 11
- 238000007599 discharging Methods 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 description 129
- 238000006243 chemical reaction Methods 0.000 description 68
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 229910017604 nitric acid Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 230000002378 acidificating effect Effects 0.000 description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- -1 nitrate ions Chemical class 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229910003460 diamond Inorganic materials 0.000 description 3
- 239000010432 diamond Substances 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- 238000010517 secondary reaction Methods 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 238000012946 outsourcing Methods 0.000 description 2
- FHHJDRFHHWUPDG-UHFFFAOYSA-N peroxysulfuric acid Chemical group OOS(O)(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical group [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000004972 metal peroxides Chemical class 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
- C02F2101/10—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/346—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from semiconductor processing, e.g. waste water from polishing of wafers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
The invention discloses a preparation method of a hydrogen peroxide remover in electronic waste liquid and a method for treating hydrogen peroxide, wherein the preparation method of the hydrogen peroxide remover comprises the following steps: preparing a titanyl sulfate solution, and mixing the titanyl sulfate solution with PVP solution to obtain a mixed solution; soaking polycrystalline silicon powder in the mixed solution, and calcining to obtain tetravalent titanium loaded polycrystalline silicon nano powder; then mixing the aqueous phase rheology modifying auxiliary agent and the nonionic surfactant A, B, and adding tetravalent titanium loaded polysilicon powder to prepare the liquid metal active catalyst. The method for treating hydrogen peroxide comprises the following steps: adding a hydrogen peroxide remover into the electronic waste liquid to be treated, heating, performing catalytic oxidation reaction to reduce the concentration of hydrogen peroxide, cooling the treated electronic waste liquid, and discharging; the addition amount of the hydrogen peroxide remover is 2-5 mg/L, and the addition amount of the hydrogen peroxide remover prepared by the method is small when the wafer waste acid cleaning liquid is treated, and compared with other processes for adding metal salt, the addition amount of the hydrogen peroxide remover is reduced by 15-200 times.
Description
Technical Field
The invention relates to a preparation method and application of a solvent for treating waste liquid, in particular to a preparation method and application of a reaction reagent for treating acidic cleaning liquid.
Background
The electronic industry adopts mixed solution of sulfuric acid and hydrogen peroxide in the wafer cleaning process, wherein the concentration of the sulfuric acid is 40-75%, and the concentration of the hydrogen peroxide is 1-10% as a surface organic matter and residual metal cleaning agent. The waste liquid after cleaning still contains high-concentration sulfuric acid and hydrogen peroxide, and the sulfuric acid and the hydrogen peroxide generate a peroxymonosulfuric acid structure due to the chemical characteristics of the sulfuric acid and the hydrogen peroxide, so that the hydrogen peroxide under the structure is difficult to degrade by itself, and oxygen is slowly released when the hydrogen peroxide contacts high temperature, so that the risk of explosion is brought.
In order to avoid the risks, the acidic cleaning agent needs to destroy the structure of the peroxymonosulfuric acid and reduce the hydrogen peroxide into oxygen and water. The current commonly adopted treatment method is a batch hydrochloric acid/nitric acid oxidation method, high-concentration hydrochloric acid/nitric acid is added into an acidic cleaning agent, the solution is heated to generate hypochlorous acid, chlorine gas/nitrogen dioxide and other substances with high oxidability, the substances react with hydrogen peroxide in the solution, and finally the concentration of the hydrogen peroxide is reduced to below 5000mg/L so as to reach the out-of-commission cleaning standard.
The batch hydrochloric acid/nitric acid oxidation process suffers from the following disadvantages: (1) The addition amount of hydrochloric acid/nitric acid is large, and 10-50% of the concentration of hydrogen peroxide is needed to be added; (2) Hypochlorous acid, chlorine gas, nitrogen dioxide and other substances generated by hydrochloric acid/nitric acid have high oxidability, and have high quality for equipment materials and construction, so that leakage is often caused at the joint of equipment pipelines. (3) The hydrochloric acid/nitric acid oxidation method has the advantages that a large amount of chloride ions and nitrate ions remain in the waste liquid, so that secondary pollution of the waste liquid is caused; (4) The batch method has low reaction efficiency, so that the unit treatment waste liquid amount is far lower than that of the continuous treatment process under the condition of the same occupied area, the treatment capacity can be reduced by more than 2 times, and the construction cost of a process system is increased.
Disclosure of Invention
The invention aims to: the invention aims to provide a preparation method of a hydrogen peroxide remover in electronic waste liquid, which has small addition amount and good removal effect;
the second object of the invention is to provide a method for treating hydrogen peroxide in electronic waste liquid by using the hydrogen peroxide remover prepared by the method.
