Compound heavy metal chelating agent containing dithiocarboxylate functionalized ethoxylated pentaerythritol core hyperbranched polymer

Patent metadata

Field	Value
Publication number	US-11242268-B2
Application number	US-202016994677-A
Country	US
Kind code	B2
Filing date	Aug 17, 2020
Priority date	Dec 2, 2019
Publication date	Feb 8, 2022
Grant date	Feb 8, 2022

Abstract

A compound heavy metal chelating agent, which relates to the field of chemical and environmental protection technology, includes dithiocarboxylate functionalized ethoxylated pentaerythritol core hyperbranched polymer and alkylene diamine-N,N′-sodium bisdithiocarboxylate with a molar ratio in a range of 1:1.0 to 1:10.0. The two different structural types of components have the synergistic positive effect. While chelating heavy metals, the compound heavy metal chelating agent alternately combine with heavy metals to form insoluble chelating super-molecular deposits, which has both chelation and flocculation functions. The compound heavy metal chelating agent meets the standard for treating heavy metal wastewater, and low concentration heavy metal wastewater. It has a wide adaptability range, and does not need to add coagulant. Moreover, it is simple in preparation method, easily available for raw materials, low in cost, and easy to be industrialized.

First claim

What is claimed is:

1. A compound heavy metal chelating agent, which comprises dithiocarboxylate functionalized ethoxylated pentaerythritol core hyperbranched polymer and alkylene diamine-N,N′-sodium bisdithiocarboxylate, wherein:
the dithiocarboxylate functionalized ethoxylated pentaerythritol core hyperbranched polymer has a chemical formula of C[CH 2 OCH 2 CH 2 OCOCH 2 CH 2 N(CSSM)(CH 2 ) n NHCSSM] 4 ; the alkylene diamine-N,N′-sodium bisdithiocarboxylate has a chemical formula of (MSSC) 2 N(CH 2 ) n N(CSSM) 2 , here n is a positive integer between 2 and 12, M is Na + , K + or NH 4 + ;
a molar ratio of the dithiocarboxylate functionalized ethoxylated pentaerythritol core hyperbranched polymer and the alkylene diamine-N,N′-sodium bisdithiocarboxylate is in a range from 1:1.0 to 1:10.0.

2. A preparation method of a compound heavy metal chelating agent, wherein:
the compound heavy metal chelating agent comprises dithiocarboxylate functionalized ethoxylated pentaerythritol core hyperbranched polymer and alkylene diamine-N,N′-sodium bisdithiocarboxylate, wherein:
the dithiocarboxylate functionalized ethoxylated pentaerythritol core hyperbranched polymer has a chemical formula of C[CH 2 OCH 2 CH 2 OCOCH 2 CH 2 N(CSSM)(CH 2 ) n NHCSSM] 4 ;
the alkylene diamine-N,N′-sodium bisdithiocarboxylate has a chemical formula of (MSSC) 2 N(CH 2 ) n N(CSSM) 2 , here n is a positive integer between 2 and 12, M is Na + , K + or NH 4 + ;
a molar ratio of the dithiocarboxylate functionalized ethoxylated pentaerythritol core hyperbranched polymer and the alkylene diamine-N,N′-sodium bisdithiocarboxylate is in a range from 1:1.0 to 1:10.0;

the preparation method comprises steps of:
(1) performing a first addition reaction, which comprises adding a first low-carbon alcohol solution drop by drop into a second low-carbon alcohol solution at 20-25° C. under nitrogen protection, wherein the first low-carbon alcohol solution contains ethoxylated pentaerythritol tetraacrylate (EPTA), the second low-carbon alcohol solution contains excessive alkylenediamine (ADA) with a chemical formula of H 2 N(CH 2 ) n NH 2 , here n is a positive integer between 2 and 12; and then obtaining a mixed low-carbon alcohol solution which contains (N-(n-aminoalkylene))-3-aminopropionate hyperbranched polymer and unreacted alkylenediamine by stirring for 20-48 h at 20-35° C.; and
(2) performing a second addition reaction, which comprises adding alkaline aqueous solution and carbon disulfide drop by drop after cooling the mixed low-carbon alcohol solution obtained by the step (1) to 10-25° C., stirring for 3-8 h at 20-35° C., standing at room temperature for 3-24 h, precipitating a solid product, filtering and drying to obtain the compound heavy metal chelating agent, wherein:
a molar ratio of the EPTA, the ADA, the alkali and the carbon disulfide is in a range of 1: ( 5 . 0 - 14 . 0 ): ( 10 . 0 - 28 . 0 ): ( 10 . 0 - 28 . 0 ).

3. The preparation method according to claim 2 , wherein each of the first low-carbon alcohol and the second low-carbon alcohol in the step (1) is one member selected from the group consisting of methanol, ethanol, propanol, ethylene glycol and propylene glycol.

4. The preparation method according to claim 2 , wherein the step (1) of performing the first addition reaction comprises adding the first low-carbon alcohol solution containing ethoxylated pentaerythritol tetraacrylate into the second low-carbon alcohol solution containing excessive alkylenediamine at 20-25° C. under nitrogen protection drop by drop, and then stirring for 4-8 h both of which are repeated for 1 to 10 times, and then obtaining the mixed low-carbon alcohol solution which contains N-(n-aminoalkylene))-3-aminopropionate hyperbranched polymer and unreacted alkylenediamine by stirring for 20-48 h at 20-35° C.

5. The preparation method according to claim 2 , wherein the alkali in the step (2) is one member selected from the group consisting of sodium hydroxide, potassium hydroxide and ammonia.

6. A method for treating heavy metal wastewater comprising applying a compound heavy metal chelating agent wherein the compound heavy metal chelating agent comprises dithiocarboxylate functionalized ethoxylated pentaerythritol core hyperbranched polymer and alkylene diamine-N,N′-sodium bisdithiocarboxylate, wherein:
the dithiocarboxylate functionalized ethoxylated pentaerythritol core hyperbranched polymer has a chemical formula of C[CH 2 OCH 2 CH 2 OCOCH 2 CH 2 N(CSSM)(CH 2 ) n NHCSSM] 4 ;
the alkylene diamine-N,N′-sodium bisdithiocarboxylate has a chemical formula of (MSSC) 2 N(CH 2 ) n N(CSSM) 2 , here n is a positive integer between 2 and 12, M is Na + , K + or NH 4 + ;
a molar ratio of the dithiocarboxylate functionalized ethoxylated pentaerythritol core hyperbranched polymer and the alkylene diamine-N,N′-sodium bisdithiocarboxylate is in a range from 1:1.0 to 1:10.0.

Assignees

• Shandong Xintai Water Treat Technology Co Ltd
• Univ Tongji

Inventors

• Cui Jin
• Zhang Bingru
• Li Fengting

Classifications

• C02F1/56

  Macromolecular compounds · CPC title

• C02F1/62 Primary

  Heavy metal compounds · CPC title

• C07C333/16 Primary

  Salts of dithiocarbamic acids · CPC title

• C02F2101/20

  Heavy metals or heavy metal compounds · CPC title

• C02F1/54

  using organic material · CPC title