CN111732174A - Demulsifier for fluorine-containing organic waste liquid, preparation method and application thereof - Google Patents
Demulsifier for fluorine-containing organic waste liquid, preparation method and application thereof Download PDFInfo
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- CN111732174A CN111732174A CN202010479081.3A CN202010479081A CN111732174A CN 111732174 A CN111732174 A CN 111732174A CN 202010479081 A CN202010479081 A CN 202010479081A CN 111732174 A CN111732174 A CN 111732174A
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- China
- Prior art keywords
- demulsifier
- fluorine
- waste liquid
- containing organic
- organic waste
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- 239000007788 liquid Substances 0.000 title claims abstract description 48
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 41
- 239000011737 fluorine Substances 0.000 title claims abstract description 41
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000010815 organic waste Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 17
- 229920000371 poly(diallyldimethylammonium chloride) polymer Polymers 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000003751 zinc Chemical class 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002699 waste material Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 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 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000007865 diluting Methods 0.000 claims description 4
- 229940037003 alum Drugs 0.000 claims description 3
- -1 fluorine ions Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000000839 emulsion Substances 0.000 description 9
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 description 4
- PUQLFUHLKNBKQQ-UHFFFAOYSA-L calcium;trifluoromethanesulfonate Chemical compound [Ca+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F PUQLFUHLKNBKQQ-UHFFFAOYSA-L 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229920006317 cationic polymer Polymers 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- NJSSICCENMLTKO-HRCBOCMUSA-N [(1r,2s,4r,5r)-3-hydroxy-4-(4-methylphenyl)sulfonyloxy-6,8-dioxabicyclo[3.2.1]octan-2-yl] 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)O[C@H]1C(O)[C@@H](OS(=O)(=O)C=2C=CC(C)=CC=2)[C@@H]2OC[C@H]1O2 NJSSICCENMLTKO-HRCBOCMUSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 230000005591 charge neutralization Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000003311 flocculating effect Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
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)
- Removal Of Specific Substances (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a demulsifier for fluorine-containing organic waste liquid, a preparation method and application thereof, belonging to the technical field of demulsifiers. The demulsifier comprises the following raw materials in percentage by mass, based on the total mass of the raw materials of the demulsifier as 100%: 0.01-1% of poly (diallyldimethylammonium chloride); 0.01-1% of inorganic salt; 1-10% of strong acid; the balance of water; the inorganic salt is ferric salt, aluminum salt or zinc salt. Inorganic salt and high molecular polymer poly diallyl dimethyl ammonium chloride are mixed, strong acid is added, and the pH is adjusted to be acidic, so that the demulsification effect on the fluorine-containing organic waste liquid is good.
Description
Technical Field
The invention relates to a demulsifier for fluorine-containing organic waste liquid, a preparation method and application thereof, belonging to the technical field of demulsifiers.
Background
At present, fluorine-containing organic waste liquid discharged by domestic fluorine chemical enterprises contains a large amount of organic fluorine anionic surfactant and calcium fluoride micro-particles, the proportion of emulsion in the waste liquid is increased, the emulsion emulsification degree is more serious, the emulsion is more stable, and the treatment difficulty is more and more increased. With the stricter and stricter environmental protection policy, the problem of demulsification and defluorination of the fluorine-containing organic waste liquid is more prominent. If the fluorine-containing organic waste liquid is directly discharged without being treated, the environment is polluted, the water body is polluted, the ecological balance is destroyed, and a large amount of water resources are wasted. Therefore, these organic waste liquids containing fluorine are generally recycled, which requires effective demulsification and flocculation treatment of the fluorine-containing waste water.
The organic cationic polymer can not only destabilize and flocculate suspended colloidal particles through charge neutralization, but also react with negatively charged dissolved matters to generate insoluble salts, and the insoluble salts are removed through flocculation precipitation, so the organic cationic polymer is the demulsifier with the best performance.
The current reverse demulsifiers used at home and abroad for demulsification of oil-in-water type emulsions can be roughly divided into the following categories: low molecular electrolytes, alcohols, surfactants, and polymers. A series of reverse demulsifiers such as diallyl dimethyl ammonium chloride homopolymer, monoallyl amine polymer, etc. were developed in succession from the 90 s of the 20 th century abroad. However, for the fluorine-containing organic waste liquid, the components are complex due to the inorganic salt and the organic fluoride, and the existing demulsifier has poor demulsification effect and cannot realize effective separation of emulsion.
Disclosure of Invention
In view of the above, the invention aims to provide a demulsifier for a fluorine-containing organic waste liquid, a preparation method and an application thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the demulsifier for the fluorine-containing organic waste liquid comprises the following raw materials in percentage by mass, based on 100% of the total mass of the raw materials of the demulsifier:
0.01-1% of poly (diallyldimethylammonium chloride);
0.01-1% of inorganic salt;
1-10% of strong acid;
the balance of water;
the inorganic salt is ferric salt, aluminum salt or zinc salt.
