CN114042433A - Quaternary ammonium base type functional silica gel material and application thereof in water purification - Google Patents
Quaternary ammonium base type functional silica gel material and application thereof in water purification Download PDFInfo
- Publication number
- CN114042433A CN114042433A CN202111161655.3A CN202111161655A CN114042433A CN 114042433 A CN114042433 A CN 114042433A CN 202111161655 A CN202111161655 A CN 202111161655A CN 114042433 A CN114042433 A CN 114042433A
- Authority
- CN
- China
- Prior art keywords
- silica gel
- quaternary ammonium
- gel material
- integer
- water purification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28019—Spherical, ellipsoidal or cylindrical
-
- 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
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/04—Non-contaminated water, e.g. for industrial water supply for obtaining ultra-pure water
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Silicon Compounds (AREA)
Abstract
The invention discloses a quaternary ammonium base type functional silica gel material and application thereof in water purification. The quaternary ammonium base type functional silica gel material used in the invention utilizes an amino quaternization mechanism to load quaternary ammonium base on silica gel, and an alkaline reagent reacts under certain conditions to obtain the quaternary ammonium base type functional silica gel material. The multi-quaternary ammonium base type functional silica gel material provided by the invention has high loading rate and large exchange capacity, can reduce low-concentration anions in water to ppb level, has long service life, can resist high temperature of 100 ℃ for 6 months, and does not cause any pollution to water quality after long-time use.
Description
Technical Field
The invention relates to the technical field of organic chemistry, and relates to a quaternary ammonium base type functional silica gel material and application thereof in water purification.
Technical Field
In the thermal power, nuclear power, marine nuclear power plant and ultrapure water quality purification system, the traditional technology with extremely high water quality purification capability is adoptedBed resin (H)+-OH-Type) to remove salts in water, and quaternary ammonium base type resins are widely used as anion resins in mixed bed resins because of their strong anion exchange capacity.
The common quaternary ammonium base type ion exchange resin is prepared by chloromethylation reaction of styrene-divinylbenzene copolymerized spheres to obtain chlorine spheres, and then carrying out ammoniation reaction on the chlorine spheres and organic amine to obtain the quaternary ammonium base type anion exchange resin. The research shows that: the loss rate of exchange capacity of the strong base resin is over 5 percent after the strong base resin is used for 140 hours at 60 ℃, the loss rate of exchange capacity is over 15 percent after the strong base resin is used for 140 hours at 80 ℃, and the loss rate of exchange capacity is 75 percent after the strong base resin is used for 24 hours at 100 ℃. Therefore, the maximum service temperature of the quaternary ammonium base type ion exchange resin is not more than 60 ℃, the maximum service temperature of the ammonium base type ion exchange resin is not more than 50 ℃ for a system with high water quality requirement, in order to avoid secondary pollution caused by degradation products and improve the service life of the resin. 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 can reach 300 ℃, and in view of the problem of negative resin, the temperature of water at 300 ℃ needs to be reduced to 50 ℃, flows through positive resin, returns to the loop and is heated to 300 ℃.
The pressurized water reactor structural material has good corrosion resistance, but because the wetting surface of the coolant to the material is very large, even if the corrosion rate is small, the total amount of corrosion products is still high. Although corrosion occurs at the surface of the material, the surface corrosion products are not stationary. When the concentration of corrosion products in the coolant has not reached equilibrium solubility, it will continue to dissolve and flow with the coolant throughout the core and the circuit. The law of influence of temperature on the solubility of corrosion products is: in corrosion products, the solubility of iron and the like decreases with an increase in temperature, but increases sharply again when reaching a certain minimum value. When the temperature is reduced from 300 ℃ to room temperature, the solubility can be increased by thousands of times. Thus, as the reactor is cooled, a significant portion of the corrosion products dissolve from the walls, causing a substantial increase in the concentration of corrosion products in the water. Once the temperature changes, the concentration of corrosion products in the coolant exceeds the equilibrium value, which quickly transforms into suspended particles, or deposits on the metal surface, or continues to flow with the coolant. The deposited corrosion products may dissolve or flake off and re-enter the coolant. This continuous solution-deposition process causes the core and the corrosion products of the circuit to be transported and mixed with each other. Corrosion products released into the coolant, which are mostly suspended in water except for a small amount of dissolution, are very easily deposited on equipment and piping surfaces, especially dead corners, crevices and low flow rates. This long-term accumulation of corrosion products will reduce the heat transfer efficiency, increase the core flow resistance, and may even cause local obstruction of the flow channels, causing serious accidents. In addition, corrosion products dissolved or suspended in the coolant can be activated by neutrons when passing through the reactor core or being deposited in the reactor core, and radioactivity is generated, so that radiation threats are generated to shutdown maintenance and overhaul of a reactor system.
