阅读说明：本技术 一种盐湖卤水中钙镁螯合树脂及其制备方法 (Calcium-magnesium chelating resin in salt lake brine and preparation method thereof ) 是由 邓茂盛 刘恒 周桂芳 于 2020-03-10 设计创作，主要内容包括：本发明公开一种盐湖卤水中钙镁螯合树脂及其制备方法,以烯丙胺和氯乙酸为反应原料反应制备烯丙胺基二乙酸,将以烯丙胺基二乙酸为原料,N,N’-亚甲基双丙烯酰胺为交联剂,并加入致孔剂、引发剂配置的水相在分散剂油相分散,反应,经离心、甩干、溶剂洗涤即得到盐湖卤水中钙镁螯合树脂；制备过程工艺路线简单,解决了传统方法工艺繁琐的问题,本发明制得的卤水中钙镁螯合树脂应用于卤水除钙镁,交换容量高。(The invention discloses a calcium-magnesium chelating resin in salt lake brine and a preparation method thereof, which takes allylamine and chloroacetic acid as reaction raw materials to prepare allylamine-based diacetic acid through reaction, takes allylamine-based diacetic acid as a raw material, takes N, N' -methylene bisacrylamide as a cross-linking agent, and adds a pore-foaming agent and an initiator to prepare a water phase, and the water phase is dispersed in a dispersant oil phase to react, and then is centrifuged, dried and washed by a solvent to obtain the calcium-magnesium chelating resin in salt lake brine; the preparation process has simple process route, solves the problem of complicated process of the traditional method, and has high exchange capacity when the calcium-magnesium chelate resin in the brine prepared by the invention is applied to removing calcium and magnesium from the brine.)

1. The calcium-magnesium chelating resin in salt lake brine is characterized by having the following structure:

wherein:is a chelating resin matrix, and m and n are the number of functional groups.

2. The preparation method of the calcium-magnesium chelating resin in the salt lake brine according to claim 1, which is characterized by comprising the following steps:

step 1)

Taking allylamine and chloroacetic acid as reaction raw materials, and reacting in a solution to prepare allylamine-based diacetic acid;

step 2)

2.1) taking 20-100 parts of allylamine diacetic acid as a raw material, 5-50 parts of N, N' -methylene bisacrylamide as a cross-linking agent, adding a pore-forming agent accounting for 50-200% of the weight of the monomer, and adding an initiator accounting for 1-2% of the weight of the monomer to prepare a water phase;

2.2) preparing a dispersant oil phase;

2.3) dispersing the water phase in the oil phase by adopting an inverse polymerization method to obtain resin with the particle size of 0.25-1.25mm, raising the temperature to 60-80 ℃, reacting for 6-10h to obtain spherical particles, and finally centrifuging, spin-drying and washing by using a solvent to obtain the calcium-magnesium chelating resin in the salt lake brine.

3. The method for preparing the calcium-magnesium chelating resin in the salt lake brine according to claim 2, wherein the method comprises the following steps: in the step 1), 10-50 parts of allylamine and 40-100 parts of chloroacetic acid are taken as reaction raw materials by mass, and reacted in 800 parts of 200-one solution to prepare allylamine diacetic acid, and the allylamine diacetic acid is obtained by evaporation after the reaction.

4. The method for preparing the calcium-magnesium chelating resin in the salt lake brine according to claim 2, wherein the method comprises the following steps: the solution is one or more of water, methanol, ethanol and propanol.

5. The method for preparing the calcium-magnesium chelating resin in the salt lake brine according to claim 2, wherein the method comprises the following steps: in the step 2.2), 1-5 parts of dispersing agent and 800-2000 parts of dispersed phase are taken by mass to prepare dispersing agent oil phase.

6. The method for preparing the calcium-magnesium chelating resin in the salt lake brine according to claim 2, wherein the method comprises the following steps: the pore-foaming agent is one or more of ethylene glycol, propylene glycol, ethylene glycol monoethyl ether, sodium chloride and sodium sulfate.

7. The method for preparing the calcium-magnesium chelating resin in the salt lake brine according to claim 2, wherein the method comprises the following steps: the initiator is one or more of azobisisobutyronitrile, ammonium persulfate and potassium persulfate.

8. The method for preparing the calcium-magnesium chelating resin in the salt lake brine according to claim 2, wherein the method comprises the following steps: the dispersed phase is one or more of liquid paraffin, turbine oil, chlorobenzene and dichlorobenzene.

9. The method for preparing the calcium-magnesium chelating resin in the salt lake brine according to claim 2, wherein the method comprises the following steps: the dispersant is span series, tween series, sodium oleate, nano calcium carbonate, nano magnesium oxide or nano zinc oxide.

10. The method for preparing the calcium-magnesium chelating resin in the salt lake brine according to claim 2, wherein the method comprises the following steps: the washing solvent is one or more of methanol, ethanol, methylal, ethyl acetate, toluene and acetone.

Technical Field

The invention belongs to the technical field of chemical industry, and relates to a calcium-magnesium chelate resin in salt lake brine and a preparation method thereof.

Background

The chelating resin is a high molecular material with a cross-linking function of forming a multi-coordination complex with metal ions, atoms such as O, N, S, P, As and the like with a fence-bond lone pair electron exist in a functional group of the chelating resin, the atoms can form a coordination bond with the metal ions by a pile of lone pair electrons to form a stable structure similar to a small molecule chelate, and the dissociable parts of some chelating functional groups can also form an ionic bond with the metal ions like common ion exchange resin. Chelating resins with iminodiacetic acid can be reacted with Cu²⁺Very stable structures are formed:

chelate resins with beta-diketones

The literature reports that the chelate resin containing S has special adsorption effect on mercury, such as can be obtained by reacting chloromethylation crosslinked styrene with thiosemicarbazide, and the functional group can reach 4.1 mmol/g.

Patent application 200910265822 discloses a chelating resin capable of effectively removing impurities in trichlorosilane, and a production method and application thereof, wherein the preparation method comprises the following steps: (1) reacting the white ball with chloromethyl ether by using zinc chloride as a catalyst to obtain a chloromethylated white ball; (2) reacting chloromethylated white balls with hexamethyltetramine, and decomposing the reaction product by using a concentrated hydrochloric acid-ethanol mixed solution to obtain primary amine resin; (3) adding primary amine resin into chloroacetic acid aqueous solution, and reacting for 10-30 hours at 55-70 ℃ under stirring to obtain the chelating resin.

The American patent US844740 discloses a preparation method of calcium and magnesium removal chelate resin, which is characterized in that polystyrene beads are prepared, chloromethylated and functionalized, and finally iminodiacetic acid chelate resin is prepared;

the existing resin preparation method has complex process and low exchange capacity of the obtained resin.

Disclosure of Invention

The invention aims to provide the calcium-magnesium chelate resin in the salt lake brine and the preparation method thereof, the preparation process is simple, and the prepared chelate resin has high exchange capacity.

In order to achieve the purpose, the invention adopts the technical scheme that:

a calcium-magnesium chelating resin in salt lake brine has the following structure:

wherein:is a chelating resin matrix, and m and n are the number of functional groups.

A preparation method of calcium-magnesium chelating resin in salt lake brine comprises the following steps:

step 1)

Taking allylamine and chloroacetic acid as reaction raw materials, and reacting in a solution to prepare allylamine-based diacetic acid;

step 2)

2.1) taking 20-100 parts of allylamine diacetic acid as a raw material, 5-50 parts of N, N' -methylene bisacrylamide as a cross-linking agent, adding a pore-forming agent accounting for 50-200% of the weight of the monomer, and adding an initiator accounting for 1-2% of the weight of the monomer to prepare a water phase;

2.2) preparing a dispersant oil phase;

2.3) dispersing the water phase in the oil phase by adopting an inverse polymerization method to obtain resin with the particle size of 0.25-1.25mm, raising the temperature to 60-80 ℃, reacting for 6-10h to obtain spherical particles, and finally centrifuging, spin-drying and washing by using a solvent to obtain the calcium-magnesium chelating resin in the salt lake brine.

Further, in the step 1), by mass, taking 10-50 parts of allylamine and 40-100 parts of chloroacetic acid as reaction raw materials, reacting in 800 parts of 200-one solution to prepare allylamine diacetic acid, and evaporating to dryness after the reaction is finished to obtain the allylamine diacetic acid.

Further, the solution is one or more of water, methanol, ethanol and propanol.

Further, in the step 2.2), 1-5 parts of dispersing agent and 800-2000 parts of dispersed phase are taken by mass to prepare a dispersing agent oil phase.

Further, the pore-foaming agent is one or more of ethylene glycol, propylene glycol, ethylene glycol monoethyl ether, sodium chloride and sodium sulfate.

Further, the initiator is one or more of azobisisobutyronitrile, ammonium persulfate and potassium persulfate.

Further, the dispersed phase is one or more of liquid paraffin, turbine oil, chlorobenzene and dichlorobenzene.

Further, the dispersant is span series, tween series, sodium oleate, nano calcium carbonate, nano magnesium oxide or nano zinc oxide.

Further, the washing solvent is one or more of methanol, ethanol, methylal, ethyl acetate, toluene and acetone.

The preparation method of the calcium-magnesium chelate resin in the salt lake brine comprises the steps of taking allylamine and chloroacetic acid as reaction raw materials to react to prepare allylamine-based diacetic acid, taking allylamine-based diacetic acid as a raw material, taking N, N' -methylene bisacrylamide as a cross-linking agent, adding a pore-foaming agent and an initiator to prepare a water phase, dispersing the water phase in a dispersant oil phase, reacting, centrifuging, spin-drying, and washing with a solvent to obtain the calcium-magnesium chelate resin in the salt lake brine; the preparation process has simple process route, solves the problem of complicated process of the traditional method, and has high exchange capacity when the calcium-magnesium chelate resin in the brine prepared by the invention is applied to removing calcium and magnesium from the brine.

Detailed Description

The present invention will be described in further detail with reference to the following examples, which are not intended to limit the invention thereto.

The calcium-magnesium chelating resin in the salt lake brine has the following structure:

wherein:is a chelating resin matrix, and m and n are the number of functional groups.

The preparation method of the calcium-magnesium chelating resin in the salt lake brine comprises the following steps:

step 1)

Taking allylamine and chloroacetic acid as reaction raw materials, and reacting in a solution to prepare allylamine-based diacetic acid;

step 2)

2.1) taking 20-100 parts of allylamine diacetic acid as a raw material, 5-50 parts of N, N' -methylene bisacrylamide as a cross-linking agent, adding a pore-forming agent accounting for 50-200% of the weight of the monomer, and adding an initiator accounting for 1-2% of the weight of the monomer to prepare a water phase;

2.2) preparing a dispersant oil phase;

2.3) dispersing the water phase in the oil phase by adopting an inverse polymerization method, raising the temperature to 60-80 ℃ to obtain resin with the particle size of 0.25-1.25mm, reacting for 6-10h to obtain spherical particles, and finally centrifuging, spin-drying and washing by using a solvent to obtain the calcium-magnesium chelating resin in the salt lake brine.

The reaction equation is as follows: