CN117101610A - Efficient defluorination medicament suitable for photovoltaic wastewater and preparation method thereof - Google Patents
Efficient defluorination medicament suitable for photovoltaic wastewater and preparation method thereof Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 40
- 238000006115 defluorination reaction Methods 0.000 title claims abstract description 36
- 239000003814 drug Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 60
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical class [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004065 semiconductor Substances 0.000 claims abstract description 24
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 23
- 239000011737 fluorine Substances 0.000 claims abstract description 23
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000007524 organic acids Chemical class 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 239000011812 mixed powder Substances 0.000 claims description 40
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 19
- 230000004048 modification Effects 0.000 claims description 18
- 238000012986 modification Methods 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 17
- 229910052845 zircon Inorganic materials 0.000 claims description 15
- 238000000498 ball milling Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- 239000003607 modifier Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- BPSIOYPQMFLKFR-UHFFFAOYSA-N trimethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CO[Si](OC)(OC)CCCOCC1CO1 BPSIOYPQMFLKFR-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- -1 fluoride ions Chemical class 0.000 abstract description 8
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 239000002105 nanoparticle Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 238000001556 precipitation Methods 0.000 description 6
- 159000000007 calcium salts Chemical class 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 4
- 238000009388 chemical precipitation Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention belongs to the technical field of fluorine-containing wastewater treatment, and particularly relates to a high-efficiency fluorine-removing medicament suitable for photovoltaic wastewater and a preparation method thereof. The invention provides a high-efficiency defluorination medicament suitable for semiconductor wastewater, which comprises the following raw materials in parts by weight: 50-80 parts of modified silica; 7-15 parts of modified zircon; 3-8 parts of organic acid; 1-3 parts of nano-scale vanadium powder; 1-3 parts of nanoscale titanium powder. The invention adopts modified silica, modified zircon, organic acid, nanoscale vanadium powder and nanoscale titanium powder as raw materials of the defluorination medicament, and can greatly improve the removal efficiency of fluoride ions in the photovoltaic wastewater.
Description
Technical Field
The invention belongs to the technical field of fluorine-containing wastewater treatment, and particularly relates to a high-efficiency fluorine-removing medicament suitable for photovoltaic wastewater and a preparation method thereof.
Background
The solar photovoltaic cell is a novel photoelectric component which converts energy by means of solar energy, converts the solar energy into electric energy, is clean and pollution-free, and has wide application prospect. The special production process of the solar cell and the use of certain raw materials and auxiliary materials in the production, especially fluorine-containing substances such as HF and the like are used in the cleaning of silicon materials and the preparation process of the cell, determine that certain environmental pollution exists in the industry. And because a large amount of chemicals such as hydrofluoric acid, nitric acid and the like are used in the production process of the crystalline silicon solar cell panel, high-concentration fluorine-containing and nitrogen-containing production wastewater is generated.
At present, a typical treatment method for fluorine-containing wastewater in wastewater treatment systems in photovoltaic and semiconductor industries is a precipitation method, and the chemical precipitation method is to add chemicals such as calcium salt and the like into the fluorine-containing wastewater to form fluoride precipitates or enable the fluoride to be adsorbed in the formed calcium salt precipitates so as to promote the common precipitation and precipitation of the fluoride and the calcium salt. However, the solubility of the calcium salt is low, the calcium salt can only be added in the form of emulsion, the generated precipitate is wrapped on the surface of the particles, the utilization rate is low, the consumption is high, the fluorine content in the wastewater treated by the chemical precipitation method at present can only be reduced to 10-15mg/L, and the national standard grade-I emission standard is difficult to reach.
In the case of the precipitation method defluorination process, the whole process has the defects of slow sediment settlement, difficult dehydration, long period for treating large-flow discharge, incapability of continuous treatment, continuous discharge and the like. Therefore, the traditional treatment process of the fluorine-containing wastewater chemical precipitation method in the photovoltaic industry belongs to primary defluorination precipitation, the effluent quality is unstable, the sludge quantity is large, the occupied area is large, the treatment cost is high, and the waste of resources is easily caused.
