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CN-117886410-B - Preparation method of hybrid flocculant, product and application thereof

CN117886410BCN 117886410 BCN117886410 BCN 117886410BCN-117886410-B

Abstract

The invention discloses a preparation method of a hybrid flocculant, a product and application thereof. The preparation method comprises the steps of (1) dissolving inorganic components in deionized water, adding organic additives, dissolving to obtain a solution I, (2) dissolving acrylamide, cationic monomers and small molecular alcohols in the deionized water to obtain a solution II, (3) slowly adding the solution II obtained in the step (2) into the solution I obtained in the step (1) to obtain a mixed solution, and (4) purging the mixed solution obtained in the step (3) with inert gas, then adding an initiator, then purging with inert gas, and then performing polymerization reaction to obtain the hybrid flocculant. The method realizes the high-efficiency in-situ polymerization of the organic component on the inorganic component with higher content, has higher molecular weight, ensures that the flocculant has the functions of electric neutralization, adsorption bridging and metal ion removal, and the agent still keeps excellent oil removal and metal ion removal capability after long-term storage.

Inventors

  • TAN XIANGDONG
  • LIU YA
  • WANG XUEQING
  • LI BAOZHONG
  • GUO HONGSHAN

Assignees

  • 中国石油化工股份有限公司
  • 中石化（大连）石油化工研究院有限公司

Dates

Publication Date
20260505
Application Date
20221013

Claims (20)

  1. 1. A method of preparing a hybrid flocculant comprising: (1) Dissolving inorganic components in deionized water, adding organic additives, and dissolving to obtain a solution I; (2) Dissolving acrylamide, a cationic monomer and small molecular alcohol in deionized water to obtain a solution II; (3) Slowly adding the solution II in the step (2) into the solution I in the step (1) to obtain a mixed solution; (4) Purging the mixed solution in the step (3) with inert gas, then adding an initiator, then purging with inert gas, and then performing polymerization reaction to obtain a hybrid flocculant; In the step (1), the organic additive is at least one of 2-phosphonic butane-1, 2, 4-tricarboxylic acid, 2-hydroxyphosphonoacetic acid, hexamethylenediamine tetramethylene phosphonic acid, sodium polyaspartate, nitrilotriacetic acid, iminodiacetic acid, sodium gluconate and potassium sodium tartrate; in the step (2), the mass ratio of the sum of the acrylamide and the cationic monomer to the inorganic component in the step (1) is (1:1) - (1:6).
  2. 2. The method according to claim 1, wherein the inorganic component comprises at least one of polyaluminum sulfate, polyaluminum chloride, polyaluminum sulfate chloride, polyaluminum silicate sulfate, polyaluminum silicate.
  3. 3. The method according to claim 1, wherein in the step (1), the organic additive is at least one of butane-2-phosphonate-1, 2, 4-tricarboxylic acid, iminodiacetic acid, and sodium potassium tartrate.
  4. 4. The method according to claim 1, wherein in the step (1), the mass fraction of the inorganic component is controlled to be 15% -50% when the inorganic component is dissolved in deionized water.
  5. 5. The method according to claim 1, wherein in the step (1), the mass fraction of the organic additive is 1 to 5% based on the mass of the inorganic component.
  6. 6. The preparation method of claim 1, wherein in the step (1), the dissolution is performed by adopting an ultrasonic mode, the ultrasonic frequency is 30 KHz-60 KHz, and the ultrasonic time is 30-60 min.
  7. 7. The method according to claim 1, wherein in the step (2), the cationic monomer comprises at least one of dimethyldiallylammonium chloride, N-trimethyl-3-allylamido-1-propylamine chloride, methacryloxyethyltrimethylammonium chloride, N-dimethylaminoethyl methacrylate, [2- (acryloyloxy) ethyl ] trimethylammonium chloride.
  8. 8. The method according to claim 1, wherein in the step (2), the small molecule alcohol comprises at least one of methanol, ethanol, propanol, and butanol.
  9. 9. The preparation method of claim 1, wherein in the step (2), the mass ratio of the sum of acrylamide and cationic monomer to the inorganic component in the step (1) is (1:2) - (1:4).
  10. 10. The preparation method according to claim 1, wherein in the step (2), the sum of mass fractions of the acrylamide and the cationic monomer in the aqueous solution is controlled to be 6% -20%.
  11. 11. The preparation method of claim 1, wherein in the step (2), the mass ratio of the cationic monomer to the acrylamide monomer is (1:1) - (4:1).
  12. 12. The method according to claim 1, wherein in the step (2), the small molecular alcohol is 1 to 5% by mass of deionized water.
  13. 13. The preparation method according to claim 1, wherein in the step (4), the mass fraction of the initiator is 0.5 to 4.0 per mill based on the sum of the mass of the acrylamide and the cationic monomer in the step (2).
  14. 14. The preparation method according to claim 1, wherein in the step (4), the polymerization reaction condition is that the reaction temperature is 40-90 ℃, the stirring rate is 100-500 r/min, and the reaction time is 1-6 h.
  15. 15. The method according to claim 1, wherein in the step (4), the initiator is persulfate, and the persulfate is at least one of sodium salt, ammonium salt and potassium salt thereof.
  16. 16. A hybrid flocculant produced by the production process of any one of claims 1 to 15.
  17. 17. The hybrid flocculant of claim 16, wherein the hybrid flocculant has an intrinsic viscosity of 1000-5000 mL g -1 .
  18. 18. Use of the hybrid flocculant according to claim 16 or 17 for simultaneous degreasing of sewage and removal of metal ions.
  19. 19. The application of claim 18, wherein the sewage contains 1000-10000 mg of L -1 and 50-500 mg of L -1 as oil, and the multifunctional hybrid flocculant is added in an amount of 10-400 mg of L -1 .
  20. 20. The use according to claim 19, wherein the multifunctional hybrid flocculant is used for removing metal ions under conditions of pH adjustment of the wastewater to 5-11.