Preferably, the polydiallyldimethylammonium chloride has a relative molecular weight of 4 × 104～3×106；
Preferably, the inorganic salt is one or more of aluminum sulfate, aluminum chloride and alum.
Preferably, the strong acid is hydrochloric acid or sulfuric acid.
A preparation method of a demulsifier for a fluorine-containing organic waste liquid comprises the following steps:
(1) adding polydiallyl dimethyl ammonium chloride into water, and stirring to form a solution;
(2) adding inorganic salt, and stirring until the inorganic salt is completely dissolved;
(3) adding strong acid, and adjusting the pH value of the solution to be strong acid; stirring and mixing uniformly to obtain the demulsifier for the fluorine-containing organic waste liquid.
The application of the demulsifier for the fluorine-containing organic waste liquid is that the demulsifier is diluted to 10-100 times by water; mixing the diluted demulsifier with the fluorine-containing organic waste liquid, and centrifuging for 1-10 min at 100-2000 r/min to obtain separated solid and liquid; wherein the fluorine-containing organic waste liquid is waste liquid containing trifluoromethyl sulfonate and fluorine ions.
Advantageous effects
The demulsifier provided by the invention realizes a good demulsification effect on the fluorine-containing organic waste liquid by compounding polydiallyl dimethyl ammonium chloride, inorganic salt, strong acid and water and controlling the dosage of each component through the mutual cooperation of the polydiallyl dimethyl ammonium chloride, the inorganic salt, the strong acid and the water. The demulsifier has the advantages of high demulsification speed, high efficiency, small dosage, low use temperature and the like. The demulsifier is obtained by mixing inorganic salt with high molecular polymer poly (diallyl dimethyl ammonium chloride), adding strong acid, and adjusting the pH value to acidity, and has the advantages of easily purchased raw materials and simple compounding method.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
(1) To 100mL of water, 1mL of poly (diallyldimethylammonium chloride) (relative molecular weight 4 × 10) was added4～3×106) Stirring to form a solution;
(2) adding 1g of aluminum sulfate, stirring and completely dissolving;
(3) and adding 10mL of concentrated hydrochloric acid (mass fraction: 37%), adjusting the pH value of the solution to acidity, and stirring and mixing uniformly to obtain the demulsifier for the fluorine-containing organic waste liquid.
(4) Taking the demulsifier, and diluting the demulsifier to 10 times with water;
(5) adding 10mL of diluted organic fluorine waste liquid demulsifier into 100mL of fluorine-containing organic waste liquid in a colorimetric tube, fully mixing uniformly and centrifuging at the rotating speed of 2000r/min for 1min to completely separate emulsion to obtain white solid precipitate and colorless transparent liquid; wherein the mass fraction of the calcium trifluoromethanesulfonate in the waste liquid is 4%, and the mass fraction of the calcium fluoride is 1%.
Example 2
(1) To 100mL of water, 2mL of poly (diallyldimethylammonium chloride) (relative molecular weight 4 × 10) was added4～3×106) Stirring to form a solution;
(2) adding 1g of aluminum chloride, and stirring to completely dissolve;
(3) and adding 10mL of sulfuric acid (the mass fraction is 75%), adjusting the pH value of the solution to be acidic, and stirring and mixing uniformly to obtain the demulsifier for the fluorine-containing organic waste liquid.
(4) Taking the demulsifier, and diluting the demulsifier to 10 times with water;
(5) adding 10mL of diluted organic fluorine waste liquid demulsifier into 100mL of fluorine-containing organic waste liquid in a colorimetric tube, fully mixing uniformly and centrifuging at the rotation speed of 1000r/min for 2min to completely separate emulsion to obtain white solid precipitate and colorless transparent liquid; wherein the mass fraction of the calcium trifluoromethanesulfonate in the waste liquid is 4%, and the mass fraction of the calcium fluoride is 2%.
Example 3
(1) To 100mL of water, 5mL of poly (diallyldimethylammonium chloride) (relative molecular weight 4 × 10) was added4～3×106) Stirring to form a solution;
(2) adding 2g of alum, and stirring to completely dissolve;
(3) adding 20mL of sulfuric acid (the mass fraction is 75%), adjusting the pH value of the solution to be acidic, and stirring and mixing uniformly to obtain the demulsifier for the fluorine-containing organic waste liquid.
(4) Taking the demulsifier, and diluting the demulsifier to 20 times with water;
(5) adding 10mL of diluted organic fluorine waste liquid demulsifier into 100mL of fluorine-containing organic waste liquid in a colorimetric tube, fully mixing uniformly and centrifuging at the rotating speed of 2000r/min for 1min to completely separate emulsion to obtain white solid precipitate and colorless transparent liquid; wherein the mass fraction of the calcium trifluoromethanesulfonate in the waste liquid is 4%, and the mass fraction of the calcium fluoride is 1%.
Under acidic conditions, inorganic salts act by neutralizing the electronegativity of the oil droplet surface and changing the lipophilic-hydrophilic balance of the emulsifier; and then polydiallyldimethylammonium chloride has the functions of neutralizing charges, adsorbing and bridging, flocculating and coalescing and the like on a liquid film of the oil-in-water type emulsion with negative charges.
In summary, the invention includes but is not limited to the above embodiments, and any equivalent replacement or local modification made under the spirit and principle of the invention should be considered as being within the protection scope of the invention.
Claims (6)
1. The demulsifier for fluorine-containing organic waste liquid is characterized by comprising the following components in parts by weight: the demulsifier comprises the following raw materials in percentage by mass, based on the total mass of the raw materials of the demulsifier as 100%:
0.01-1% of poly (diallyldimethylammonium chloride);
0.01-1% of inorganic salt;
1-10% of strong acid;
the balance of water;
the inorganic salt is ferric salt, aluminum salt or zinc salt.
2. The demulsifier for fluorine-containing organic waste liquid according to claim 1, wherein the relative molecular weight of the poly (diallyldimethylammonium chloride) is 4 × 104～3×106。
3. The demulsifier for a fluorine-containing organic waste liquid according to claim 1, wherein: the inorganic salt is more than one of aluminum sulfate, aluminum chloride and alum.
4. The demulsifier for a fluorine-containing organic waste liquid according to claim 1, wherein: the strong acid is hydrochloric acid or sulfuric acid.
5. The preparation method of the demulsifier for a fluorine-containing organic waste liquid according to any one of claims 1 to 4, characterized by comprising: the method comprises the following steps:
(1) adding polydiallyl dimethyl ammonium chloride into water, and stirring to form a solution;
(2) adding inorganic salt, and stirring until the inorganic salt is completely dissolved;
(3) adding strong acid, stirring and mixing uniformly to obtain the demulsifier for the fluorine-containing organic waste liquid.
6. The application of the demulsifier for fluorine-containing organic waste liquid according to any one of claims 1 to 4, wherein: diluting the demulsifier to 10-100 times by using water; mixing the diluted demulsifier with the fluorine-containing organic waste liquid, and centrifuging for 1-10 min at 100-2000 r/min to obtain separated solid and liquid; wherein the fluorine-containing organic waste liquid is waste liquid containing trifluoromethyl sulfonate and fluorine ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010479081.3A CN111732174A (en) | 2020-05-29 | 2020-05-29 | Demulsifier for fluorine-containing organic waste liquid, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010479081.3A CN111732174A (en) | 2020-05-29 | 2020-05-29 | Demulsifier for fluorine-containing organic waste liquid, preparation method and application thereof |
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| Publication Number | Publication Date |
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| CN111732174A true CN111732174A (en) | 2020-10-02 |
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| CN202010479081.3A Pending CN111732174A (en) | 2020-05-29 | 2020-05-29 | Demulsifier for fluorine-containing organic waste liquid, preparation method and application thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101687643A (en) * | 2007-06-25 | 2010-03-31 | 3M创新有限公司 | Remove the method for fluorinated compound from the aqueous phase of the preparation that is derived from fluoropolymer |
| WO2019105599A1 (en) * | 2017-11-29 | 2019-06-06 | Brenntag Spa | Composition, method and apparatus for treating water containing fluorides |
-
2020
- 2020-05-29 CN CN202010479081.3A patent/CN111732174A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101687643A (en) * | 2007-06-25 | 2010-03-31 | 3M创新有限公司 | Remove the method for fluorinated compound from the aqueous phase of the preparation that is derived from fluoropolymer |
| WO2019105599A1 (en) * | 2017-11-29 | 2019-06-06 | Brenntag Spa | Composition, method and apparatus for treating water containing fluorides |
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| Date | Code | Title | Description |
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| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 057550 No. five Weir Road, chemical industry gathering area, Feixiang District, Handan, Hebei, 1 Applicant after: China shipbuilding (Handan) Perry Special Gas Co.,Ltd. Address before: No.1 Weiwu Road, chemical industry gathering area, Feixiang County, Handan City, Hebei Province Applicant before: PERIC SPECIAL GASES Co.,Ltd. |
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| CB02 | Change of applicant information | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201002 |
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| RJ01 | Rejection of invention patent application after publication |