CN111136084A - Preparation method of high-stability heavy metal ion trapping agent - Google Patents
Preparation method of high-stability heavy metal ion trapping agent Download PDFInfo
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- CN111136084A CN111136084A CN201911310092.2A CN201911310092A CN111136084A CN 111136084 A CN111136084 A CN 111136084A CN 201911310092 A CN201911310092 A CN 201911310092A CN 111136084 A CN111136084 A CN 111136084A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
- B09B—DISPOSAL OF SOLID WASTE
- B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
Abstract
The invention provides a preparation method of a high-stability heavy metal ion trapping agent, which comprises the following steps: adding deionized water into the reaction kettle, adding montmorillonite particles, adding cyclodextrin, heating and stirring until the montmorillonite particles and the cyclodextrin are completely dissolved; adjusting pH, adding triethanolamine and hydrazine hydrate, and stirring at 60-90 deg.C for reaction; after the above process is finished, cooling to 30-40 ℃, adding piperazine solution, potassium hydroxide solution and polyvinyl alcohol into the reaction kettle, stirring and controlling the temperature to be 30-45 ℃, then slowly adding carbon disulfide into the reaction kettle, controlling the temperature to be 30-45 ℃, and stopping adding the carbon disulfide when the temperature rise rate in the reaction kettle is less than 1 ℃/min; and continuously adding the potassium hydroxide solution to a set liquid level, then adding the aluminum glue, and stirring and reacting at a controlled temperature for a period of time to obtain a liquid product. The product prepared by the invention has excellent heavy metal chelating performance and good stability.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method of a high-stability heavy metal ion trapping agent.
Background
The piperazine-N, N-potassium bisdithiocarbamate is a fly ash trapping agent with high efficiency and strong environmental friendliness, is valued and applied in the harmless treatment of waste incineration fly ash, has strong binding capacity with various heavy metal ions, and is widely used in the fields of treatment of industrial wastewater containing the heavy metal ions, remediation of polluted soil and the like. In view of the fact that piperazine-N, N-potassium bisdithiocarbamate has good heavy metal ion pollution treatment application performance, people carry out innovative research on a synthesis method of piperazine-N, N-potassium bisdithiocarbamate in order to improve the production capacity of substances of piperazine-N, N-potassium bisdithiocarbamate.
In recent years, long-time detection of the piperazine-N, N-potassium bisdithiocarbamate chelating stabilization treatment of waste incineration fly ash shows that a trapping agent in the chelated fly ash is degraded after the chelated fly ash is buried for 2-3 years, so that the chelating ability is reduced, and the leaching performance of heavy metals in the fly ash is poor. Therefore, in the production and application of the product of piperazine-N, N-bis-dithiocarbamate, not only the production efficiency and the production cost of the product need to be improved, but also the long-term stability of the chelate ash in storage in a storage yard and the stability of the product of piperazine-N, N-bis-dithiocarbamate as a fly ash collector need to be improved. Therefore, a preparation method of a heavy metal ion trapping agent with high stability is urgently needed.
Disclosure of Invention
The invention aims to provide a preparation method of a high-stability heavy metal ion trapping agent aiming at the defects of the prior art, the preparation method is convenient to operate and control, chemical processes such as separation and extraction are not needed, waste water, waste gas and waste residues are not generated, and the prepared product has excellent heavy metal chelating performance and good stability.
The invention provides the following technical scheme:
a preparation method of a high-stability heavy metal ion trapping agent comprises the following steps:
s1, adding 200-500L deionized water into the reaction kettle, adding 10-30kg of montmorillonite particles, adding 3-10kg of cyclodextrin, heating to 50-60 ℃, and stirring until the montmorillonite particles are completely dissolved;
s2, adjusting the pH value to be 9-11, then adding 2-5kg of triethanolamine and 5-10kg of hydrazine hydrate, and stirring and reacting for 3-4h at the temperature of 60-90 ℃;
s3, after the above processes are completed, cooling to 30-40 ℃, adding 50-100L of piperazine solution, 20-50L of potassium hydroxide solution and 5-10L of polyvinyl alcohol into a reaction kettle, stirring and controlling the temperature to be 30-45 ℃, then slowly adding carbon disulfide into the reaction kettle, measuring the temperature rise rate in the reaction kettle, controlling the temperature to be 30-45 ℃, and stopping adding the carbon disulfide when the temperature rise rate in the reaction kettle is less than 1 ℃/min;
s4, continuously adding the potassium hydroxide solution to a set liquid level, then adding 5-20kg of aluminum glue, controlling the temperature at 30-45 ℃, and stirring for 1h to obtain a liquid product.
Preferably, the particle size of the montmorillonite particles is 20-50 nm.
