CN113368829A - Spherical bio-based adsorption resin and preparation method and application thereof - Google Patents
Spherical bio-based adsorption resin and preparation method and application thereof Download PDFInfo
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- 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
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- 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
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- 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
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- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a spherical bio-based adsorption resin which is prepared from the following raw materials in parts by mass: 1 part of non-aromatic ring-containing bio-based polymer, 0.1-2 parts of aromatic ring-containing bio-based polymer, 10-100 parts of water, 10-20 parts of mineral oil, 0.1-10 parts of emulsifier and 0.05-1 part of cross-linking agent; the aromatic ring-free bio-based polymer is at least one of chitosan, gelatin, cellulose and sodium alginate; the aromatic ring-containing bio-based polymer is at least one of lignin, sodium lignosulfonate and tannic acid. The invention also relates to a preparation method and application of the spherical bio-based adsorption resin. The invention can reduce the dependence on petroleum resources, has simple preparation process and is beneficial to industrial production; the adsorption resin prepared by the invention realizes high efficiency and low energy consumption adsorption and regeneration of pollutants, can simultaneously adsorb metal ions and organic pollutants, and has excellent adsorption performance.
Description
Technical Field
The invention belongs to the technical field of high-molecular adsorption resin, and particularly relates to spherical bio-based adsorption resin as well as a preparation method and application thereof.
Background
The polymer adsorption resin as a functional polymer material has the advantages of simple synthesis process, convenient use, high efficiency, reproducibility, no secondary pollution, good stability and the like, and is widely concerned in the adsorption and recovery of metal ions and organic wastewater. However, the conventional polymeric adsorbent resin is prepared from non-renewable petroleum resources such as styrene and acrylic ester as main raw materials, which is not conducive to sustainable development.
In order to realize sustainable development of polymer adsorption materials, more and more bio-based polymers are used for preparation of adsorption materials, including chitosan, gelatin, cellulose, lignin and compounds thereof, and most of the obtained adsorption materials are in the forms of gel, film, powder and the like, and although the adsorption materials have a good adsorption effect, the adsorption materials have the following problems: 1) the preparation process is complex: for example, the preparation of the gel bio-based adsorption material usually needs freeze drying, which not only has long time consumption and high energy consumption, but also needs special freeze drying equipment; the preparation of the membrane bio-based adsorption material usually needs vacuum filtration and heating drying, and the problems of long time consumption and high energy consumption exist, so that the preparation method is not beneficial to industrial production; 2) low adsorption efficiency and high energy consumption: the traditional spherical petroleum-based adsorption resin has high porosity and can treat wastewater with high flux under lower pressure, the porosity of gel, membrane, powder and other adsorption materials is very low, the wastewater passing rate is very low in the continuous treatment process, and higher pressure is often needed, so that the adsorption efficiency is low, the energy consumption is high, the same problems exist in the regeneration process, and the industrial application is not facilitated.
For example, chinese patent application CN110003390A discloses a starch or cellulose-based polymeric porous adsorbent resin and a preparation method thereof. The high molecular porous adsorption resin is a porous structure with high specific surface area, which is prepared by taking starch or cellulose as a raw material and sequentially carrying out graft copolymerization of styrene and Friedel-crafts alkylation reaction. The preparation method of the high molecular porous adsorption resin comprises the following steps: dispersing starch or cellulose in water, adding an initiator, heating to 70 ℃, adding a certain amount of styrene monomer, reacting for 4 hours, stopping the reaction, extracting the generated grafted solid product, and drying at 60 ℃ for 24 hours to obtain a starch or cellulose grafted styrene copolymer; the graft copolymer is soaked in a reaction solvent 1, 2-dichloroethane in advance, after the graft copolymer is fully swelled for 12 hours, a certain amount of external cross-linking agent and a certain amount of catalyst are sequentially added, the temperature is raised to 80 ℃, the reaction is carried out for 8 hours under stirring, the obtained solid is extracted, and the solid is dried for 24 hours at the temperature of 60 ℃ to obtain the starch or cellulose-based polymer porous resin. The preparation of the high molecular porous adsorption resin not only consumes long time and has high energy consumption, but also needs complex devices, such as a Soxhlet extractor, and is not beneficial to industrial production.
Disclosure of Invention
The invention provides a spherical bio-based adsorption resin, a preparation method and application thereof, aiming at the technical problems in the prior art, and effectively solves the problems that the traditional petroleum-based polymer adsorption resin is not renewable and the existing bio-based polymer adsorption material is not beneficial to industrial production and application.
The technical scheme for solving the technical problems is as follows:
the spherical bio-based adsorption resin is prepared from the following raw materials in parts by weight: 1 part of non-aromatic ring-containing bio-based polymer, 0.1-2 parts of aromatic ring-containing bio-based polymer, 10-100 parts of water, 10-20 parts of mineral oil, 0.1-10 parts of emulsifier and 0.05-1 part of cross-linking agent;
wherein the aromatic ring-free bio-based polymer is at least one of chitosan, gelatin, cellulose and sodium alginate; the aromatic ring-containing bio-based polymer is at least one of lignin, sodium lignosulfonate and tannic acid.
On the basis of the technical scheme, the invention can be further improved as follows.
Preferably, the mineral oil is one of No. 5, No. 10, No. 26, No. 32 and No. 68 technical white oils.
Preferably, the emulsifier is one of span 20, span 65, span 80, tween 40, tween 61, tween 80 and tween 85.
Preferably, the cross-linking agent is one of glyoxal, malonaldehyde, succinaldehyde, glutaraldehyde, and adipaldehyde.
Preferably, the weight parts of the raw materials are as follows: 1 part of non-aromatic ring-containing bio-based polymer, 0.6-2 parts of aromatic ring-containing bio-based polymer, 50-100 parts of water, 12-18 parts of mineral oil, 3-10 parts of emulsifier and 0.1-1 part of cross-linking agent.
The invention also aims to provide a preparation method of the spherical bio-based adsorption resin, which comprises the following steps:
s1, weighing aromatic ring-free bio-based polymer, aromatic ring-containing bio-based polymer, water, mineral oil, an emulsifier and a cross-linking agent according to parts by weight;
s2, dissolving the aromatic ring-free bio-based polymer and the aromatic ring-containing bio-based polymer in water to obtain a polymer solution;
s3, dispersing the polymer solution into mineral oil dissolved with an emulsifier under the condition of high-speed stirring, adding a cross-linking agent under the condition of heating, and filtering after complete cross-linking reaction to obtain the spherical bio-based adsorption resin.
Preferably, in S3, the stirring speed is 300-800 r/min.
Preferably, in S3, the crosslinking reaction temperature is 40-90 ℃ and the crosslinking reaction time is 0.1-2 h.
The invention also relates to application of the spherical biological-based adsorption resin in treating wastewater containing metal ions and/or organic pollutants.
The invention has the beneficial effects that:
1) the spherical bio-based adsorption resin takes bio-based macromolecules as raw materials, can reduce the dependence on petroleum resources and is beneficial to sustainable development;
2) the preparation process of the spherical bio-based adsorption resin is simple and is beneficial to industrial production;
3) the prepared adsorption resin is spherical, can treat wastewater at high flux under lower pressure, and is beneficial to high-efficiency and low-energy-consumption adsorption and regeneration of pollutants;
4) the spherical bio-based adsorption resin simultaneously introduces polar heteroatoms and aromatic ring structures, can simultaneously adsorb metal ions and organic pollutants, has excellent adsorption performance and has wide application prospect.
Drawings
FIG. 1 is a schematic diagram of a spherical bio-based adsorbent resin in example 1 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Unless otherwise indicated, the raw materials and equipment used in the present invention are conventional in the art (conventional commercial products) and are commercially available.
Aiming at the problems that the traditional petroleum-based polymer adsorption resin is not renewable and the existing bio-based polymer adsorption material is not beneficial to industrial production and application, the inventor aims to provide a bio-based adsorption resin which can reduce the dependence on petroleum resources, has simple production process, convenient use, easy regeneration, high efficiency and low energy consumption and is beneficial to industrial production and application. The preparation of the bio-based adsorption resin not only has short time consumption, low energy consumption and low production cost, but also has lower requirements on reaction conditions, high stability, no need of complex devices and no need of hiring professional personnel for operation, and has simple operation, high safety, contribution to industrial production and good economic benefit. In addition, the prepared bio-based adsorption resin is spherical, can treat wastewater at high flux under lower pressure, and is beneficial to high-efficiency and low-energy-consumption adsorption and regeneration of pollutants; the prepared bio-based adsorption resin simultaneously introduces polar heteroatoms and aromatic ring structures, can simultaneously adsorb metal ions and organic pollutants, has excellent adsorption performance and wide application prospect.
Example 1
The spherical bio-based adsorption resin designed by the embodiment is prepared from the following raw materials in parts by mass: 1 part of chitosan, 0.1 part of lignin, 10 parts of water, 10 parts of No. 5 industrial white oil, 200.1 parts of span and 0.05 part of glyoxal.
