阅读说明：本技术 一种氨基磺酸型功能化硅胶材料及其在水质净化中的应用 (Sulfamic acid type functionalized silica gel material and application thereof in water purification ) 是由 杨南超 张婷 杨晓伟 于 2021-09-30 设计创作，主要内容包括：本发明公开了一种氨基磺酸型功能化硅胶材料及其在水质净化中的应用。本发明使用的氨基磺酸型功能化硅胶材料合成包含以下步骤：1)(CH-(3)O)-(3)Si(CH-(2))-(x)S(CH-(2))-(y)Cl,x是从2到12的整数,y是从3到12的整数,和多乙烯多胺NH-(2)(CH-(2)CH-(2)NH)-(z)H,z取值为1-100,回流反应得到多胺硅烷偶联剂；2)多胺硅烷偶联剂在溶剂体系中与硅胶回流反应得多胺功能化硅胶材料；3)多胺功能化硅胶材料与氯磺酸在溶剂体系中于一定温度反应得氨基磺酸型功能化硅胶材料。本发明中提供的氨基磺酸型功能化硅胶材料负载率高,交换容量大,能将水中的阳离子降低到ppb级别,使用寿命长,能耐受150℃高温长达6个月,且长时间使用不对水质造成任何污染。(The invention discloses a sulfamic acid type functional silica gel material and application thereof in water purification. The synthesis of the sulfamic acid type functionalized silica gel material used in the invention comprises the following steps: 1) (CH) 3 O) 3 Si(CH 2 ) x S(CH 2 ) y Cl, x is an integer from 2 to 12, y is an integer from 3 to 12And polyethylene polyamine NH 2 (CH 2 CH 2 NH) z H and z are 1-100, and polyamine silane coupling agent is obtained through reflux reaction; 2) polyamine silane coupling agent and silica gel are subjected to reflux reaction in a solvent system to obtain polyamine functional silica gel material; 3) the polyamine functional silica gel material and chlorosulfonic acid react in a solvent system at a certain temperature to obtain the sulfamic acid functional silica gel material. The sulfamic acid type functionalized silica gel material provided by the invention has high loading rate and large exchange capacity, can reduce cations in water to ppb level, has long service life, can resist high temperature of 150 ℃ for 6 months, and does not cause any pollution to water quality after long-time use.)

1. A sulfamic acid type functionalized silica gel material is characterized in that: the structural formula of the compound is:

[(O_3/2)Si(CH₂)_xS(CH₂)_yNSO₃H(CH₂CH₂NSO₃H)_zH]_a[Si(O_4/2)]_bwherein x is an integer from 2 to 12; y is an integer from 3 to 12; z is an integer from 1 to 100; a and b are integers, and a: the ratio of b is between 0.000001 and 100.

2. The functionalized silica gel material of sulfamic acid type according to claim 1, characterized in that: the value of z is 2-9.

3. The method for synthesizing a sulfamic acid type functionalized silica gel material according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:

1)(CH₃O)₃Si(CH₂)_xS(CH₂)_ycl, x is an integer from 2 to 12, y is an integer from 3 to 12, and polyethylenepolyamine NH₂(CH₂CH₂NH)_zH and z are 1-100, and polyamine silane coupling agent (CH) is obtained by reflux reaction₃O)₃Si(CH₂)_xS(CH₂)_yNH(CH₂CH₂NH)_zH；

2) Polyamine silane coupling agent and silica gel reflux reaction in solvent system to obtain polyamine functional silica gel material [ (O)_3/2)Si(CH₂)_xS(CH₂)_yNH(CH₂CH₂NH)_z H]_a[Si(O_4/2)]_b；

3) Reacting polyamine functional silica gel material with chlorosulfonic acid in a solvent system at a certain temperature to obtain sulfamic acid type functional silica gel material [ (O)_3/2)Si(CH₂)_xS(CH₂)_yNSO₃H(CH₂CH₂NSO₃H)_zH]_a[Si(O_4/2)]_b。

4. The production method according to claim 3, characterized in that: in step 1): the reflux reaction temperature is 90-150 ℃, the reaction time is 0.5-24h, and the solvent is toluene, xylene, heptane and water; in step 2): the reaction temperature is 0-160 ℃, the reaction time is 0.5-24h, and the solvent is toluene, xylene, heptane and water; in step 3): the reaction temperature is-20-20 ℃, the reaction time is 0.5-18h, the solvent is dichloromethane, trichloromethane or tetrachloroethane, and the catalyst is used in the step 3), and the catalyst is triethylamine, pyridine or derivatives thereof.

5. The production method according to claim 3, characterized in that: the ratio of the polyamine silane coupling agent to the silica gel is 0.05-20: 1.