Disclosure of Invention
Therefore, the invention aims to overcome the defects that the traditional treatment process of the fluorine-containing wastewater chemical precipitation method in the photovoltaic industry belongs to primary fluorine removal precipitation, the effluent quality is unstable, the sludge quantity is large, the occupied area is large, the treatment cost is high, and the waste of resources is easy to cause in the prior art, thereby providing the efficient fluorine removal medicament suitable for the photovoltaic wastewater and the preparation method thereof.
Therefore, the invention provides the following technical proposal,
the invention provides a high-efficiency defluorination medicament suitable for semiconductor wastewater, which comprises the following raw materials in parts by weight:
in the above-mentioned high-efficiency defluorinating agent, as a preferred embodiment, the preparation method of the modified zircon comprises the following steps:
and (3) melting and ball milling zircon and sodium hydroxide solution to obtain modified zircon.
In the high-efficiency defluorinating agent, as a preferred embodiment, the mass fraction of the sodium hydroxide solution is 10-20%;
and/or, the mass ratio of zircon to sodium hydroxide in the sodium hydroxide solution is 1: (2-3).
In the above-described highly efficient defluorinating agent, as a preferred embodiment, the melting temperature is 680-750 ℃;
and/or, the melting time is 5-8h.
In the above-mentioned high-efficiency defluorinating agent, as a preferred embodiment, the organic acid includes at least one of citric acid, malic acid, and tartaric acid;
and/or, the average particle size of the nano-scale vanadium powder is 1-10nm;
and/or the average particle diameter of the nano-grade titanium powder is 1-10nm.
The invention also provides a preparation method of the efficient defluorination medicament suitable for the semiconductor wastewater, which comprises the following steps:
s1: after modifying silica, adding nano-scale vanadium powder and nano-scale titanium powder for mixing; obtaining mixed powder A;
s2: mixing the modified zircon with the mixed powder A, and then melting and ball milling to obtain mixed powder B;
s3: mixing and heating the mixed powder B and the organic acid to obtain the high-efficiency defluorination medicament.
In the above preparation method, as a preferred embodiment, the method for modifying silica is:
ball milling silica, and adding a modifier for modification to obtain modified silica;
and/or the modifier is a silane coupling agent;
and/or the silane coupling agent is one of gamma- (methacryloyloxy) propyl trimethoxy silane and gamma-glycidoxypropyl trimethoxy silane;
and/or, the mass ratio of the silica to the modifier is (95-99): (1-5);
and/or, the modification time is 50-80min;
and/or, the temperature of the modification is 100-120 ℃;
and/or stirring while the modification is performed;
and/or the stirring speed is 1000-2000r/min.
In the above preparation method, as a preferred embodiment, in step S1, the mixing rate is 500-800r/min;
the mixing time is 10-30min.
In the above preparation method, as a preferred embodiment, in step S2, the mixing speed is 100-300r/min;
and/or, the mixing time is 5-10min;
and/or, the melting temperature is 300-600 ℃;
and/or, the melting time is 1-2h.
In the above preparation method, as a preferred embodiment, in step S3, the heating temperature is 150 to 250 ℃;
and/or the heating temperature is 5-15min.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention provides a high-efficiency defluorination medicament suitable for semiconductor wastewater, which comprises the following raw materials in parts by weight: 50-80 parts of modified silica; 7-15 parts of modified zircon; 3-8 parts of organic acid; 1-3 parts of nano-scale vanadium powder; 1-3 parts of nanoscale titanium powder. The invention adopts modified silica, modified zircon, organic acid, nanoscale vanadium powder and nanoscale titanium powder as raw materials of the defluorination medicament, and can greatly improve the removal efficiency of fluoride ions in the photovoltaic wastewater.
2. According to the invention, zircon is modified, and the modified zircon and modified silica have synergistic effect in removing fluoride ions.
3. According to the invention, the organic acid is added into the raw materials, so that the pore channels in the modified silica and zircon can be further enlarged, and fluoride ions can be better adsorbed.
4. The nanoscale vanadium powder and the nanoscale titanium powder can synergistically improve the adsorption efficiency of the modified silica and the modified zircon on fluoride ions.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides a preparation method of a high-efficiency defluorination medicament for semiconductor wastewater, which comprises the following steps:
s1: after 98kg of silica balls were pulverized, 2kg of gamma- (methacryloyloxy) propyltrimethoxysilane was added for modification for 60min at 110℃while stirring rapidly at a rate of 1500r/min to give modified silica.
S2: 70kg of modified silica and 2kg of nano-sized vanadium powder (average particle size: 5 nm) and 2kg of nano-sized titanium powder (average particle size: 5 nm) were mixed at a rate of 700r/min for 20 minutes to obtain a mixed powder A.
S3: 100kg of zircon and 150kg of sodium hydroxide solution (15% by mass) were mixed and then melted at 700℃for 6 hours, followed by ball milling, to obtain modified zircon.
S4: 10kg of modified zircon and mixed powder A are mixed for 8min at the speed of 200r/min, and then melted for 1.5h at 400 ℃ and ball-milled to obtain mixed powder B.
S5: mixing the mixed powder B with 5kg of citric acid, and heating at 200 ℃ for 10min to obtain the high-efficiency defluorination medicament.
Example 2
The embodiment provides a preparation method of a high-efficiency defluorination medicament for semiconductor wastewater, which comprises the following steps:
s1: after 99kg of silica balls were pulverized, 1kg of gamma- (methacryloyloxy) propyltrimethoxysilane was added for modification for 80min at 100℃while stirring rapidly at 2000r/min to give modified silica.
S2: 50kg of modified silica and 3kg of nano-sized vanadium powder (average particle diameter: 10 nm) and 1kg of nano-sized titanium powder (average particle diameter: 1 nm) were mixed at a rate of 800r/min for 10 minutes to obtain a mixed powder A.
S3: 100kg of zircon and 150kg of sodium hydroxide solution (15% by mass) were mixed and then melted at 750 ℃ for 5 hours, followed by ball milling, to obtain modified zircon.
S4: 15kg of modified zircon and the mixed powder A are mixed for 10min at the speed of 100r/min, and then are melted for 2h at 300 ℃ and ball-milled to obtain mixed powder B.
S5: mixing the mixed powder B with 3kg of citric acid, and heating at 250 ℃ for 5min to obtain the high-efficiency defluorination medicament.
Example 3
The embodiment provides a preparation method of a high-efficiency defluorination medicament for semiconductor wastewater, which comprises the following steps:
s1: after 95kg of silica balls were pulverized, 5kg of gamma- (methacryloyloxy) propyltrimethoxysilane was added for modification for 50min at 120℃while rapidly stirring at a rate of 1000r/min to give modified silica.
S2: 80kg of modified silica and 1kg of nano-sized vanadium powder (average particle diameter: 1 nm) and 3kg of nano-sized titanium powder (average particle diameter: 10 nm) were mixed at a rate of 500r/min for 30 minutes to obtain a mixed powder A.
S3: 100kg of zircon and 150kg of sodium hydroxide solution (15% by mass) were mixed and then melted at 680℃for 8 hours, followed by ball milling, to obtain modified zircon.
S4: 7kg of modified zircon and the mixed powder A are mixed for 5min at the speed of 300r/min, and then melted for 1h at 600 ℃ and ball-milled to obtain mixed powder B.
S5: mixing the mixed powder B with 8kg of citric acid, and heating at 250 ℃ for 15min to obtain the high-efficiency defluorination medicament.
Example 4
The embodiment provides a preparation method of a high-efficiency defluorination medicament for semiconductor wastewater, which comprises the following steps:
s1: after 98kg of silica balls were ground into powder, 2kg of gamma-glycidoxypropyl trimethoxysilane was added for modification at a temperature of 110℃for 60 minutes while rapidly stirring at a rate of 1500r/min to obtain modified silica.
