CN110372075A - A kind of new and effective fluorine removal medicament and its application - Google Patents
A kind of new and effective fluorine removal medicament and its application Download PDFInfo
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- CN110372075A CN110372075A CN201910396476.4A CN201910396476A CN110372075A CN 110372075 A CN110372075 A CN 110372075A CN 201910396476 A CN201910396476 A CN 201910396476A CN 110372075 A CN110372075 A CN 110372075A
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- fluorine removal
- removal medicament
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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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
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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
- C02F1/28—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
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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
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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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
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a kind of new and effective fluorine removal medicament and its applications, belong to fluoride wastewater treatment technical field.The fluorine removal medicament is by following mass fraction at being grouped as: poly-ferric chloride 8%, bodied ferric sulfate 16%, polyaluminium sulfate 16%, polymeric aluminum sulfate iron 16%, aluminium polychloride 18%, tealeaves iron 7%, modified coal ash 6%, modified zeolite 6%, calcium monohydrogen phosphate 4%, flocculation aid 3%.When being handled using the defluorinating agent fluoride waste, being stirred to react 15min can make the removal rate of fluorine ion reach 95% or more, and fluorine removal speed is fast, and defluorination effect is good.
Description
Technical field
The present invention relates to a kind of fluorine removal medicaments, and in particular to a kind of new and effective fluorine removal medicament belongs to fluoride wastewater treatment
Technical field.
Background technique
Coal chemical industrial waste water is the industrial wastewater generated in coal chemical industry production technology.Coal chemical industry production technology is with coal for original
Material converts coal into gaseous state, liquid, solid-state by chemical production processes such as carbonization of coal, coal gasification, coal liquefaction, tar chemical industry
Product and a variety of chemical products.The waste water generated by the production technology mainly has coking wastewater, gasification waste water and liquefaction useless
Water.Coal chemical industrial waste water, which includes polluter mainly, the multiple pollutants such as fluoride.
The processing method of fluorinated water mainly has absorption method, electrocoagulation, hyperfiltration, ion-exchange, chemistry heavy at present
Shallow lake method and coagulation sedimentation etc..These processing methods respectively have its advantage and deficiency, and in general ion-exchange is costly, and
Stringent, regenerative operation complexity is required waste water quality.Electrocoagulation and hyperfiltration device are complicated, and equipment is expensive, and power consumption is big,
It is high to operate level requirement, thus all few use.Chemical precipitation method handle fluoride waste, simple process is with low investment, be at present most
For a kind of method of widely applied processing fluoride waste.
Traditional calcium salt precipitation method mainly adds calcium oxide (CaO), calcium hydroxide (Ca (OH) into waste water2), chlorination
Calcium (CaCl2) etc. calcium salts, make its reacted with the fluorine ion in waste water generate CaF2Precipitating.However, single use CaO or Ca
(OH)2To handle fluoride waste, the CaF of generation2Precipitating can be wrapped in Ca (OH)2Particle surface so that calcium salt utilization efficiency compared with
It is low, and precipitation process is very slow, is only capable of the concentration of fluorine ion being reduced to 20~30mg/L, and the discharge mark of country is not achieved
It is quasi-.Therefore, a kind of new and effective fluorine removal medicament is researched and developed to be a problem to be solved.
Summary of the invention
For the problems of the prior art, the present invention provides a kind of new and effective fluorine removal medicament and its application, is removed using this
When fluorine agent handles fluoride waste, fluorine removal speed is fast, and defluorination effect is good.
To realize the above technical purpose, the technical scheme is that
A kind of new and effective fluorine removal medicament, by following mass fraction at being grouped as: poly-ferric chloride 8%, polyaluminum sulfate
Iron 16%, polyaluminium sulfate 16%, polymeric aluminum sulfate iron 16%, aluminium polychloride 18%, tealeaves iron 7%, modified coal ash
6%, modified zeolite 6%, calcium monohydrogen phosphate 4%, flocculation aid 3%.
Preferably, the preparation step of the modified coal ash are as follows: mix flyash with calcium hydroxide 1:0.3 in mass ratio
It is placed in crucible after uniformly, is then cooled to room temperature with Muffle furnace in 500~600 DEG C of 2~3h of calcination, grind, be cooled to room
It is ground after temperature, appropriate distilled water then is added in mixture after grinding, is evaporated after being uniformly mixed, ground.
