CN113526627A - Water body silicide removing system based on capacitance adsorption - Google Patents
Water body silicide removing system based on capacitance adsorption Download PDFInfo
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- CN113526627A CN113526627A CN202110717890.8A CN202110717890A CN113526627A CN 113526627 A CN113526627 A CN 113526627A CN 202110717890 A CN202110717890 A CN 202110717890A CN 113526627 A CN113526627 A CN 113526627A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 51
- 229910021332 silicide Inorganic materials 0.000 title claims abstract description 32
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 56
- 239000011259 mixed solution Substances 0.000 claims description 40
- 239000010405 anode material Substances 0.000 claims description 26
- 239000010406 cathode material Substances 0.000 claims description 24
- -1 polytetrafluoroethylene Polymers 0.000 claims description 24
- 229910021389 graphene Inorganic materials 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 20
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- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
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- 238000007605 air drying Methods 0.000 claims description 10
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- 239000002131 composite material Substances 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 239000000741 silica gel Substances 0.000 claims description 5
- 229910002027 silica gel Inorganic materials 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- 239000003814 drug Substances 0.000 abstract 1
- 229940079593 drug Drugs 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 17
- 229910052710 silicon Inorganic materials 0.000 description 16
- 239000010703 silicon Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000001110 calcium chloride Substances 0.000 description 3
- 229910001628 calcium chloride Inorganic materials 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 229910002706 AlOOH Inorganic materials 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 239000000701 coagulant Substances 0.000 description 2
- 229910052593 corundum Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ULGYAEQHFNJYML-UHFFFAOYSA-N [AlH3].[Ca] Chemical compound [AlH3].[Ca] ULGYAEQHFNJYML-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910000421 cerium(III) oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
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Classifications
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- 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
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4691—Capacitive deionisation
-
- 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
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a water body silicide removal system based on capacitance adsorption, which comprises a water treatment box body, a capacitance adsorption component arranged in the water treatment box body, a water inlet pipe communicated with the water treatment box body, a pump arranged on the water inlet pipe, a stirring device arranged at the bottom of the water treatment box body and a water outlet pipe communicated with the water treatment box body, wherein the capacitance adsorption component comprises a first support plate and a second support plate which are oppositely distributed in parallel, an anode sheet attached to the surface of the first support plate, a cathode sheet attached to the surface of the second support plate, a gasket for separating the anode sheet from the cathode sheet and a direct current power supply which is electrically connected with the cathode sheet and the anode sheet to form a capacitance structure. The invention does not need chemical drugs, can stably, continuously, efficiently and selectively adsorb silicide in the water body, and improves the water treatment efficiency and effect.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of water treatment, and particularly relates to a water body silicide removal system based on capacitance adsorption.
[ background of the invention ]
Silicon in water used in the electronics industry has a significant impact on the materials, device performance, and end products of integrated circuits. It reduces the reliability of thermally grown oxides, resulting in phosphorous haze, threshold voltage variation, and plasma breakdown. It also causes particle contamination, affects pattern defects, and degrades the quality of tubes and solid state circuits. The recently developed electronic material growth process movpe (metallic vapor phase epitaxy) also has very strict requirements on the silicon content in ultrapure water. At present, metal organic manufacturers require that the silicon content of ultrapure water should be less than 3. mu.g/L.
The traditional silicon removal method for ultrapure water mainly comprises a reverse osmosis method (RO) and an ion exchange mixed bed Method (MB). The average silicon removal rate of reverse osmosis can reach 80%. When water is fed into SiO2When the concentration is 8.8mg/L, the reverse osmosis silicon removal rate can reach 95.35 percent, the silicon concentration in product water can reach 410 mu g/L, the reverse osmosis process has overhigh operation cost and large power consumption, and can not meet the requirement of industrial water. Treating 0.3mg/L SiO by using ion exchange mixed bed method2The silicon content of the effluent can be reduced to 0.02mg/L, but after MB is used for a period of time, chemical regeneration is needed, which consumes a large amount of regeneration reagent, requires more labor and pollutes the environment. Other removing methods such as coagulant, coagulant adding clarification filtration, flotation, ultrafiltration and the like can only remove part of silicon compounds in water, and the removing rate is not high.
Therefore, it is desirable to provide a new water body silicide removal system based on capacitive adsorption to solve the above problems.
[ summary of the invention ]
The invention mainly aims to provide a water body silicide removal system based on capacitance adsorption, which does not need chemicals, can stably, continuously, efficiently and selectively adsorb silicide in a water body, and improves the water treatment efficiency and effect.
The invention realizes the purpose through the following technical scheme: a water body silicide removal system based on capacitance adsorption comprises a water treatment box body, a capacitance adsorption assembly arranged in the water treatment box body, a water inlet pipe communicated with the water treatment box body, a pump arranged on the water inlet pipe, a stirring device arranged at the bottom of the water treatment box body and a water outlet pipe communicated with the water treatment box body, wherein the capacitance adsorption assembly comprises a first support plate and a second support plate which are oppositely distributed in parallel, an anode piece attached to the surface of the first support plate, a cathode piece attached to the surface of the second support plate, a silica gel gasket for separating the anode piece from the cathode piece and a direct current power supply which is electrically connected with the cathode piece and the anode piece to form a capacitance structure;
the anode sheet is of a laminated structure containing a first mixture, the first mixture comprises an anode material, polytetrafluoroethylene and graphene oxide, the anode material is a composite, and the composite contains a mixture formed by three metal oxides, namely cerium oxide, calcium oxide and aluminum oxide, and the graphene oxide;
the preparation method of the anode sheet comprises the following steps: obtaining the anode material, mixing the anode material, polytetrafluoroethylene and graphene oxide according to a mass ratio of 60-75: 10: 10-15, adding ethanol, grinding to obtain a mixed solution, uniformly coating the mixed solution on a carbon felt, and controlling the mass of the mixed solution to be 0.1-0.2 g; standing and air-drying, and drying in an oven at 60-100 ℃ for 20-40 min to obtain the anode sheet;
the preparation method of the anode material comprises the following steps: dispersing 35-40 mL of graphene oxide in 150-250 mL of deionized water, carrying out ultrasonic treatment for 20-40 min, weighing two inorganic metal salts of Ca and Al according to a molar ratio of 2: 1-4: 1, dissolving the inorganic metal salts in the deionized water, carrying out ultrasonic treatment for 20-40 min, adding an alkali source urea to obtain a mixed solution, filling the mixed solution into a reaction kettle, putting the reaction kettle into an oven to react for 20-30 h at 100-150 ℃, washing a product to be neutral after the reaction is finished, drying the product at 60-90 ℃, and grinding the product to be small particles; then roasting for 4-6 h at 300-500 ℃ in an argon atmosphere, wherein the heating rate is 2-5 ℃/min; and doping Ce element according to the atomic ratio of Ce/Al of 1: 100-10: 100.
Further, the capacitance adsorption assembly further comprises a first non-woven fabric covering the surface of the anode sheet and a second non-woven fabric covering the cathode sheet.
Further, the first carrier plate has a first surface facing the second carrier plate, the second carrier plate has a second surface facing the first carrier plate, the anode tab is attached to the first surface, and the cathode tab is disposed on the second surface.
Further, the voltage of the direct current power supply acting on the two ends of the anode strip and the cathode strip is 0.4-1.2V.
Further, the cathode sheet is of a layered structure containing a second mixture, the second mixture comprises a cathode material, polytetrafluoroethylene and graphene oxide, and the cathode material is activated carbon powder treated by a nitric acid solution.
Further, the preparation method of the cathode sheet comprises the following steps: preparing a cathode material, mixing the cathode material, polytetrafluoroethylene and graphene oxide according to a mass ratio of 60-75: 10: 10-15, adding ethanol, grinding to obtain a mixed solution, and uniformly coating the mixed solution on a carbon felt, wherein the mass of the mixed solution is controlled to be 0.1-0.2 g; and standing, air-drying, and drying in an oven at 60-100 ℃ for 20-40 min to obtain the cathode sheet.
Further, the preparation method of the cathode material comprises the following steps: weighing a proper amount of activated carbon, adding the activated carbon into a nitric acid solution with the volume fraction of 35-50%, and carrying out heat treatment for 4-6 h at the temperature of 50-70 ℃; and cooling to room temperature after the reaction is finished, washing the material to be neutral, and drying at 60-90 ℃ to obtain the cathode material.
Compared with the prior art, the water body silicide removal system based on capacitance adsorption has the beneficial effects that: the technology adopts a closed loop formed by a deionized capacitor module and a direct-current voltage circuit, and oxygen-containing acid radical water with silicon flows through the deionized capacitor module and then the oxygen-containing acid radical of the silicon is adsorbed; the closed loop adsorbs the oxygen-containing acid radicals of silicon under the constant current voltage of 0.4-1.2V, the whole device does not need chemicals, and the device can stably, continuously, efficiently and selectively adsorb silicide in a water body, thereby greatly improving the water treatment efficiency and effect.
[ description of the drawings ]
FIG. 1 is a schematic structural diagram of an embodiment of the present invention;
FIG. 2 is a schematic structural diagram of a capacitive adsorption element according to an embodiment of the present disclosure;
FIG. 3 is a graph showing the results of testing the silicide adsorption rate at different Ca/Al ratios according to the embodiment of the present invention;
FIG. 4 is a graph of the test results of silicide adsorption rates at different Ce/Al ratios in the embodiment of the present invention;
FIG. 5 is a graph of the silicide adsorption rate at different output voltages according to the embodiment of the present invention;
the figures in the drawings represent:
100 a water body silicide removal system based on capacitance adsorption;
1, a water treatment tank body;
2, a capacitive adsorption component, 21 a first carrier plate, 22 an anode sheet, 23 a first non-woven fabric, 24 a silica gel gasket, 25 a second non-woven fabric, 26 a second carrier plate, 27 a cathode sheet and 28 a direct current power supply;
3, water inlet pipe; 4, pumping; 5, a stirring device; 6, discharging a water pipe; 7 a water stop valve.
[ detailed description ] embodiments
The first embodiment is as follows:
referring to fig. 1-2, the present embodiment is a water silicide removal system 100 based on capacitive adsorption, which includes a water treatment tank 1, a capacitive adsorption component 2 disposed in the water treatment tank 1, a water inlet pipe 3 communicated with the water treatment tank 1, a pump 4 disposed on the water inlet pipe 3, a stirring device 5 disposed at the bottom of the water treatment tank 1, and a water outlet pipe 6 communicated with the water treatment tank 1.
The capacitance adsorption assembly 2 comprises a first carrier plate 21 and a second carrier plate 26 which are distributed oppositely in parallel, an anode sheet 22 attached on the surface of the first carrier plate 21, a first non-woven fabric 23 covered on the surface of the anode sheet 22, a cathode sheet 27 attached on the surface of the second carrier plate 26, a second non-woven fabric 25 covered on the cathode sheet 27, a silica gel gasket 24 for separating the anode sheet 22 from the cathode sheet 27, and a direct current power supply 28 which is electrically connected with the cathode sheet 27 and the anode sheet 22 to form a capacitance structure.
The first carrier plate 21 has a first surface facing the second carrier plate 26, the second carrier plate 26 has a second surface facing the first carrier plate 21, the anode tab 22 is attached on the first surface, and the cathode tab 27 is disposed on the second surface. The first non-woven fabric 23 serves to confine the anode sheet 22 on the surface of the first support plate 21, and the second non-woven fabric 25 serves to confine the cathode sheet 27 on the surface of the second support plate 26. The first carrier plate 21 and the second carrier plate 26 may be made of organic glass plates or stainless steel plates. The silica gel gasket 24 is used for separating the anode strip 22 from the cathode strip 27 to prevent short circuit and form a water flow space for the water body to be treated to flow through, and silicate ions in the water body are adsorbed through a capacitance space formed between the anode strip 22 and the cathode strip 27, so that the effect of removing silicide in the water body is realized.
The voltage applied to the two ends of the anode strip 22 and the cathode strip 27 by the DC power supply 28 is 0.4-1.2V.
A water stop valve 7 is arranged on the upstream of the pump 4 on the water inlet pipe 3 to prevent water flow from flowing backwards.
The stirring device 5 can adopt a common stirring device in the prior art, and the main purpose is to accelerate the water flow speed in the water treatment tank body 1, so that the upper water body and the lower water body are fully mixed, and the treatment effect of silicide in the water body is improved. In this embodiment, the stirring device 5 is a magnetic stirrer, a main machine of the magnetic stirrer is disposed outside the water treatment tank 1 and below the water treatment tank 1, and a rotor of the magnetic stirrer is disposed inside the water treatment tank 1 and at the center of the bottom of the water treatment tank 1.
The method of making the anode sheet 22 includes the steps of: preparing an anode material, mixing the anode material, polytetrafluoroethylene (PTFE for short) and graphene oxide according to a mass ratio of 67.5:10:12.5, adding ethanol, grinding to obtain a mixed solution, uniformly coating the mixed solution on a carbon felt of 5 multiplied by 3cm, wherein the mass of the mixed solution is controlled to be 0.1-0.2 g; standing, air drying, and drying in oven at 80 deg.C for 30min to obtain anode sheet 22.
The preparation method of the anode material comprises the following steps: 40mL and 5mg/mL of graphene oxide were dispersed in 200mL of deionized waterUltrasonically vibrating in water for 30min, and adding 0.03mol of CaCl2And 0.01mol of Al (NO)3)3Continuing to perform ultrasonic treatment for 30min, and then adding 7.3g of urea to obtain a mixed solution; putting the mixed solution into a reaction kettle, reacting for 24 hours at 120 ℃, washing and centrifuging the obtained product to be neutral, and drying for 12 hours at 80 ℃ to obtain a sample; and (3) roasting the obtained sample for 5 hours at the temperature rise rate of 2 ℃/min to 400 ℃ under the protection of argon to obtain the first compound of the graphene/calcium-aluminum layered metal oxide.
The preparation method of the anode material also comprises the step of adding Ce (NO) with a set proportion into the first composite3)3And preparing a second compound of the cerium oxide modified graphene/calcium-aluminum layered metal oxide, namely the anode material. In the set ratio, the atomic ratio of Ce/Al is 1%.
The preparation method of the cathode sheet 27 includes the steps of: preparing a cathode material, mixing the cathode material, polytetrafluoroethylene (PTFE for short) and graphene oxide according to a mass ratio of 67.5:10:12.5, adding ethanol, grinding to obtain a mixed solution, uniformly coating the mixed solution on a carbon felt of 5 multiplied by 3cm, wherein the mass of the mixed solution is controlled to be 0.1-0.2 g; standing, air drying, and drying in an oven at 80 deg.C for 30min to obtain cathode sheet 27.
The preparation method of the cathode material comprises the following steps: weighing 5g of activated carbon, adding the activated carbon into a nitric acid solution with the volume fraction of 40%, and carrying out heat treatment for 5h at the temperature of 60 ℃; and cooling to room temperature after the reaction is finished, washing the material to be neutral, and drying at 80 ℃ to obtain the cathode material.