The technical scheme is as follows: the preparation method of the hydrogen peroxide remover in the electronic waste liquid comprises the following steps:
(1) Adding the titanyl sulfate solid powder into hot concentrated sulfuric acid to obtain a titanyl sulfate solution;
(2) Adding a titanyl sulfate solution into a PVP solution to obtain a mixed solution for loading;
(3) Soaking polycrystalline silicon powder in a mixed solution for loading, and calcining to obtain tetravalent titanium loaded polycrystalline silicon nano powder;
(4) Mixing an aqueous phase rheology modifying auxiliary agent, a nonionic surfactant A and a nonionic surfactant B, adding tetravalent titanium-loaded polysilicon powder, and mixing to obtain a liquid metal active catalyst;
the aqueous phase rheology modifying auxiliary agent is hydroxyethyl cellulose ether, hydroxypropyl cellulose or alkali swelling non-association thickener; when the aqueous phase rheology modifying auxiliary agent is an alkali swelling non-association thickener, the aqueous phase rheology modifying auxiliary agent also comprises ammonia water or xanthan gum; the nonionic surfactant A is any one of condensate of octyl phenol and ethylene oxide, polyoxyethylene ether, fatty alcohol polyoxyethylene ether or condensate of fatty alcohol and ethylene oxide; the nonionic surfactant B is polyethylene glycol, span 80 or tween 60.
Wherein, in the step (1), the concentration of the titanyl sulfate solution is 50-70 wt%; heating the concentrated sulfuric acid to 120-130 ℃; the addition amount of the titanyl sulfate solid powder is 600-1200 g/L H 2 SO 4 。
In the step (2), the mass ratio of the titanyl sulfate solution to the PVP solution is 3:20-5:22.
Wherein in the step (3), the calcining temperature is 660-760 ℃, the calcining time is 20-50 min, and the heating rate is 100 ℃/30min.
In the step (4), the mass ratio of the tetravalent titanium loaded polycrystalline silicon powder to the aqueous phase rheology modification auxiliary agent, the nonionic surfactant A and the nonionic surfactant B is 70:8:10:10-90:15:20:30.
The method for treating the hydrogen peroxide in the electronic waste liquid by using the hydrogen peroxide remover prepared by the method comprises the following steps: adding a hydrogen peroxide remover into the electronic waste liquid to be treated, heating, performing catalytic oxidation reaction, reducing the concentration of hydrogen peroxide, cooling the treated recovery liquid, and discharging.
Wherein the adding amount of the hydrogen peroxide remover is 2-5 mg/L. The heating temperature is 110-130 ℃, and the reaction time is 1-5min. Concentrating the treated electronic waste liquid to improve the sulfuric acid concentration in the electronic waste liquid. Specifically, the sulfuric acid concentration is raised from 50-55 wt% to 55-63 wt%.
The method for treating the hydrogen peroxide in the electronic waste liquid comprises the following specific steps of:
(1) Conveying the hydrogen peroxide remover and the electronic waste liquid to be treated into a mixer for full mixing, and carrying out heat exchange on the mixed liquid in the mixer to heat up the mixed liquid, so as to carry out catalytic oxidation reaction and reduce the concentration of the hydrogen peroxide;
(2) Heat exchange is carried out on the treated recovery liquid, the heat exchange reduces the temperature of the recovery liquid, and meanwhile, the temperature of the electronic waste liquid to be treated is increased;
(3) And discharging the cooled recovery liquid.
And (3) detecting the concentration of the hydrogen peroxide in the treated recovery liquid, discharging if the recovery liquid is qualified, and performing cyclic treatment on the recovery liquid if the recovery liquid is unqualified.
Wherein the treated recovery liquid is separated from the gas generated by the reaction. And (3) discharging the gas generated by the reaction after washing.
As a further preferable scheme, the device used by the method for treating the hydrogen peroxide in the electronic waste liquid by using the hydrogen peroxide remover comprises a micro-channel heat recovery reaction device; the micro-channel heat recovery reaction device comprises a reaction zone and heat recovery layers positioned on two sides of the reaction zone, wherein the reaction zone is formed by arranging a plurality of mutually communicated chambers, each chamber comprises an inner cavity and an outer cavity which are arranged in a nested mode, a channel for fluid circulation is formed in a surrounding area between the inner cavity and the outer cavity, fluid entering the chamber is split at a channel inlet, and the fluid is converged at a channel outlet.
Wherein the profile of the inner cavity at the outlet of the channel is arc-shaped. The outline of the outer cavity is diamond-shaped; the outline of the inner cavity is an inverted triangle, the rhombus and the inverted triangle share an apex to form a channel inlet, and the opposite side is a channel outlet.
Wherein the length ratio of two diagonal lines of the diamond is 1.8-2.2:1. The ratio of the length of the short diagonal line of the section of the inner cavity near the outlet of the channel to the length of the short diagonal line of the section of the inner cavity near the outlet of the channel is 1.8-2.2:1. The ratio of the width of the channel outlet to the linear length of the base of the inverted triangle is 1.8-2.2:1.
Wherein the microchannel heat recovery reaction device is made of silicon carbide material.
