CN115340210A - Special medicament, device and method for recycling treatment of titanium dioxide wastewater produced by sulfuric acid process - Google Patents
Special medicament, device and method for recycling treatment of titanium dioxide wastewater produced by sulfuric acid process Download PDFInfo
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- CN115340210A CN115340210A CN202210974746.7A CN202210974746A CN115340210A CN 115340210 A CN115340210 A CN 115340210A CN 202210974746 A CN202210974746 A CN 202210974746A CN 115340210 A CN115340210 A CN 115340210A
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- 239000003814 drug Substances 0.000 title claims abstract description 203
- 239000002351 wastewater Substances 0.000 title claims abstract description 127
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000000034 method Methods 0.000 title claims abstract description 75
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 42
- 238000004064 recycling Methods 0.000 title claims description 31
- 230000008569 process Effects 0.000 title claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 86
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 72
- 238000005188 flotation Methods 0.000 claims abstract description 67
- 238000000926 separation method Methods 0.000 claims abstract description 60
- 238000001556 precipitation Methods 0.000 claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 23
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 16
- 230000014759 maintenance of location Effects 0.000 claims description 16
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 15
- 239000000920 calcium hydroxide Substances 0.000 claims description 15
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 15
- 229920002401 polyacrylamide Polymers 0.000 claims description 15
- 235000006408 oxalic acid Nutrition 0.000 claims description 13
- 239000007787 solid Substances 0.000 claims description 13
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 12
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 10
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 8
- RNIHAPSVIGPAFF-UHFFFAOYSA-N Acrylamide-acrylic acid resin Chemical compound NC(=O)C=C.OC(=O)C=C RNIHAPSVIGPAFF-UHFFFAOYSA-N 0.000 claims description 6
- 229920006322 acrylamide copolymer Polymers 0.000 claims description 6
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 6
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 6
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 5
- 150000003839 salts Chemical class 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 30
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 11
- 239000011575 calcium Substances 0.000 description 11
- 150000002500 ions Chemical class 0.000 description 10
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 9
- 229910001424 calcium ion Inorganic materials 0.000 description 9
- 229910001425 magnesium ion Inorganic materials 0.000 description 9
- 239000002699 waste material Substances 0.000 description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 5
- 235000011941 Tilia x europaea Nutrition 0.000 description 5
- 239000004571 lime Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 210000005056 cell body Anatomy 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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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
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- 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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
-
- 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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
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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
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
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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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/05—Conductivity or salinity
- C02F2209/055—Hardness
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/11—Turbidity
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/44—Time
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Abstract
The invention relates to the technical field of wastewater reuse treatment, in particular to a special medicament, a special device and a special method for the reuse treatment of sulfuric acid method titanium dioxide wastewater, wherein the special medicament, the special device and the special method for the reuse treatment of sulfuric acid method titanium dioxide wastewater comprise a medicament adding module, a separation module and a neutralization air flotation module; the wastewater sequentially flows through the precipitation separation module and the neutralization air flotation module, and the hard substances are separated and removed through reaction with the special medicament; the system not only has the advantages of simple and convenient operation, low dosage of the medicament and stable water quality of the effluent, but also reflects the characteristic that the total salt content in the treated water is reduced, and has important significance for reusing in the production process.
Description
Technical Field
The invention relates to the technical field of wastewater recycling treatment, in particular to a special medicament, a device and a method for recycling treatment of titanium dioxide wastewater by a sulfuric acid method.
Background
The titanium dioxide production has large discharge amount of three wastes, high treatment cost and low added value of the comprehensive utilization product. With the stricter and stricter national requirements on environmental protection, the treatment of three wastes can reach the standard and becomes an important factor restricting the sustainable development of enterprises. The production of titanium dioxide by the sulfuric acid method needs to discharge waste acid with higher concentration and a large amount of acid waste water, and the waste water and the waste acid can cause great pollution to the environment if being directly discharged without being treated, thereby seriously affecting the health of people in the area. At present, the acid wastewater of titanium dioxide in sulfuric acid process is treated by adopting a neutralization process at home and abroad, and waste alkali, carbide mud, lime and the like can be adopted for neutralization according to local conditions. The treated discharged wastewater has the potential of recycling, if the discharged wastewater is directly discharged, certain sewage discharge cost is paid, and the great waste of water resources is also caused. The concentration of heavy metals in the titanium dioxide waste water is basically lower than that of secondary washing water in production, calcium in the waste water mainly exists in a supersaturated state calcium sulfate form and is accompanied by a small amount of calcium hydroxide and calcium carbonate, and if the waste water is completely used for the titanium dioxide production process, the calcium content in the titanium dioxide is increased, so that the product quality is reduced. Therefore, calcium and magnesium ions in the discharged wastewater need to be removed to a certain extent so as to meet the requirement of recycled water quality.
