CN112028296A - Recovery treatment process of fluorine-containing waste liquid - Google Patents
Recovery treatment process of fluorine-containing waste liquid Download PDFInfo
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- CN112028296A CN112028296A CN202010710669.5A CN202010710669A CN112028296A CN 112028296 A CN112028296 A CN 112028296A CN 202010710669 A CN202010710669 A CN 202010710669A CN 112028296 A CN112028296 A CN 112028296A
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- waste liquid
- fluorine
- containing waste
- concentration
- alkaline
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- 239000007788 liquid Substances 0.000 title claims abstract description 84
- 239000002699 waste material Substances 0.000 title claims abstract description 82
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 34
- 239000011737 fluorine Substances 0.000 title claims abstract description 34
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000011084 recovery Methods 0.000 title claims abstract description 12
- 150000001450 anions Chemical class 0.000 claims abstract description 13
- 239000002351 wastewater Substances 0.000 claims abstract description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 9
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims abstract description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 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 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 239000003456 ion exchange resin Substances 0.000 claims description 6
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 238000000909 electrodialysis Methods 0.000 claims description 3
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 claims description 3
- 239000002370 magnesium bicarbonate Substances 0.000 claims description 3
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 claims description 3
- 235000014824 magnesium bicarbonate Nutrition 0.000 claims description 3
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 claims description 3
- 239000001095 magnesium carbonate Substances 0.000 claims description 3
- 229910000021 magnesium carbonate Inorganic materials 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000009297 electrocoagulation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 fluorine ions Chemical class 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- 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
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a recovery treatment process of fluorine-containing waste liquid, which comprises the following steps: step A, a collecting tank is arranged to collect the fluorine-containing waste liquid; b, lifting the fluorine-containing waste liquid in the collecting tank to a pH adjusting tank by a pump, adding an alkaline solvent into the pH adjusting tank, and adjusting the pH value of the original acidic fluorine-containing waste liquid into alkaline waste water; step C, separating the alkaline waste liquid into high-concentration waste liquid and low-concentration waste liquid by using an anti-pollution reverse osmosis membrane; d, dissociating the high-concentration waste liquid to separate the high-concentration waste liquid into anion-containing waste liquid and cation-containing waste liquid containing fluorinion; and E, recovering the fluoride-containing waste liquid containing the anions. The invention has high recovery efficiency and low recovery cost, and greatly improves the resource utilization rate.
Description
Technical Field
The invention relates to a recovery treatment process of fluorine-containing waste liquid, belonging to the technical field of chemical production.
Background
With global warming, global water resources are changed, the number of global population is rapidly increased, science and technology are rapidly developed, and water resources are more and more in shortage. Therefore, if the industrial wastewater can be effectively recycled and reused, the method contributes to the global environmental protection industry and benefits the descendants. However, in recent years, the modern industry in China has been rapidly developed, the industrial production values of fluoride synthesis, metal smelting, electronics, pesticides and the like are increasingly increased, a large amount of fluorine-containing wastewater generated by construction and production of a large amount of fluorine industrial bases is also increased rapidly, and the problem of fluorine pollution in China is increasingly serious. For example, the concentration of fluorine in wastewater discharged by a fluorination plant is more than 1000mg/L, the concentration of fluorine-containing wastewater generated by a fertilizer plant is about 1500mg/L, and the concentration of fluorine-containing wastewater generated in the glass manufacturing process is between 200 and 2000 mg/L.
At present, various methods for treating fluorine-containing wastewater at home and abroad are available, and mainly comprise a chemical precipitation method, a coagulation sedimentation method, an adsorption method, a reverse osmosis method, an electrocoagulation method, an ion exchange resin method and the like. The chemical precipitation method, the coagulation sedimentation method and the adsorption method are more applied, and other methods are less applied. The traditional precipitation coagulation treatment technology has poor settleability, high water content of sludge, difficult solid-liquid separation and difficult recycling of the sludge. The electrocoagulation method consumes a large amount of electric energy and has higher treatment cost.