At present, no quaternary ammonium base type anion exchange material which can be applied at the temperature of more than 80 ℃ is reported, so that the anion exchange material which can resist high temperature and has long service life is developed to replace the existing water quality purification resin material, and has important safety and economic significance for each loop purification system of a pressurized water reactor of a nuclear power plant for thermal power, nuclear power and ships.
Disclosure of Invention
The invention aims to solve the problem of the prior art and provides a quaternary ammonium base 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 quaternary ammonium base type functional silica gel material, which has a structural formula as follows:
[(O3/2)Si(CH2)xS(CH2)yN+R2(OH-)[CH2CH2N+R2(OH-)]zR]a[Si(O4/2)]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, R is an alkane group, an alkylene oxide group; a, the number of the first-time contact points is less than the number of the second-time contact points,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 quaternary ammonium base type functionalized silica gel material 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 the polyamine functional silica gel material [ (O) is obtained by one-pot reflux reaction of the H and z and silica gel in a solvent system3/2)Si(CH2)xS(CH2)yNH(CH2CH2NH)zH]a[Si(O4/2)]b；
2) Polyamine functional silica gel material reacts with halogenated alkane (RX) and acid-binding agent under certain conditions to obtain multi-quaternary ammonium salt type functional silica gel material [ (O)3/2)Si(CH2)xS(CH2)yN+R2X-(CH2CH2N+R2X-)zR]a[Si(O4/2)]b；
3) Reacting the multi-quaternary ammonium salt type functional silica gel material with an alkaline reagent under a certain condition to obtain the quaternary ammonium salt type functional silica gel material [ (O)3/2)Si(CH2)xS(CH2)yN+R2(OH-)[CH2CH2N+R2(OH-)]zR]a[Si(O4/2)]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 60-160 ℃, and the optimal temperature is 80-120 ℃; the reaction time is 0.5-12 h; the step (2) is a solvent-free system or a solvent system reaction, wherein the solvent is toluene; in the halogenated alkanes (RX), X is halogen, preferably Cl, Br, I; r is alkyl and alkylene oxide, preferably methyl, ethyl and propylene oxide; the acid-binding agent is weak alkali agent, preferably sodium carbonate and sodium bicarbonate.
The technical scheme of the invention is that in the step 3): the reaction temperature is 50-130 ℃, the reaction time is 0.5-8h, and the solvent is absolute methanol, absolute ethanol and the like; the alkaline agent is sodium alkoxide, preferably sodium methoxide or sodium ethoxide.
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 amount ratio of the polyethylene polyamine to the halogenated alkane feeding material is 1: 0.1-50, preferably 1: 1-20; the weight ratio of the polyethylene polyamine to the acid-binding agent is 1: 0.1-20, preferably 1: 0.5-5; the mass ratio of the polyethylene polyamine to the alkaline reagent is 1: 0.1-50, 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 pore size is
The preferred particle size is 37um-1000um, the preferred pore size is
The invention provides the application of the quaternary ammonium base type functional silica gel material as an adsorbent in adsorbing anions in a water quality purification system.
The technical scheme of the invention is that 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 anion includes but is not limited to: f-、Cl-、Br-、I-、NO3 -、NO2 -、 CO3 2-、HCO3 -、SiO3 2-、PO4 3-、HPO4 2-、H2PO4 -、C2O4 2-、S2O3 2-、SCN-、CN-And metal complex anion MLn m-M is a noble metal, a transition metal or a rare earth metal, L is F-、Cl-、Br-、I-、S2O3 2-、SCN-、CN-、 C2O4 2-N is an integer of 1 to 6, and m is an integer of 1 to 3.