Preferably, ammonia is slowly added to adjust the pH in the S2 step.
Preferably, the mass concentration of the piperazine solution in the step S3 is 60-70%.
Preferably, the mass concentration of the polyvinyl alcohol in the step S3 is 2 to 10%.
The method is characterized in that the mass concentration of the potassium hydroxide solution in the S3 and S4 steps is 45-55%.
The method is characterized in that the content of the piperazine-N, N-bis-dithiocarbamate potassium in the liquid product obtained in the step S4 is 20-40%, and the density of the liquid product is 1.1-1.4 g/mL.
The invention has the beneficial effects that:
according to the invention, by utilizing the characteristics that montmorillonite unit cells have a layered structure and are easy to carry out cation exchange, potassium ions in potassium hydroxide are exchanged in the montmorillonite unit cells and form strong basicity on the surfaces of the layered structure to react with piperazine-N, N-dithiocarbamic acid to generate piperazine-N, N-dithiocarbamic acid potassium, and the generated piperazine-N, N-dithiocarbamic acid potassium is embedded in the layered structure of the montmorillonite unit cells and has strong dispersibility and strong interaction with a montmorillonite carrier, so that the stability of the piperazine-N, N-dithiocarbamic acid potassium is greatly improved, the degradation under the effects of long-term heating, illumination, oxygen and the like is inhibited, and the effective working period of the fly ash heavy metal trapping agent is prolonged; in addition, in the preparation process, the heating temperature is lower, the cooling temperature is close to the normal temperature, the temperature control operation is easy, the prepared product is liquid, chemical processes such as separation and extraction are not needed, waste water, waste gas and waste residues are not generated, the liquid product is beneficial to the field mixing of the product and the use of fly ash, the problem of secondary pollution of the solid product in the production process is avoided, and the preparation method has good application operability and environmental friendliness.
Detailed Description
Example 1
A preparation method of a high-stability heavy metal ion trapping agent comprises the following steps:
s1, adding 300L of deionized water into the reaction kettle, adding 10kg of montmorillonite particles with the particle size of 50nm, adding 5kg of cyclodextrin, heating to 50 ℃, and stirring until the montmorillonite particles are completely dissolved;
s2, slowly adding ammonia water to adjust the pH value to be within the range of 9.0-9.5, then adding 5kg of triethanolamine and 5kg of hydrazine hydrate, and stirring and reacting for 3 hours at the temperature of 60-65 ℃;
s3, after the above process is completed, cooling to 30-35 ℃, adding 80L of piperazine solution with the mass concentration of 68%, 30L of potassium hydroxide solution with the mass concentration of 48% and 8L of polyvinyl alcohol with the mass concentration of 5% into a reaction kettle, stirring and controlling the temperature to be 30-35 ℃, then slowly adding carbon disulfide into the reaction kettle, measuring the temperature rise rate in the reaction kettle, controlling the temperature in the kettle to be 30-35 ℃, and stopping adding the carbon disulfide when the temperature rise rate in the reaction kettle is less than 1 ℃/min;
s4, continuously adding a potassium hydroxide solution with the mass concentration of 48% to a set liquid level, then adding 10kg of aluminum glue, controlling the temperature at 30-35 ℃, and stirring for 1h to obtain a liquid product, wherein the content of the piperazine-N, N-bis-dithiocarbamate in the liquid product is 32.5%, and the density of the liquid product is 1.18 g/mL.
Example 2
A preparation method of a high-stability heavy metal ion trapping agent comprises the following steps:
s1, adding 250L of deionized water into the reaction kettle, adding 15kg of montmorillonite particles with the particle size of 50nm, adding 5kg of cyclodextrin, heating to 50 ℃, and stirring until the montmorillonite particles are completely dissolved;
s2, slowly adding ammonia water to adjust the pH value to be 9.0-9.5, then adding 2kg of triethanolamine and 10kg of hydrazine hydrate, and stirring and reacting for 3 hours at the temperature of 65-70 ℃;
s3, after the above process is completed, cooling to 30-35 ℃, adding 50L of piperazine solution with the mass concentration of 68%, 20L of potassium hydroxide solution with the mass concentration of 48% and 5L of polyvinyl alcohol with the mass concentration of 5% into a reaction kettle, stirring and controlling the temperature to be 30-35 ℃, then slowly adding carbon disulfide into the reaction kettle, measuring the temperature rise rate in the reaction kettle, controlling the temperature in the kettle to be 30-35 ℃, and stopping adding the carbon disulfide when the temperature rise rate in the reaction kettle is less than 1 ℃/min;
s4, continuously adding a potassium hydroxide solution with the mass concentration of 48% to a set liquid level, then adding 5kg of aluminum glue, controlling the temperature at 30-35 ℃, and stirring for 1h to obtain a liquid product, wherein the content of the piperazine-N, N-bis-dithiocarbamate potassium in the liquid product is 27.5%, and the density of the liquid product is 1.15 g/mL.
Example 3
A preparation method of a high-stability heavy metal ion trapping agent comprises the following steps:
s1, adding 300L of deionized water into the reaction kettle, adding 15kg of montmorillonite particles with the particle size of 50nm, adding 10kg of cyclodextrin, heating to 50 ℃, and stirring until the montmorillonite particles are completely dissolved;
s2, slowly adding ammonia water to adjust the pH value to be within the range of 10.0-10.5, then adding 5kg of triethanolamine and 5kg of hydrazine hydrate, and stirring and reacting for 2 hours at the temperature of 80-90 ℃;
s3, after the above process is completed, cooling to 30-40 ℃, adding 100L of piperazine solution with the mass concentration of 68%, 50L of potassium hydroxide solution with the mass concentration of 48% and 10L of polyvinyl alcohol with the mass concentration of 5% into a reaction kettle, stirring and controlling the temperature to be 40-45 ℃, then slowly adding carbon disulfide into the reaction kettle, measuring the temperature rise rate in the reaction kettle, controlling the temperature in the kettle to be 40-45 ℃, and stopping adding the carbon disulfide when the temperature rise rate in the reaction kettle is less than 1 ℃/min;
s4, continuously adding a potassium hydroxide solution with the mass concentration of 48% to a set liquid level, then adding 15kg of aluminum glue, controlling the temperature at 40-45 ℃, and stirring for 1h to obtain a liquid product, wherein the content of piperazine-N, N-bis-dithiocarbamate in the liquid product is 35.0%, and the density of the liquid product is 1.31 g/mL.
For a fly ash sample of a waste incineration power plant, heavy metal leaching experiments of an original fly ash sample, a sample obtained after chelating fly ash with a conventional trapping agent and a sample obtained after chelating fly ash with a product corresponding to examples 1 to 3 of the present invention are respectively performed according to a method HJ/T300-2007 "acetic acid buffer solution method for leaching toxicity of solid waste", and results of different heavy metal contents of each leaching solution are shown in table 1, wherein a leaching solution corresponding to the original fly ash sample is denoted as a blank example, and a leaching solution corresponding to the sample obtained after chelating fly ash with the conventional trapping agent is denoted as a comparative example.
TABLE 1 chelating Properties test results
| Blank example | Comparative example | Example 1 | Example 2 | Example 3 | |
| Cu2+ | 9.12mg/L | 0.16mg/L | 0.05mg/L | 0.05mg/L | 0.03mg/L |
| Pb2+ | 15.32mg/L | 0.11mg/L | 0.02mg/L | 0.03mg/L | 0.06mg/L |
| Zn2+ | 136.8mg/L | 2.48mg/L | 0.43mg/L | 0.56mg/L | 0.76mg/L |
| Cd2+ | 8.15mg/L | 0.22mg/L | 0.03mg/L | 0.02mg/L | 0.02mg/L |
| Cr3+ | 2.43mg/L | 0.005mg/L | 0.002mg/L | 0.006mg/L | 0.002mg/L |
Meanwhile, the decomposition performance of the conventional piperazine-N, N-potassium bisdithiocarbamate collectors and the piperazine-N, N-potassium bisdithiocarbamate collectors prepared in examples 1 to 3 of the present invention was tested by an experiment of heating pure oxygen at 80 ℃ for accelerated degradation for 50 hours, and the chemical content of the conventional piperazine-N, N-potassium bisdithiocarbamate collectors was 40%, and the specific results are shown in Table 2.
TABLE 2 decomposition Performance test results
In the preparation process, the heating temperature is lower, the cooling temperature is close to the normal temperature, the temperature control operation is easy, the prepared product is liquid, separation and extraction and other chemical processes are not needed, no waste water, waste gas and waste residue is generated, and the environment friendliness is excellent. As is apparent from Table 1, the piperazine-N, N-potassium bisdithiocarbamate prepared by the invention has excellent heavy metal chelating property, and the heavy metal content in the waste incineration fly ash is greatly reduced; as can be seen from Table 2, through a 50-hour experiment of heating pure oxygen at 80 ℃, the degradation rate of the piperazine-N, N-bis-dithiocarbamate potassium in the product is less than 3.5%, which is lower than that of the conventional product by more than half, and the product prepared by the invention has good stability.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of a high-stability heavy metal ion trapping agent is characterized by comprising the following steps:
s1, adding 200-500L deionized water into the reaction kettle, adding 10-30kg of montmorillonite particles, adding 3-10kg of cyclodextrin, heating to 50-60 ℃, and stirring until the montmorillonite particles are completely dissolved;
s2, adjusting the pH value to be 9-11, then adding 2-5kg of triethanolamine and 5-10kg of hydrazine hydrate, and stirring and reacting for 3-4h at the temperature of 60-90 ℃;
s3, after the above processes are completed, cooling to 30-40 ℃, adding 50-100L of piperazine solution, 20-50L of potassium hydroxide solution and 5-10L of polyvinyl alcohol into a reaction kettle, stirring and controlling the temperature to be 30-45 ℃, then slowly adding carbon disulfide into the reaction kettle, measuring the temperature rise rate in the reaction kettle, controlling the temperature to be 30-45 ℃, and stopping adding the carbon disulfide when the temperature rise rate in the reaction kettle is less than 1 ℃/min;
s4, continuously adding the potassium hydroxide solution to a set liquid level, then adding 5-20kg of aluminum glue, controlling the temperature at 30-45 ℃, and stirring for 1h to obtain a liquid product.
2. The method of claim 1, wherein the particle size of the montmorillonite particles is 20-50 nm.
3. The method for preparing a high-stability heavy metal ion trapping agent according to claim 1, wherein ammonia water is slowly added to adjust the pH in the step of S2.
4. The method according to claim 1, wherein the mass concentration of the piperazine solution in the step S3 is 60-70%.
5. The method according to claim 1, wherein the mass concentration of the polyvinyl alcohol in the step S3 is 2-10%.
6. The method for preparing a high-stability heavy metal ion trapping agent according to claim 1, wherein the mass concentration of the potassium hydroxide solution in the steps of S3 and S4 is 45-55%.
7. The method for preparing a high-stability heavy metal ion trapping agent according to claim 1, wherein the content of the potassium piperazine-N, N-bisdithiocarbamate in the liquid product obtained in the step of S4 is 20-40%, and the density of the liquid product is 1.10-1.4 g/mL.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86102713A (en) * | 1985-04-17 | 1986-10-22 | 东洋曹达工业株式会社 | Be used to reclaim the sorbent material of bromine and use the technology that this sorbent material reclaims bromine |
| CN101007261A (en) * | 2006-12-17 | 2007-08-01 | 于向真 | Zeolite adsorbent and its preparation method |
| CN101757885A (en) * | 2008-12-25 | 2010-06-30 | 恩达电路(深圳)有限公司 | Heavy metal chelating agent and preparation method thereof |
| CN102766406A (en) * | 2012-06-25 | 2012-11-07 | 深圳市力合材料有限公司 | Polishing composition for removing surface defect of semiconductor silicon wafer and preparation method thereof |
| CN108997262A (en) * | 2018-08-18 | 2018-12-14 | 泰山医学院 | A kind of production method of heavy metal chelant piperazine-N, N- bisdithiocarbamic potassium |
| CN109081417A (en) * | 2018-08-18 | 2018-12-25 | 青岛中科荣达新材料有限公司 | A kind of production method of heavy metal chelating agent piperazine-N, N- bisdithiocarbamic potassium |
| US10427953B1 (en) * | 2016-05-24 | 2019-10-01 | King Fahd University Of Petroleum And Minerals | Dithiocarbamate alkali metal cross-linked resin for adsorbing metal ions |
-
2019
- 2019-12-18 CN CN201911310092.2A patent/CN111136084A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN86102713A (en) * | 1985-04-17 | 1986-10-22 | 东洋曹达工业株式会社 | Be used to reclaim the sorbent material of bromine and use the technology that this sorbent material reclaims bromine |
| CN101007261A (en) * | 2006-12-17 | 2007-08-01 | 于向真 | Zeolite adsorbent and its preparation method |
| CN101757885A (en) * | 2008-12-25 | 2010-06-30 | 恩达电路(深圳)有限公司 | Heavy metal chelating agent and preparation method thereof |
| CN102766406A (en) * | 2012-06-25 | 2012-11-07 | 深圳市力合材料有限公司 | Polishing composition for removing surface defect of semiconductor silicon wafer and preparation method thereof |
| US10427953B1 (en) * | 2016-05-24 | 2019-10-01 | King Fahd University Of Petroleum And Minerals | Dithiocarbamate alkali metal cross-linked resin for adsorbing metal ions |
| CN108997262A (en) * | 2018-08-18 | 2018-12-14 | 泰山医学院 | A kind of production method of heavy metal chelant piperazine-N, N- bisdithiocarbamic potassium |
| CN109081417A (en) * | 2018-08-18 | 2018-12-25 | 青岛中科荣达新材料有限公司 | A kind of production method of heavy metal chelating agent piperazine-N, N- bisdithiocarbamic potassium |
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Application publication date: 20200512 |