Description

Preparation method of hybrid flocculant, product and application thereof Technical Field The invention belongs to the technical field of wastewater treatment, and particularly relates to a preparation method of a hybrid flocculant, a product and application thereof. Background CN103351047a discloses an organic-inorganic hybrid flocculant and a preparation method thereof. Adding initiator ammonium persulfate in the polymerization process of dimethyl diallyl ammonium chloride (DMDAAC), and obtaining the PAC-PDMDAAC organic-inorganic hybrid ionic bond flocculant through in-situ polymerization. However, as the dimethyl diallyl ammonium chloride does not have special functional groups, the grafting of an organic phase onto an inorganic phase is difficult, the grafting rate is low, and the organic monomer synthesized by the medicament is only the dimethyl diallyl ammonium chloride which is relatively expensive, so that the cost is high when the medicament is used for water treatment according to the same mass concentration, the molecular weight is small, the bridging adsorption capacity to particles is weak, in addition, the flocculant has single performance, and the removal effect on water containing metal ions is poor. CN106745624a discloses an inorganic-organic hybrid flocculation material and a preparation method thereof. The raw material components of the flocculant comprise an initiator, and an inorganic flocculant and an organic monomer in a mass ratio of 1:9-1:6, wherein the organic monomer comprises dimethyl diallyl ammonium chloride and acrylamide in a mass ratio of 1:9-1:5, and the mass of the initiator is 0.02-5% of the mass of the organic monomer. The hybrid flocculant is obtained by introducing acrylamide and dimethyl diallyl ammonium chloride into an inorganic flocculant to initiate in-situ copolymerization of two monomers in an inorganic system. The flocculant can improve the sedimentation rate of tailing suspension liquid and reduce the turbidity of supernatant liquid. However, the flocculant mainly comprises an organic component with high price, the content of an inorganic component is low, so that the flocculant cost is high, the flocculant is low due to the low inorganic component, the flocculant has poor removal effect on turbid and oily wastewater with low zeta potential, especially oily wastewater with high emulsification degree, and in addition, the flocculant performance is poor due to partial crosslinking caused by the flocculant synthesis process, and the flocculant is single in functionality and has no obvious effect on synchronously removing metal ions in the wastewater. In view of the above, it is necessary to develop an inorganic-organic hybrid flocculant which is low in cost, high in performance, high in electric neutralization performance, high in molecular weight, stable in storage for a long period of time, and capable of synergistically removing metal ions. Disclosure of Invention Aiming at the defects of the prior art, the invention provides a preparation method of a hybrid flocculant, a product and application thereof. The method realizes the high-efficiency in-situ polymerization of the organic component on the inorganic component with higher content, has higher molecular weight, ensures that the flocculant has the functions of electric neutralization, adsorption bridging and metal ion removal, and has wide application prospect in the aspects of synchronous oil removal and metal ion removal of sewage because the medicament still keeps excellent oil removal and metal ion removal capability after long-term storage. The first aspect of the invention provides a method for preparing a hybrid flocculant, comprising: (1) Dissolving inorganic components in deionized water, adding organic additives, and dissolving to obtain a solution I; (2) Dissolving acrylamide, a cationic monomer and small molecular alcohol in deionized water to obtain a solution II; (3) Slowly adding the solution II in the step (2) into the solution I in the step (1) to obtain a mixed solution; (4) And (3) purging the mixed solution in the step (3) with inert gas, then adding an initiator, then purging with inert gas, and then performing polymerization reaction to obtain the hybrid flocculant. In the present invention, in the step (1), the inorganic component includes at least one of polyaluminum sulfate (PAS), polyaluminum chloride (PAC), polyaluminum sulfate chloride (PACs), polyaluminum silicate chloride (PASiC), polyaluminum silicate sulfate (PSAS), polyaluminum silicate (PASI), preferably at least one of polyaluminum sulfate (PAS) and polyaluminum chloride (PAC). In the present invention, in the step (1), the organic additive is at least one of 2-butane-1, 2, 4-tricarboxylic acid (PBTCA), 2-hydroxyphosphonoacetic acid (HPAA), hexamethylenediamine tetramethylene phosphonic acid (HDTMPA), sodium polyaspartate (PASP), nitrilotriacetic acid (NTA), iminodiacetic acid (IDA), sodium gluconate, sodium potassium tart