The stability of the C-N bond in quaternary amines is related to the induction effect of the groups attached to the carbon, electron withdrawing substituents are helpful for generating benzyl alcohol and tertiary amines, and electron withdrawing substituents can make the C-N bond more stable in alkaline media, so that the thermal stability of saturated chain quaternary amines is higher than that of quaternary amines with electron withdrawing groups such as benzene rings, and the thermal stability of long chain quaternary amines is higher than that of short chain quaternary amines. Silica gel is used as a carrier, polyamine with controllable saturated chain length is loaded on the silica gel, electron pushing density is greatly increased, and therefore heat resistance of the material is improved. Therefore, the effects of good heat resistance, high quaternary ammonium hydroxide loading rate and high anion removal rate, and being capable of reducing anions in water to ppb level are achieved, and the problems that the service life of an anion resin material is short, organic impurities decomposed by quaternary ammonium hydroxide are dissolved out, and water quality is polluted in the prior art are solved.
The invention has the beneficial effects that:
the multi-quaternary ammonium base type functional silica gel material provided by the invention has high loading rate and large exchange capacity, can reduce low-concentration anions in water to ppb level, has long service life, can resist high temperature of 100 ℃ 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 1 h, cooling, adding a mixed solution of xylene (125mL) and spherical silica gel (90g,300-, the compound formula I is obtained, wherein x is 3, y is 3, z is 2, the exchange capacity of GBT5760-2000 hydroxide type anion exchange resin is 3.7 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 filtration and washing with ethanol for 5 times and drying, the product was put into a 500mL three-necked flask containing 300mL of epoxypropyl chloride, 40g of sodium bicarbonate was added and stirred at 100 ℃ for 8 hours, filtration and washing with ethanol for 5 times and drying were carried out, the product was added into 250mL of anhydrous ethanol, 50g of sodium methoxide was added and stirred at 80 ℃ for 4 hours, filtration and washing with ethanol for 2 times, and then washing with deionized water for 5 times and drying were carried out to obtain compound I having an exchange capacity of 5.6mmol/g (1.75 mmol/g as measured by the exchange capacity test of quaternary ammonium base type resin of Zhenzhou company, Ltd.) of compound I having an exchange capacity of 3 x, 3 y, 9 z.
Example 3
The anion 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 Cl-2.669ppm，SO4 2-0.521ppm，SiO3 2-0.834ppm，F-1.087ppm, 100 ℃ condensate was passed through the purification column packed with the material of example 1, and water quality at the outlet was measured after 6 months, with the following concentrations of each anion: cl-0.045ppm，SO4 2-0.011ppm，SiO3 2-0.013ppm，F-0.042ppm。
Example 4
The anion purification column of the second loop condensed water purification simulation system of a certain nuclear power station is filled with the silica gel material of the embodiment 2, and the water at the water inlet contains Cl-3.01ppm，SO4 2-0.928ppm，SiO3 2-0.726ppm，F-1.139ppm, 100 ℃ condensate was passed through the column packed with the material of example 2, and then a water quality test was conducted at the outlet after 6 months, wherein the concentrations of the anions in the water were as follows: cl-0.032ppm，SO4 2-0.018ppm，SiO3 2-0.015ppm，F-0.011ppm。
In examples 3 and 4, the 100 ℃ condensed water is treated by the silica gel material, and after 6 months, the exchange material has better exchange capacity and can reduce the anion concentration in water to ppb level, which shows that the polyquaternary ammonium base type functionalized silica gel material provided by the invention has high heat resistance, high adsorption and low residue level.
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 the anions 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 multi-quaternary ammonium base type functional silica gel of the invention basically has no dissolution of quaternary ammonium base and decomposed substances after being used for 12 months, the service life of the material is long and is more than 12 months, and the material does not cause any pollution to water quality after being used for a long time.
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.
Claims (10)
1. A quaternary ammonium base type functionalized silica gel material has a structural formula as follows:
[(O3/2)Si(CH2)xS(CH2)yN+R2(OH-)[CH2CH2N+R2(OH-)]zR]a[Si(O4/2)]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, R is an alkane group, an alkylene oxide group; a and b are integers, and a: the ratio of b is between 0.000001 and 100.
2. The quaternary ammonium hydroxide-type functionalized silica gel material according to claim 1, wherein: and z is 2-9.