Preferably, the preparation step of the modified zeolite are as follows: natural zeolite is placed in the hydrochloric acid solution of 3mol/L first
Middle immersion treatment, then will treated is added into ferric chloride solution after zeolite grinds, and simultaneously to ferric chloride solution
Middle addition calcium hydroxide suspension, at 60~80 DEG C react 4~for 24 hours, through drying and grinding up to modified zeolite.
Preferably, the flocculation aid is activated silicic acid.
Application of the above-mentioned fluorine removal medicament in fluoride wastewater treatment, step are as follows:
(1) above-mentioned fluorine removal medicament dissolution is configured to the solution that mass fraction is 10~30wt.% in deionized water;
(2) it takes fluoride waste sodium hydroxide to adjust pH to 7.5~8.5, is then added in step (1) into fluoride waste
Prepared solution, wherein added 1mg fluorine removal medicament in every 1L fluoride waste, stirred, standing sedimentation.
Preferably, the mixing time is 15min, sedimentation time 10min.
From the above, it can be seen that the present invention has following advantages:
1. the present invention has obtained a kind of high performance agent for removing fluorin GMS-F2 by selecting suitable component and optimizing each group distribution ratio,
When being handled using the defluorinating agent centering high-concentration fluorine-containing waste water (fluorinion concentration >=20mg/L), it is stirred to react 15min i.e.
The removal rate of fluorine ion can be made to reach 95% or more, fluorine removal speed is fast, and fluoride removing rate is high.
2. the presence of the aluminium salt (polyaluminium sulfate and aluminium polychloride) in fluorine removal medicament GMS-F2 of the present invention primarily serves
Adsorption-flocculation effect, the presence of molysite (poly-ferric chloride and bodied ferric sulfate), can be with while playing the role of adsorption-flocculation
Change wadding body construction, improve wadding body itself specific gravity, obtain more preferable settling efficiency, polyaluminium sulfate iron rule has both aluminium salt and molysite
Characteristic.
3. the calcium monohydrogen phosphate in fluorine removal medicament GMS-F2 of the present invention can form the fluorapatite of more indissoluble with fluorine ion, mention
The removal rate of high fluorine ion.
4. tealeaves matter iron is to keep tealeaves surface and formaldehyde sulfuric acid molten by the way that tealeaves to be added in formalin and sulfuric acid solution
Liquid comes into full contact with reaction, then handles to obtain with ferric trichloride again.The net of tealeaves matter iron in fluorine removal medicament GMS-F2 of the present invention
The complicated active group having on shape porous structure and its surface, can strong adsorption fluorine ion, to improve fluorine removal medicine
Removal effect of the agent to fluorine ion.
5. the present invention is modified flyash to form flyash-calcium hydroxide system, one side Ca using calcium hydroxide
(OH)2It can provide the calcium ion for acting on fluorine ion and generating precipitating, constitute absorption-flocculation sedimentation with flyash and act synergistically, mention
The defluorination effect of high modified coal ash, another aspect Ca (OH)2SiO in flyash can be excited2、Al2O3Deng potential activity, make
Hydration reaction occurs in they, to greatly improve the chemisorption activity of modified coal ash, further increases modified coal ash
Defluorination effect.Meanwhile surface roughness increases flyash after modified, helps to improve its in modified coal ash and fluorine removal medicament
Synergistic effect between his component.But work as Ca (OH)2When too high levels, Powder ash adsorption duct can be blocked, makes its adsorption energy
Power decline, therefore Ca (OH)2It needs to control in reasonable range with the mass ratio of flyash.
6. the present invention is first handled zeolite using hydrochloric acid, a small amount of impurity in zeolite can be removed, zeolite is expanded
Duct is adsorbed, then zeolite is handled with iron chloride and calcium hydroxide, forms zeolite-calcium chloride-iron hydroxide system,
In, calcium chloride can provide solubility higher calcium ion matrix, and iron hydroxide can be used as flocculation and binding matrix, the two
Absorption-flocculation sedimentation is formed with zeolite to act synergistically, and is greatly improved the fluorine removal speed and fluoride removing rate of fluorine removal medicament.
7. aluminium salt, molysite, polymeric aluminum sulfate iron, tealeaves iron, modified coal ash in fluorine removal medicament GMS-F2 of the present invention,
Absorption-flocculation sedimentation synergistic effect can be played between modified zeolite and calcium monohydrogen phosphate, improve fluorine removal medicament and fluorine in wastewater from
The reaction speed and fluoride removing rate of son.
8. the presence of the flocculation aid activated silicic acid in fluorine removal medicine GMS-F2 of the present invention can be eliminated between each flocculation component
Electrostatic repulsion, the tiny loose floccule body for being conducive to be formed in water body become larger to rapid subsidence, improve to fluorine ion
Removal efficiency.
Specific embodiment
Below by examples of implementation, the characteristics of the present invention is further explained, but claim of the invention is not done any
It limits.
Embodiment 1:
A kind of new and effective fluorine removal medicament, by following mass fraction at being grouped as: poly-ferric chloride 8%, polyaluminum sulfate
Iron 16%, polyaluminium sulfate 16%, polymeric aluminum sulfate iron 16%, aluminium polychloride 18%, tealeaves iron 7%, modified coal ash
6%, modified zeolite 6%, calcium monohydrogen phosphate 4%, activated silicic acid 3%.
Wherein, poly-ferric chloride, bodied ferric sulfate, polyaluminium sulfate, polymeric aluminum sulfate iron, aluminium polychloride, phosphoric acid hydrogen
Calcium, activated silicic acid are commercial product;Tealeaves iron is according to document (Huang Jiangsheng, Tao Tingxian, He Suwan, Zhang Yong, Wu Qi tealeaves
Absorption property and dynamics research [J] chemistry world of matter iron, 2010,51 (09): 516-519+523+526.) it is prepared;
The preparation step of modified coal ash are as follows: place flyash and calcium hydroxide 1:0.3 in mass ratio after mixing
In in crucible, then ground after being cooled to room temperature, then in mixture after grinding with Muffle furnace in 550 DEG C of calcination 2.5h
Distilled water is added, wherein 5g distilled water can be added in every 1g mixture, be evaporated and ground up to modified fine coal after being uniformly mixed
Ash.
The preparation step of modified zeolite are as follows: natural zeolite is placed in immersion treatment in the hydrochloric acid solution of 3mol/L first,
Then will treated is added into ferric chloride solution after zeolite grinds, and hydroxide is added into ferric chloride solution simultaneously
Calcium suspension, wherein the mass ratio of natural zeolite, iron chloride and calcium hydroxide is 1:1:1,12h is reacted at 70 DEG C, through drying
It grinds up to modified zeolite.
Above-mentioned each ingredient of formula ratio, which is uniformly mixed, can be prepared by high-effective defluorination medicament GMS-F2;
We take fluoride waste as fluoride waste to be processed from a certain coal chemical industrial waste water factory in Shandong, wherein to be processed to contain
The pH of fluorine waste water is 6.0, fluorinion concentration c0For 40mg/L, using fluorine removal medicament GMS-F2 obtained to fluoride waste to be processed
It is handled, to investigate the defluorination effect of fluorine removal medicament, the specific steps are as follows:
(1) taking the dissolution of fluorine removal medicament GMS-F2 made from 1mg to be configured to mass fraction in deionized water is 20wt.%'s
Solution;Above-mentioned solution prepares 4 parts;
(2) 1L fluoride waste to be processed is added into four beakers, adjusts water body pH to 7.5~8.5 with sodium hydroxide,
Then the solution of 1 part of step (1) preparation is respectively added into four beakers, is stirred to react 5min, 10min, 15min, 20min respectively
Standing sedimentation 15min afterwards takes supernatant to detect fluorinion concentration c using spectrophotometerxAnd calculate fluoride removing rate η=(c0-cx)/
c0, wherein the detection method of fluorinion concentration is referring to " the measurement Spectrophotometry of fluorine reagent of water quality fluoride " (HJ488-
2009), the results are shown in Table 1.
Comparative example 1:
Ingredient 6wt.% modified coal ash in the formula of embodiment 1 is substituted for 6wt.% flyash, other compositions and use
Amount remains unchanged, and prepares fluorine removal medicament using method same as Example 1, fluorine removal medicament obtained is used to handle and implement
The identical fluoride waste to be processed of example 1, processing method is with embodiment 1, and the results are shown in Table 1.
Comparative example 2:
Ingredient 6wt.% modified zeolite in the formula of embodiment 1 is substituted for 6wt.% natural zeolite, other compositions and use
Amount remains unchanged, and prepares fluorine removal medicament using method same as Example 1, fluorine removal medicament obtained is used to handle and implement
The identical fluoride waste to be processed of example 1, processing method is with embodiment 1, and the results are shown in Table 1.
Comparative example 3:
A kind of fluorine removal medicament, by following mass fraction at being grouped as: poly-ferric chloride 9%, bodied ferric sulfate 16%, poly-
Close aluminum sulfate 16%, polymeric aluminum sulfate iron 18%, aluminium polychloride 18%, tealeaves iron 7%, modified coal ash 3%, modified boiling
Stone 6%, calcium monohydrogen phosphate 4%, activated silicic acid 3%.
Wherein, the preparation method is the same as that of Example 1 for modified coal ash and modified zeolite.
Each ingredient of formula ratio is uniformly mixed to prepare fluorine removal medicament, fluorine removal medicament obtained is used for processing and embodiment
1 identical fluoride waste to be processed, processing method is with embodiment 1, and the results are shown in Table 1.
Comparative example 4:
A kind of fluorine removal medicament, by following mass fraction at being grouped as: poly-ferric chloride 8%, bodied ferric sulfate 18%, poly-
Close aluminum sulfate 16%, polymeric aluminum sulfate iron 16%, aluminium polychloride 18%, tealeaves iron 8%, modified coal ash 5%, modified boiling
Stone 4%, calcium monohydrogen phosphate 4%, activated silicic acid 3%.
Wherein, the preparation method is the same as that of Example 1 for modified coal ash and modified zeolite.
Each ingredient of formula ratio is uniformly mixed to prepare fluorine removal medicament, fluorine removal medicament obtained is used for processing and embodiment
1 identical fluoride waste to be processed, processing method is with embodiment 1, and the results are shown in Table 1.
Table 1
It is understood that being merely to illustrate the present invention above with respect to specific descriptions of the invention and being not limited to this
Technical solution described in inventive embodiments.Those skilled in the art should understand that still can be carried out to the present invention
Modification or equivalent replacement, to reach identical technical effect;As long as meet use needs, all protection scope of the present invention it
It is interior.
Claims (6)
1. a kind of new and effective fluorine removal medicament, which is characterized in that by following mass fraction at being grouped as: poly-ferric chloride 8%,
Bodied ferric sulfate 16%, polymeric aluminum sulfate iron 16%, aluminium polychloride 18%, tealeaves iron 7%, changes polyaluminium sulfate 16%
Property flyash 6%, modified zeolite 6%, calcium monohydrogen phosphate 4%, flocculation aid 3%.
2. new and effective fluorine removal medicament as described in claim 1, which is characterized in that the preparation step of the modified coal ash
Are as follows: flyash and calcium hydroxide 1:0.3 in mass ratio are placed in crucible after mixing, then with Muffle furnace 500~
600 DEG C of 2~3h of calcination, are cooled to room temperature, and grinding is ground after being cooled to room temperature, and are then added in mixture after grinding suitable
Distilled water is measured, is evaporated after being uniformly mixed, is ground.
3. new and effective fluorine removal medicament as described in claim 1, which is characterized in that the preparation step of the modified zeolite are as follows:
Natural zeolite is placed in immersion treatment in the hydrochloric acid solution of 3mol/L first, then will treated after zeolite grinds plus
Enter into ferric chloride solution, and simultaneously into ferric chloride solution be added calcium hydroxide suspension, at 60~80 DEG C react 4~
For 24 hours, through drying and grinding up to modified zeolite.
4. new and effective fluorine removal medicament as described in claim 1, which is characterized in that the flocculation aid is activated silicic acid.
5. a kind of using application of the fluorine removal medicament in fluoride wastewater treatment described in claim 1, which is characterized in that step are as follows:
(1) fluorine removal medicament dissolution is configured to the solution that mass fraction is 10~30wt.% in deionized water;
(2) it takes fluoride waste sodium hydroxide to adjust pH to 7.5~8.5, is then added in step (1) and is matched into fluoride waste
The solution of system, wherein added 1mg fluorine removal medicament in every 1L fluoride waste, stirred, standing sedimentation.
6. application as claimed in claim 5, which is characterized in that the mixing time is 15min, sedimentation time 10min.
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Cited By (10)
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CN111302536A (en) * | 2020-04-10 | 2020-06-19 | 四川恒泰环境技术有限责任公司 | Treatment system and treatment process for wastewater containing fluorine and phosphorus |
CN111547804A (en) * | 2020-05-15 | 2020-08-18 | 苏州清控环保科技有限公司 | Composite defluorinating agent for industrial wastewater, preparation method and method for defluorinating industrial wastewater |
CN111620390A (en) * | 2020-06-01 | 2020-09-04 | 王世民 | Broad-spectrum reinforced organic-inorganic composite fluorine-phosphorus remover and preparation and application methods thereof |
CN113262805A (en) * | 2021-04-20 | 2021-08-17 | 煤炭科学技术研究院有限公司 | Defluorination catalyst, preparation method thereof and defluorination method |
CN113582372A (en) * | 2021-06-24 | 2021-11-02 | 江西金环颜料有限公司 | Method for treating high-temperature environment-friendly scarlet pigment cadmium-containing or/and fluorine-containing wastewater |
CN114477516A (en) * | 2021-12-27 | 2022-05-13 | 哈德逊(苏州)水技术有限公司 | Fluoride wastewater treatment process |
CN116102142A (en) * | 2023-02-27 | 2023-05-12 | 和淼环境科技(江苏)有限公司 | Efficient defluorinating agent and preparation method thereof |
CN116177702A (en) * | 2022-12-28 | 2023-05-30 | 明金阳 | A medicament suitable for the treatment of fluorine-containing wastewater in the semiconductor industry |
CN117463305A (en) * | 2023-12-27 | 2024-01-30 | 西安益维普泰环保股份有限公司 | Deep defluorinating agent and preparation method thereof |
CN117699938A (en) * | 2023-12-15 | 2024-03-15 | 苏州苏沃特环境科技股份有限公司 | Low-concentration fluorine-containing wastewater inorganic composite defluorination medicament and application thereof |
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CN111620390A (en) * | 2020-06-01 | 2020-09-04 | 王世民 | Broad-spectrum reinforced organic-inorganic composite fluorine-phosphorus remover and preparation and application methods thereof |
CN113262805B (en) * | 2021-04-20 | 2023-09-29 | 煤炭科学技术研究院有限公司 | Defluorination catalyst, preparation method thereof and defluorination method |
CN113262805A (en) * | 2021-04-20 | 2021-08-17 | 煤炭科学技术研究院有限公司 | Defluorination catalyst, preparation method thereof and defluorination method |
CN113582372A (en) * | 2021-06-24 | 2021-11-02 | 江西金环颜料有限公司 | Method for treating high-temperature environment-friendly scarlet pigment cadmium-containing or/and fluorine-containing wastewater |
CN114477516A (en) * | 2021-12-27 | 2022-05-13 | 哈德逊(苏州)水技术有限公司 | Fluoride wastewater treatment process |
CN116177702A (en) * | 2022-12-28 | 2023-05-30 | 明金阳 | A medicament suitable for the treatment of fluorine-containing wastewater in the semiconductor industry |
CN116102142A (en) * | 2023-02-27 | 2023-05-12 | 和淼环境科技(江苏)有限公司 | Efficient defluorinating agent and preparation method thereof |
CN116102142B (en) * | 2023-02-27 | 2023-09-19 | 和淼环境科技(江苏)有限公司 | Efficient defluorinating agent and preparation method thereof |
CN117699938A (en) * | 2023-12-15 | 2024-03-15 | 苏州苏沃特环境科技股份有限公司 | Low-concentration fluorine-containing wastewater inorganic composite defluorination medicament and application thereof |
CN117463305A (en) * | 2023-12-27 | 2024-01-30 | 西安益维普泰环保股份有限公司 | Deep defluorinating agent and preparation method thereof |
CN117463305B (en) * | 2023-12-27 | 2024-04-02 | 西安益维普泰环保股份有限公司 | Deep defluorinating agent and preparation method thereof |
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