The calcium aluminum oxide formed in the production process of the anode material of the present application may form 4CaO · Al having a layered structure2O3·19H2O，4CaO·Al2O3·13H2O or 2 CaO. Al2O3·8H2O, which is composed of a calcium-aluminum main layer plate with positive charges and OH existing in an interlayer space-Anion composition, thus interlayer OH-The anion is readily exchanged for silicate anion. The doping of Ce element can widen the energy gap, because Ce element can carry out Ce in the process of electric adsorption3+And Ce4+The valence state transformation and the widened electronic bandwidth can create more opportunities to produce OH-And thus can be exchanged with more silicate ions.
In the preparation process of the anode plate, Ca and Al inorganic salts are used as precursors, urea is added as an alkali source, and the structural formula [ M ] can be generated1-x 2+Mx 3+(OH)2x(An-)x/n]Wherein M is2+Is a divalent metal, here Ca, M3+Which is a trivalent metal, here Al, has a layered structure parallel to each other with a positive point, and between the layers consists of anions and water molecules. The structure has the characteristics of interchangeability of anions between layers, structural collapse memory benefit, capability of water molecule flowing between main layers and the like, and can have good application effect in the field of electric adsorption. In addition to the doping of Ce, the Ce element is generally doped into the layered structure as a positive trivalent metal to replace Al, so as to form 4CaO & Ce2O3·nH2O molecular structure while it can perform Ce3+And Ce4+The effect of which is to increase the contact of electrons with water molecules in electrochemical reactions, producing OH-And further has more opportunities to replace silicate ions, thereby greatly improving the adsorption capacity to the silicide.
The anode strip and the cathode strip prepared in the embodiment can greatly improve the adsorption capacity to silicic acid heel ions. Specifically, first, Ca and silicate ions can form stable CaSiO3Is the main component of adsorption; the doping of Al can introduce a certain amount of hydroxyl structures, so that the hydrophilicity of the material is improved, and meanwhile, the doping of Ce is more beneficial to the hydroxylation of the material, so that Ce-AlOOH with abundant metal hydroxyl groups is formed; on one hand, the silicate can replace hydroxyl and is adsorbed on the surface of the electrode through chemical bonds, and on the other hand, the Ce-AlOOH has higher zero charge point and is positively charged in a wider pH range, which is beneficial to adsorbing silicate ions with negative points.
In the embodiment, a capacitance adsorption module and a direct-current voltage circuit form a closed loop, a pump 4 is utilized to send a sodium silicate solution with silicon mass concentration of 68.73ppm into a water treatment box body 1 through a silicone tube via a water inlet pipe 3, and an effluent water sample is collected at the end of a water outlet pipe 6 after adsorption. Wherein a voltage of 1.2V is applied to the DC power supply 28 and the flow rate of the pump 4 is 3 mL/min. Taking out 100uL of water at 5 min, 10 min, 15 min, 30min, 60 min, 90 min and 120min after the reaction starts, measuring the concentration of silicate in the solution by using an atomic fluorescence spectrophotometer, and calculating the adsorption quantity of silicon atoms, wherein the result shows that the adsorption efficiency can reach 99.7%; when the voltages applied by the direct current power supply 28 were 0.2V, 0.6V, 1.2V, and 1.5V, respectively, the initial mass concentration of the sodium silicate solution was 68.73ppm, and the water sample was collected under the above-mentioned voltage output conditions, and the change in the concentration of silicon was measured, and the result showed that the maximum adsorption amount reached 649 mg/g.
In order to verify the effectiveness of the embodiment after optimizing the ratio of Ca and Al, the embodiment adopts different Ca/Al ratios and detects the adsorption rate of silicide, and the detection result is shown in fig. 3, and it is obvious from fig. 3 that when Ca/Al is 3:1, a better removal rate can be obtained.
In order to verify the effectiveness of the embodiment after optimizing the ratio of Ce and Al, the embodiment adopts different mixture ratios of Ce/Al, and detects the adsorption rate of silicide, and the detection result is shown in fig. 4, and it is obvious from fig. 4 that when Ce/Al is 5%, a better removal rate can be obtained.
In order to verify the influence of the present embodiment on the silicide adsorption rate under different voltages and verify the effectiveness of the present embodiment, the present embodiment adopts different output voltages and detects the adsorption rate of silicide, and the detection result is shown in fig. 5, as shown in fig. 5, it is apparent from fig. 5 that the adsorption efficiency is significantly improved with the increase of voltage within a specific range, and the adsorption efficiency under 1.5V is equivalent to that under 1.2V, so that the adsorption amount can reach 649mg/g under the optimal condition of selecting 1.2V.
In the embodiment, the water body silicide removal system 100 based on capacitance adsorption utilizes a capacitance deionization technology that layered metal oxide adsorbs oxygen-containing acid radicals of silicon, the technology adopts a closed loop formed by a deionization capacitance module and a direct-current voltage circuit, and oxygen-containing acid radical water with silicon is adsorbed after flowing through the deionization capacitance module; the closed loop adsorbs the oxygen-containing acid radicals of silicon under the constant current voltage of 0.4-1.2V, the whole device does not need chemicals, and the device can stably, continuously, efficiently and selectively adsorb silicide in a water body, thereby greatly improving the water treatment efficiency and effect.
Example two:
this embodiment provides another embodiment of the first embodiment of the anode strip 22 and the cathode strip 27 of the capacitive adsorption assembly 2.
The method of making the anode sheet 22 includes the steps of: preparing an anode material, mixing the anode material, polytetrafluoroethylene (PTFE for short) and graphene oxide according to a mass ratio of 60:10:10, adding ethanol, grinding to obtain a mixed solution, uniformly coating the mixed solution on a carbon felt of 5 x 3cm, wherein the mass of the mixed solution is controlled to be 0.1-0.2 g; standing, air drying, and drying in oven at 60 deg.C for 20min to obtain anode sheet 22.
The preparation method of the anode material comprises the following steps: dispersing 45mL and 5mg/mL graphite oxide in 150mL deionized water, ultrasonically vibrating for 20min, and adding 0.02mol CaCl2And 0.01mol of Al (NO)3)3Continuing to perform ultrasonic treatment for 20min, and then adding 6.5g of urea to obtain a mixed solution; putting the mixed solution into a reaction kettle, reacting for 20 hours at 100 ℃, washing and centrifuging the obtained product to be neutral, and drying for 12 hours at 60 ℃ to obtain a sample; and (3) roasting the obtained sample to 300 ℃ at the heating rate of 3 ℃/min under the protection of argon for 4 hours to obtain the first compound of the graphene/calcium-aluminum layered metal oxide.
The preparation method of the anode material also comprises the step of adding Ce (NO) with a set proportion into the first composite3)3And preparing a second compound of the cerium oxide modified graphene/calcium-aluminum layered metal oxide, namely the anode material. In the set ratio, the atomic ratio of Ce/Al is 5%.
The preparation method of the cathode sheet 27 includes the steps of: preparing a cathode material, mixing the cathode material, polytetrafluoroethylene (PTFE for short) and graphene oxide according to a mass ratio of 60:10:10, adding ethanol, grinding to obtain a mixed solution, uniformly coating the mixed solution on a carbon felt of 5 x 3cm, wherein the mass of the mixed solution is controlled to be 0.1-0.2 g; standing, air drying, and drying in an oven at 60 deg.C for 20min to obtain cathode sheet 27.
The preparation method of the cathode material comprises the following steps: weighing 4g of activated carbon, adding the activated carbon into a nitric acid solution with the volume fraction of 35%, and carrying out heat treatment for 4 hours at 50 ℃; and cooling to room temperature after the reaction is finished, washing the material to be neutral, and drying at 60 ℃ to obtain the cathode material.
Example three:
this embodiment provides another embodiment of the first embodiment of the anode strip 22 and the cathode strip 27 of the capacitive adsorption assembly 2.
The method of making the anode sheet 22 includes the steps of: preparing an anode material, mixing the anode material, polytetrafluoroethylene (PTFE for short) and graphene oxide according to a mass ratio of 75:10:15, adding ethanol, grinding to obtain a mixed solution, uniformly coating the mixed solution on a carbon felt of 5 x 3cm, wherein the mass of the mixed solution is controlled to be 0.1-0.2 g; standing, air drying, and drying in oven at 100 deg.C for 40min to obtain anode sheet 22.
The preparation method of the anode material comprises the following steps: dispersing 35mL and 5mg/mL of graphite oxide in 250mL of deionized water, ultrasonically vibrating for 40min, and adding 0.03mol of CaCl2And 0.01mol of Al (NO)3)3Continuing to perform ultrasonic treatment for 40min, and then adding 7.3g of urea to obtain a mixed solution; putting the mixed solution into a reaction kettle, reacting for 30h at 150 ℃, washing and centrifuging the obtained product to be neutral, and drying for 12h at 90 ℃ to obtain a sample; and (3) roasting the obtained sample for 6 hours at the temperature rise rate of 5 ℃/min to 500 ℃ under the protection of argon to obtain the first compound of the graphene/calcium-aluminum layered metal oxide.
The preparation method of the anode material also comprises the step of adding Ce (NO) with a set proportion into the first composite3)3And preparing a second compound of the cerium oxide modified graphene/calcium-aluminum layered metal oxide, namely the anode material. In the set ratio, the atomic ratio of Ce/Al is 10%.
The preparation method of the cathode sheet 27 includes the steps of: preparing a cathode material, mixing the cathode material, polytetrafluoroethylene (PTFE for short) and graphene oxide according to a mass ratio of 75:10:15, adding ethanol, grinding to obtain a mixed solution, uniformly coating the mixed solution on a carbon felt of 5 x 3cm, wherein the mass of the mixed solution is controlled to be 0.1-0.2 g; standing, air drying, and drying in an oven at 100 deg.C for 40min to obtain cathode sheet 27.
The preparation method of the cathode material comprises the following steps: weighing 6g of activated carbon, adding the activated carbon into a nitric acid solution with the volume fraction of 50%, and carrying out heat treatment for 6h at 70 ℃; and cooling to room temperature after the reaction is finished, washing the material to be neutral, and drying at 90 ℃ to obtain the cathode material.
What has been described above are merely some embodiments of the present invention. It will be apparent to those skilled in the art that various changes and modifications can be made without departing from the inventive concept thereof, and these changes and modifications can be made without departing from the spirit and scope of the invention.
Claims (7)
1. A water body silicide removes system based on electric capacity is adsorbed which characterized in that: the water treatment device comprises a water treatment box body, a capacitance adsorption component arranged in the water treatment box body, a water inlet pipe communicated with the water treatment box body, a pump arranged on the water inlet pipe, a stirring device arranged at the bottom of the water treatment box body and a water outlet pipe communicated with the water treatment box body, wherein the capacitance adsorption component comprises a first support plate and a second support plate which are distributed oppositely in parallel, an anode sheet attached to the surface of the first support plate, a cathode sheet attached to the surface of the second support plate, a silica gel gasket for separating the anode sheet from the cathode sheet and a direct current power supply which is electrically connected with the cathode sheet and the anode sheet to form a capacitance structure;
the anode sheet is of a laminated structure containing a first mixture, the first mixture comprises an anode material, polytetrafluoroethylene and graphene oxide, the anode material is a composite, and the composite contains a mixture formed by three metal oxides, namely cerium oxide, calcium oxide and aluminum oxide, and the graphene oxide;
the preparation method of the anode sheet comprises the following steps: obtaining the anode material, mixing the anode material, polytetrafluoroethylene and graphene oxide according to a mass ratio of 60-75: 10: 10-15, adding ethanol, grinding to obtain a mixed solution, uniformly coating the mixed solution on a carbon felt, and controlling the mass of the mixed solution to be 0.1-0.2 g; standing and air-drying, and drying in an oven at 60-100 ℃ for 20-40 min to obtain the anode sheet;
the preparation method of the anode material comprises the following steps: dispersing 35-40 mL of graphene oxide in 150-250 mL of deionized water, carrying out ultrasonic treatment for 20-40 min, weighing two inorganic metal salts of Ca and Al according to a molar ratio of 2: 1-4: 1, dissolving the inorganic metal salts in the deionized water, carrying out ultrasonic treatment for 20-40 min, adding an alkali source urea to obtain a mixed solution, filling the mixed solution into a reaction kettle, putting the reaction kettle into an oven to react for 20-30 h at 100-150 ℃, washing a product to be neutral after the reaction is finished, drying the product at 60-90 ℃, and grinding the product to be small particles; then roasting for 4-6 h at 300-500 ℃ in an argon atmosphere, wherein the heating rate is 2-5 ℃/min; and doping Ce element according to the atomic ratio of Ce/Al of 1: 100-10: 100.
2. The capacitive adsorption based water body silicide removal system of claim 1, wherein: the capacitance adsorption assembly further comprises a first non-woven fabric covering the surface of the anode sheet and a second non-woven fabric covering the cathode sheet.
3. The capacitive adsorption based water body silicide removal system of claim 2, wherein: the first carrier plate is provided with a first surface facing the second carrier plate, the second carrier plate is provided with a second surface facing the first carrier plate, the anode sheet is attached to the first surface, and the cathode sheet is arranged on the second surface.
4. The capacitive adsorption based water body silicide removal system of claim 1, wherein: the voltage of the direct current power supply acting on the two ends of the anode strip and the cathode strip is 0.4-1.2V.
5. The capacitive adsorption based water body silicide removal system of claim 1, wherein: the cathode sheet is of a layered structure containing a second mixture, the second mixture comprises a cathode material, polytetrafluoroethylene and graphene oxide, and the cathode material is activated carbon powder treated by a nitric acid solution.
6. The capacitive adsorption based water body silicide removal system of claim 1, wherein: the preparation method of the cathode sheet comprises the following steps: preparing a cathode material, mixing the cathode material, polytetrafluoroethylene and graphene oxide according to a mass ratio of 60-75: 10: 10-15, adding ethanol, grinding to obtain a mixed solution, and uniformly coating the mixed solution on a carbon felt, wherein the mass of the mixed solution is controlled to be 0.1-0.2 g; and standing, air-drying, and drying in an oven at 60-100 ℃ for 20-40 min to obtain the cathode sheet.
7. The capacitive adsorption based water body silicide removal system of claim 6, wherein: the preparation method of the cathode material comprises the following steps: weighing a proper amount of activated carbon, adding the activated carbon into a nitric acid solution with the volume fraction of 35-50%, and carrying out heat treatment for 4-6 h at the temperature of 50-70 ℃; and cooling to room temperature after the reaction is finished, washing the material to be neutral, and drying at 60-90 ℃ to obtain the cathode material.
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| CN107555554A (en) * | 2017-09-27 | 2018-01-09 | 大连理工大学 | A kind of capacitive deionization technology of oxygen-containing acid group using layered metal oxide arsenic-adsorbing |
| EP3686966A1 (en) * | 2019-01-23 | 2020-07-29 | Karlsruher Institut für Technologie | An electrochemical energy storage device and a method for producing an anode active material for the electrochemical energy storage device |
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| CN107555554A (en) * | 2017-09-27 | 2018-01-09 | 大连理工大学 | A kind of capacitive deionization technology of oxygen-containing acid group using layered metal oxide arsenic-adsorbing |
| EP3686966A1 (en) * | 2019-01-23 | 2020-07-29 | Karlsruher Institut für Technologie | An electrochemical energy storage device and a method for producing an anode active material for the electrochemical energy storage device |
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