The preparation method of the spherical bio-based adsorption resin comprises the following steps: s1, dissolving chitosan and lignin in water to obtain a polymer solution; s2, dissolving span 20 in No. 5 industrial white oil; s3, dispersing the polymer solution in 5 # industrial white oil dissolved with span 20 at a stirring speed of 300r/min, dropwise adding glyoxal at a temperature of 90 ℃ for crosslinking reaction for 0.1h, and filtering to obtain the spherical bio-based adsorption resin.
Example 2
The spherical bio-based adsorption resin designed by the embodiment is prepared from the following raw materials in parts by mass: 1 part of gelatin, 2 parts of sodium lignosulphonate, 100 parts of water, 20 parts of No. 10 industrial white oil, 6510 parts of span and 1 part of malonaldehyde.
The preparation method of the spherical bio-based adsorption resin comprises the following steps: s1, dissolving gelatin and sodium lignosulfonate in water to obtain a polymer solution; s2, dissolving span 65 in No. 10 industrial white oil; s3, dispersing the polymer solution in No. 10 industrial white oil dissolved with span 65 at a stirring speed of 800r/min, dropwise adding malonaldehyde at the temperature of 40 ℃ for crosslinking reaction for 2h, and filtering to obtain the spherical bio-based adsorption resin.
Example 3
The spherical bio-based adsorption resin designed by the embodiment is prepared from the following raw materials in parts by mass: 1 part of cellulose, 0.6 part of tannic acid, 50 parts of water, 10 parts of No. 26 industrial white oil, 801 parts of span and 0.1 part of succinaldehyde.
The preparation method of the spherical bio-based adsorption resin comprises the following steps: s1, dissolving cellulose and tannic acid in water to obtain a polymer solution; s2, dissolving span 80 in No. 26 industrial white oil; s3, dispersing the polymer solution in 26 # industrial white oil dissolved with span 80 at a stirring speed of 500r/min, dropwise adding succinaldehyde at a temperature of 60 ℃ for crosslinking reaction for 1h, and filtering to obtain the spherical bio-based adsorption resin.
Example 4
The spherical bio-based adsorption resin designed by the embodiment is prepared from the following raw materials in parts by mass: 1 part of sodium alginate, 1 part of tannic acid, 50 parts of water, 12 parts of No. 32 industrial white oil, 403 parts of tween and 0.3 part of hexanedial.
The preparation method of the spherical bio-based adsorption resin comprises the following steps: s1, dissolving sodium alginate and tannic acid in water to obtain a polymer solution; s2, dissolving Tween 40 in No. 32 industrial white oil; s3, dispersing the polymer solution in 32 # industrial white oil dissolved with Tween 40 at a stirring speed of 400r/min, dropwise adding adipaldehyde to perform crosslinking reaction for 0.5h at a temperature of 50 ℃, and filtering to obtain the spherical bio-based adsorption resin.
Example 5
The spherical bio-based adsorption resin designed by the embodiment is prepared from the following raw materials in parts by mass: 0.5 part of each of chitosan and gelatin, 0.6 part of lignin, 30 parts of water, 14 parts of No. 68 industrial white oil, 616 parts of tween and 0.5 part of glutaraldehyde.
The preparation method of the spherical bio-based adsorption resin comprises the following steps: s1, dissolving chitosan, gelatin and lignin in water to obtain a polymer solution; s2, dissolving Tween 61 in No. 68 industrial white oil; s3, dispersing the polymer solution in 68 # industrial white oil dissolved with Tween 61 at a stirring speed of 600r/min, dropwise adding glutaraldehyde at a temperature of 70 ℃ for crosslinking reaction for 1.5h, and filtering to obtain the spherical bio-based adsorption resin.
Example 6
The spherical bio-based adsorption resin designed by the embodiment is prepared from the following raw materials in parts by mass: 0.5 part of gelatin and cellulose, 1.5 parts of sodium lignosulfonate, 80 parts of water, 16 parts of No. 32 industrial white oil, 805 parts of Tween and 0.7 part of glutaraldehyde.
The preparation method of the spherical bio-based adsorption resin comprises the following steps: s1, dissolving gelatin, cellulose and sodium lignosulfonate in water to obtain a polymer solution; s2, dissolving Tween 80 in No. 32 industrial white oil; s3, dispersing the polymer solution in 32 # industrial white oil dissolved with Tween 80 at a stirring speed of 700r/min, dropwise adding glutaraldehyde at a temperature of 80 ℃ for crosslinking reaction for 1h, and filtering to obtain the spherical bio-based adsorption resin.
Example 7
The spherical bio-based adsorption resin designed by the embodiment is prepared from the following raw materials in parts by mass: 0.5 part of each of cellulose and sodium alginate, 0.6 part of each of lignin and tannic acid, 60 parts of water, 18 parts of No. 32 industrial white oil, 858 parts of Tween and 0.9 part of glutaraldehyde.
The preparation method of the spherical bio-based adsorption resin comprises the following steps: s1, dissolving cellulose, sodium alginate, lignin and tannic acid in water to obtain a polymer solution; s2, dissolving Tween 85 in No. 32 industrial white oil; s3, dispersing the polymer solution in 32 # industrial white oil dissolved with Tween 85 at a stirring speed of 500r/min, dropwise adding glutaraldehyde at a temperature of 60 ℃ for crosslinking reaction for 1.2h, and filtering to obtain the spherical bio-based adsorption resin.
Comparative example 1
The spherical bio-based adsorption resin designed by the comparative example is prepared from the following raw materials in parts by mass: 1 part of chitosan, 0.05 part of lignin, 10 parts of water, 10 parts of No. 5 industrial white oil, 200.05 parts of span and 1.1 parts of glyoxal.
The preparation method of the spherical bio-based adsorption resin comprises the following steps: s1, dissolving chitosan and lignin in water to obtain a polymer solution; s2, dissolving span 20 in No. 5 industrial white oil; s3, dispersing the polymer solution in 5 # industrial white oil dissolved with span 20 at a stirring speed of 200r/min, dropwise adding glyoxal at the temperature of 30 ℃ for crosslinking reaction for 0.1h, and filtering to obtain the spherical bio-based adsorption resin.
The above examples 1 to 7 are all examples of the present invention, the comparative example 1 is a comparative example of the present invention, the performance of the spherical bio-based adsorption resins in the examples 1 to 7 and the comparative example 1 is tested, and the test results are shown in the following table 1.
The specific measurement method is as follows:
first, measurement of Water content
The water content of the spherical bio-based adsorbent resins in examples 1-7 and comparative example 1 was measured according to the method specified in the national standard GB5757-86, and the specific operations were as follows: weighing 1g of spherical bio-based adsorption resin, baking at 105 ℃ for 2h, and calculating the water content of the spherical bio-based adsorption resin according to the reduced weight.
Second, measurement of adsorption Property
1) Adsorption of Congo red dye: taking analytically pure Congo red as a raw material, and preparing 1L of Congo red to-be-adsorbed solution with the concentration of 300 mg/L; taking 20mL of the Congo red solution to be adsorbed, adding 20mg of bio-based adsorption resin, oscillating for 6h at room temperature to reach balance, measuring the absorbance of the adsorbed solution by using an ultraviolet spectrophotometer, and substituting into a standard curve: and calculating the concentration of the dye in the solution after adsorption, and calculating the adsorption capacity of the spherical bio-based adsorption resin on the congo red according to the concentration of the solution before and after adsorption.
2) Adsorption of rare earth cerium ions: taking analytically pure cerium nitrate as a raw material, and preparing 1L of cerium ion solution to be adsorbed with the concentration of 200 mg/L; taking 20mL of the cerium ion solution to be adsorbed, adding 20mg of spherical bio-based adsorption resin, oscillating at room temperature for 6h to reach balance, taking 1mL of the solution after adsorption, adding oxalic acid-azo chlorophosphorus acid developer, measuring the absorbance of the solution after adsorption by using an ultraviolet spectrophotometer, and substituting into a standard curve: and calculating the concentration of cerium ions in the solution after adsorption, and calculating the adsorption capacity of the spherical bio-based adsorption resin on the cerium ions according to the concentration of the solution before and after adsorption.
TABLE 1 detection results of properties of spherical bio-based adsorbent resins
As can be seen from Table 1, the spherical bio-based adsorbent resins in examples 1 to 7 of the present invention all have high water content, and have good adsorption effect on Congo red, and the adsorption capacity is above 120mg/g, wherein the adsorption capacity of the spherical bio-based adsorbent resin in example 6 on Congo red is 156 mg/g; meanwhile, the spherical bio-based adsorption resin has a good adsorption effect on rare earth cerium ions, and the adsorption capacity is over 80mg/g, wherein the adsorption capacity of the spherical bio-based adsorption resin in the embodiment 2 on the rare earth cerium ions is 106mg/g, so that the spherical bio-based adsorption resin disclosed by the invention has strong adsorption capacity on organic dyes and rare earth ions. By adopting the technical scheme of the invention, the adsorption performance of the metal ions and the organic pollutants is remarkably improved, and the technical problems in the prior art can be effectively solved.
The specific technology not described in the present invention is the prior art.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. The spherical bio-based adsorption resin is characterized by being prepared from the following raw materials in parts by mass: 1 part of non-aromatic ring-containing bio-based polymer, 0.1-2 parts of aromatic ring-containing bio-based polymer, 10-100 parts of water, 10-20 parts of mineral oil, 0.1-10 parts of emulsifier and 0.05-1 part of cross-linking agent;
wherein the aromatic ring-free bio-based polymer is at least one of chitosan, gelatin, cellulose and sodium alginate; the aromatic ring-containing bio-based polymer is at least one of lignin, sodium lignosulfonate and tannic acid.
2. The spherical bio-based adsorption resin according to claim 1, wherein the mineral oil is one of No. 5, No. 10, No. 26, No. 32 and No. 68 technical white oil.
3. The spherical bio-based adsorbent resin according to claim 1, wherein said emulsifier is one of span 20, span 65, span 80, tween 40, tween 61, tween 80 and tween 85.
4. The spherical bio-based adsorbent resin according to claim 1, wherein said cross-linking agent is one of glyoxal, malondialdehyde, succindialdehyde, glutaraldehyde, and adipaldehyde.
5. The spherical bio-based adsorption resin according to claim 1, wherein the mass parts of the raw materials are as follows: 1 part of non-aromatic ring-containing bio-based polymer, 0.6-2 parts of aromatic ring-containing bio-based polymer, 50-100 parts of water, 12-18 parts of mineral oil, 3-10 parts of emulsifier and 0.1-1 part of cross-linking agent.
6. The method for preparing spherical bio-based adsorption resin according to any one of claims 1 to 5, comprising the steps of:
s1, weighing aromatic ring-free bio-based polymer, aromatic ring-containing bio-based polymer, water, mineral oil, an emulsifier and a cross-linking agent according to parts by weight;
s2, dissolving the aromatic ring-free bio-based polymer and the aromatic ring-containing bio-based polymer in water to obtain a polymer solution;
s3, dispersing the polymer solution into mineral oil dissolved with an emulsifier under the condition of high-speed stirring, adding a cross-linking agent under the condition of heating, and filtering after complete cross-linking reaction to obtain the spherical bio-based adsorption resin.
7. The method for preparing spherical bio-based adsorbent resin according to claim 6, wherein in S3, the stirring speed is 300-800 r/min.
8. The method for preparing spherical bio-based adsorption resin according to claim 6, wherein the crosslinking reaction temperature in S3 is 40-90 ℃ and the crosslinking reaction time is 0.1-2 h.
9. Use of the spherical bio-based adsorption resin of any one of claims 1 to 8 for treating wastewater containing metal ions and/or organic contaminants.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817443A (en) * | 2006-01-06 | 2006-08-16 | 华南理工大学 | Production of spherical adsorbing materials with and production thereof lignin base |
| CN103508508A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Application of porous biomass resin in adsorptive separation |
| CN104437396A (en) * | 2014-11-04 | 2015-03-25 | 广西大学 | Preparation method of lignin-amine microsphere |
| JP2017018843A (en) * | 2014-03-17 | 2017-01-26 | 株式会社クラレ | Water treatment method, water treatment polymer adsorbent, and regeneration method therefor |
| CN111116943A (en) * | 2020-01-10 | 2020-05-08 | 天津科技大学 | Composite cellulose nanofibril hydrogel sphere and preparation method and application thereof |
| WO2020127834A1 (en) * | 2018-12-21 | 2020-06-25 | L'oreal | Composition of the gel/gel type comprising boron nitride particles and at least one encapsulated pigment |
-
2021
- 2021-04-28 CN CN202110466885.4A patent/CN113368829A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817443A (en) * | 2006-01-06 | 2006-08-16 | 华南理工大学 | Production of spherical adsorbing materials with and production thereof lignin base |
| CN103508508A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Application of porous biomass resin in adsorptive separation |
| JP2017018843A (en) * | 2014-03-17 | 2017-01-26 | 株式会社クラレ | Water treatment method, water treatment polymer adsorbent, and regeneration method therefor |
| CN104437396A (en) * | 2014-11-04 | 2015-03-25 | 广西大学 | Preparation method of lignin-amine microsphere |
| WO2020127834A1 (en) * | 2018-12-21 | 2020-06-25 | L'oreal | Composition of the gel/gel type comprising boron nitride particles and at least one encapsulated pigment |
| CN111116943A (en) * | 2020-01-10 | 2020-05-08 | 天津科技大学 | Composite cellulose nanofibril hydrogel sphere and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 廖润华 等编著: "《环境治理功能材料》", 北京：中国建材工业出版社, pages: 33 * |
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