6. The production method according to claim 3, characterized in that: the ratio of the amount of the polyethylene polyamine and the amount of the chlorosulfonic acid feed material is 1: 0.1-50.

7. The production method according to claim 3, characterized in that: the silica gel is amorphous granule or spherical granule.

8. The production method according to claim 3, characterized in that: the silica gel used has a particle size of 10nm to 30mm, preferably a particle size of 37um to 1000 um.

9. Use of the sulfamic acid type functionalized silica gel material according to claim 1 as an adsorbent for adsorbing cations in a water purification system.

10. Use according to claim 9, characterized in that: the water quality purification system is an ultrapure water purification system, a power plant water quality purification system, a nuclear power plant water quality purification system or a thermal power plant water quality purification system; such cations include, but are not limited to: li⁺、Na⁺、K⁺、Ca⁺、Mg²⁺、Al³⁺、Zn²⁺、Fe³⁺、Fe²⁺、Sn⁴⁺、Pb²⁺、Ti⁴⁺、V⁵⁺、Cr²⁺、Mn²⁺、Ni²⁺、Ag⁺、Ba²⁺、Co²⁺、Cu²⁺、As³⁺、Pb²⁺、Hg²⁺、Cd²⁺。

Technical Field

The invention relates to the technical field of organic chemistry, and relates to a sulfamic acid type functional silica gel material, synthesis and application thereof in water purification.

Technical Field

At present, mixed bed resin (H) in the traditional technology is adopted in thermal power, nuclear power, marine nuclear power plants and ultrapure water quality purification systems⁺-OH^-Type) to remove salts in water, sulfonic acid type resins are widely used as the cation resins in mixed bed resins because they have strong cation exchange capacity.

However, in the actual operation of water purification systems, many problems of cation resins are gradually discovered: 1. the service life is short, generally 6-10 months; 2. the low molecular weight skeleton substance is dissolved out, and secondary pollution is caused to water quality; 3. long-term use of corrosive system equipment; 4. poor heat resistance and decomposition at 105 ℃. The reason is that the cation resin is gradually oxidized after being used for a period of time (about 5 months), and the low molecular weight polystyrene sulfonic acid (PSS) is gradually dissolved out under the impact force of water flow, and a part of the PSS is adsorbed by anion resin, so that the anion exchange performance is reduced and even lost, and a part of PSS leaks into effluent to cause water quality organic matter pollution. PSS leaked from the mixed bed resin layer can be decomposed under the conditions of irradiation oxidation and the like to generate sulfate ions, and certain corrosion can be caused to system equipment. Although specialized resins have been improved against these problems, the structural disintegration of the resin backbone due to swelling is difficult to overcome, so the use temperature of such resins is limited, typically below 120 ℃. For example, in a water quality purification system of a nuclear power plant for thermal power, nuclear power and ships, the temperature of water in a secondary loop of a pressurized water reactor reaches 300 ℃, in view of the problem of cation resin, the temperature of water at 300 ℃ needs to be reduced to about 100 ℃ and then flows through the cation resin for treatment, then the water returns to a loop and is heated to 300 ℃, in the process, the resin is decomposed, and in addition, the resin is also decomposed after being soaked for a long time.

To overcome the problems of the resin backbone, studies on sulfonic acid loading of inorganic carriers have been receiving attention. At present, the methodSome reports have been made on the loading of sulfonic acid groups on activated carbon and silica. The preparation method of the active carbon loaded sulfonic acid comprises the steps of carbonizing organic matters under high temperature or acidic conditions, and then sulfonating, wherein the method has the advantages of harsh reaction conditions, difficult process control and low sulfonic acid loading rate, so that the active carbon loaded sulfonic acid is not basically used as a cation resin. Chinese patent CN108435248 prepares Fe₃O₄@SiO₂And (2) oxidizing the mercapto-SH by using hydrogen peroxide to obtain sulfonic acid type silicon dioxide, wherein the oxidation of the mercapto is incomplete, so that the sulfonic acid loading rate is low, the exchange capacity is poor, and the use of the sulfonic acid type silicon dioxide as a cation resin in a water quality purification system is limited.

In conclusion, the water purification cation exchange material with high exchange capacity, long service life, high heat resistance, no corrosion to equipment and no secondary pollution is developed, and the water purification cation exchange material has important significance for replacing the existing water purification resin material.

Disclosure of Invention

The invention aims to solve the problem of the prior art and provides a sulfamic acid type functional silica gel material and application thereof in water purification.

In order to solve the technical problems, the technical scheme adopted by the invention is as follows:

the invention provides a sulfamic acid type functionalized silica gel material, the structural formula of the compound is as follows:

[(O_3/2)Si(CH₂)_xS(CH₂)_yNSO₃H(CH₂CH₂NSO₃H)_zH]_a[Si(O_4/2)]_bwherein x is an integer from 2 to 12; y is an integer from 3 to 12; z is an integer from 1 to 100; a and b are integers, and a: the ratio of b is between 0.000001 and 100.

