CN116212976A - Modified cation exchange resin and preparation method thereof - Google Patents
Modified cation exchange resin and preparation method thereof Download PDFInfo
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- CN116212976A CN116212976A CN202310035272.4A CN202310035272A CN116212976A CN 116212976 A CN116212976 A CN 116212976A CN 202310035272 A CN202310035272 A CN 202310035272A CN 116212976 A CN116212976 A CN 116212976A
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- exchange resin
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- 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
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- 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/04—Processes using organic exchangers
- B01J39/05—Processes using organic exchangers in the strongly acidic form
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- 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/17—Organic material containing also inorganic materials, e.g. inert material coated with an ion-exchange resin
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- 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
- B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
- B01J39/16—Organic material
- B01J39/18—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/32—Hydrocarbons, e.g. oil
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Organic 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)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention discloses a modified cation exchange resin and a preparation method thereof, wherein the modified cation exchange resin comprises the following raw materials, by weight, 30-40 parts of cation exchange resin, 5-8 parts of a cross-linking agent, 8-12 parts of dodecyl dimethyl benzyl ammonium chloride or dodecyl dimethyl benzyl ammonium bromide, 50-80 parts of an organic solvent and 8-12 parts of kaolin. The beneficial effects of the invention are as follows: according to the modified cation exchange resin, the lipophilic group is contained, and the contact area of the modified cation exchange resin is increased by adding the kaolin, so that the adsorption effect of the modified cation exchange resin is improved, and the oil removal rate is improved.
Description
Technical Field
The invention belongs to the technical field of sewage treatment, and particularly relates to a modified cation exchange resin and a preparation method thereof.
Background
The influence of oil pollution on the environment is various, such as pollution to a water body, oil film formation on the water surface can prevent the ozone action of the water body, the photosynthesis of algae is limited due to the reduction of dissolved oxygen in the water body, the normal growth of aquatic organisms is influenced, the aquatic animals and plants have oil taste or toxicity, even the water body becomes odorous, and the utilization value of water resources is destroyed.
Oil and derivatives thereof cover the soil and plant surfaces, block the pores of the soil, prevent air penetration, prevent the soil and microorganisms from metabolism normally, reduce the quality and practical value of agricultural products, reduce the yield of crops when serious, and cause serious groundwater pollution when the oil migrates downwards in the soil.
Disclosure of Invention
The invention aims to provide a modified cation exchange resin with better oil removal effect and a preparation method thereof.
In order to achieve the above object, the present invention adopts the following technical scheme:
the modified cation exchange resin comprises, by weight, 30-40 parts of a cation exchange resin, 5-8 parts of a cross-linking agent, 8-12 parts of dodecyl dimethyl benzyl ammonium chloride or dodecyl dimethyl benzyl ammonium bromide, 50-80 parts of an organic solvent and 8-12 parts of kaolin.
The cation exchange resin contained in the modified cation exchange resin reacts with dodecyl dimethyl benzyl ammonium chloride or dodecyl dimethyl benzyl ammonium bromide, and the lipophilic group of the dodecyl dimethyl benzyl ammonium chloride or the dodecyl dimethyl benzyl ammonium bromide is grafted onto the resin group through the ion exchange reaction, so that the surface of the modified resin is provided with a long-chain lipophilic group, the lipophilicity is enhanced, and the oil removing effect is better.
Since kaolin is composed of clay minerals and non-clay minerals, the basic structure is formed by combining a layer of silicon-oxygen tetrahedron and an octahedral layer of aluminum hydroxide, and central cations of the silicon tetrahedron and aluminum octahedron are often replaced by other low-valence cations in nature, so that the kaolin has partial negative charges on crystal faces, and the negative charges are usually balanced by cations adsorbed between layers, so that the kaolin has good adsorption performance. The combination of kaolin and a cation exchange resin increases the adsorptive properties of the cation exchange resin.
The modified cation exchange resin comprises, as a preferred embodiment, 35 parts of cation exchange resin, 6 parts of cross-linking agent, 10 parts of dodecyl dimethyl benzyl ammonium chloride or dodecyl dimethyl benzyl ammonium bromide, 65 parts of organic solvent and 10 parts of kaolin.
In a preferred embodiment, the modified cation exchange resin is a macroporous strong acid cation exchange resin or a gel-type strong acid cation exchange resin.
The macroporous strong acid cation exchange resin and the gel strong acid cation exchange resin adopted by the application are purchased from the chemical industry Co., ltd.
In a preferred embodiment of the modified cation exchange resin, the cross-linking agent is a polyvinyl alcohol cross-linking agent.
In a preferred embodiment of the modified cation exchange resin, the organic solvent is ethanol or ethylene glycol.
In a second aspect of the present application, there is provided a method of preparing a modified cation exchange resin comprising the steps of:
(1) Washing cation exchange resin with ethanol, soaking in saturated saline water, and washing with pure water to neutrality;
(2) Adding cation exchange resin, a cross-linking agent, dodecyl dimethyl benzyl ammonium chloride or dodecyl dimethyl benzyl ammonium bromide into an organic solvent, mixing and stirring uniformly under the heating condition, filtering and drying to obtain modified cation exchange resin powder;
(3) And (3) mixing and stirring the modified cation exchange resin powder obtained in the step (2) and kaolin uniformly, and granulating to obtain the modified cation exchange resin.
And (3) washing the cation exchange resin by adopting ethanol to remove impurities on the surface of the cation exchange resin. The pore canal of the cation exchange resin can be completely opened by soaking in saturated saline water.
Under the heating condition, the cation exchange resin and the dodecyl dimethyl benzyl ammonium chloride or the dodecyl dimethyl benzyl ammonium bromide are subjected to ion exchange reaction, and the lipophilic group of the dodecyl dimethyl benzyl ammonium chloride or the dodecyl dimethyl benzyl ammonium bromide is grafted on the ion exchange resin, so that the effect of the ion exchange resin on adsorbing oil is improved.
Because the cation exchange resin is degreased by adsorption of the resin before the modification, the degreasing effect is lowered when the pores on the surface of the resin particles are covered with the oil. After modification, the oil removal and adsorption are combined through lipophilic groups, so that the oil removal effect is better.
In addition, the kaolin has strong adsorptivity, and the adsorption area is increased by compounding the kaolin, so that the adsorption effect is further improved.
In the preparation method of the modified cation exchange resin, as a preferred embodiment, in the step (2), the heating temperature is 35-40 ℃, and the mixing and stirring time is 3.5-4h.
In the preparation method of the modified cation exchange resin, as a preferred embodiment, in the step (2), the drying is naturally dried at 25-30 ℃.
In the above method for preparing a modified cation exchange resin, in the step (3), the fineness of the modified cation exchange resin powder and the fineness of the kaolin are both 50 to 80 mesh.
The beneficial effects of the invention are as follows: according to the modified cation exchange resin, the lipophilic group is contained, and the contact area of the modified cation exchange resin is increased by adding the kaolin, so that the adsorption effect of the modified cation exchange resin is improved, and the oil removal rate is improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
Example 1
The modified cation exchange resin of the embodiment 1 comprises the following raw materials in parts by weight:
30 parts of macroporous strong acid cation exchange resin, 5 parts of polyvinyl alcohol cross-linking agent, 8 parts of dodecyl dimethyl benzyl ammonium chloride, 50 parts of organic solvent ethanol and 8 parts of kaolin.
The method for preparing the modified cation exchange resin in the embodiment 1 comprises the following steps:
(1) Washing cation exchange resin with ethanol, soaking in saturated saline water, and washing with pure water to neutrality;
(2) Adding cation exchange resin, cross-linking agent and dodecyl dimethyl benzyl ammonium chloride into organic solvent, mixing and stirring for 4h at 35 ℃, filtering, and naturally drying at 25 ℃ to obtain modified cation exchange resin powder;
(3) Sieving the modified cation exchange resin powder obtained in the step (2) and kaolin to obtain modified cation exchange resin powder with fineness of 50-80 meshes, mixing and stirring uniformly, and granulating to obtain modified cation exchange resin.
Example 2
The modified cation exchange resin of the embodiment 2 comprises the following raw materials in parts by weight:
35 parts of macroporous strong acid cation exchange resin, 6 parts of polyvinyl alcohol cross-linking agent, 10 parts of dodecyl dimethyl benzyl ammonium chloride, 60 parts of organic solvent ethanol and 10 parts of kaolin.
The method for preparing the modified cation exchange resin in the embodiment 2 comprises the following steps:
(1) Washing cation exchange resin with ethanol, soaking in saturated saline water, and washing with pure water to neutrality;
(2) Adding cation exchange resin, cross-linking agent and dodecyl dimethyl benzyl ammonium chloride into organic solvent, mixing and stirring for 3.5h under the condition of heating temperature of 38 ℃, filtering, and naturally drying under the condition of temperature of 28 ℃ to obtain modified cation exchange resin powder;
(3) Sieving the modified cation exchange resin powder obtained in the step (2) and kaolin to obtain modified cation exchange resin powder with fineness of 50-80 meshes, mixing and stirring uniformly, and granulating to obtain modified cation exchange resin.
Example 3
The modified cation exchange resin of the embodiment 3 comprises the following raw materials in parts by weight:
38 parts of gel type strong acid cation exchange resin, 7 parts of polyvinyl alcohol cross-linking agent, 10 parts of dodecyl dimethyl benzyl ammonium bromide, 70 parts of organic solvent ethanol and 11 parts of kaolin.
The method for preparing the modified cation exchange resin in the embodiment 3 comprises the following steps:
(1) Washing cation exchange resin with ethanol, soaking in saturated saline water, and washing with pure water to neutrality;
(2) Adding cation exchange resin, cross-linking agent and dodecyl dimethyl benzyl ammonium bromide into an organic solvent, mixing and stirring for 4 hours at the heating temperature of 38 ℃, filtering, and naturally drying at the temperature of 28 ℃ to obtain modified cation exchange resin powder;
(3) Sieving the modified cation exchange resin powder obtained in the step (2) and kaolin to obtain modified cation exchange resin powder with fineness of 50-80 meshes, mixing and stirring uniformly, and granulating to obtain modified cation exchange resin.
Example 4
The modified cation exchange resin of the embodiment 4 comprises the following raw materials in parts by weight:
40 parts of gel type strong acid cation exchange resin, 8 parts of polyvinyl alcohol cross-linking agent, 12 parts of dodecyl dimethyl benzyl ammonium bromide, 80 parts of organic solvent glycol and 12 parts of kaolin.
The method for preparing the modified cation exchange resin in the embodiment 4 comprises the following steps:
(1) Washing cation exchange resin with ethanol, soaking in saturated saline water, and washing with pure water to neutrality;
(2) Adding cation exchange resin, cross-linking agent and dodecyl dimethyl benzyl ammonium bromide into an organic solvent, mixing and stirring for 4 hours at the heating temperature of 40 ℃, filtering, and naturally drying at the temperature of 30 ℃ to obtain modified cation exchange resin powder;
(3) Sieving the modified cation exchange resin powder obtained in the step (2) and kaolin to obtain modified cation exchange resin powder with fineness of 50-80 meshes, mixing and stirring uniformly, and granulating to obtain modified cation exchange resin.
Comparative example 1
The modified cation exchange resin of comparative example 1 differs from the modified cation exchange resin of example 1 in that: the modified cation exchange resin described in comparative example 1 contained no starting dodecyldimethylbenzyl ammonium chloride. The other raw materials and the preparation method were the same as in example 1.
Comparative example 2
Comparative example 2 the modified cation exchange resin was different from the modified cation exchange resin described in example 2 in that: the modified cation exchange resin described in comparative example 2 contained no raw kaolin clay. The remaining materials and preparation methods were the same as in example 2 (steps of removal and kaolin compounding).
Performance studies of the modified cation exchange resins described herein:
6 10cm columns were taken and equally divided into 3 groups, the first group of columns was packed with the modified cation exchange resin described in example 1 of the present application, the second group of columns was packed with the modified cation exchange resin described in comparative example 1, and the third group of columns was packed with the modified cation exchange resin described in comparative example 2. Oily wastewater was treated at a water temperature of 25℃and a flow rate of 8m l/min, and after 30 min of operation, water was taken out to measure turbidity and C-oil, and the results were averaged and shown in Table 1:
TABLE 1
As can be seen from table 1: the modified cation exchange resin has the best adsorption effect, the oil removal rate can reach 84.3 percent, the turbidity removal rate can reach 93.3 percent, and compared with the modified cation exchange resin which does not contain raw material dodecyl dimethyl benzyl ammonium chloride, the oil removal rate is 68.5 percent, and the turbidity removal rate is 87.1 percent; comparative example 2 did not contain the raw kaolin clay relative to the modified cation exchange resin described herein, had a removal rate of 73.6% and a turbidity removal rate of 89.8%, which was reduced relative to the performance of the modified cation exchange resin described herein.
The foregoing description is only of the preferred embodiments of the present application and is not intended to limit the same, but rather, various modifications and variations may be made by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application should be included in the protection scope of the present application.
Claims (9)
1. The modified cation exchange resin is characterized by comprising, by weight, 30-40 parts of a cation exchange resin, 5-8 parts of a cross-linking agent, 8-12 parts of dodecyl dimethyl benzyl ammonium chloride or dodecyl dimethyl benzyl ammonium bromide, 50-80 parts of an organic solvent and 8-12 parts of kaolin.
2. The modified cation exchange resin according to claim 1, which comprises the following raw materials, by weight, 35 parts of a cation exchange resin, 6 parts of a crosslinking agent, 10 parts of dodecyl dimethyl benzyl ammonium chloride or dodecyl dimethyl benzyl ammonium bromide, 65 parts of an organic solvent, and 10 parts of kaolin.
3. A modified cation exchange resin according to claim 1, wherein the cation exchange resin is a macroporous strong acid cation exchange resin or a gel-type strong acid cation exchange resin.
4. A modified cation exchange resin as claimed in claim 1, wherein the cross-linking agent is a polyvinyl alcohol cross-linking agent.
5. A modified cation exchange resin according to claim 1, wherein the organic solvent is ethanol or ethylene glycol.
6. A process for preparing a modified cation exchange resin as defined in any one of claims 1 to 5, comprising the steps of:
(1) Washing cation exchange resin with ethanol, soaking in saturated saline water, and washing with pure water to neutrality;
(2) Adding cation exchange resin, a cross-linking agent, dodecyl dimethyl benzyl ammonium chloride or dodecyl dimethyl benzyl ammonium bromide into an organic solvent, mixing and stirring uniformly under the heating condition, filtering and drying to obtain modified cation exchange resin powder;
(3) And (3) mixing and stirring the modified cation exchange resin powder obtained in the step (2) and kaolin uniformly, and granulating to obtain the modified cation exchange resin.
7. The process for producing a modified cation exchange resin as claimed in claim 6, wherein in the step (2), the heating temperature is 35 to 40℃and the mixing and stirring time is 3.5 to 4 hours.
8. The method for preparing a modified cation exchange resin as claimed in claim 6, wherein in the step (2), the drying is naturally carried out at 25-30 ℃.
9. The method according to claim 6, wherein in the step (3), the fineness of the modified cation exchange resin powder and the kaolin is 50 to 80 mesh.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310035272.4A CN116212976A (en) | 2023-01-10 | 2023-01-10 | Modified cation exchange resin and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310035272.4A CN116212976A (en) | 2023-01-10 | 2023-01-10 | Modified cation exchange resin and preparation method thereof |
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| CN116212976A true CN116212976A (en) | 2023-06-06 |
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| CN202310035272.4A Pending CN116212976A (en) | 2023-01-10 | 2023-01-10 | Modified cation exchange resin and preparation method thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298058A (en) * | 2008-06-13 | 2008-11-05 | 华东理工大学 | Modified cation-exchange resin and preparation and use thereof |
| CN104086679A (en) * | 2014-06-17 | 2014-10-08 | 宁波争光树脂有限公司 | High polymer resin, and apparatus and method for removing oil by using it |
| CN105753119A (en) * | 2016-03-16 | 2016-07-13 | 山东五洲检测有限公司 | Oily wastewater treating agent and preparation method and application thereof |
| CN107285431A (en) * | 2017-07-17 | 2017-10-24 | 安徽三品技术服务有限公司 | A kind of modified cation-exchange resin filter element of water purifier |
-
2023
- 2023-01-10 CN CN202310035272.4A patent/CN116212976A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101298058A (en) * | 2008-06-13 | 2008-11-05 | 华东理工大学 | Modified cation-exchange resin and preparation and use thereof |
| CN104086679A (en) * | 2014-06-17 | 2014-10-08 | 宁波争光树脂有限公司 | High polymer resin, and apparatus and method for removing oil by using it |
| CN105753119A (en) * | 2016-03-16 | 2016-07-13 | 山东五洲检测有限公司 | Oily wastewater treating agent and preparation method and application thereof |
| CN107285431A (en) * | 2017-07-17 | 2017-10-24 | 安徽三品技术服务有限公司 | A kind of modified cation-exchange resin filter element of water purifier |
Non-Patent Citations (2)
| Title |
|---|
| 周彦波，等: "季铵盐改性树脂处理含乳化油废水的研究", 中国给水排水, vol. 24, no. 3, pages 61 * |
| 李方文，等: "阳离子表面活性剂改性树脂及处理轧钢乳化含油废水的性能", 功能材料, vol. 42, pages 50 * |
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