The commonly used method for removing calcium and magnesium ions mainly comprises a medicament softening method, an ion exchange method, an adsorption method, a membrane separation method and the like. The ion exchange method replaces calcium and magnesium ions by cation exchange resin so as to achieve the aim of removing the calcium and magnesium ions, has high removal rate and stable treatment effect, but the ion exchange resin is easy to block and pollute, and has higher resin cost and fussy regeneration process. In addition, the dosage of the regenerant is large, the salt concentration is high, and the pollution of the discharge of the regenerated waste liquid to the environment needs to be considered. The adsorption method is to utilize the adsorbent to adsorb calcium and magnesium ions on the surface or inside the adsorbent so as to reduce the concentration of the calcium and magnesium ions in the wastewater, and has the advantages of simple operation, good treatment effect and low price of the adsorbent, but the adsorbent generally has limited adsorption capacity and large using amount, and the water treatment process generates more waste residues and has large solid waste treatment capacity. The membrane separation method realizes the separation of calcium and magnesium ions by utilizing the driving force formed by pressure difference, concentration difference and the like at two ends of the membrane, thereby reducing the hardness of effluent, has high efficiency, simple operation and good separation performance, can effectively avoid secondary pollution, but also has the problems of easy pollution of the membrane surface and concentration polarization, and the processing capacity is not easy to recover. In addition, the membrane influent water has certain water quality requirements, and the pretreatment requirement is generally higher. The most widely used is the pharmaceutical softening process. The traditional chemical softening method is divided into lime softening method, lime gypsum softening method and lime soda softening method, mainly by adding chemical agents to convert calcium and magnesium ions in water into hydroxide or carbonate precipitates, the used agents are low in price and wide in source and convenient to use, but the water treated by the method is alkaline and needs to be adjusted in pH value. In addition, the method has a great disadvantage that calcium and magnesium ions in water are mainly replaced by sodium ions, and other anions except for bicarbonate are not basically removed, so that the salt content in the water is higher and higher, the quality of the product is influenced when the certain concentration is reached, the hardness ions are removed, and the product cannot be normally recycled, and the water quality cannot meet the recycling requirement simply by chemical softening.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a special medicament, a device and a method for recycling and treating titanium dioxide wastewater by a sulfuric acid method. The device for recycling and treating the titanium dioxide wastewater by the sulfuric acid method consists of a medicament adding module, a separation module and a neutralization air flotation module; the wastewater sequentially flows through the precipitation separation module and the neutralization air flotation module, and the hard substances are separated and removed through reaction with the special medicament; the system not only has the advantages of simple and convenient operation, low dosage of the medicament and stable effluent quality, but also embodies the characteristic that the total salt content in the treated water is reduced, has important significance for reusing in the production process, and is the important advantage of the invention.
The purpose of the invention can be realized by the following technical scheme:
the invention provides a device for recycling and treating titanium dioxide wastewater by a sulfuric acid method, which comprises a medicament adding module, a precipitation and separation module and a neutralization air flotation module;
the medicament adding module comprises a first medicament adding tank, a second medicament adding tank, a third medicament adding tank and a fourth medicament adding tank;
the bottom of the precipitation separation module is provided with a water inlet pipe for wastewater to flow in, and the bottom of the neutralization air floatation module is provided with a water outlet pipe;
the first dosing tank, the second dosing tank and the fourth dosing tank are connected with the dosing pipe and the water inlet pipe of the precipitation separation module through the dosing pump; and the third dosing tank and the fourth dosing tank are connected with the neutralization air flotation module through a dosing pump and a dosing pipe.