In the technical scheme of the invention, the preferable value of z is 2-9.

The synthesis method of the sulfamic acid type functionalized silica gel material comprises the following steps:

1)(CH₃O)₃Si(CH₂)_xS(CH₂)_ycl, x is a whole number from 2 to 12A number, y is an integer from 3 to 12, and polyethylene polyamine NH₂(CH₂CH₂NH)_zH and z are 1-100, and polyamine silane coupling agent (CH) is obtained by reflux reaction₃O)₃Si(CH₂)_xS(CH₂)_yNH(CH₂CH₂NH)_zH；

2) Polyamine silane coupling agent and silica gel reflux reaction in solvent system to obtain polyamine functional silica gel material [ (O)_3/2)Si(CH₂)_xS(CH₂)_yNH(CH₂CH₂NH)_zH]_a[Si(O_4/2)]_b；

3) Reacting polyamine functional silica gel material with chlorosulfonic acid in a solvent system at a certain temperature to obtain sulfamic acid type functional silica gel material [ (O)_3/2)Si(CH₂)_xS(CH₂)_yNSO₃H(CH₂CH₂NSO₃H)_zH]_a[Si(O_4/2)]_b。

The technical scheme of the invention is that in the step 1): the reflux reaction temperature is 90-150 ℃, the reaction time is 0.5-24h, and the solvent is toluene, xylene, heptane, water and the like.

The technical scheme of the invention is that in the step 2): the reaction temperature is 0-160 ℃, the reaction time is 0.5-24h, and the solvent is toluene, xylene, heptane, water and the like.

The technical scheme of the invention is that in the step 3): the reaction temperature is-20-20 ℃, the reaction time is 0.5-18h, the solvent is dichloromethane, trichloromethane, tetrachloroethane and the like, and the catalyst is used in the step (3), and the catalyst is triethylamine, pyridine, derivatives thereof and the like.

According to the technical scheme, the mass ratio of the polyamine silane coupling agent to the silica gel is 0.05-20: 1, and preferably 1.5-5: 1.

According to the technical scheme, the ratio of the amount of the polyethylene polyamine to the amount of the chlorosulfonic acid feeding material is 1: 0.1-50, and preferably 1: 1-20.

According to the technical scheme, the silica gel is amorphous particles or spherical particles, and preferably spherical particles.

According to the technical scheme, the particle size of the silica gel is 10nm-30mm, and the preferable particle size is 37um-1000 um.

The invention provides the application of the sulfamic acid type functionalized silica gel material as an adsorbent in adsorbing cations in a water quality purification system.

In the technology of the invention, the application is an ultrapure water purification system, a power plant water purification system, a nuclear power plant water purification system or a thermal power plant water purification system.

In the technical scheme of the invention, the cation includes but is not limited to: alkali metal ion, alkaline earth metal ion, transition metal ion, noble metal ion, and metal cation complex ML_n ^m+M is transition metal or noble metal, L is H₂O、NH₃N is an integer of 1 to 4, and m is an integer of 1 to 4. Specifically, including but not limited to: li⁺、Na⁺、K⁺、Ca⁺、Mg²⁺、Al³⁺、Zn²⁺、Fe³⁺、Fe²⁺、Sn^{4 +}、Pb²⁺、Ti⁴⁺、V⁵⁺、Cr²⁺、Mn²⁺、Ni²⁺、Ag⁺、Ba²⁺、Co²⁺、Cu²⁺、As³⁺、Pb²⁺、Hg²⁺、Cd²⁺。

According to the invention, silica gel is used as a carrier, a polyamine silane coupling agent is firstly obtained, polyamine is loaded on the silica gel, then a plurality of sulfonic acid groups are introduced by utilizing sulfonation of amino and chlorosulfonic acid, so that the sulfonic acid group loading rate is greatly improved, in addition, the amino which is not loaded with sulfonic acid has complexing capacity, and has very good adsorption capacity on chelate metal cations, and finally, the purposes of good heat resistance, high sulfonic acid loading rate and high cation removal rate can be achieved, and the cations in water can be reduced to ppb level, so that the problems of short service life, impurity dissolution and pollution to water quality of the cation resin material in the prior art are solved.

The invention has the beneficial effects that:

the sulfamic acid type functionalized silica gel material provided by the invention has high loading rate and large exchange capacity, can reduce cations in water to ppb level, has long service life, can resist high temperature of 150 ℃ for 6 months, and does not cause any pollution to water quality after long-time use.

Detailed Description

For the sake of understanding, the present invention will be described in detail below by way of specific examples. It is to be expressly understood that the description is illustrative only and is not intended as a definition of the limits of the invention. Many variations and modifications of the present invention will be apparent to those skilled in the art in light of the teachings of this specification.

Example 1

Adding diethylenetriamine (0.4mol) and 3- (3-chloropropyl) thiopropyltrimethoxysilane (0.4mol) into a 500mL three-neck flask provided with a glass plug and a condensation reflux device, refluxing for 2.5h at 130 ℃, cooling to 60 ℃, adding methanol (40mL), refluxing for 1h, cooling, adding a mixed solution of xylene (125mL) and spherical silica gel (90g,300-, the exchange capacity was 3.98 mmol/g.

Example 2

A500 mL three-neck flask equipped with a glass stopper and a condensation reflux device was charged with polyethylene (0.4mol) and 3- (3-chloropropyl) thiopropyltrimethoxysilane (0.4mol) and refluxed at 150 ℃ for 2.5 hours, then cooled to 70 ℃, then charged with methanol (40mL) and refluxed for 1 hour, after cooling, a mixed solution of xylene (125mL) and spherical silica gel (90g, 200-. After filtering and washing 5 times by ethanol and drying, adding the product into a 500mL three-neck flask containing 150mL trichloromethane, adding 1.5mL pyridine, then dropwise adding 5mol chlorosulfonic acid for 60min, stirring at room temperature for 8h, filtering and washing 5 times by ethanol and drying to obtain the compound formula I, wherein x is 3, y is 3, and z is 9, and the exchange capacity is 6.82mmol/g according to the method for measuring the exchange capacity of the cation exchange resin of the national standard GB/T8144-2008 (the measured data of the exchange capacity of the sulfonic acid resin of a company in Zheng State is 2.75 mmol/g).

Example 3

The cation purification column of the condensed water purification simulation system of a certain thermal power plant is filled with the silica gel material of the embodiment 1, and the water at the water inlet contains Na⁺2.412ppm，Mg²⁺0.651ppm，K⁺0.975ppm，Ca²⁺1.486ppm，Fe³⁺1.728ppm, 150 ℃ condensate was passed through the purification column packed with the material of example 1 and tested at the outlet after 6 months for water quality, the concentrations of the cations in the water were as follows: na (Na)⁺0.036ppm，Mg²⁺0.063ppm，K⁺0.013ppb，Ca²⁺0.035ppm，Fe³⁺0.002ppm。

Example 4

The cation purifying column of the simulation system for purifying condensed water in a secondary loop of a certain nuclear power station is filled with the silica gel material in the embodiment 2, and the water at the water inlet contains Na⁺1.958ppm，Mg²⁺0.486ppm，K⁺0.679ppm，Ca²⁺1.254ppm，Fe³⁺After 1.532ppm of 150 ℃ condensed water passes through the purification column filled with the material in example 2, water quality at the water outlet is tested after 6 months, and the concentrations of cations in the water are as follows: na (Na)⁺0.025ppm，Mg²⁺0.003ppm，K⁺0.005ppm，Ca²⁺0.001ppm，Fe³⁺0.001ppm。

The 150 ℃ condensed water flow in the examples 3 and 4 is treated by the silica gel material of the invention, and still has better exchange capacity for 6 months, which shows that the material has high heat resistance.

Example 5

The secondary purification system of a laboratory water production 200L/d ultrapure water purification device was filled with 1kg of the silica gel material of example 2, and the concentrations of cations in the water outlet after 1, 3, 6, and 12 months from the water inlet thereof were as follows:

tests prove that the exchange capacity of the material in the embodiment of the invention is basically kept unchanged after the material is used for 12 months, which shows that the material is basically free from sulfonic acid dissolution after being used for 12 months, and the service life is more than 12 months.

The data in example 5 shows that the exchange capacity of the material is not obviously changed after the material is used for 12 months, which indicates that no sulfonic acid is dissolved out, and the material has long service life and does not cause any pollution to water quality after long-term use.

Example 6

Simulating and preparing low-level radionuclide with the concentration of Ag in the water inlet of a primary circuit water quality purification system of a pressurized water reactor of a nuclear power plant⁺0.941ppm，Co²⁺0.584ppm，Sr²⁺0.329ppm solution, 2 parts of 100ml of the simulant were added to 5g of the material of example 2 and a sulfonic acid resin of Zhengzhou corporation, respectively, and after stirring at room temperature for 1 hour, the respective cation concentrations in water treated with the silica gel material of Experimental example 2 were as follows: ag⁺0.077ppm，Co²⁺0.003ppm，Sr²⁺0.026ppm, the respective cation concentrations in the sulfonic acid resin water using Zheng Zhou company are as follows: ag⁺0.123ppm，Co²⁺0.376ppm，Sr²⁺0.102ppm。

The above examples are only for illustrating the technical idea and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.