CN110937676A - Preparation method of hyperbranched dithiocarbamate heavy metal remover - Google Patents
Preparation method of hyperbranched dithiocarbamate heavy metal remover Download PDFInfo
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- CN110937676A CN110937676A CN201911322645.6A CN201911322645A CN110937676A CN 110937676 A CN110937676 A CN 110937676A CN 201911322645 A CN201911322645 A CN 201911322645A CN 110937676 A CN110937676 A CN 110937676A
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- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
- C02F1/62—Heavy metal compounds
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Abstract
The invention provides a preparation method of a hyperbranched dithiocarbamate heavy metal remover, which comprises the following steps: (1) dropwise adding methyl acrylate into a methanol solution of the amine compound, reacting at 30-40 ℃ for 5-8h, evaporating the methanol, continuously heating to 80-100 ℃ for reacting for 2-4h, and then heating to 140-160 ℃ again for reacting for 1-2h to obtain the hyperbranched polyamide-amine compound. (2) Dissolving the hyperbranched polyamide-amine compound in water, simultaneously dropwise adding carbon disulfide and an inorganic strong base solution, and reacting for a certain time to obtain the hyperbranched dithiocarbamate heavy metal remover. The preparation method of the hyperbranched dithiocarbamate heavy metal remover provided by the invention has the advantages of low cost, simple and safe process and high yield, the obtained heavy metal remover has the characteristics of wide applicable pH range, small addition amount and high chelation rate, and the treated floc is large, has high settling speed and is easy for subsequent treatment.
Description
The technical field is as follows:
the invention belongs to the technical field of wastewater treatment, and particularly relates to a preparation method of a hyperbranched dithiocarbamate heavy metal remover.
Background art:
the heavy metal wastewater is wastewater containing heavy metals discharged in the industrial production processes of mining and metallurgy, mechanical manufacturing, chemical industry, electronics, instruments and the like. Heavy metal (such as cadmium, nickel, copper, zinc and the like) wastewater is one of the industrial wastewater which has the most serious environmental pollution and the most serious harm to human beings, and the sewage amount of the wastewater is increased along with the development of the industry. At present, the treatment technologies mainly comprise a neutralization precipitation method, a heavy metal removal agent precipitation method, an electrolytic precipitation or electrolytic floating method, a diaphragm electrolysis method, a reverse osmosis method, an ion exchange method and the like. The heavy metal remover precipitation method has the advantages of low equipment investment, high treatment efficiency, low cost and the like, and is most widely applied to the heavy metal wastewater treatment industry.
The heavy metal ion remover is an organic matter which has chelating functional groups and can selectively trap, separate and precipitate specific metal ions from a solution containing the metal ions. The dithiocarbamate Derivatives (DTCs) are the most widely used in practical research. Among them, the small molecular DTC trapping agent has small alum floc formed by combining with heavy metals, and needs to use flocculant to assist precipitation, while the high molecular DTC product directly generates insoluble dithiocarbamate (TDC salt) because of containing a large amount of polar groups, and has good settleability, thus becoming a hotspot for development. The polymer TDC is synthesized by introducing a chain group having a chelating function through a chemical reaction using a synthetic or natural polymer. Generally speaking, the higher the branching degree of the polymer chain segment is, the more chain groups with chelating function can be introduced, the better the treatment effect is, and meanwhile, the higher the molecular weight is, the larger the chelate salt floc finally formed is, and the easier the treatment is. In view of this, attempts have been made in recent years to develop more efficient heavy metal removal agents. Patent 201310450155.0 discloses a method for preparing a urea-based dithiocarbamate heavy metal ion remover, which is mainly prepared from urea, amine compounds, carbon disulfide, an auxiliary agent, an alkaline substance and distilled water; patent 201410431509.1 discloses a hyperbranched heavy metal remover, which is prepared by polymerizing a ternary epoxy compound and a binary primary amine compound to obtain a hyperbranched polyamine compound, and then reacting the hyperbranched polyamine compound with carbon disulfide to obtain a heavy metal remover; patent 201811593038.9 provides a preparation method of a hyperbranched three-dimensional heavy metal remover, which utilizes polyamine compounds to generate hyperbranched high molecular compounds under the action of a cross-linking agent, a surfactant and epichlorohydrin, and synthesizes the hyperbranched high molecular compounds with carbon disulfide under alkaline conditions to form a three-dimensional high molecular heavy metal trapping agent. Although some results have been obtained in the research of polymer TDC, with the development of industry, the composition of wastewater becomes more and more complex, and the complex and various industrial wastewater in each industry is difficult to reach the emission standard requirement through a certain heavy metal remover, its formula and treatment process, so that the development of efficient heavy metal removers with different structures to meet the requirements of more industries is always urgent and important.