The inlet of the micro-channel heat recovery reaction device is respectively communicated with the waste liquid collecting tank and the reaction agent, and the outlet of the micro-channel heat recovery reaction device is respectively connected with a gas washing device for washing gas generated in the heat recovery process, a concentration evaporation device for generating, a cooling device and a recovery liquid collecting tank connected with the cooling device.
The method for treating the hydrogen peroxide in the electronic waste liquid by utilizing the device comprises the following specific steps of:
(1) Delivering the hydrogen peroxide remover and the electronic waste liquid to be treated into a reaction zone for mixing,
introducing a heating medium into the heat recovery layer, heating the mixed solution in the reaction zone, and performing catalytic oxidation reaction;
(2) Separating the treated recovery liquid from the gas generated by the reaction, concentrating the recovery liquid in a concentrating and evaporating device, and discharging the gas after being treated by a gas washing device;
(3) The concentrated recovery liquid enters a heat recovery layer to be used as a heating medium, and exchanges heat with the electronic waste liquid to be treated in the reaction zone;
(4) The recovery liquid from the heat recovery layer is further cooled by a cooling device, if the concentration of hydrogen peroxide in the recovery liquid is qualified, the recovery liquid is discharged, and if the concentration of hydrogen peroxide in the recovery liquid is unqualified, the recovery liquid is subjected to circulating treatment.
Reaction principle: the tetravalent titanium in the active metal and hydrogen peroxide produce catalytic double reaction, and a large amount of free hydroxyl groups, superoxide groups and the like are produced in the process. The free radicals attack the hydrogen peroxide to oxidize the hydrogen peroxide into water to generate hydroxyl superoxide radicals, the hydroxyl superoxide radicals, superoxide radicals and hydroxyl radicals reduce the tetravalent titanium into trivalent titanium, the trivalent titanium reacts with the hydrogen peroxide to generate a large number of free radicals and tetravalent titanium, and the hydroxyl superoxide radicals react with the trivalent titanium to generate tetravalent titanium. The final product is oxygen and water, and tetravalent titanium is not consumed in the reaction. Compared with the common ionic titanium dissolved in the solution, the solution is lost as the treated solution leaves the system, the polycrystalline silicon loaded tetravalent titanium belongs to heterogeneous catalysis, the solid catalysis can increase the time for the active metal to stay in the reactor, the loss is less, and the dosage of the active metal can be greatly reduced.
The beneficial effects are that: compared with the prior art, the invention has the following remarkable effects: (1) The polycrystalline silicon is used for loading tetravalent titanium, so that loss of tetravalent titanium is less, the dosage of the added liquid metal active catalyst is less and is lower than 5mg/L, 2mg/L can be achieved, and compared with the dosage of metal salt of 30 mg/L-400 mg/L in the prior art, the dosage is reduced by 15-200 times; meanwhile, the better hydrogen peroxide removal rate can be still achieved; (2) Compared with the hydrochloric acid/nitric acid oxidation method in the prior art, the method can avoid residual chlorine, hypochlorous acid, nitric acid and other plasma or free strong oxidation substances in the recovered acid. (3) Can avoid secondary pollution caused by the recovery liquid and increase the recovery and utilization value.
Drawings
FIG. 1 is an X-ray diffraction pattern of tetravalent titanium-loaded polycrystalline silicon nanopowder prepared in example 1;
FIG. 2 is a cross-sectional view of a microchannel heat recovery reaction device of the invention;
FIG. 3 is a side view of a microchannel heat recovery reactor of the present invention;
FIG. 4 is a schematic view of the structure of the chamber in the microchannel heat recovery reactor of the present invention;
FIG. 5 is a schematic diagram of an apparatus for treating spent wafer cleaning fluid according to the present invention.
Detailed Description
The present invention is described in further detail below.
Example 1
The preparation method of the hydrogen peroxide remover in the electronic waste liquid comprises the following steps:
the first step: heating 98wt% concentrated sulfuric acid to 120 deg.c, adding solid powder of 99% pure titanyl sulfate into 150-100 g concentrated sulfuric acid to obtain titanyl sulfate solution, and cooling to 25 deg.c.
Second step, preparing the adhesive average molecular weight of 6-10 5 100g to 1000g of deionized water is added and mixed until the polyvinylpyrrolidone is completely dissolved.
And a third step of: the titanyl sulfate solution is slowly added into PVP solution and stirred for 30 minutes, the solution is kept at 25 ℃ in the stirring process, and the danger caused by too fast heat release of sulfuric acid dilution is avoided, so that the mixed solution for loading is obtained.
Fourth step: preparing 800nm polycrystalline silicon powder with purity of 99.99%, soaking 100g in a mixed solution for loading, stirring for 60 minutes, placing in a calcining furnace, heating to 700 ℃ at a heating rate of 100 ℃ every 30 minutes, maintaining the temperature for 30 minutes, and cooling to 25 ℃ to obtain tetravalent titanium loaded polycrystalline silicon nano powder. As shown in FIG. 1, according to the corresponding scattering angle of the intensity of the diffraction peak of the tetravalent titanium loaded polysilicon nano-powder shown in the X-ray diffraction pattern, the literature database speculates that the crystal structure contains polysilicon and tetravalent titanium, wherein the silicon is represented by polysilicon, and the rubble and anatase are represented by tetravalent titanium.
Fifth step: 1000g of deionized water is heated to 50 ℃, 5g of hydroxyethyl cellulose ether is added and stirred until the solution is sticky and transparent, 10g of octyl phenol and ethylene oxide condensate OP-15, 10g of polyoxyethylene ether, 20g of polyethylene glycol with 400 viscosity average molecular weight and 80g of tetravalent titanium-loaded polysilicon are added, and stirring is carried out for 10 minutes at 8000rpm of a vacuum homogenizer, so that a sticky ferrous metal active catalyst is obtained, namely the hydrogen peroxide remover in the electronic waste liquid.
Example 2
The preparation method of the hydrogen peroxide remover in the electronic waste liquid comprises the following steps:
the first step: heating 98wt% concentrated sulfuric acid to 130 ℃, adding 200g to 100g of pure titanyl sulfate 99% solid powder into the concentrated sulfuric acid to obtain titanyl sulfate solution, and cooling to 25 ℃.
Second step, preparing the adhesive average molecular weight of 6-10 5 Is added into 200g to 1800g deionized water and stirred and mixed until the polyvinylpyrrolidone is completely dissolved.
And a third step of: the titanyl sulfate solution is slowly added into PVP solution and stirred for 30 minutes, the solution is kept at 25 ℃ in the stirring process, and the danger caused by too fast heat release of sulfuric acid dilution is avoided, so that the mixed solution for loading is obtained.
Fourth step: preparing 800nm polycrystalline silicon powder with purity of 99.99%, soaking 100g in a mixed solution for loading, stirring for 60 minutes, placing in a calcining furnace, heating to 760 ℃ at a heating rate of 100 ℃ every 30 minutes, maintaining the temperature for 30 minutes, and cooling to 25 ℃ to obtain tetravalent titanium loaded polycrystalline silicon nano powder.
Fifth step: 1000g of deionized water is heated to 50 ℃, 5g of hydroxyethyl cellulose ether is added and stirred until the solution is sticky and transparent, 10g of octyl phenol and ethylene oxide condensate OP-15, 20g of polyoxyethylene ether, 30g of polyethylene glycol with 400 viscosity average molecular weight and 70g of tetravalent titanium-loaded polysilicon are added, and stirring is carried out for 10 minutes at 8000rpm of a vacuum homogenizer, so that a sticky ferrous metal active catalyst is obtained, namely the hydrogen peroxide remover in the electronic waste liquid.
Example 3
The preparation method of the hydrogen peroxide remover in the electronic waste liquid comprises the following steps:
the first step: heating 98wt% concentrated sulfuric acid to 124 ℃, adding 100g to 100g of concentrated sulfuric acid into 99% solid powder of pure titanyl sulfate, and cooling to 25 ℃.
Second step, preparing the adhesive average molecular weight of 6-10 5 Adding 80g to 800g of deionized water, and stirring and mixing until the polyvinylpyrrolidone is completely dissolved.
And a third step of: the titanyl sulfate solution is slowly added into PVP solution and stirred for 30 minutes, the solution is kept at 25 ℃ in the stirring process, and the danger caused by too fast heat release of sulfuric acid dilution is avoided, so that the mixed solution for loading is obtained.
Fourth step: preparing 800nm polycrystalline silicon powder with purity of 99.99%, soaking 100g in a mixed solution for loading, stirring for 60 minutes, placing in a calcining furnace, heating to 660 ℃ at a heating rate of 100 ℃ every 30 minutes, maintaining the temperature for 30 minutes, and cooling to 25 ℃ to obtain tetravalent titanium loaded polycrystalline silicon nano powder.
Fifth step: 1000g of deionized water is heated to 50 ℃, 3g of hydroxyethyl cellulose ether is added and stirred until the solution is sticky and transparent, 5g of octyl phenol and ethylene oxide condensate OP-15, 10g of polyoxyethylene ether, 10g of polyethylene glycol with 400 viscosity average molecular weight and 90g of tetravalent titanium-loaded polysilicon are added, and stirring is carried out for 10 minutes at 8000rpm of a vacuum homogenizer, so that a sticky ferrous metal active catalyst is obtained, namely the hydrogen peroxide remover in the electronic waste liquid.