S2: 70kg of modified silica and 2kg of nano-sized vanadium powder (average particle size: 5 nm) and 2kg of nano-sized titanium powder (average particle size: 5 nm) were mixed at a rate of 700r/min for 20 minutes to obtain a mixed powder A.
S3: 100kg of zircon and 150kg of sodium hydroxide solution (15% by mass) were mixed and then melted at 700℃for 6 hours, followed by ball milling, to obtain modified zircon.
S4: 10kg of modified zircon and mixed powder A are mixed for 8min at the speed of 200r/min, and then melted for 1.5h at 400 ℃ and ball-milled to obtain mixed powder B.
S5: mixing the mixed powder B with 5kg of malic acid, and heating at 200 ℃ for 10min to obtain the high-efficiency defluorination medicament.
Example 5
The embodiment provides a preparation method of a high-efficiency defluorination medicament for semiconductor wastewater, which comprises the following steps:
s1: after 98kg of silica balls were pulverized, 2kg of gamma- (methacryloyloxy) propyltrimethoxysilane was added for modification for 60min at 110℃while stirring rapidly at a rate of 1500r/min to give modified silica.
S2: 70kg of modified silica and 2kg of nano-sized vanadium powder (average particle size: 5 nm) and 2kg of nano-sized titanium powder (average particle size: 5 nm) were mixed at a rate of 700r/min for 20 minutes to obtain a mixed powder A.
S3: 100kg of zircon and 150kg of sodium hydroxide solution (15% by mass) were mixed and then melted at 700℃for 6 hours, followed by ball milling, to obtain modified zircon.
S4: 10kg of modified zircon and mixed powder A are mixed for 8min at the speed of 200r/min, and then melted for 1.5h at 400 ℃ and ball-milled to obtain mixed powder B.
S5: mixing the mixed powder B with 5kg of tartaric acid, and heating at 200 ℃ for 10min to obtain the high-efficiency defluorination medicament.
Comparative example 1
The comparative example provides a preparation method of a high-efficiency defluorination medicament for semiconductor wastewater, which comprises the following steps:
s1: after 98kg of silica balls were pulverized, 2kg of gamma- (methacryloyloxy) propyltrimethoxysilane was added for modification for 60min at 110℃while stirring rapidly at a rate of 1500r/min to give modified silica.
S2: 70kg of modified silica and 2kg of nano-sized vanadium powder (average particle size: 5 nm) and 2kg of nano-sized titanium powder (average particle size: 5 nm) were mixed at a rate of 700r/min for 20 minutes to obtain a mixed powder A.
S3: 100kg of zircon and 150kg of sodium hydroxide solution (15% by mass) were mixed and then melted at 700℃for 6 hours, followed by ball milling, to obtain modified zircon.
S4: 10kg of modified zircon and mixed powder A are mixed for 8min at the speed of 200r/min, and then melted for 1.5h at 400 ℃ and ball-milled to obtain the high-efficiency defluorination medicament.
Comparative example 2
The comparative example provides a preparation method of a high-efficiency defluorination medicament for semiconductor wastewater, which comprises the following steps:
s1: 70kg of silica and 2kg of nano-sized vanadium powder (average particle size: 5 nm) and 2kg of nano-sized titanium powder (average particle size: 5 nm) were mixed at a rate of 700r/min for 20 minutes to obtain a mixed powder A.
S2: 100kg of zircon and 150kg of sodium hydroxide solution (15% by mass) were mixed and then melted at 700℃for 6 hours, followed by ball milling, to obtain modified zircon.
S3: 10kg of modified zircon and mixed powder A are mixed for 8min at the speed of 200r/min, and then melted for 1.5h at 400 ℃ and ball-milled to obtain mixed powder B.
S4: mixing the mixed powder B with 5kg of citric acid, and heating at 200 ℃ for 10min to obtain the high-efficiency defluorination medicament.