In one embodiment of the invention, a bubble releaser is arranged at the upper part of the water outlet pipe of the neutralization air flotation module.
In one embodiment of the present invention, the first dosing tank contains a first medicament selected from one of aluminum sulfate or polyaluminum sulfate;
the second medicine adding tank is used for containing a second medicine, and the second medicine is selected from one of barium hydroxide or calcium hydroxide;
the third medicine adding tank is filled with a third medicine selected from one of oxalic acid or phosphoric acid;
the fourth medicine adding tank is filled with a fourth medicine, and the fourth medicine is selected from one of polyacrylamide, sodium polystyrene sulfonate or acrylic acid-acrylamide copolymer.
The second purpose of the invention is to provide a special medicament for the reuse treatment of the sulfuric acid method titanium dioxide wastewater, which comprises a first medicament, a second medicament, a third medicament and a fourth medicament,
the first agent is selected from one of aluminum sulfate or polyaluminum sulfate; the second agent is selected from one of barium hydroxide or calcium hydroxide; the third agent is selected from one of oxalic acid or phosphoric acid; the fourth medicament is selected from one of polyacrylamide, sodium polystyrene sulfonate or acrylic acid-acrylamide copolymer.
The third purpose of the invention is to provide a method for recycling and treating titanium dioxide wastewater by a sulfuric acid method, which comprises the following steps:
(S1) the wastewater enters a precipitation separation module through a water inlet pipe;
(S2) respectively adding a first medicament, a second medicament and a fourth medicament into the precipitation and separation module through a medicament adding pump by a first medicament adding tank, a second medicament and a fourth medicament adding tank to obtain pretreated wastewater, wherein solid suspended matters are precipitated and subsided after the first medicament, the second medicament and the fourth medicament are mixed and reacted with the wastewater, and the pretreated wastewater flows upwards and enters the neutralization air flotation module;
(S3) respectively adding a third medicament and a fourth medicament into the neutralization and air flotation module through a medicament adding pump by a third medicament adding tank and a fourth medicament adding tank to obtain reuse water, wherein the pretreated wastewater, the third medicament and the fourth medicament are subjected to acid-base neutralization reaction to separate out solid suspended matters;
and (S4) carrying the solid suspended matters released in the step (S3) by bubbles released by the bubble releaser to float to the top of the neutralization air flotation module, and discharging the reclaimed water from a water outlet pipe after the reclaimed water flows downwards in the tank body of the neutralization air flotation module.
In one embodiment of the invention, the mass ratio of the first medicament to the hardness of the wastewater in the precipitation separation module is 2:1 to 10.
In one embodiment of the invention, the pH value in the precipitation separation module after the second medicament is added is 11.5-12.
In one embodiment of the invention, the pH value in the neutralization air flotation module after the third agent is added is 7-7.5.
In one embodiment of the invention, the dosage ratio of the fourth agent to the pretreated wastewater in the neutralization air flotation module is 0.5-3 mg:1L of the total amount of the active ingredients.
In one embodiment of the invention, the dosage ratio of the fourth medicament to the wastewater in the precipitation separation module is 0.5-5 mg:1L of the total amount of the active ingredients.
In one embodiment of the invention, the hydraulic retention time of the wastewater in the precipitation separation module is 10-45 min; the hydraulic retention time of the pretreated wastewater in the neutralization air flotation module is 5-20 min.
Compared with the prior art, the invention has the following beneficial effects:
(1) The special medicament treatment device for removing the hardness ions in the sulfuric acid method titanium dioxide wastewater provided by the invention has the advantages of rapid precipitate precipitation, low residue of the removed substances, simple operation, stable operation and the like.
(2) After the medicament and the device are used for treatment, the total amount of anions and cations in the wastewater is reduced, and after the wastewater is treated, recycled, treated and recycled for a plurality of cycles, the salt content in the water is increased to the extent of influencing the quality of the produced product due to the accumulation of inorganic salt caused by adding the recycled treatment medicament, so that the zero discharge of the wastewater can be realized.
Drawings
FIG. 1 is a schematic diagram of a device for recycling treatment of titanium dioxide wastewater produced by a sulfuric acid process according to the present invention;
reference numbers in the figures: 1. a medicament adding module; 2. a precipitation separation module; 3. a neutralization air flotation module; 4. a first dosing tank; 5. a second dosing tank; 6. a third dosing tank; 7. a fourth medicine adding tank; 8. a water inlet pipe; 9. a water outlet pipe; 10. and a bubble releaser.
Detailed Description
The invention provides a device for recycling and treating titanium dioxide wastewater by a sulfuric acid method, which comprises a medicament adding module, a precipitation and separation module and a neutralization air flotation module;
the medicament adding module comprises a first medicament adding tank, a second medicament adding tank, a third medicament adding tank and a fourth medicament adding tank;
the bottom of the precipitation separation module is provided with a water inlet pipe for wastewater to flow in, and the bottom of the neutralization air floatation module is provided with a water outlet pipe;
the first dosing tank, the second dosing tank and the fourth dosing tank are connected with the dosing pipe and the water inlet pipe of the precipitation separation module through the dosing pump; and the third dosing tank and the fourth dosing tank are connected with the neutralization air flotation module through a dosing pump and a dosing pipe.
In one embodiment of the invention, a bubble releaser is arranged at the upper part of the water outlet pipe of the neutralization air flotation module.
In one embodiment of the present invention, the first dosing tank contains a first medicament selected from one of aluminum sulfate or polyaluminum sulfate;
the second medicine adding tank is used for containing a second medicine, and the second medicine is selected from one of barium hydroxide or calcium hydroxide;
the third medicine adding tank is filled with a third medicine selected from one of oxalic acid or phosphoric acid;
the fourth medicine adding tank is filled with a fourth medicine, and the fourth medicine is selected from one of polyacrylamide, sodium polystyrene sulfonate or acrylic acid-acrylamide copolymer.
The invention provides a special medicament for recycling and treating titanium dioxide wastewater by a sulfuric acid method, which comprises a first medicament, a second medicament, a third medicament and a fourth medicament,
the first agent is selected from one of aluminum sulfate or polyaluminum sulfate; the second agent is selected from one of barium hydroxide or calcium hydroxide; the third agent is selected from one of oxalic acid or phosphoric acid; the fourth medicament is selected from one of polyacrylamide, sodium polystyrene sulfonate or acrylic acid-acrylamide copolymer.
The invention provides a method for recycling and treating titanium dioxide wastewater by a sulfuric acid method, which comprises the following steps:
(S1) the wastewater enters a precipitation separation module through a water inlet pipe;
(S2) respectively adding a first medicament, a second medicament and a fourth medicament into the precipitation and separation module through a medicament adding pump by a first medicament adding tank, a second medicament and a fourth medicament adding tank to obtain pretreated wastewater, wherein solid suspended matters are precipitated and subsided after the first medicament, the second medicament and the fourth medicament are mixed and reacted with the wastewater, and the pretreated wastewater flows upwards and enters the neutralization air flotation module;
(S3) respectively adding a third medicament and a fourth medicament into the neutralization and air floatation module through a medicament adding pump by a third medicament adding tank and a fourth medicament adding tank to obtain reuse water, wherein the pretreated wastewater, the third medicament and the fourth medicament are subjected to acid-base neutralization reaction to separate out solid suspended matters;
and (S4) the solid suspended matters in the step (S3) are carried by the bubbles released by the bubble releaser to float to the top of the neutralization air flotation module, and the reuse water flows downwards in the neutralization air flotation module and is discharged by a water outlet pipe.
In one embodiment of the present invention, the mass ratio of the first chemical to the hardness of the wastewater in the precipitation separation module is 2:1 to 10.
In one embodiment of the invention, the pH value in the precipitation separation module after the second medicament is added is 11.5-12.
In one embodiment of the invention, the pH value in the neutralization air flotation module after the third agent is added is 7-7.5.
In one embodiment of the invention, the dosage ratio of the fourth agent to the pretreated wastewater in the neutralization air flotation module is 0.5-3 mg:1L of the compound.
In one embodiment of the invention, the dosage ratio of the fourth medicament to the wastewater in the precipitation separation module is 0.5-5 mg:1L of the compound.
In one embodiment of the invention, the hydraulic retention time of the wastewater in the precipitation separation module is 10-45 min; the hydraulic retention time of the pretreated wastewater in the neutralization air flotation module is 5-20 min.