Example 4
The concentration of hydrogen peroxide is 5-6wt%, the concentration of sulfuric acid is 55-60wt% and the pH value is 5-6wt% of waste acid cleaning liquid in a semiconductor factory in Shanghai<0, density of 1450-1500 kg/m 3 The water amount was 1 ton/hour and the run time was 24 hours. The method for treating the waste acid cleaning liquid comprises the following steps:
the first step: delivering the waste acid cleaning liquid to 1m at a flow rate of 4 tons/hour 3 In the reaction tank, the conveying time is 10 minutes, and when the liquid level of the reaction tank reaches a liquid level control point, the conveying is stopped.
And secondly, circularly conveying the waste acid cleaning liquid into a heat exchanger to start circular heating, wherein the heating time is 10 minutes, and the heated waste acid cleaning liquid reaches 60 ℃.
Thirdly, 1.5mg/L active metal is added into the reaction tank, and the total addition amount is 1500mg.
Fourth step: after the addition of the active metal is completed, a circulating pump is started for circulating reaction, and the reaction time is 60 minutes.
Fifth step: after the reaction time is reached, the treated waste acid cleaning liquid is circularly conveyed into a heat exchanger to start to circularly cool, the cooling time is about 30 minutes, and the cooled waste acid cleaning liquid is lower than 30 ℃.
Sixth step: and conveying the cooled waste acid cleaning liquid to a storage tank after treatment, wherein the conveying time is about 10 minutes. At the moment, the residual concentration of the hydrogen peroxide in the waste acid cleaning liquid in the storage tank is about 500mg/L, and the hydrogen peroxide removal rate reaches 99.44%.
Eighth step: and (5) performing outsourcing treatment on the treated waste acid cleaning liquid.
Example 5
As shown in fig. 2-3, a device for treating waste acid cleaning liquid of a wafer comprises a micro-channel heat recovery reaction device 1, wherein the micro-channel heat recovery reaction device comprises a reaction zone 2 and heat recovery layers 3 positioned on two sides of the reaction zone 2. The reaction zone 2 is formed by arranging a plurality of chambers which are communicated with each other. As shown in fig. 4, each chamber includes an outer cavity 4, an inner cavity 5 provided in the outer cavity 4, and a region between the inner cavity 5 and the outer cavity 4 forms a passage through which a liquid flows. The inner cavity 5 coincides with one end of the outer cavity 4, the coinciding end is the inlet 6 of the channel, the liquid entering the cavity is split at the inlet 6 of the channel and converged at the outlet 7 of the channel. The outline of the outer cavity 4 in this embodiment is diamond-shaped, with one vertex of the diamond being the inlet 6 of the channel and the opposite vertex being the outlet of the channel. The outline of the inner cavity 5 of this embodiment is an inverted triangle, the base of the inverted triangle is arc-shaped, and the vertex angle of the inverted triangle is the inlet 6 of the channel. The length ratio of the two diagonal lines of the diamond shape of this embodiment is 2:1, and the ratio may be 1.8-2.2:1. The ratio of the short diagonal length of the diamond-shaped cross section of the inner cavity 5 near the channel outlet is 2:1, which may be 1.8-2.2:1. The ratio of the width of the channel outlet to the linear length of the base of the inverted triangle is 2:1, which may be 1.8-2.2:1.
As shown in fig. 5, the inlet of the microchannel heat recovery reaction device 1 is respectively communicated with a waste liquid collecting tank 8 and a reaction agent 9, and the outlet of the microchannel heat recovery reaction device 1 is respectively connected with a gas washing device 10 for washing gas generated in the heat recovery process, a concentration evaporation device 11 for generating the gas, a cooling device 12 and a recovery liquid collecting tank 13 connected with the cooling device 12. The temperature reducing device 13 is connected with H 2 O 2 An unqualified tank 15 is also connected between the analyzer 14, the cooling device 12 and the recovery liquid collecting tank and is used for storing unqualified recovery liquid with residual hydrogen peroxide concentration of more than 500mg/L.
Example 6
Waste acid cleaning liquid of certain semiconductor factory in Fujian province has hydrogen peroxide concentration of 8-9 wt%, sulfuric acid concentration of 50-55 wt% and pH value of<0, the density is 1400-1450 kg/m 3 The water amount was 0.5 ton/hr and the run time was 24 hours. The method for treating the above-mentioned waste acidic cleaning solution by using the apparatus of example 5 comprises the following steps:
the first step: the spent acid cleaning solution was fed to the inlet of the microchannel heat recovery reactor at a flow rate of 0.5 tons/hour.
And secondly, adding 3mg/L of the ferrous metal active catalyst of the embodiment 1 at the inlet of the micro-channel heat recovery reaction device as a catalytic medium, and introducing the waste acid cleaning liquid and the active metal mixed liquid into the reaction zone of the micro-channel heat recovery reaction device.
And a third step of: introducing 58kg/h of 0.4MPa steam into the heat recovery layer of the heat recovery reaction device, heating the waste acid cleaning liquid, generating common chain catalytic oxidation reaction between the active metal, sulfuric acid and hydrogen peroxide, and raising the temperature of the mixed liquid from 25 ℃ to 125 ℃ to stay for 2 minutes in the reaction zone, wherein the concentration of the hydrogen peroxide is less than 500mg/L.