Disclosure of Invention
The invention aims to provide a process for recovering and treating fluorine-containing waste liquid, which is used for recovering and treating the fluorine-containing waste liquid and improving the resource utilization rate.
The technical scheme adopted by the invention is as follows: a recovery treatment process of fluorine-containing waste liquid comprises the following steps:
step A, a collecting tank is arranged to collect the fluorine-containing waste liquid;
b, lifting the fluorine-containing waste liquid in the collecting tank to a pH adjusting tank by a pump, adding an alkaline solvent into the pH adjusting tank, and adjusting the pH value of the original acidic fluorine-containing waste liquid into alkaline waste water;
step C, separating the alkaline waste liquid into high-concentration waste liquid and low-concentration waste liquid by using an anti-pollution reverse osmosis membrane;
d, dissociating the high-concentration waste liquid to separate the high-concentration waste liquid into anion-containing waste liquid and cation-containing waste liquid containing fluorinion;
and E, recovering the fluoride-containing waste liquid containing the anions.
Further, in the step B, the pH value of the original acidic fluorine-containing waste liquid is adjusted to be not less than 9, so that alkaline waste water is formed.
Further, the alkaline solvent is selected from any one or at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium bicarbonate, ammonia, ammonium carbonate and ammonium bicarbonate.
Further, the high-concentration waste liquid is separated into the anion-containing waste liquid and the cation-containing waste liquid by using an electrodialysis module or an ion exchange resin.
The invention has the beneficial effects that: the process has high recovery efficiency of fluoride in the waste liquid and low recovery cost, and greatly improves the resource utilization rate.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
As shown in fig. 1, a process for recovering and treating fluorine-containing waste liquid comprises the following steps:
step A, a collecting tank is arranged to collect the fluorine-containing waste liquid;
b, lifting the fluorine-containing waste liquid in the collection tank to a pH adjusting tank by a pump, adding an alkaline solvent into the pH adjusting tank, and adjusting the pH value of the original acidic fluorine-containing waste liquid to be not less than 9, usually about 10, so as to form alkaline waste water;
step C, separating the alkaline waste liquid into high-concentration waste liquid and low-concentration waste liquid by using an anti-pollution reverse osmosis membrane;
d, dissociating the high-concentration waste liquid to separate the high-concentration waste liquid into anion-containing waste liquid and cation-containing waste liquid containing fluorinion;
and E, recovering the fluoride-containing waste liquid containing the anions.
In the process, the alkaline solvent is any one or at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium bicarbonate, ammonia, ammonium carbonate and ammonium bicarbonate.
In the process, the high-concentration waste liquid is separated into the anion-containing waste liquid and the cation-containing waste liquid by using an electrodialysis module or ion exchange resin.
Detailed description of the process principle: the alkaline liquid can make the reverse osmosis membrane negatively charged, so that the reverse osmosis membrane can reject fluorine ions (with the chemical formula of F-) which are also negatively charged, and further more fluorine ions are reserved in the high-concentration waste liquid. Therefore, in this embodiment, step B is performed first, and the fluorine-containing waste liquid which is originally acidic is adjusted to an alkaline waste liquid by an alkaline solvent. Then, when the alkaline waste liquid is separated into a high-concentration waste liquid and a low-concentration waste liquid by the reverse osmosis membrane in step C, the fluorine ion content in the high-concentration waste liquid can be increased. At this time, the low-concentration waste liquid having an extremely low fluorine ion content can be recovered and reused, and as shown in step D, the high-concentration waste liquid is subjected to dissociation treatment using an ion exchange resin to separate the high-concentration waste liquid into an anion-containing waste liquid and a cation-containing waste liquid. Compared with the prior art, in this embodiment, the low-concentration fluorine-containing waste liquid is concentrated into the high-concentration waste liquid in step C, so that the ion exchange resin can more efficiently dissociate the high-concentration waste liquid into the anion-containing waste liquid and the cation-containing waste liquid. Therefore, the process has high fluoride recovery efficiency and low recovery cost.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It should be understood by those skilled in the art that the above embodiments do not limit the scope of the present invention in any way, and all technical solutions obtained by using equivalent substitution methods fall within the scope of the present invention.