3. The method for synthesizing the quaternary ammonium hydroxide-type functionalized silica gel material according to claim 1, wherein: 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 the polyamine functional silica gel material [ (O) is obtained by one-pot reflux reaction of the H and z and silica gel in a solvent system3/2)Si(CH2)xS(CH2)yNH(CH2CH2NH)zH]a[Si(O4/2)]b；
2) Polyamine functional silica gel material reacts with halogenated alkane (RX) and acid-binding agent under certain conditions to obtain multi-quaternary ammonium salt type functional silica gel material [ (O)3/2)Si(CH2)xS(CH2)yN+R2X-(CH2CH2N+R2X-)zR]a[Si(O4/2)]b；
3) Reacting the multi-quaternary ammonium salt type functional silica gel material with an alkaline reagent under a certain condition to obtain the quaternary ammonium salt type functional silica gel material [ (O)3/2)Si(CH2)xS(CH2)yN+R2(OH-)[CH2CH2N+R2(OH-)]zR]a[Si(O4/2)]b。
4. The method of synthesis according to claim 3, characterized in that: in step 1): reflux reaction temperature is 90-150 deg.C, reaction time is 0.5-24h, solvent is selected from toluene, xylene, heptane, water; in step 2): the reaction temperature is 60-160 ℃; the reaction time is 0.5-12 h; the step (2) is a solvent-free system or a solvent system reaction, and the solvent is toluene; in the halogenated alkanes (RX), X is halogen; r is alkyl, alkylene oxide; the acid-binding agent is a weak base reagent; in step 3): the reaction temperature is 50-130 ℃, the reaction time is 0.5-8h, and the solvent is selected from absolute methanol and absolute ethanol; the alkaline agent is sodium alkoxide.
5. The method of synthesis 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 method of synthesis according to claim 3, characterized in that: the amount ratio of the polyethylene polyamine to the halogenated alkane feeding material is 1: 0.1-50; the weight ratio of the polyethylene polyamine to the acid-binding agent is 1: 0.1-20; the mass ratio of the polyethylene polyamine to the alkaline reagent is 1: 0.1-50.
7. The method of synthesis according to claim 3, characterized in that: the silica gel is amorphous granule or spherical granule.
8. The method of synthesis 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 quaternary ammonium hydroxide-type functionalized silica gel material according to claim 1 as an adsorbent for adsorbing anions in a water purification system.
10. Use according to claim 9, characterized in that: 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; such anions include, but are not limited to: f-、Cl-、Br-、I-、NO3 -、NO2 -、CO3 2-、HCO3 -、SiO3 2-、PO4 3-、HPO4 2-、H2PO4 -、C2O4 2-、S2O3 2-、SCN-、CN-And metal complex anion MLn m-M is a noble metal, a transition metal or a rare earth metal, L is F-、Cl-、Br-、I-、S2O3 2-、SCN-、CN-、C2O4 2-N is an integer of 1 to 6, and m is an integer of 1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111161655.3A CN114042433A (en) | 2021-09-30 | 2021-09-30 | Quaternary ammonium base type functional silica gel material and application thereof in water purification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111161655.3A CN114042433A (en) | 2021-09-30 | 2021-09-30 | Quaternary ammonium base type functional silica gel material and application thereof in water purification |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114042433A true CN114042433A (en) | 2022-02-15 |
Family
ID=80204814
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111161655.3A Pending CN114042433A (en) | 2021-09-30 | 2021-09-30 | Quaternary ammonium base type functional silica gel material and application thereof in water purification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114042433A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113952942A (en) * | 2021-12-22 | 2022-01-21 | 苏州硒诺唯新新材料科技有限公司 | Modified functional silica gel material and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781437A (en) * | 2010-01-12 | 2010-07-21 | 南京大学 | Magnetic acrylic acid series strongly basic anion exchange microballoon resin and preparation method thereof |
| CN108503731A (en) * | 2018-04-16 | 2018-09-07 | 浙江工业大学 | A kind of preparation method of high temperature resistant quaternary ammonium type strong alkali anion exchange media |
| CN109126720A (en) * | 2017-06-15 | 2019-01-04 | 中国科学院大连化学物理研究所 | The multi-functional mesoporous silica gel solid phase extractant of one kind and preparation and application |