Fourth step: the treated recovery liquid is separated from oxygen generated by the reaction, and concentrated evaporation is carried out, so that the recovery liquid is reduced from 125 ℃ to 110 ℃ due to the use of steam evaporation in the recovery liquid, and the concentration of sulfuric acid is increased from 50-55 wt% to 55-63 wt%.
Fifth step: and conveying the recovery liquid at 110 ℃ to a heat recovery layer of the microchannel heat recovery reaction device, reducing the recovery liquid from 110 ℃ to 35 ℃, and heating the acidic cleaning liquid to be treated in the cold flow pipeline from 25 ℃ to 100 ℃.
Sixth step: the recovery liquid is further cooled to 36 ℃ through a heat recovery layer of the micro-channel heat recovery reaction device and a cooling device.
Seventh step: and if the residual concentration of the hydrogen peroxide in the detected and cooled recovery liquid is less than 500mg/L, conveying the recovery liquid to a recovery liquid collecting tank for storage. If the residual concentration is more than 500mg/L, the recovery liquid is conveyed to a disqualified tank for storage. Meanwhile, the additional addition amount of the active metal is calculated according to the residual concentration and added into the reaction device.
Eighth step: when the liquid level of the recovery liquid collecting tank reaches more than 50%, the recovery liquid is discharged out of the system for recovery use or for cleaning outside a commission, the concentration of the recovery liquid sulfuric acid reaches 55-63 wt%, the residual concentration of hydrogen peroxide is less than 1mg/L, and the hydrogen peroxide removal rate reaches 99.999%.
Ninth step: and (3) conveying the unqualified recovery liquid to an inlet of the microchannel heat recovery reaction device, wherein the conveying flow is 1/20 of the raw water flow, and conveying the unqualified recovery liquid to a recovery liquid collecting tank for storage together with the recovery liquid after the residual concentration of the hydrogen peroxide is lower than 500mg/L after secondary reaction treatment.
Example 7
The concentration of hydrogen peroxide is 5-6wt%, the concentration of sulfuric acid is 55-60wt% and the pH value is 5-6wt% of waste acid cleaning liquid in a semiconductor factory in Shanghai<0, density of 1450-1500 kg/m 3 The water amount was 1 ton/hour and the run time was 24 hours. The method for treating the above-mentioned waste acidic cleaning solution by using the apparatus of example 5 comprises the following steps:
the first step: the spent acid cleaning solution was fed to the inlet of the microchannel heat recovery reactor at a flow rate of 0.5 tons/hour.
And secondly, adding 2mg/L of the ferrous metal active catalyst of the embodiment 1 at the inlet of the microchannel heat recovery reaction device as a catalytic medium, and introducing the waste acid cleaning liquid and the active metal mixed liquid into a reaction zone of the silicon carbide microchannel heat recovery reaction device.
And a third step of: and (3) introducing 0.4MPa steam for 100kg/h into a heat recovery layer of the heat recovery reaction device, heating the waste acid cleaning liquid, carrying out a common chain catalytic oxidation reaction on the active metal, sulfuric acid and hydrogen peroxide at the moment, raising the temperature of the mixed liquid from 25 ℃ to 125 ℃, and keeping the residence time in a reaction zone for 2 minutes, wherein the concentration of the hydrogen peroxide is less than 500mg/L.
Fourth step: the treated recovery liquid is separated from oxygen generated by the reaction, and concentrated and evaporated, and the recovery liquid is reduced from 125 ℃ to 110 ℃ due to the water vapor evaporation in the recovery liquid, and the sulfuric acid concentration is increased from 55-60 wt% to 60-67 wt%.
Fifth step: and conveying the recovery liquid at 110 ℃ to a heat recovery layer of the microchannel heat recovery reaction device, reducing the recovery liquid from 110 ℃ to 35 ℃, and heating the acidic cleaning liquid to be treated in the cold flow pipeline from 25 ℃ to 100 ℃.
Sixth step: the recovery liquid passes through the heat recovery layer of the micro-channel heat recovery reaction device and is further cooled to 36 ℃ by the cooling device.
Seventh step: detecting the concentration of hydrogen peroxide in the cooled recovery liquid, and if the residual concentration of hydrogen peroxide is less than 500mg/L, conveying the recovery liquid to a recovery liquid collecting tank for storage. And if the residual concentration is more than 500mg/L, conveying the recovery liquid to a disqualified tank for storage. Meanwhile, the additional addition amount of the active metal is calculated according to the residual concentration and added into the reaction device.
Eighth step: when the liquid level of the recovery liquid collecting tank reaches more than 50%, the recovery liquid is discharged out of the system for recovery use or for cleaning outside a commission, the concentration of the recovery liquid sulfuric acid reaches 60-67 wt%, the residual concentration of hydrogen peroxide is less than 1mg/L, and the hydrogen peroxide removal rate reaches 99.998%.
Ninth step: and (3) conveying the unqualified recovery liquid to an inlet of the microchannel heat recovery reaction device, wherein the conveying flow is 1/20 of the raw water flow, and conveying the unqualified recovery liquid to a recovery liquid collecting tank for storage together with the recovery liquid after the residual concentration of the hydrogen peroxide is lower than 500mg/L after secondary reaction treatment.
Example 8
Waste acid cleaning liquid of some semiconductor factory in Shandong province has hydrogen peroxide concentration of 2-3 wt%, sulfuric acid concentration of 55-60 wt% and pH value of<0, density of 1450-1500 kg/m 3 The water amount was 1 ton/hour and the run time was 24 hours. The method for treating the above-mentioned waste acidic cleaning solution by using the apparatus of example 5 comprises the following steps:
the first step: the spent acid cleaning solution was fed to the inlet of the microchannel heat recovery reactor at a flow rate of 0.5 tons/hour.
And secondly, adding 1.5mg/L of the ferrous metal active catalyst of the embodiment 1 at the inlet of the microchannel heat recovery reaction device as a catalytic medium, and introducing the waste acid cleaning liquid and the active metal mixed liquid into a reaction zone of the silicon carbide microchannel heat recovery reaction device.
And a third step of: and (3) introducing 0.4MPa steam for 100kg/h into a heat recovery layer of the heat recovery reaction device, heating the waste acid cleaning liquid, carrying out a common chain catalytic oxidation reaction on the active metal, sulfuric acid and hydrogen peroxide at the moment, raising the temperature of the mixed liquid from 25 ℃ to 125 ℃, and keeping the residence time in a reaction zone for 2 minutes, wherein the concentration of the hydrogen peroxide is less than 500mg/L.
Fourth step: the treated recovery liquid is separated from oxygen generated by the reaction, and concentrated and evaporated, and the recovery liquid is reduced from 125 ℃ to 110 ℃ due to the water vapor evaporation in the recovery liquid, and the sulfuric acid concentration is increased from 55-60 wt% to 60-67 wt%.
Fifth step: and conveying the recovery liquid at 110 ℃ to a heat recovery layer of the microchannel heat recovery reaction device, reducing the recovery liquid from 110 ℃ to 35 ℃, and heating the acidic cleaning liquid in the cold flow pipeline from 25 ℃ to 100 ℃.
Sixth step: the recovery liquid passes through the heat recovery layer of the micro-channel heat recovery reaction device and is further cooled to 36 ℃.
Seventh step: detecting the concentration of hydrogen peroxide in the cooled recovery liquid, and if the residual concentration of hydrogen peroxide is less than 500mg/L, conveying the recovery liquid to a recovery liquid collecting tank for storage. And if the residual concentration is more than 500mg/L, conveying the recovery liquid to a disqualified tank for storage. Meanwhile, the additional addition amount of the active metal is calculated according to the residual concentration and added into the reaction device.
Eighth step: when the liquid level of the recovery liquid collecting tank reaches more than 50%, the recovery liquid is discharged out of the system for recovery use or for cleaning outside a commission, the concentration of the recovery liquid sulfuric acid reaches 60-67 wt%, the residual concentration of hydrogen peroxide is less than 1mg/L, and the hydrogen peroxide removal rate reaches 99.995%.
Ninth step: and (3) conveying the unqualified recovery liquid to an inlet of the microchannel heat recovery reaction device, wherein the conveying flow is 1/20 of the raw water flow, and conveying the unqualified recovery liquid to a recovery liquid collecting tank for storage together with the recovery liquid after the residual concentration of the hydrogen peroxide is lower than 500mg/L after secondary reaction treatment.
Comparative example
The concentration of hydrogen peroxide is 5-6wt%, the concentration of sulfuric acid is 55-60wt% and the pH value is 5-6wt% of waste acid cleaning liquid in a semiconductor factory in Shanghai<0, density of 1450-1500 kg/m 3 Water, waterThe amount was 1 ton/hour and the run time was 24 hours. The method for treating the waste acid cleaning liquid comprises the following steps:
the first step: delivering the waste acid cleaning liquid to 1m at a flow rate of 4 tons/hour 3 In the reaction tank, the conveying time is 10 minutes, and when the liquid level of the reaction tank reaches a liquid level control point, the conveying is stopped.
And secondly, circularly conveying the waste acid cleaning liquid into a heat exchanger to start circular heating, wherein the heating time is 10 minutes, and the heated waste acid cleaning liquid reaches 60 ℃.
In the third step, 68wt% nitric acid was added to the reaction tank in an amount of 2.2L per batch for 10 minutes.
Fourth step: after the nitric acid is added, a circulating pump is started to perform a circulating reaction, and the reaction time is 60 minutes.
Fifth step: and after the reaction time is reached, circularly conveying the waste acid cleaning liquid into a heat exchanger to start circular cooling, wherein the cooling time is about 30 minutes, and the cooled waste acid cleaning liquid is lower than 30 ℃.
Sixth step: and conveying the waste acid cleaning liquid in the reaction tank to a storage tank after treatment, wherein the conveying time is about 10 minutes.
Seventh step: at the moment, the residual concentration of the hydrogen peroxide in the waste acid cleaning liquid in the storage tank is about 5000mg/L, and the hydrogen peroxide removal rate reaches 94.44%.
Eighth step: and (5) carrying out outsourcing treatment on the waste acid cleaning liquid.
According to the invention, hydrogen peroxide in the waste acid cleaning liquid is catalytically decomposed, and the waste acid cleaning liquid is concentrated to generate sulfuric acid recovery liquid, so that the sulfuric acid is recycled, and the waste acid cleaning liquid can be used for neutralizing acid and alkali in water treatment or replacing industrial grade sulfuric acid under the permission of standard standards. Meanwhile, the treatment time is short, the construction cost and the operation cost can be further reduced, and the recovery liquid has less additional substances and higher recovery application value.
Claims (4)
1. The preparation method of the hydrogen peroxide remover in the electronic waste liquid is characterized by comprising the following steps of:
(1) Adding the titanyl sulfate solid powder into hot concentrated sulfuric acid to obtain a titanyl sulfate solution;
(2) Adding a titanyl sulfate solution into a PVP solution to obtain a mixed solution for loading;
(3) Soaking polycrystalline silicon powder in a mixed solution for loading, and calcining to obtain tetravalent titanium loaded polycrystalline silicon nano powder;
(4) Mixing an aqueous phase rheology modifying additive, a nonionic surfactant A and a nonionic surfactant B, adding tetravalent titanium-loaded polysilicon powder, and mixing to obtain a liquid metal active catalyst, namely a hydrogen peroxide remover in the electronic waste liquid; the mass ratio of the tetravalent titanium loaded polysilicon powder to the aqueous phase rheology modification auxiliary agent, the nonionic surfactant A and the nonionic surfactant B is 70:8:10:10-90:15:20:30;
the aqueous phase rheology modifying auxiliary agent is hydroxyethyl cellulose ether, hydroxypropyl cellulose or alkali swelling non-association thickener; when the aqueous phase rheology modifying additive is an alkali swelling non-association thickener, the aqueous phase rheology modifying additive also comprises ammonia waterOr xanthan gum;the nonionic surfactant A is any one of condensate of octyl phenol and ethylene oxide, polyoxyethylene ether, fatty alcohol polyoxyethylene ether or condensate of fatty alcohol and ethylene oxide; the nonionic surfactant B is polyethylene glycol, span 80 or tween 60.
2. The method for preparing the hydrogen peroxide remover in the electronic waste liquid according to claim 1, wherein in the step (2), the mass ratio of the titanyl sulfate solution to the PVP solution is 3:20-5:22.
3. The method for preparing the hydrogen peroxide remover in the electronic waste liquid according to claim 1, wherein in the step (3), the calcination temperature is 660-760 ℃ and the calcination time is 20-50 min.
4. The method for preparing a hydrogen peroxide remover in an electronic waste liquid according to claim 1, wherein in the step (1), the addition amount of the titanyl sulfate solid powder is 600-1200 g/L H 2 SO 4 。
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US4002574A (en) * | 1971-11-08 | 1977-01-11 | Ventron Corporation | Photosensitive redox solutions |
| CN104741150A (en) * | 2013-12-30 | 2015-07-01 | 国际壳牌研究有限公司 | Relating to epoxidation catalysts |
| CN106564863A (en) * | 2016-11-15 | 2017-04-19 | 四川龙蟒钛业股份有限公司 | Hydrogen peroxide addition level control equipment for concentrated waste acid iron removal process |
| CN114524890A (en) * | 2020-01-28 | 2022-05-24 | 切弗朗菲利浦化学公司 | Method for preparing catalyst by using hydration reagent |
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| JP4265212B2 (en) * | 2002-12-19 | 2009-05-20 | 住友化学株式会社 | Method for producing titanium-containing silicon oxide catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4002574A (en) * | 1971-11-08 | 1977-01-11 | Ventron Corporation | Photosensitive redox solutions |
| CN104741150A (en) * | 2013-12-30 | 2015-07-01 | 国际壳牌研究有限公司 | Relating to epoxidation catalysts |
| CN106564863A (en) * | 2016-11-15 | 2017-04-19 | 四川龙蟒钛业股份有限公司 | Hydrogen peroxide addition level control equipment for concentrated waste acid iron removal process |
| CN114524890A (en) * | 2020-01-28 | 2022-05-24 | 切弗朗菲利浦化学公司 | Method for preparing catalyst by using hydration reagent |
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