Comparative example 3
The comparative example provides a preparation method of a high-efficiency defluorination medicament for semiconductor wastewater, which comprises the following steps:
s1: after 98kg of silica balls were pulverized, 2kg of gamma- (methacryloyloxy) propyltrimethoxysilane was added for modification for 60min at 110℃while stirring rapidly at a rate of 1500r/min to give modified silica.
S2: 70kg of modified silica and 2kg of nano-sized vanadium powder (average particle size: 5 nm) and 2kg of nano-sized titanium powder (average particle size: 5 nm) were mixed at a rate of 700r/min for 20 minutes to obtain a mixed powder A.
S3: 10kg of zircon and the mixed powder A are mixed for 8min at the speed of 200r/min, and then melted for 1.5h at 400 ℃ and ball-milled to obtain the mixed powder B.
S4: mixing the mixed powder B with 5kg of citric acid, and heating at 200 ℃ for 10min to obtain the high-efficiency defluorination medicament.
Comparative example 4
The comparative example provides a preparation method of a high-efficiency defluorination medicament for semiconductor wastewater, which comprises the following steps:
s1: after 98kg of silica balls were pulverized, 2kg of gamma- (methacryloyloxy) propyltrimethoxysilane was added for modification for 60min at 110℃while stirring rapidly at a rate of 1500r/min to give modified silica.
S2: 100kg of zircon and 150kg of sodium hydroxide solution (15% by mass) were mixed and then melted at 700℃for 6 hours, followed by ball milling, to obtain modified zircon.
S3: 70kg of modified silica and 10kg of modified zircon are mixed for 8min at a rate of 200r/min, and then melted for 1.5h at 400 ℃ and ball-milled to obtain mixed powder B.
S4: mixing the mixed powder B with 5kg of citric acid, and heating at 200 ℃ for 10min to obtain the high-efficiency defluorination medicament.
Test case
Taking fluorine-containing wastewater from a certain photovoltaic factory, wherein the pH value of the fluorine-containing wastewater is 6, and the concentration of fluorine ions is C 0 =100 mg/L, dividing the obtained fluorine-containing wastewater into 9 parts, 1L each, dissolving the fluorine-removing agents prepared in examples 1-5 and comparative examples 1-4 in deionized water to prepare a solution with a mass fraction of 15%, adding the solution into the fluorine-containing wastewater, stirring for 20min, standing for 15min, collecting the supernatant, and detecting the concentration C of fluorine ions by using a spectrophotometer x And calculates the fluorine removal rate eta= (C 0 -C x )/C 0 X 100%, wherein the method for detecting the concentration of fluorine ions is described in "spectrophotometry for measuring fluorine reagent for aqueous fluoride" (HJ 488-2009), and the results are shown in the following table:
| C x (mg/L) | η(％) | |
| example 1 | 0.15 | 99.85 |
| Example 2 | 1.43 | 98.57 |
| Example 3 | 2.76 | 97.24 |
| Example 4 | 0.18 | 99.82 |
| Example 5 | 0.19 | 99.81 |
| Comparative example 1 | 8.72 | 91.28 |
| Comparative example 2 | 15.79 | 84.21 |
| Comparative example 3 | 23.47 | 76.53 |
| Comparative example 4 | 10.64 | 89.36 |
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (10)
1. The efficient defluorination medicament suitable for the semiconductor wastewater is characterized by comprising the following raw materials in parts by weight:
50-80 parts of modified silica;
7-15 parts of modified zircon;
3-8 parts of organic acid;
1-3 parts of nano-scale vanadium powder;
1-3 parts of nanoscale titanium powder.
2. The efficient fluorine removal agent for semiconductor wastewater as claimed in claim 1, wherein the preparation method of the modified zircon comprises the following steps:
and (3) melting and ball milling zircon and sodium hydroxide solution to obtain modified zircon.
3. The efficient defluorinating agent for semiconductor wastewater according to claim 2, wherein the mass fraction of the sodium hydroxide solution is 10-20%;
and/or, the mass ratio of zircon to sodium hydroxide in the sodium hydroxide solution is 1: (2-3).
4. The high efficiency fluorine removal agent for use in semiconductor wastewater as claimed in claim 2, wherein said melting temperature is 680-750 ℃;
and/or, the melting time is 5-8h.
5. The high efficiency fluorine removal agent for semiconductor wastewater of claim 1, wherein the organic acid comprises at least one of citric acid, malic acid, tartaric acid;
and/or, the average particle size of the nano-scale vanadium powder is 1-10nm;
and/or the average particle diameter of the nano-grade titanium powder is 1-10nm.
6. A method of preparing the highly effective defluorination medicament for semiconductor wastewater according to any one of claims 1 to 5, comprising the steps of:
s1: after modifying silica, adding nano-scale vanadium powder and nano-scale titanium powder for mixing; obtaining mixed powder A;
s2: mixing the modified zircon with the mixed powder A, and then melting and ball milling to obtain mixed powder B;
s3: mixing and heating the mixed powder B and the organic acid to obtain the high-efficiency defluorination medicament.
7. The method for preparing a highly effective defluorination agent for semiconductor wastewater according to claim 6, wherein the method for modifying silica comprises the following steps:
ball milling silica, and adding a modifier for modification to obtain modified silica;
and/or the modifier is a silane coupling agent;
and/or the silane coupling agent is one of gamma- (methacryloyloxy) propyl trimethoxy silane and gamma-glycidoxypropyl trimethoxy silane;
and/or, the mass ratio of the silica to the modifier is (95-99): (1-5);
and/or, the modification time is 50-80min;
and/or, the temperature of the modification is 100-120 ℃;
and/or stirring while the modification is performed;
and/or the stirring speed is 1000-2000r/min.
8. The method for preparing a highly effective defluorination agent for semiconductor wastewater according to claim 6, wherein in step S1, the mixing speed is 500-800r/min;
the mixing time is 10-30min.
9. The method for preparing a highly effective defluorination agent for semiconductor wastewater according to claim 6, wherein in step S2, the mixing speed is 100-300r/min;
and/or, the mixing time is 5-10min;
and/or, the melting temperature is 300-600 ℃;
and/or, the melting time is 1-2h.
10. The method for preparing a highly efficient defluorination medicament suitable for semiconductor wastewater according to claim 6, wherein in step S3, the heating temperature is 150-250 ℃;
and/or the heating temperature is 5-15min.
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|---|---|---|---|---|
| CN101780397A (en) * | 2010-01-29 | 2010-07-21 | 广东药学院 | Preparation method of lanthanum oxide-carrying zeolite for removing fluorine |
| CN102114402A (en) * | 2009-12-31 | 2011-07-06 | 中国科学院生态环境研究中心 | Defluorinating adsorbent and preparation method thereof |
| US20160016823A1 (en) * | 2013-02-26 | 2016-01-21 | Consejo Superior De Investigaciones Científicas (Csic) | Natural zeolite-nanohydroxyapatite compound material, method for preparing same and use thereof for removing fluoride from water |
| CN107497401A (en) * | 2017-09-15 | 2017-12-22 | 南京汉尔斯生物科技有限公司 | A kind of environmentally friendly preparation for originally water fluoridation |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102114402A (en) * | 2009-12-31 | 2011-07-06 | 中国科学院生态环境研究中心 | Defluorinating adsorbent and preparation method thereof |
| CN101780397A (en) * | 2010-01-29 | 2010-07-21 | 广东药学院 | Preparation method of lanthanum oxide-carrying zeolite for removing fluorine |
| US20160016823A1 (en) * | 2013-02-26 | 2016-01-21 | Consejo Superior De Investigaciones Científicas (Csic) | Natural zeolite-nanohydroxyapatite compound material, method for preparing same and use thereof for removing fluoride from water |
| CN107497401A (en) * | 2017-09-15 | 2017-12-22 | 南京汉尔斯生物科技有限公司 | A kind of environmentally friendly preparation for originally water fluoridation |
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