The invention is described in detail below with reference to the figures and specific embodiments.
In the following examples, all reagents used are commercially available reagents unless otherwise specified; the detection means and the method are conventional detection means and methods in the field.
Example 1
The special agent for removing hardness ions in titanium dioxide wastewater produced by a sulfuric acid process is a combination of polymeric aluminum sulfate, calcium hydroxide, oxalic acid and polyacrylamide.
A retrieval and utilization processing apparatus for cooperating special medicament use to get rid of hardness ion in titanium white powder waste water, as shown in figure 1, the device is thrown module 1, is appeared separating module 2 and well and is floated module 3 by the medicament and constitutes, and the whole inlet tube 8 of device sets up in appearing separating module 2 bottom, and the whole outlet pipe 9 of device sets up in well and floats module 3 bottom, sets up bubble releaser 10 above the outlet pipe 9. The medicament feeding module 1 is respectively connected with the precipitation separation module 2 and the middle and air flotation module 3 through a medicament feeding pipe. The reagent feeding module 1 comprises 4 dosing tanks (a first dosing tank 4, a second dosing tank 5, a third dosing tank 6 and a fourth dosing tank 7), wherein the first dosing tank 4 contains polyaluminium sulfate and is connected with the precipitation separation module 2 at a water inlet pipe 8 through a dosing pump and a dosing pipe; the second dosing tank 5 is filled with calcium hydroxide and is connected with the precipitation separation module 2 at the water inlet pipe 8 through a dosing pump and a dosing pipe. The third medicine adding tank 6 is filled with oxalic acid and is connected with the neutralization air flotation module 3 at the top of the tank body through a medicine adding pump and a medicine adding pipe. The fourth dosing tank 7 is filled with polyacrylamide and is respectively connected with the precipitation and separation module 2 at the water inlet pipe 8 and the medium and air flotation module 3 at the top of the tank body through a dosing pump and a dosing pipe. The precipitation separation module 2 and the neutralization air flotation module 3 are communicated at the top of the tank body, and water flows upwards from the bottom in the tank body of the precipitation separation module 2 and flows downwards from the top in the tank body of the neutralization air flotation module 3 through a connecting port.
The method is characterized in that the content of hardness substances in the wastewater is measured in advance, and the medicament and the device are applied to treat the sulfuric acid method titanium dioxide wastewater with the total hardness of 2000mg/L, the turbidity of 5NTU and the pH value of 6.8 so as to achieve the recycling target, and the method comprises the following steps:
(S1) the wastewater enters a precipitation separation module 2 through a water inlet pipe 8, a first dosing tank 4, a second dosing tank 5 and a fourth dosing tank 7 add medicaments (a first medicament, a second medicament and a fourth medicament) into the precipitation separation module 2 through a dosing pump, the dosage of polyaluminium sulfate (the first medicament) is 1200mg/L water, the dosage of calcium hydroxide (the second medicament) is 500mg/L water, the pH value of the wastewater is 11.5, the dosage of polyacrylamide (the fourth medicament) is 3mg/L water, the medicaments and the wastewater are mixed and reacted to precipitate solid suspended matters and sink, the water flows upwards and enters an air flotation module 3 from the top, and the retention time of the wastewater in the precipitation separation module 2 is 40min to obtain pretreated wastewater.
(S2) the pretreated wastewater passing through the precipitation separation module 2 flows downwards in the neutralization air flotation module 3, the third medicine adding tank 6 and the fourth medicine adding tank 7 add medicines (a third medicine and a fourth medicine) into the neutralization air flotation module 3 through a medicine adding pump, the adding amount of oxalic acid (the third medicine) is controlled to control the pH value of neutralized water to be 7, the adding amount of polyacrylamide (the fourth medicine) is 0.5mg/L, a small amount of suspended matters are generated after the pretreated wastewater and the medicines are neutralized in pH value to obtain reuse water, the suspended matters are carried by bubbles released by a bubble releaser 10 to float to the top of the cell body of the neutralization air flotation module 3, the reuse water flows downwards in the neutralization air flotation module 3 and is discharged from a water outlet pipe 9, and the residence time of the pretreated wastewater in the neutralization air flotation module 3 is 8min;
the total hardness of the reuse water obtained after the wastewater is treated is reduced to about 100mg/L, the turbidity is lower than 1NTU, and the pH value is in the range of 6.8-7.5.
Example 2
The special agent for removing hardness ions in titanium dioxide wastewater produced by a sulfuric acid process is a combination of polymeric aluminum sulfate, calcium hydroxide, oxalic acid and polyacrylamide.
The recycling treatment device for removing the hardness ions in the titanium dioxide wastewater by matching with a special medicament is basically the same as the embodiment 1, and is different in that the volume ratio of the precipitation separation module 2 to the neutralization air flotation module 3 is different, so that the retention time ratio of water in the two modules is different.
The method is characterized in that the content of hardness substances in the wastewater is measured in advance, and the medicament and the device are applied to treat the sulfuric acid process titanium dioxide wastewater with the total hardness of 2000mg/L, the turbidity of 5NTU and the pH value of 6.7 so as to achieve the recycling target, and the method comprises the following steps:
(S1) wastewater enters a precipitation separation module 2 from a water inlet pipe 8, a medicament is added into the precipitation separation module 2 through a medicament adding pump by a first medicament adding tank 4, a second medicament adding tank 5 and a fourth medicament adding tank 7, the dosage of polymeric aluminum sulfate is 4000mg/L water, the dosage of calcium hydroxide is 700mg/L water, the pH value of the added wastewater is 12, the dosage of polyacrylamide is 5mg/L water, the medicament is mixed with the wastewater to react to precipitate solid suspended matters, the water flows upwards and enters a neutralization air flotation module 3 from the top, and the retention time of the wastewater in the precipitation separation module 2 is 45min, so that pretreated wastewater is obtained.
(S2) the pretreated wastewater passing through the precipitation separation module 2 flows downwards in the neutralization air flotation module 3, a medicament is added into the neutralization air flotation module 3 through a medicament adding pump by a third medicament adding tank 6 and a fourth medicament adding tank 7, the pH value of the neutralized water is controlled to be 7 by oxalic acid adding amount, the adding amount of polyacrylamide is 1mg/L, a small amount of suspended matters are generated after the wastewater is neutralized, reuse water is obtained, the suspended matters are carried by bubbles released by a bubble releaser 10 and float to the top of a tank body of the neutralization air flotation module 3, the reuse water flows downwards in the neutralization air flotation module and is discharged from an outlet pipe 9, and the retention time of the pretreated wastewater in the neutralization air flotation module 3 is 20min.
The total hardness of the reuse water obtained after the wastewater is treated is reduced to about 40mg/L, the turbidity is lower than 0.5NTU, and the pH value is about 7.
Example 3
The special agent for removing hardness ions in titanium dioxide wastewater produced by a sulfuric acid process is a combination of polymeric aluminum sulfate, calcium hydroxide, phosphoric acid and sodium polystyrene sulfonate.
The recycling treatment device for removing the hardness ions in the titanium dioxide wastewater by matching with a special medicament is basically the same as the embodiment 1, and is different in that the volume ratio of the precipitation separation module 2 to the neutralization air flotation module 3 is different, so that the retention time ratio of water in the two modules is different.
The method is characterized in that the content of hardness substances in the wastewater is measured in advance, and the medicament and the device are applied to treat the sulfuric acid process titanium dioxide wastewater with the total hardness of 3000mg/L, the turbidity of 8NTU and the pH value of 6.8 so as to achieve the recycling target, and the method comprises the following steps:
(S1) wastewater enters a precipitation separation module 2 through a water inlet pipe 8, a medicament is added into the precipitation separation module 2 through a medicament adding pump by a first medicament adding tank 4, a second medicament adding tank 5 and a fourth medicament adding tank 7, the dosage of polymeric aluminum sulfate is 600mg/L water, the dosage of calcium hydroxide is 600mg/L water, the pH value of the wastewater is adjusted to 11.7, the dosage of polyacrylamide is 5mg/L water, the medicament and the wastewater are mixed and reacted to precipitate solid suspended matters, the water flows upwards and enters a neutralization air flotation module 3 from the top, and the retention time of the wastewater in the precipitation separation module 2 is 10min, so that pretreated wastewater is obtained.
(S2) the pretreated wastewater passing through the precipitation separation module 2 flows downwards in the neutralization air flotation module 3, a medicament is added into the neutralization air flotation module 3 through a medicament adding pump by a third medicament adding tank 6 and a fourth medicament adding tank 7, the adding amount of oxalic acid controls the pH value of the neutralized water to be 7, the adding amount of sodium polystyrene sulfonate is 3mg/L, a small amount of suspended matters are generated after the wastewater is neutralized in the pH value and recycled water is obtained, the suspended matters are carried by bubbles released by a bubble releaser 10 and float to the top of the tank body of the neutralization air flotation module 3, the recycled water flows downwards in the tank body of the neutralization air flotation module 3 and is discharged from an outlet pipe 9, and the retention time of the pretreated wastewater in the neutralization air flotation module 3 is 10min.
The total hardness of the reuse water obtained after the wastewater is treated is reduced to about 130mg/L, the turbidity is lower than 0.5NTU, and the pH value is about 7.
Example 4
The special agent for removing hardness ions in titanium dioxide wastewater produced by a sulfuric acid process is a combination of polymeric aluminum sulfate, lime, phosphoric acid and sodium polystyrene sulfonate.
The recycling treatment device for removing the hardness ions in the titanium dioxide wastewater by matching with a special medicament is basically the same as the embodiment 1, and is different in that the volume ratio of the precipitation separation module 2 to the neutralization air flotation module 3 is different, so that the retention time ratio of water in the two modules is different.
The method is characterized in that the content of hardness substances in the wastewater is measured in advance, and the medicament and the device are applied to treat the sulfuric acid process titanium dioxide wastewater with the total hardness of about 1000mg/L so as to achieve the recycling target, and the method comprises the following steps:
(S1) wastewater enters a precipitation separation module 2 through a water inlet pipe 8, a medicament is added into the precipitation separation module 2 through a medicament adding pump by a first medicament adding tank 4, a second medicament adding tank 5 and a fourth medicament adding tank 7, the dosage of polyaluminium sulfate is 500mg/L water, the dosage of calcium hydroxide is 600mg/L water, the pH value of the wastewater is adjusted to 12, the dosage of polyacrylamide is 0.5mg/L water, the medicament and the wastewater are mixed and reacted to precipitate solid suspended matters, the water flows upwards and enters a neutralization air flotation module 3 from the top, and the retention time of the wastewater in the precipitation separation module 2 is 30min to obtain pretreated wastewater.
(S2) the pretreated wastewater passing through the precipitation separation module 2 flows downwards in the neutralization air flotation module 3, a medicament is added into the neutralization air flotation module 3 through a medicament adding pump by a third medicament adding tank 6 and a fourth medicament adding tank 7, the adding amount of oxalic acid is controlled to be 7 of the pH value of neutralized water, the adding amount of sodium polystyrene sulfonate is 0.5mg/L, a small amount of suspended matters are generated after the pH value of the wastewater is neutralized and recycled water is obtained, the suspended matters are carried by bubbles released by a bubble releaser 10 and float to the top of a tank body of the neutralization air flotation module 3, the recycled water flows downwards in the tank body of the neutralization air flotation module 3 and is discharged from an outlet pipe 9, and the retention time of the pretreated wastewater in the neutralization air flotation module 3 is 5min.
The total hardness of the reuse water obtained after the wastewater is treated is reduced to about 60mg/L, the turbidity is lower than 1NTU, and the pH value is about 7.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make modifications and alterations without departing from the scope of the present invention.
Claims (10)
1. A device for recycling and treating titanium dioxide wastewater by a sulfuric acid method is characterized by comprising a medicament adding module (1), a separation module (2) and a neutralization air flotation module (3);
the medicament adding module (1) comprises a first medicament adding tank (4), a second medicament adding tank (5), a third medicament adding tank (6) and a fourth medicament adding tank (7);
a water inlet pipe (8) for wastewater to flow into is arranged at the bottom of the precipitation separation module (2), and a water outlet pipe (9) is arranged at the bottom of the neutralization air flotation module (3);
the first dosing tank (4), the second dosing tank (5) and the fourth dosing tank (7) are connected with a dosing pipe and a water inlet pipe (8) of the precipitation separation module (2) through a dosing pump; the third medicine adding tank (6) and the fourth medicine adding tank (7) are connected with the neutralization air flotation module (3) through a medicine adding pump and a medicine adding pipe.
2. The device for recycling and treating titanium dioxide wastewater produced by a sulfuric acid process according to claim 1, wherein a bubble releaser (10) is arranged at the upper part of the water outlet pipe (9) of the neutralization air flotation module (3).
3. The device for recycling and treating the wastewater generated in the production of titanium dioxide by the sulfuric acid process according to claim 1, wherein the first medicine adding tank (4) contains a first medicine, and the first medicine is selected from one of aluminum sulfate and polyaluminum sulfate;
the second medicine adding tank (5) contains a second medicine which is selected from one of barium hydroxide or calcium hydroxide;
the third medicine adding tank (6) contains a third medicine which is selected from one of oxalic acid or phosphoric acid;
the fourth medicine adding tank (7) contains a fourth medicine, and the fourth medicine is selected from one of polyacrylamide, sodium polystyrene sulfonate or acrylic acid-acrylamide copolymer.
4. A special medicament for recycling and treating titanium dioxide wastewater by a sulfuric acid method is characterized by comprising a first medicament, a second medicament, a third medicament and a fourth medicament,
the first agent is selected from one of aluminum sulfate or polyaluminum sulfate; the second agent is selected from one of barium hydroxide or calcium hydroxide; the third agent is selected from one of oxalic acid or phosphoric acid; the fourth medicament is selected from one of polyacrylamide, sodium polystyrene sulfonate or acrylic acid-acrylamide copolymer.
5. A method for recycling and treating titanium dioxide wastewater produced by a sulfuric acid method is characterized by comprising the following steps:
(S1) the wastewater enters a precipitation separation module (2) through a water inlet pipe (8);
(S2) a first medicine adding tank (4), a second medicine adding tank (5) and a fourth medicine adding tank (7) respectively add a first medicine, a second medicine and a fourth medicine into the precipitation and separation module (2) through a medicine adding pump to obtain pretreated wastewater, the first medicine, the second medicine and the fourth medicine are mixed with the wastewater and react to precipitate solid suspended matters and sink, and the pretreated wastewater flows upwards and enters the neutralization and air flotation module (3);
(S3) respectively adding a third medicament and a fourth medicament into the neutralization air flotation module (3) through a third medicament adding tank (6) and a fourth medicament adding tank (7) through a medicament adding pump to obtain reuse water, wherein the pretreated wastewater, the third medicament and the fourth medicament undergo acid-base neutralization reaction to separate out solid suspended matters;
and (S4) the solid suspended matters in the step (S3) are carried by the bubbles released by the bubble releaser (10) to float to the top of the neutralization air flotation module (3), and the reuse water flows downwards in the tank body of the neutralization air flotation module (3) and is discharged by a water outlet pipe (9).
6. The method for recycling treatment of titanium dioxide wastewater produced by sulfuric acid process according to claim 5, wherein the mass ratio of the first agent to the hardness of wastewater in the precipitation separation module (2) is 2:1 to 10.
7. The method for recycling the titanium dioxide wastewater produced by the sulfuric acid process according to claim 5, wherein the pH value in the precipitation module (2) after the second agent is added is 11.5-12.
8. The method for recycling and treating titanium dioxide wastewater produced by a sulfuric acid process according to claim 5, wherein the pH value in the neutralization air flotation module (3) is 7-7.5 after the third agent is added.
9. The method for recycling and treating titanium dioxide wastewater generated by a sulfuric acid process according to claim 5, wherein the dosage ratio of the fourth agent to the wastewater in the precipitation and separation module (2) is 0.5-5 mg:1L;
the dosage ratio of the fourth medicament to the pretreated wastewater in the neutralization air flotation module (3) is 0.5-5 mg:1L of the total amount of the active ingredients.
10. The method for recycling the titanium dioxide wastewater generated by the sulfuric acid process according to claim 5, wherein the hydraulic retention time of the wastewater in the precipitation and separation module (2) is 5-45 min; the hydraulic retention time of the pretreated wastewater in the neutralization air flotation module (3) is 2-20 min.
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