The parts not involved in the present invention are the same as or can be implemented using the prior art.
Claims (4)
1. A recovery treatment process of fluorine-containing waste liquid is characterized by comprising the following steps:
step A, a collecting tank is arranged to collect the fluorine-containing waste liquid;
b, lifting the fluorine-containing waste liquid in the collecting tank to a pH adjusting tank by a pump, adding an alkaline solvent into the pH adjusting tank, and adjusting the pH value of the original acidic fluorine-containing waste liquid into alkaline waste water;
step C, separating the alkaline waste liquid into high-concentration waste liquid and low-concentration waste liquid by using an anti-pollution reverse osmosis membrane;
d, dissociating the high-concentration waste liquid to separate the high-concentration waste liquid into anion-containing waste liquid and cation-containing waste liquid containing fluorinion;
and E, recovering the fluoride-containing waste liquid containing the anions.
2. The process according to claim 1, wherein in the step B, the pH of the acidic waste liquid containing fluorine is adjusted to not less than 9, thereby forming an alkaline waste water.
3. The process of claim 1, wherein the alkaline solvent is selected from one or at least one of sodium hydroxide, sodium carbonate, sodium bicarbonate, potassium hydroxide, potassium carbonate, potassium bicarbonate, magnesium oxide, magnesium hydroxide, magnesium carbonate, magnesium bicarbonate, ammonia, ammonium carbonate, and ammonium bicarbonate.
4. The process according to claim 1, wherein the high-concentration waste liquid is separated into the anion-containing waste liquid and the cation-containing waste liquid by an electrodialysis module or an ion exchange resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010710669.5A CN112028296A (en) | 2020-07-22 | 2020-07-22 | Recovery treatment process of fluorine-containing waste liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010710669.5A CN112028296A (en) | 2020-07-22 | 2020-07-22 | Recovery treatment process of fluorine-containing waste liquid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112028296A true CN112028296A (en) | 2020-12-04 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010710669.5A Pending CN112028296A (en) | 2020-07-22 | 2020-07-22 | Recovery treatment process of fluorine-containing waste liquid |
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| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115072910A (en) * | 2021-03-15 | 2022-09-20 | 兆德（南通）电子科技有限公司 | Recovery treatment method of ammonia-containing waste liquid |
| CN115072894A (en) * | 2021-03-15 | 2022-09-20 | 兆德（南通）电子科技有限公司 | Method for recycling sulfuric acid-containing waste liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102897940A (en) * | 2011-07-26 | 2013-01-30 | 兆联实业股份有限公司 | Method and equipment for recovering and treating fluorine-containing waste liquid |
| TW201502084A (en) * | 2013-07-11 | 2015-01-16 | Mega Union Technology Inc | Method and system for treating sewage containing flourine |
| CN106946385A (en) * | 2017-04-27 | 2017-07-14 | 合肥科佳高分子材料科技有限公司 | A kind of recoverying and utilizing method of high-concentration fluorine-containing waste water |
-
2020
- 2020-07-22 CN CN202010710669.5A patent/CN112028296A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102897940A (en) * | 2011-07-26 | 2013-01-30 | 兆联实业股份有限公司 | Method and equipment for recovering and treating fluorine-containing waste liquid |
| TW201502084A (en) * | 2013-07-11 | 2015-01-16 | Mega Union Technology Inc | Method and system for treating sewage containing flourine |
| CN106946385A (en) * | 2017-04-27 | 2017-07-14 | 合肥科佳高分子材料科技有限公司 | A kind of recoverying and utilizing method of high-concentration fluorine-containing waste water |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115072910A (en) * | 2021-03-15 | 2022-09-20 | 兆德（南通）电子科技有限公司 | Recovery treatment method of ammonia-containing waste liquid |
| CN115072894A (en) * | 2021-03-15 | 2022-09-20 | 兆德（南通）电子科技有限公司 | Method for recycling sulfuric acid-containing waste liquid |
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