The invention content is as follows:
in order to further improve the removal efficiency of the heavy metal remover and develop a heavy metal remover product with a novel structure to meet the sewage treatment requirements of various industries, the invention provides a preparation method of a hyperbranched dithiocarbamate heavy metal remover.
The invention relates to a preparation method of a hyperbranched dithiocarbamate heavy metal remover, which comprises the following steps:
(1) dropwise adding methyl acrylate into a methanol solution of an amine compound, reacting at 30-40 ℃ for 5-8h, evaporating methanol, continuously heating to 80-100 ℃ for reacting for 2-4h, and then heating to 140-160 ℃ again for reacting for 1-2h to obtain a hyperbranched polyamide-amine compound; wherein the amine compound is one or more of ethylenediamine, diethylenetriamine, triethylene tetramine and propylene diamine, and the molar ratio of the amine compound to methyl acrylate is 1:1-1: 4;
(2) dissolving a hyperbranched polyamide-amine compound in water, simultaneously dropwise adding carbon disulfide and an inorganic strong base solution, controlling the reaction temperature to be less than or equal to 30 ℃ in the dropwise adding process, reacting for 0.5-1h after dropwise adding, heating to 60-80 ℃, and preserving heat for 2-3h to obtain a hyperbranched dithiocarbamate heavy metal remover; wherein the inorganic strong base is one or two of sodium hydroxide and potassium hydroxide, and the mass ratio of the hyperbranched polyamide-amine compound to the carbon disulfide to the strong base is (2.5-3.5): (1.5-2.5):1.
In the step (1), the amine compound is preferably one or two of ethylenediamine and triethylene tetramine, and the molar ratio of the amine compound to methyl acrylate is preferably 1 (1.5-2.5); in step (2) of the method, the inorganic strong base is preferably sodium hydroxide.
The invention also provides the hyperbranched dithiocarbamate heavy metal remover prepared by the preparation method.
The preparation method of the hyperbranched dithiocarbamate heavy metal remover provided by the invention has the advantages of low cost, simple and safe process and high yield, and the heavy metal remover obtained according to the provided preparation method has the characteristics of wide applicable pH range, small addition amount and high chelation rate, and is large in floc after treatment, high in settling velocity and easy for subsequent treatment.
The specific implementation mode is as follows:
the present invention will be described in detail with reference to specific examples, which are not intended to limit the scope of the present invention. Examples 1 to 7 were the preparation of hyperbranched dithiocarbamate type heavy metal remover, and examples 8 to 12 were the evaluation of the effect of the heavy metal remover prepared in examples 1 to 7 on the removal of part of heavy metals.
Example 1
(1) Dissolving 601g of ethylenediamine in 500mL of methanol, slowly dropwise adding 861g of methyl acrylate at 20 ℃, heating to 30 ℃ after dropwise adding, reacting for 8 hours, evaporating the methanol, continuously heating to 80 ℃ for reacting for 4 hours, and then heating to 140 ℃ again for reacting for 2 hours to obtain the light yellow viscous liquid hyperbranched polyamide-amine compound.
(2) Dissolving the obtained hyperbranched polyamide-amine compound in 1647g of water, simultaneously dropwise adding 1462g of carbon disulfide and 1949g of 30% sodium hydroxide aqueous solution at room temperature, controlling the reaction temperature to be less than or equal to 30 ℃ in the dropwise adding process, reacting for 0.5h after dropwise adding, heating to 80 ℃, and preserving heat for 2h to obtain the hyperbranched dithiocarbamate heavy metal remover T-1.
Example 2
(1) Dissolving 601g of ethylenediamine in 500mL of methanol, slowly dropwise adding 1722g of methyl acrylate at 20 ℃, heating to 35 ℃ after dropwise adding, reacting for 7h, steaming to remove the methanol, continuously heating to 90 ℃ for reacting for 3h, and then heating to 150 ℃ again for reacting for 1.5h to obtain the pale yellow viscous liquid hyperbranched polyamide-amine compound.
(2) Dissolving the obtained hyperbranched polyamide-amine compound in 2181g of water, simultaneously dropwise adding 1549g of carbon disulfide and 2581g of 30% sodium hydroxide aqueous solution at room temperature, controlling the reaction temperature to be less than or equal to 30 ℃ in the dropwise adding process, reacting for 0.5h after dropwise adding, heating to 70 ℃, and preserving heat for 2.5h to obtain the hyperbranched dithiocarbamate type heavy metal remover T-2.
Example 3
(1) Dissolving 601g of ethylenediamine in 500mL of methanol, slowly dropwise adding 2583g of methyl acrylate at 20 ℃, heating to 40 ℃ after dropwise adding, reacting for 5h, steaming to remove the methanol, continuously heating to 100 ℃ for reacting for 2h, and then heating to 160 ℃ again for reacting for 1h to obtain the light yellow viscous liquid hyperbranched polyamide-amine compound.
(2) Dissolving the obtained hyperbranched polyamide-amine compound in 2293g of water, simultaneously dropwise adding 1365g of carbon disulfide and 3032g of 30% sodium hydroxide aqueous solution at room temperature, controlling the reaction temperature to be less than or equal to 30 ℃ in the dropwise adding process, reacting for 1h after dropwise adding, heating to 60 ℃, and keeping the temperature for 3h to obtain the hyperbranched dithiocarbamate heavy metal remover T-3.
Example 4
(1) Dissolving 601g of ethylenediamine in 500mL of methanol, slowly dropwise adding 3444g of methyl acrylate at 20 ℃, heating to 40 ℃ after dropwise adding, reacting for 5h, evaporating to remove the methanol, continuously heating to 100 ℃ for reacting for 2h, and then heating to 160 ℃ again for reacting for 1h to obtain the light yellow viscous liquid hyperbranched polyamide-amine compound.
(2) Dissolving the obtained hyperbranched polyamide-amine compound in 3256g of water, simultaneously dropwise adding 1734g of carbon disulfide and 3853g of 30% sodium hydroxide aqueous solution at room temperature, controlling the reaction temperature to be less than or equal to 30 ℃ in the dropwise adding process, reacting for 1h after dropwise adding, heating to 60 ℃, and keeping the temperature for 3h to obtain the hyperbranched dithiocarbamate heavy metal remover T-3.
Example 5
(1) 1032g of diethylenetriamine is dissolved in 500mL of methanol, 2583g of methyl acrylate is slowly dripped at the temperature of 20 ℃, the temperature is raised to 35 ℃ after dripping for reaction for 7h, the methanol is evaporated, the temperature is continuously raised to 90 ℃ for reaction for 3h, and then the temperature is raised to 150 ℃ again for reaction for 1.5h to obtain the light yellow viscous liquid hyperbranched polyamide-amine compound.
(2) Dissolving the obtained hyperbranched polyamide-amine compound in 3447g of water, simultaneously dropwise adding 1836g of carbon disulfide and 3060g of 30% sodium hydroxide aqueous solution at room temperature, controlling the reaction temperature to be less than or equal to 30 ℃ in the dropwise adding process, after the dropwise adding reaction is finished for 0.5h, heating to 70 ℃, and keeping the temperature for 2.5h to obtain the hyperbranched dithiocarbamate type heavy metal remover T-5.
Example 6
(1) 1462g of triethylene tetramine is dissolved in 500mL of methanol, 3444g of methyl acrylate is slowly dripped at the temperature of 20 ℃, the temperature is raised to 40 ℃ after dripping for reaction for 5h, the methanol is evaporated, the temperature is continuously raised to 100 ℃ for reaction for 2h, and then the temperature is raised to 160 ℃ again for reaction for 1h to obtain the light yellow viscous liquid hyperbranched polyamide-amine compound.
(2) Dissolving the obtained hyperbranched polyamide-amine compound in 4606g of water, simultaneously dropwise adding 3271g of carbon disulfide and 5451g of 30% potassium hydroxide aqueous solution at room temperature, controlling the reaction temperature to be less than or equal to 30 ℃ in the dropwise adding process, reacting for 1h after dropwise adding, heating to 60 ℃, and keeping the temperature for 3h to obtain the hyperbranched dithiocarbamate heavy metal remover T-6.
Example 7
(1) Dissolving 741g of propane diamine in 500mL of methanol, slowly dropwise adding 1722g of methyl acrylate at 20 ℃, heating to 35 ℃ after dropwise adding, reacting for 7h, steaming to remove the methanol, continuously heating to 90 ℃ for reacting for 3h, and then heating to 150 ℃ again for reacting for 1.5h to obtain the light yellow viscous liquid hyperbranched polyamide-amine compound.
(2) Dissolving the obtained hyperbranched polyamide-amine compound in 2463g of water, simultaneously dropwise adding 1642g of carbon disulfide and 2737g of 30% potassium hydroxide aqueous solution at room temperature, controlling the reaction temperature to be less than or equal to 30 ℃ in the dropwise adding process, reacting for 0.5h after dropwise adding, heating to 70 ℃, and preserving heat for 2.5h to obtain the hyperbranched dithiocarbamate type heavy metal remover T-7.
Example 8
For containing Zn2+The simulated solution treatment effect of (1).
Accurately weighing a certain amount of Zn2+The compound of (1) is dissolved and fixed in volume to prepare 5 mg.L-1The simulated solution of (1). The T-1-T-7 agent and a certain dithiocarbamate heavy metal remover TM sold in the market are respectively diluted by deionized water for use.
500mL of each Zn-containing solution was taken2+Respectively adding heavy metal removal agents T-1-T-7 and TM diluent to the solution of (1) under stirring until the concentration of the agent is 80 mg.L-1After 5min of reaction, the precipitation was completed, and the supernatant was taken to measure the ion concentration, the results are shown in Table 1.
TABLE 1 Pair of Zn in Water2+Removing effect of
Example 9
To the content of Cu2+The simulated solution treatment effect of (1).
Accurately weighing a certain amount of Cu2+The compound of (1) is dissolved and fixed in volume to prepare 5 mg.L-1The simulated solution of (1). The T-1-T-7 agent and a certain dithiocarbamate heavy metal remover TM sold in the market are respectively diluted by deionized water for use.
500mL of each sample containing Cu2+Respectively adding heavy metal removal agents T-1-T-7 and TM diluent to the solution of (1) under stirring until the concentration of the agent is 70 mg.L-1After the reaction was completed for 5min and the sedimentation was completed, the supernatant was taken to measure the ion concentration, and the results are shown in Table 2.
TABLE 2 vs. Cu in water2+Removing effect of
Example 10
To Ni2+The simulated solution treatment effect of (1).
Accurately weighing a certain amount of Ni2+The compound of (1) is dissolved and fixed in volume to prepare 5 mg.L-1The simulated solution of (1). The T-1-T-7 agent and a certain dithiocarbamate heavy metal remover TM sold in the market are respectively diluted by deionized water for use.
500mL of Ni-containing solution was taken2+Respectively adding heavy metal removal agents T-1-T-7 and TM diluent to the solution of (1) under stirring until the concentration of the agent is 70 mg.L-1After the reaction was completed for 5min and the sedimentation was completed, the supernatant was taken to measure the ion concentration, and the results are shown in Table 3.
TABLE 3 Pair of Ni in Water2+Removing effect of
Example 11
For the content of Cr3+The simulated solution treatment effect of (1).
Accurately weighing a certain amount of Cr3+The compound of (1) is dissolved and fixed in volume to prepare 5 mg.L-1The simulated solution of (1). The T-1-T-7 agent and a certain dithiocarbamate heavy metal remover TM sold in the market are respectively diluted by deionized water for use.
Respectively taking 500mL of Cr-containing alloy3+Respectively adding heavy metal removal agents T-1-T-7 and TM diluent to the solution of (1) under stirring until the concentration of the agent is 50 mg.L-1After the reaction was completed for 5min and the sedimentation was completed, the supernatant was taken to measure the ion concentration, and the results are shown in Table 4.
TABLE 4 Cr in Water3+Removing effect of
Example 12
The treatment effect on the comprehensive wastewater containing heavy metals.
Taking certain comprehensive wastewater with pH of 6.0 and Zn content2+、Cu2+、Cr3+、Ni2+Are respectively 4.356 mg.L-1、5.715mg·L-1、4.639mg·L-1、3.822mg·L-1Adding 200 mg.L-1The post-treatment effect of the agents is shown in table 5.
TABLE 5 removal of heavy metal ions from the comprehensive wastewater
Claims (5)
1. A preparation method of a hyperbranched dithiocarbamate heavy metal remover is characterized by comprising the following steps:
(1) dropwise adding methyl acrylate into a methanol solution of an amine compound, reacting at 30-40 ℃ for 5-8h, evaporating methanol, continuously heating to 80-100 ℃ for reacting for 2-4h, and then heating to 140-160 ℃ again for reacting for 1-2h to obtain a hyperbranched polyamide-amine compound; wherein the amine compound is one or more of ethylenediamine, diethylenetriamine, triethylene tetramine and propylene diamine, and the molar ratio of the amine compound to the methyl acrylate is 1 (1-4);
(2) dissolving a hyperbranched polyamide-amine compound in water, simultaneously dropwise adding carbon disulfide and an inorganic strong base solution, controlling the reaction temperature to be less than or equal to 30 ℃ in the dropwise adding process, reacting for 0.5-1h after dropwise adding, heating to 60-80 ℃, and preserving heat for 2-3h to obtain a hyperbranched dithiocarbamate heavy metal remover; wherein the inorganic strong base is one or two of sodium hydroxide and potassium hydroxide, and the mass ratio of the hyperbranched polyamide-amine compound to the carbon disulfide to the strong base is (2.5-3.5): (1.5-2.5):1.
2. The method for preparing a hyperbranched dithiocarbamate-type heavy metal remover according to claim 1, wherein the hyperbranched dithiocarbamate-type heavy metal remover comprises: in the step (1), the amine compound is one or two of ethylenediamine and triethylene tetramine.
3. The method for preparing a hyperbranched dithiocarbamate-type heavy metal remover according to claim 1, wherein the hyperbranched dithiocarbamate-type heavy metal remover comprises: in the step (1), the molar ratio of the amine compound to the methyl acrylate is 1 (1.5-2.5).
4. The method for preparing a hyperbranched dithiocarbamate-type heavy metal remover according to claim 1, wherein the hyperbranched dithiocarbamate-type heavy metal remover comprises: in the step (2), the inorganic strong base is sodium hydroxide.
5. A hyperbranched dithiocarbamate-type heavy metal remover obtained by the preparation method of any one of claims 1 to 4.
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