TW202449005A - Derivatized polyamine polymers for use in metal scavenging applications - Google Patents

Abstract

Provided herein is a method of preparing a metal ion scavenger comprising adding an effective amount of a piperazine derivative to a polyamine and epihalohydrin condensation reaction. Further provided herein is a method of treating aqueous and non-aqueous streams comprising adding a metal ion scavenger prepared by adding an effective amount of a piperazine derivative to a polyamine and epihalohydrin condensation reaction to the aqueous and non-aqueous streams.

Description

Derivatized polyamine polymers for metal scavenging applications

The disclosed technology provides a method for preparing a polyamine prepolymer skeleton for preparing a metal ion scavenger and a chelating agent. More specifically, the disclosed technology provides a method for preparing a polyamine prepolymer skeleton for preparing a polydithiocarbamate-based metal ion scavenger and a chelating agent, which comprises: The derivatives are introduced into the condensation reaction of polyamine and epihalohydrin. Cross-references to related applications

This application claims priority to U.S. Provisional Patent Application No. 63/464,231 filed on May 5, 2023, which is hereby incorporated by reference in its entirety.

Heavy metal pollution is an existing and growing problem worldwide. For example, wastewater from waste treatment facilities, the chlorine and alkali industries, the metal finishing industries, cooling tower blowdowns, incinerator scrubbers, municipal streams, refineries, and from certain municipal landfills often present metal pollution problems. Similarly, the metal content of water effluent from either or both working and abandoned mines in geographic areas with mining industries is a significant environmental concern. In addition to aqueous process waters and wastewater streams, non-aqueous hydrocarbon streams commonly found in petroleum refining processes or petrochemical processes also contain significant levels of heavy metal content that need to be reduced. Heavy metal ions can cause problems for the environment and their concentrations in water are regulated.

Various treatment technologies have been developed to remove either or both dissolved or suspended, or both dissolved and suspended heavy metal ions from industrial liquid streams. A common practice in aqueous streams is to precipitate the bulk of the heavy metal contaminants as their metal hydroxides. Metal ions such as copper and lead, for example, are readily precipitated in this manner, but the minimum concentration that can be obtained is limited by the limited solubility of the hydroxide complexes. The effluent resulting from the hydroxide precipitation can be treated with metal scavengers to remove any trace metal contaminants to meet discharge standards. These agents can be precipitants, absorbents, or metal-specific ion exchange resins. Metal scavenger precipitants may also be effective when added in parallel with the hydroxide precipitation. Typical compounds used as precipitation scavengers include sulfides, (thio) carbonates, alkyl dithiocarbamates, mercaptans, and polydithiocarbamates.

The use of water-soluble polymeric dithiocarbamate-based scavengers to remove heavy metal ions from contaminated water is well known in the industry. These polymeric products have benefits in both their aquatic toxicity profile and their ability to settle compared to smaller dithiocarbamates or other organic sulfide compounds. However, existing prepolymer backbone materials, particularly polyethyleneimine (PEI), are expensive and may not be able to remove specific metal ions.

There is therefore a need in the art for less expensive backbone replacements that have improved processing performance when converted to dithiocarbamate products.

The disclosed technology provides a method for preparing a polyamine prepolymer skeleton for producing a metal ion scavenger and a chelating agent, which comprises: The derivatives are introduced into polyamines through condensation reaction with epihalogen alcohols.

The disclosed technology is related to a method for preparing a metal ion scavenger, which comprises: The derivative is added to the polyamine and epihalogen alcohol for condensation reaction.

In many aspects, piperine The derivative may be ethylaminopiperidin , the polyamine may be polyethylene polyamine and the epihalogen alcohol may be epichlorohydrin.

In various aspects, the metal ion scavenger can be a transition metal scavenger such as a dithiocarbamate.

In various aspects, the metal ion scavenger can be used to treat aqueous or non-aqueous streams.

Various aspects of the disclosed technology further relate to a method for preparing a polyamine prepolymer backbone, which comprises: The derivative is added to the polyamine and epihalogen alcohol for condensation reaction.

The disclosed technology is more about a method for preparing a polyamine prepolymer skeleton, which comprises: The derivative is reacted with a first portion of the epihalogen alcohol to form a first reaction mixture; the polyamine is added to the first reaction mixture to form a second reaction mixture; and the second portion of the epihalogen alcohol is added to the second reaction mixture.

The disclosed technology provides a method for preparing a polyamine prepolymer skeleton for making a metal ion scavenger and a chelating agent. More specifically, the disclosed technology provides a method for preparing a polyamine prepolymer skeleton for making a metal ion scavenger and a chelating agent, which comprises: The derivative is introduced into the condensation reaction step of the polyamine and epihalogen alcohol.

The disclosed technology provides a design and synthesis method for a polyamine prepolymer skeleton for preparing a polyvalent metal ion chelating agent and/or scavenging agent. The polyamine prepolymer skeleton is designed and synthesized by introducing the derivative into the condensation reaction of polyamine and epihalogen alcohol. Without being limited by theory, the piperidine in the polyamine prepolymer skeleton The amount can help control the structure, branching, conformation, and solubility curve of the final metal ion chelator and/or scavenger product.

The disclosed technology further provides a method for synthesizing a polyamine polymer backbone that is easy to control and highly cost-effective. It has been surprisingly discovered that the order of addition of reactants affects the effectiveness of the prepolymer backbone synthesis process, wherein the piperidine is added before the polyamine is added to the reaction vessel. The derivatives react with epihalogen alcohols. If this addition sequence is not followed, or if the piperidine In some embodiments, when the polyamine polymer backbone prepared by the synthesis method of the present disclosure is converted into a corresponding metal ion scavenger and/or chelating agent, i) improved sensitivity and affinity to specific metal ions, ii) a wider effective dosage range, and iii) a desired floc formation curve can be observed.

As used herein, the term "metal ion scavenger" or "metal ion chelator" may be understood to mean an organic compound or polymer material capable of binding metal ions to form a chelate structure. Examples of metal ion scavengers or chelators may include dithiocarbamates, polydithiocarbamates or other organic sulfide compounds.

As used herein, the term "effective amount" is understood to mean an amount of the piperidine effective to provide the desired properties to the final metal ion chelator and/or scavenger product. Any amount of a derivative.

As used herein, the term "aqueous solution stream" may be understood to mean process water used in industry, manufacturing processes, power generation, and the like.

As used herein, the term "wastewater" shall be understood to mean used water from any combination of domestic, industrial, commercial, or agricultural activities, surface runoff/stormwater, and any sewer inflow or sewer seepage.

As used herein, the term "non-aqueous solution stream" may be understood to mean a non-aqueous hydrocarbon stream used in petroleum refining processes, petrochemical processes, and the like.

In various aspects, the disclosed technology provides a method for preparing a polyamine prepolymer backbone, which comprises: The derivative is added to the polyamine and epihalogen alcohol for condensation reaction. The disclosed technology further provides a metal ion scavenger, which comprises a polyamine polymer skeleton prepared by the method of the present disclosure.

In some aspects, the method may include: The derivative is reacted with a first portion of epihalogen alcohol to form a first reaction mixture; a polyamine is added to the first reaction mixture to form a second reaction mixture; and a second portion of epihalogen alcohol is added to the second reaction mixture to prepare a polyamine prepolymer backbone.

Suitable Piperidone The derivatives may include any piperyls capable of forming a prepolymer backbone with polyamines and epihalogen alcohols. In various aspects, suitable piperidine Derivatives may include soluble piperidine In some aspects, suitable piperidine Derivatives may include ethylamine (aminoethyl piperazine, AEP).

Suitable polyamines may include those capable of reacting with piperidine In some embodiments, the present invention relates to any polyamine compound that can form a prepolymer backbone with a derivative of ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), hexaethyleneheptamine (HEHA), other higher amines, and mixtures thereof.

Suitable epihalogen alcohols may include those capable of reacting with piperidine The present invention relates to any epihalohydrin compound that can form a prepolymer backbone together with a derivative and a polyamine. In some aspects, suitable epihalohydrin compounds can include epichlorohydrin, epibromohydrin, epifluorohydrin, or epiiodohydrin.

In various aspects, the methods of the present disclosure may include adding piperidine in a molar ratio of about 1:1 to about 1:5, or about 1:1, 1:2, 1:3, 1:4 or 1:5, or any value between any of these ratios, or about 1:2. Derivatives and polyamines.

In various aspects, the methods of the present disclosure can include adding the polyamine and the epihalogen alcohol at a molar ratio of total amine to epihalogen alcohol of between 1:1 to about 1:1.35 (or any value between these ratios).

In various aspects, the disclosed technology provides metal ion scavengers and/or chelating agents prepared using the methods of the present disclosure. In some aspects, the metal ion scavengers and/or chelating agents may be transition metal ion scavengers and/or chelating agents, such as polydithiocarbamates. In some aspects, the metal ion scavengers and/or chelating agents may be used to treat aqueous and non-aqueous streams. In some aspects, aqueous streams that may be treated by the metal ion scavengers and/or chelating agents of the present disclosure may include process water, such as wastewater. In some aspects, non-aqueous streams that may be treated by the metal ion scavengers and/or chelating agents of the present disclosure may include non-aqueous hydrocarbon streams, such as those used in petroleum refining processes, petrochemical processes, and the like.

In various aspects, the disclosed technology further provides a method for preparing a metal ion scavenger and/or chelating agent, comprising: The derivative is added to the polyamine and the epihalogen alcohol condensation reaction. In some embodiments, the disclosed technology provides a method for preparing a polydithiocarbamate, which comprises adding an effective amount of piperidine to the The derivative is added to the step of preparing a polyamine prepolymer skeleton by condensing a polyamine with epihalogen alcohol and reacting the prepolymer skeleton with carbon disulfide.

In various aspects, the disclosed technology further provides a method for removing metal ions from aqueous and non-aqueous streams, comprising adding a metal ion scavenger and/or chelating agent prepared according to the method of the present disclosure to the aqueous and non-aqueous streams. In various aspects, any amount of metal ion scavenger and/or chelating agent effective to remove metal ions from the aqueous and non-aqueous streams can be added to the aqueous and non-aqueous streams. In some aspects, metal ion scavengers and/or chelating agents may be added in an amount of about 0.1 ppm to about 10000 ppm, or about 0.1, 1, 10, 50, 100, 500, 1000, 1500, 2000, 2500, 3000, 3500, 4000, 4500, 5000, 5500, 6000, 6500, 7000, 7500, 8000, 8500, 9000, 9500, or 10000 ppm, or about 0.1 ppm to about 1000 ppm, or about 0.1 ppm to about 500 ppm, or any amount between any of these values.

In various aspects, aqueous and non-aqueous solutions treated with the metal ion scavengers and/or chelating agents of the present disclosure may contain metal ion contents within regulatory limits as understood by those of ordinary skill in the art. In various aspects, metal ions that may be removed from aqueous and non-aqueous solutions using the metal ion scavengers and/or chelating agents of the present disclosure may include cadmium, cobalt, copper, nickel, zinc, mercury, etc. Examples

The present technology will be further described in the following embodiments, which should be regarded as exemplary and should not be interpreted as limiting the scope of the disclosed technology or limiting the scope to any specific implementation.

Embodiment 1

Synthesis of AEP-EPI-TEPA prepolymer (1A)

62 gr of deionized water (DI) was charged into a reactor equipped with a stirrer, a thermometer and a reflux condenser. 42 gr of ethylamine (AEP) was added to the reactor and the temperature was adjusted to or below 25°C. 60 gr of epichlorohydrin (EPI) was pumped into the stirred solution at a constant flow rate over 30 minutes and the reaction temperature was not allowed to exceed 30°C. After the EPI feed was completed, tetraethylenepentamine (TEPA) solution (123 gr TEPA + 103 gr deionized water) was added to the reactor in portions over 5 minutes while maintaining the temperature between 35°C and 40°C. When the temperature was stable below 40°C, 39 gr of EPI (second portion) was fed into the reactor over 20 minutes (AEP:EPI:TEPA molar ratio of 1:3.15:2). After the EPI feed was completed, the batch was heated to 88°C over 30 minutes and maintained at 88°C for 3 hours. Then the heating was turned off and 99 gr of deionized water were added to the product (adjust the solid content to about 50%). The product was allowed to cool to room temperature. The obtained viscous (dark) yellow product was used in the next reaction without any purification.

¹³ C NMR: 70 ppm-35 ppm (aliphatic ¹³ C nucleus in the skeleton, -N-CH ₂ CH ₂ -N-CH ₂ -CH(OH)-CH ₂ -)

Dithiocarbamate Functionalization of AEP-EPI-TEPA Prepolymer (AEP-EPI-TEPA-CS ₂ ) (1B)

In a reactor equipped with a stirrer, thermometer, and reflux condenser, 93 gr of AEP-EPI-TEPA prepolymer (50%) solution was diluted with 204 gr of deionized water and kept under _N2 blanket. 52 gr of NaOH (50%) was added to this solution over 20 minutes. The light yellow solution was cooled to 38°C before starting the carbon disulfide ( _CS2 ) feed. 43.55 gr of _CS2 (34.4 mL) was continuously fed to the reactor at a constant rate over 90 minutes, and the temperature was gradually increased to 43°C during the addition. After the CS ₂ feed was complete, the reaction was held at 44 °C for 90 min and at 47-50 °C for an additional 30 min until a bright orange to red product was obtained (solids content 29.57%). The product was charged under N ₂ .

¹³ C NMR: 211 ppm (N-CS ₂ ); 70 ppm-40 ppm (aliphatic ¹³ C nuclei in the backbone)

Embodiment 2

AEP-EPI-E100 prepolymer synthesis (2A)

Charge 62 gr of deionized (DI) water to a reactor equipped with a stirrer, thermometer and reflux condenser. Add 42 gr of AEP to the reactor and adjust the temperature to or below 25°C. Pump 60 gr of EPI to the stirred solution at a constant flow rate over 30 minutes and do not allow the reaction temperature to exceed 30°C. After the EPI feed is completed, add E100 (mixture of TEPA, PEHA and HEHA) solution (179 gr E100 + 160 gr DI water) to the reactor in portions over 5 minutes while maintaining the temperature between 35°C-40°C. While the temperature was stable below 40°C, 39 gr of EPI (second part) was fed into the reactor over 20 minutes (AEP:EPI:E100 molar ratio 1:3.15:2). After the EPI feed was completed, the batch was heated to 88°C over 30 minutes and maintained at 88°C for 3 hours. The heating was then turned off and 98 gr of deionized water were added to the product (adjusted to about 50% solids) and allowed to cool to room temperature. The obtained viscous (dark) yellow product was used in the next reaction without any purification.

Dithiocarbamate functionalization of AEP-EPI-E100 prepolymer (AEP-EPI-E100-CS ₂ )(2B)

In a reactor equipped with a stirrer, thermometer and reflux condenser, AEP-EPI-E100 prepolymer (50%) solution (86 gr) was diluted with 190 gr of deionized water and kept under _N2 blanket. 63 gr of NaOH (50%) was added to this solution over 20 minutes. The light yellow solution was cooled to 38°C before starting the carbon disulfide ( _CS2 ) feed (prepolymer: _CS2 molar ratio was 1:6.5-8.1). 48 gr of _CS2 (38 mL) was continuously fed to the reactor at a constant rate over 90 minutes and the temperature was gradually increased to 43°C during the addition. After the _CS2 feed was complete, the reaction was held at 44°C for 90 minutes and at 47-50°C for an additional 30 minutes until a slightly hazy red product (31.7% solids) was obtained. The product was charged under _N2 and became a clearer red solution on storage.

¹³ C NMR: 210 ppm (N-CS ₂ ); 75 ppm-40 ppm (aliphatic ¹³ C nuclei in the backbone)

Embodiment 3

TEPA-EPI prepolymer synthesis (3A) Charge 300 gr of deionized (DI) water into a reactor equipped with a stirrer, thermometer and reflux condenser. Slowly add 300 gr of TEPA to the reactor and maintain the temperature below 40°C. Pump 191 gr of EPI into the stirred solution at a constant flow rate over 90 minutes (TEPA:EPI molar ratio 1:1.2-1.35). During the EPI feed, the reaction temperature was not allowed to exceed 43°C and maintained between 37°C-43°C. After the completion of the EPI feed, heat the batch to 88°C over 30 minutes and maintain at 88°C for 3 hours. Then the heating was turned off and 191 gr of deionized water were added to the product (adjusting the solid content to about 50%) and allowed to cool to room temperature. The obtained viscous (dark) yellow product was used in the next reaction without any purification.

¹³ C NMR: 70 ppm-35 ppm (aliphatic ¹³ C nucleus in the skeleton, -N-CH ₂ CH ₂ -N-CH ₂ -CH(OH)-CH ₂ -)

Dithiocarbamate Functionalization of TEPA-EPI Prepolymer (TEPA-EPI-CS ₂ ) (3B)

In a reactor equipped with a stirrer, thermometer, reflux condenser, 87.3 gr of TEPA-EPI prepolymer (50%) solution was diluted with 307.5 gr of deionized water and kept under _N2 blanket. 56.4 gr of NaOH (50%) was added to this solution over 20 minutes. The pale yellow solution was cooled to 38°C before starting the carbon disulfide ( _CS2 ) feed (molar ratio of copolymer: _CS2 was 1:4.5-5.1). 48.8 gr of _CS2 (83.3 mL) was continuously fed to the reactor at a constant rate over 90 minutes and the temperature was gradually increased to 43°C during the addition. After the _CS2 feed was complete, the reaction was held at 44°C for 90 minutes and at 47-50°C for an additional 30 minutes until a slightly hazy orange to red product was obtained (solids content 24.16%). The product was charged under _N2 and turned into a clearer orange-red solution on storage.

¹³ C NMR: 210 ppm (N-CS ₂ ); 75 ppm-40 ppm (aliphatic ¹³ C nuclei in the backbone)

Embodiment 4

Premixed (AEP+TEPA)-EPI prepolymer synthesis (4A)

Charge 165 gr of deionized (DI) water to a reactor equipped with a stirrer, thermometer and reflux condenser. Slowly add 42 gr of AEP and 123 gr of TEPA to the reactor and maintain the temperature below 40°C. Pump 99 gr of epichlorohydrin (EPI) to the stirred solution at a constant flow rate over 90 minutes (AEP:TEPA:EPI molar ratio of 1:2:3.15). During the EPI feed, the reaction temperature is not allowed to exceed 43°C and is maintained between 37°C-43°C. After the EPI feed is completed, heat the batch to 88°C over 30 minutes and maintain at 88°C for 3 hours. Then the heating was turned off and 99 gr of deionized water were added to the product (adjust the solid content to about 50%) and allowed to cool to room temperature. The obtained viscous (dark) yellow product was used in the next reaction without any purification.

¹³ C NMR: 70 ppm-35 ppm (aliphatic ¹³ C nucleus in the skeleton, -N-CH ₂ CH ₂ -N-CH ₂ -CH(OH)-CH ₂ -)

(AEP+TEPA)-EPI prepolymer (AEP+TEPA)-EPI-CS ₂ dithiocarbamate (4B)

In a reactor equipped with a stirrer, thermometer and reflux condenser, 76.5 gr of AEP-TEPA-EPI prepolymer (50%) solution was diluted with 118.6 gr of deionized water and kept under _N2 blanket. 40.5 gr of NaOH (50%) was added to this solution over 20 minutes. The light yellow solution was cooled to 38°C before starting the carbon disulfide ( _CS2 ) feed. 35.8 gr of _CS2 (28.3 mL) was continuously fed to the reactor at a constant rate over 90 minutes and the temperature was gradually increased to 43°C during the addition. After the _CS2 feed was complete, the reaction was held at 44°C for 90 min and at 47-50°C for an additional 30 min until a bright orange to red product was obtained (solids content 34.75%). The product was charged under _N2 .

¹³ C NMR: 211 ppm (N-CS ₂ ); 70 ppm-40 ppm (aliphatic ¹³ C nuclei in the backbone)

Embodiment 5

E100-EPI prepolymer synthesis (5A)

Charge 300 gr of deionized (DI) water to a reaction kettle equipped with a stirrer, thermometer and reflux condenser. Slowly add 300 gr of E100 (mixture of TEPA, PEHA and HEHA) to the reactor and maintain the temperature below 40°C. Pump 137 gr of EPI at a constant flow rate to the stirred solution over 90 minutes (E100:EPI molar ratio of 1:1.2-1.35). During the EPI feed, the reaction temperature was not allowed to exceed 43°C and maintained between 37°C-43°C. After the completion of the EPI feed, heat the batch to 88°C over 30 minutes and maintain at 88°C for 3 hours. Then the heating was turned off and 137 gr of deionized water were added to the product (adjusting the solid content to about 50%) and allowed to cool to room temperature. The obtained viscous (dark) yellow product was used in the next reaction without any purification.

¹³ C NMR: 70 ppm-35 ppm (aliphatic ¹³ C nucleus in the skeleton, -N-CH ₂ CH ₂ -N-CH ₂ -CH(OH)-CH ₂ -)

Dithiocarbamate Functionalization of E100-EPI Prepolymer (E100-EPI-CS ₂ )(5B)

In a reactor equipped with stirrer, thermometer, reflux condenser, E100-EPI prepolymer (50%) solution (77 gr) was diluted with 134.3 gr of deionized water and kept under _N2 blanket. 55.7 gr of NaOH (50%) was added to this solution over 20 minutes. The light yellow solution was cooled to 38°C before starting carbon disulfide ( _CS2 ) feed (prepolymer: _CS2 molar ratio is 1:6.5-8.1). 49 gr of _CS2 (38.7 mL) was continuously fed to the reactor at a constant rate over 90 minutes and the temperature was gradually increased to 43°C during the addition. After the _CS2 feed was complete, the reaction was held at 44°C for 90 minutes and at 47-50°C for an additional 30 minutes until a slightly hazy red product (36.5% solids) was obtained. The product was charged under _N2 and turned into a clear red solution on storage.

¹³ C NMR: 210 ppm (N-CS ₂ ); 75 ppm-40 ppm (aliphatic ¹³ C nuclei in the backbone)

Various properties of the dithiocarbamate polymers of Examples 1-5 are shown in Table 1 below.

Embodiment 6

Removing Metals from Synthetic Water

The hard and soft acid (Lewis) classification classifies compounds as hard or soft acids and hard or soft bases. Unbound ionic metals are Lewis acids due to their ability to accept electron pairs from donors (Lewis bases). They can be hard, soft, or intermediate, depending on the electron orbital structure, charge, and size. Alkali metal and alkaline earth metal ions are considered hard acids while transition metal ions are typically soft or intermediate. Because transition metals can pose environmental and public health problems, their concentrations in water are regulated. Because like reacts with like, soft bases such as sulfur compounds and/or ligands (dithiocarbamates and trithiocarbonates) are typically used to remove these metals by physical-chemical separation. Highly functionalized polyamine-based polymers containing dithiocarbamate functionality are preferred over small molecules due to their lower toxicity.

However, these products may not be able to remove intermediate acid metals such as cobalt, nickel and zinc.

In this example, synthetic water was made with approximately 1.2 ppm of Cd+2, Co+2, Cu+2, Ni+2, and Zn+2. To make the synthetic water, HEPES buffer was dissolved in deionized water to make a final solution of 0.01N HEPES. A stock solution of chloride salt was then added to the buffered water to achieve the desired amount of metal ions. The water was then slowly adjusted to pH 8 with 1N NaOH.

A 250 mL aliquot of synthetic water was tested using a standard agglutination tester. The metal removal product (i.e., Examples 1-5) was injected into the jar while mixing at 100 rpm. Two minutes were allowed to elapse before reducing the mixing to 35 rpm. Mixing was stopped after 5 minutes and the jar was allowed to stand for an additional 5 minutes. A sample of the supernatant was removed for ICP analysis of residual metals. The supernatant metal concentrations of the unfiltered (total) and 0.45 micron filtered samples (soluble) were measured.

The percentage removal from the supernatant and the percentage removal of soluble metals after addition of the metal removal products of Examples 1-5 are shown in Tables 2 and 3 below.

As shown in Tables 2 and 3 and Figures 1-6, by changing the polyamine-based polymer backbone and controlling the structure, the ability of the polymers of the present disclosure to remove metals such as cobalt, nickel and zinc can be improved in both removal percentage and operating window.

More specifically, as shown in Figures 1-3, the dithiocarbamate polymer of Example 1B exhibits improved removal of cobalt, nickel, and zinc compared to the control polymer of Example 3B and the comparative polymer of Example 4B and the industry standard. Similarly, the dithiocarbamate polymer of Example 2B exhibits improved removal of cobalt, nickel, and zinc compared to the control polymer of Example 5B and the industry standard.

Additionally, as shown in Tables 2 and 3, the dithiocarbamate polymer of Example 1B exhibits improved and/or similar cadmium and copper removal compared to the control polymer of Example 3B and the comparative polymer of Example 4B and industry standards. The dithiocarbamate polymer of Example 2B also exhibits improved and/or similar cadmium and copper removal compared to the control polymer of Example 5B and industry standards.

Although the embodiments of the disclosed technology have been described, it should be understood that the present disclosure is not limited thereto and can be modified without departing from the disclosed technology. The scope of the disclosed technology is defined by the attached patent application scope, and is intended to cover all devices, processes, and methods within the meaning of the patent application scope, either literally or equally.

Those skilled in the art will appreciate that the drawings described below are for exemplary purposes only and are not intended to limit the scope of the present teachings in any way.

[FIG. 1] shows the cobalt concentration in the supernatant of a synthetic water sample treated with an embodiment of the metal ion scavenger of the present disclosure.

[FIG. 2] shows the nickel concentration in the supernatant of a synthetic water sample treated with an embodiment of the metal ion scavenger of the present disclosure.

[FIG. 3] shows the zinc concentration in the supernatant of a synthetic water sample treated with an embodiment of the metal ion scavenger of the present disclosure.

[FIG. 4] shows the cobalt concentration in the supernatant of a synthetic water sample treated with an embodiment of the metal ion scavenger of the present disclosure.

[FIG. 5] shows the nickel concentration in the supernatant of a synthetic water sample treated with an embodiment of the metal ion scavenger of the present disclosure.

[FIG. 6] shows the zinc concentration in the supernatant of a synthetic water sample treated with an embodiment of the metal ion scavenger of the present disclosure.

Claims (34)

A method for preparing a polyamine prepolymer skeleton comprises: The derivative is added to the polyamine and subjected to a condensation reaction with epihalohydrin. The method of claim 1, wherein the piperazine Derivatives of ethylaminopiperidin . The method of claim 1, wherein the polyamine is polyethylene polyamine. The method of claim 1, wherein the epihalogen alcohol is epichlorohydrin. The method of claim 1, wherein the piperine is added in a molar ratio of about 1:1 to about 1:5. Derivatives with the polyamine. The method of claim 5, wherein the piperine is added in a molar ratio of about 1:2 Derivatives with the polyamine. A metal ion scavenger comprising a polyamine prepolymer skeleton prepared according to the method of claim 1. The metal ion scavenger of claim 7, wherein the metal ion scavenger is a transition metal ion scavenger. The metal ion scavenger of claim 8, wherein the transition metal ion scavenger is a dithiocarbamate. A method for removing metal ions from an aqueous or non-aqueous solution stream, comprising adding a metal ion scavenger according to claim 7. The method of claim 10, wherein the aqueous solution stream comprises wastewater. The method of claim 10, wherein the metal ion is selected from the group consisting of cobalt, nickel, zinc, mercury, and mixtures thereof. The method of claim 10, wherein the metal ion scavenger is added in an amount of about 0.1 ppm to about 1000 ppm. The method of claim 13, wherein the metal ion scavenger is added in an amount of about 0.1 ppm to about 500 ppm. A method for preparing a metal ion scavenger comprises: The derivative is added to the polyamine and epihalogen alcohol for condensation reaction. The method of claim 15, wherein the piperazine Derivatives are aminoethylpiperidin . The method of claim 15, wherein the polyamine is polyethylene polyamine. The method of claim 15, wherein the epihalogen alcohol is epichlorohydrin. The method of claim 15, wherein the metal ion scavenger is a transition metal ion scavenger. The method of claim 19, wherein the transition metal ion scavenger is a dithiocarbamate. A method for preparing a polyamine prepolymer skeleton comprises: The invention relates to a method for preparing a polyamine-containing compound. The method comprises reacting a first portion of the polyamine derivative with a first portion of the epihalogen alcohol to form a first reaction mixture; adding a polyamine to the first reaction mixture to form a second reaction mixture; and adding a second portion of the epihalogen alcohol to the second reaction mixture. The method of claim 21, wherein the piperazine Derivatives of ethylaminopiperidin . The method of claim 21, wherein the polyamine is polyethylene polyamine. The method of claim 21, wherein the epihalogen alcohol is epichlorohydrin. The method of claim 21, wherein the piperine is added in a molar ratio of about 1:1 to about 1:5. Derivatives with the polyamine. The method of claim 25, wherein the piperine is added in a molar ratio of about 1:2 Derivatives with the polyamine. A metal ion scavenger comprising a polyamine prepolymer skeleton prepared according to the method of claim 21. The metal ion scavenger of claim 27, wherein the metal ion scavenger is a transition metal ion scavenger. A metal ion scavenger as claimed in claim 28, wherein the transition metal ion scavenger is a dithiocarbamate. A method for removing metal ions from an aqueous or non-aqueous solution stream comprising adding a metal ion scavenger according to claim 27. The method of claim 30, wherein the aqueous solution stream comprises wastewater. The method of claim 30, wherein the metal ion is selected from the group consisting of cobalt, nickel, zinc, mercury, and mixtures thereof. The method of claim 30, wherein the metal ion scavenger is added in an amount of about 0.1 ppm to about 1000 ppm. The method of claim 33, wherein the metal ion scavenger is added in an amount of about 0.1 ppm to about 500 ppm.

Images