| CN110368905A (en) * | 2019-06-15 | 2019-10-25 | 苏州硒诺唯新新材料科技有限公司 | A kind of sulfydryl amine type functional silica gel material and its application |
| US20200071205A1 (en) * | 2018-08-29 | 2020-03-05 | Ecolab Usa Inc. | Use of multiple charged ionic compounds derived from polyamines for waste water clarification |
| CN112237898A (en) * | 2019-07-17 | 2021-01-19 | 上海安谱实验科技股份有限公司 | Strong anion type solid phase extraction column filler and preparation method thereof |
-
2021
- 2021-09-30 CN CN202111161655.3A patent/CN114042433A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101781437A (en) * | 2010-01-12 | 2010-07-21 | 南京大学 | Magnetic acrylic acid series strongly basic anion exchange microballoon resin and preparation method thereof |
| CN109126720A (en) * | 2017-06-15 | 2019-01-04 | 中国科学院大连化学物理研究所 | The multi-functional mesoporous silica gel solid phase extractant of one kind and preparation and application |
| CN108503731A (en) * | 2018-04-16 | 2018-09-07 | 浙江工业大学 | A kind of preparation method of high temperature resistant quaternary ammonium type strong alkali anion exchange media |
| US20200071205A1 (en) * | 2018-08-29 | 2020-03-05 | Ecolab Usa Inc. | Use of multiple charged ionic compounds derived from polyamines for waste water clarification |
| CN110368905A (en) * | 2019-06-15 | 2019-10-25 | 苏州硒诺唯新新材料科技有限公司 | A kind of sulfydryl amine type functional silica gel material and its application |
| CN112237898A (en) * | 2019-07-17 | 2021-01-19 | 上海安谱实验科技股份有限公司 | Strong anion type solid phase extraction column filler and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| LIN WANG ET AL.: "Comparative analysis on adsorption properties and mechanisms of nitrate and phosphate by modified corn stalks", 《RSC ADVANCES》, vol. 8, pages 36468 - 36476 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113952942A (en) * | 2021-12-22 | 2022-01-21 | 苏州硒诺唯新新材料科技有限公司 | Modified functional silica gel material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102060995B (en) | Method for preparing silica gel supported dithiocarbamate heavy metal chelating resin | |
| CN114042433A (en) | Quaternary ammonium base type functional silica gel material and application thereof in water purification | |
| CN104370333B (en) | The preparation method of the active reverse-phase emulsifier of a kind of strong interface | |
| CN110863204B (en) | Water-soluble bis-imidazoline corrosion inhibitor and preparation method thereof | |
| CN113952942B (en) | Modified functional silica gel material and preparation method and application thereof | |
| CN102485711B (en) | A preparation method of N1-(2-aminoethyl)-1, 2-ethylenediamine | |
| CN106694008A (en) | Method for catalyzing hydrazine hydrate dehydrogenation by using supported RhNi/CeO2@C3N4 nano-catalyst | |
| CN109608636A (en) | Rich in heteroatomic triazine radical cup [4] aromatic polymer, preparation method and applications | |
| CN110982508B (en) | Mannich base acidizing corrosion inhibitor and preparation method thereof | |
| ES2373720T3 (en) | METHOD FOR THE PRODUCTION OF 4-AMINODYPHENYLAMINE. | |
| CN114292413A (en) | Preparation method and application of self-repairing material based on aromatic carboxylic acids MOFs | |
| CN111875504B (en) | Cyclohexyl diamine ionic liquid and application thereof in sulfur dioxide absorption | |
| CN113893886A (en) | Sulfamic acid type functionalized silica gel material and application thereof in water purification | |
| CN109865528B (en) | Semiconductor photocatalyst material and processing technology thereof | |
| EP1564188B1 (en) | A method for processing spent ion-exchange resins | |
| CN110760853A (en) | Water-soluble gemini polyether imidazoline corrosion inhibitor and preparation method thereof | |
| EP2684862B1 (en) | Method for preparing n-(2-aminoethyl)ethane-1,2-diamine | |
| CN108676023B (en) | High-efficiency preparation of boron hydride anion [ RnH4-nB]-Method (2) | |
| CN116323693A (en) | Novel chelating resins | |
| CN106001095B (en) | Remediation method for heavy metal pollution of acid soil | |
| TWI839848B (en) | Processing method of radioactive ionic resins | |
| CN109852979A (en) | A kind of restrainer | |
| CN113416169B (en) | Process for producing cyanuric chloride | |
| CA1071527A (en) | Apparatus and process for use in absorbing in a liquid medium a gas which evolves heat on absorption | |
| CN109055778B (en) | Method for removing metal potassium from metal sodium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |