CN110698722A - Preparation method of oil-water separation type alginate aerogel with nano-micron gradient hierarchical pore structure - Google Patents
Preparation method of oil-water separation type alginate aerogel with nano-micron gradient hierarchical pore structure Download PDFInfo
- Publication number
- CN110698722A CN110698722A CN201910960877.8A CN201910960877A CN110698722A CN 110698722 A CN110698722 A CN 110698722A CN 201910960877 A CN201910960877 A CN 201910960877A CN 110698722 A CN110698722 A CN 110698722A
- Authority
- CN
- China
- Prior art keywords
- aerogel
- alginate
- oil
- nano
- water separation
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/36—After-treatment
- C08J9/40—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0202—Separation of non-miscible liquids by ab- or adsorption
-
- 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
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/048—Bimodal pore distribution, e.g. micropores and nanopores coexisting in the same foam
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/04—Alginic acid; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention relates to a preparation method of an oil-water separation type alginate aerogel with a nano-micron gradient hierarchical pore structure. The sponge is immersed into a calcium ion solution with a certain concentration to further absorb water for crosslinking, and is immersed in a hydrophobic modified mixed solution to prepare the super-hydrophobic calcium alginate material with rich nano-micron pore channels. The method is simple and easy to implement, has low preparation cost, and does not use harmful organic solvents. Physical foaming technology, nano hole making technology and freeze drying technology are combined, and the hydrophobic aerogel is further subjected to hydrophobic modification by an inorganic modifier so as to achieve the aim of oil-water separation. The cheap calcium alginate material prepared by the method has good oil-water separation capacity, high application potential and higher economic production value.
Description
Technical Field
The invention relates to a preparation method of an oil-water separation type alginate aerogel with a special pore structure, in particular to a preparation method of an oil-water separation type alginate aerogel with a nano-micron gradient hierarchical pore structure, and belongs to the technical field of preparation of biomass-based functional materials.
Technical Field
In the past century, marine pollution caused by frequent oil leakage accidents brings huge damage to marine ecological environment. Therefore, how to realize the efficient separation of oil and water has become a hot research direction. A simple and feasible method for solving the problem is developed by using a super-hydrophobic and super-oleophilic functional material. At present, sodium alginate aerogel is low in price, environment-friendly and easy for calcium ions to form hydrophobic gel, the structure of the sodium alginate aerogel contains a large number of functional groups such as hydroxyl and carboxyl, and the sodium alginate aerogel can be used as modification sites and widely researched for oil-water separation, however, the pure sodium alginate aerogel has the problems of low oil absorption, poor mechanical performance and the like, the adsorption capacity and mechanical performance of the pure sodium alginate aerogel are generally improved by adding high-adsorption-performance nano particles such as carbon nano tubes and graphene, and the defect is that the large-scale production cost is high. Aiming at the problems of low adsorption capacity and poor mechanical property of the pure sodium alginate oil-water separation material.
The invention designs an oil-water separation type alginate aerogel with a nano-micron gradient hierarchical pore structure, which is characterized in that firstly sodium alginate, a foaming agent, a nano pore-making agent and a chemical cross-linking agent are prepared into a foaming solution with a certain foaming ratio, and then the foaming solution is freeze-dried by utilizing a freeze-drying technology to obtain the ultra-light spongy alginate aerogel with a fluffy porous structure. The sponge is immersed into a calcium ion solution with a certain concentration to further absorb water for crosslinking, and is immersed in a hydrophobic modified mixed solution to prepare the super-hydrophobic calcium alginate material with rich nano-micron pore channels. The method is simple and easy to implement, low in preparation cost and free of harmful organic solvents. The cheap calcium alginate material prepared by the method has excellent oil-water separation capability.
Disclosure of Invention
The invention aims to provide a preparation method of an oil-water separation type alginate aerogel with a nano-micron gradient hierarchical pore structure. The invention combines a physical foaming technology, a nano pore making technology and a freeze drying technology to construct a pore channel structure of sodium alginate, realizes the controllable construction of the pore structure of the sodium alginate, forms a special pore structure with a macroporous-mesoporous-microporous gradient structure, further performs hydrophobic modification on hydrophobic aerogel by an inorganic modifier, constructs super-hydrophobic alginate aerogel with the special pore structure, and realizes the purpose of oil-water separation, and the specific technology comprises the following steps:
(1) preparation of alginate with nano-micron gradient hierarchical pore structure
Adding 0.3-5% of foaming agent into 0.5-5% of sodium alginate solution, and then stirring at 20-150 rpm for 20-180 min to fully foam and expand to form sodium alginate foaming liquid; adding 0.3-15% of a nano hole-making agent into the sodium alginate foaming liquid in the previous step, then adding sodium carbonate to adjust the pH value to 6-8, stirring at 20-200 rpm for 1-60 min, and uniformly mixing; and then adding 0.1-5% of cross-linking agent, stirring at 20-200 rpm for 1-60 min, uniformly mixing, and putting the foaming solution containing the nano-pore-making agent into a container with a certain shape for freeze drying for 24-48 h.
(2) Hydrophobic modification of alginate aerogel
Taking out the aerogel prepared in the last step, and putting the aerogel into 0.3-5% calcium chloride solution for crosslinking for 3-24 h to form calcium alginate gel; taking out the calcium alginate gel, washing until the pH value is neutral, adding the calcium alginate gel into a modifier mixed solution with the concentration of 0.1-5%, and soaking for 3-24 hours; and taking out the calcium alginate gel, washing until the pH value is neutral, and airing for later use.
Detailed Description
Aiming at the preparation method of the oil-water separation type alginate aerogel with the nano-micron gradient hierarchical pore structure, the invention is specifically implemented in the following way. The embodiments of the present invention are not limited thereto.
Example 1
Preparation of alginate with nano-micron gradient hierarchical pore structure
Adding 0.8% foaming agent into 0.5% sodium alginate solution, and stirring at 80rpm for 50min to foam and expand sufficiently to form sodium alginate foaming solution; adding 1% of nano pore-making agent into the sodium alginate foaming liquid in the previous step, then adding sodium carbonate to adjust the pH value to 7, stirring at 20rpm for 20min, and uniformly mixing; then 2% of cross-linking agent is added, the mixture is stirred for 5min at 80rpm and is uniformly mixed, and the foaming solution containing the nano-pore-making agent is filled into a container with a certain shape and is subjected to freeze drying treatment for 48 h.
Example 2
Hydrophobic modification of alginate aerogel
Taking out the aerogel prepared in the last step, putting the aerogel into a 3% calcium chloride solution, and crosslinking for 24 hours to form calcium alginate gel; taking out the calcium alginate gel, washing until the pH value is neutral, adding the calcium alginate gel into a modifier mixed solution with the concentration of 2%, and soaking for 24 hours; and taking out the calcium alginate gel, washing until the pH value is neutral, and airing for later use.
Claims (5)
1. A preparation method of oil-water separation type alginate aerogel with a nano-micron gradient hierarchical pore structure is characterized by comprising the following preparation steps:
(1) preparing alginate with a nano-micron gradient hierarchical pore structure:
adding 0.3-5% of foaming agent into 0.5-5% of sodium alginate solution, and then stirring at 20-150 rpm for 20-180 min to fully foam and expand to form sodium alginate foaming liquid; adding 0.3-15% of a nano hole-making agent into the sodium alginate foaming liquid in the previous step, then adding sodium carbonate to adjust the pH value to 6-8, stirring at 20-200 rpm for 1-60 min, and uniformly mixing; and then adding 0.1-5% of cross-linking agent, stirring at 20-200 rpm for 1-60 min, uniformly mixing, and putting the foaming solution containing the nano-pore-making agent into a container with a certain shape for freeze drying for 24-48 h.
(2) Carrying out hydrophobic modification on alginate aerogel:
taking out the aerogel prepared in the last step, and putting the aerogel into 0.3-5% calcium chloride solution for crosslinking for 3-24 h to form calcium alginate gel; taking out the calcium alginate gel, washing until the pH value is neutral, adding the calcium alginate gel into a modifier mixed solution with the concentration of 0.1-5%, and soaking for 3-24 hours; and taking out the calcium alginate gel, washing until the pH value is neutral, and airing for later use.
2. The method for preparing the oil-water separation type alginate aerogel with the nanometer-micron gradient hierarchical pore structure as claimed in claim 1, wherein the foaming agent in step (1) is one or more of sodium dodecyl sulfate, ammonium dodecyl sulfate, dodecyl phosphate ester triethanol ammonium, alcohol polyoxyethylene ether sodium sulfate, rosin soap foaming agent and animal and vegetable protein foaming agent.
3. The method for preparing the oil-water separation type alginate aerogel with the nanometer-micron gradient hierarchical pore structure according to claim 1, wherein the nanometer pore-making agent in the step (1) is one or more of nanometer calcium carbonate, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol and ammonium bicarbonate.
4. The method for preparing the oil-water separation type alginate aerogel with the nanometer-micrometer gradient hierarchical pore structure according to claim 1, wherein the cross-linking agent in the step (1) is one or more of NN-methylenebisacrylamide, 1, 2, 3, 4-butanetetracarboxylic acid (BTCA), a silane coupling agent, an APE cross-linking agent, glutaraldehyde, polyethyleneimine, chitosan and melamine.
5. The method for preparing the oil-water separation type alginate aerogel with the nanometer-micrometer gradient hierarchical pore structure according to claim 1, wherein the modifier in the step (2) is one or more of hexadecyl trimethoxy silane, hexamethyl disilazane, polydimethylsiloxane, methyl trichlorosilane and octyl trimethoxy siloxane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910960877.8A CN110698722A (en) | 2019-10-10 | 2019-10-10 | Preparation method of oil-water separation type alginate aerogel with nano-micron gradient hierarchical pore structure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910960877.8A CN110698722A (en) | 2019-10-10 | 2019-10-10 | Preparation method of oil-water separation type alginate aerogel with nano-micron gradient hierarchical pore structure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110698722A true CN110698722A (en) | 2020-01-17 |
Family
ID=69200080
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910960877.8A Pending CN110698722A (en) | 2019-10-10 | 2019-10-10 | Preparation method of oil-water separation type alginate aerogel with nano-micron gradient hierarchical pore structure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110698722A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437404A (en) * | 2022-03-01 | 2022-05-06 | 浙江大学 | Preparation method of calcium alginate porous hydrogel |
| CN115058039A (en) * | 2022-05-19 | 2022-09-16 | 珠海钛然科技有限公司 | Biomass-based transparent super-hydrophobic composite membrane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013129413A1 (en) * | 2012-02-29 | 2013-09-06 | 株式会社メディオン・リサーチ・ラボラトリーズ | Kit for preparing carbon-dioxide-containing composition |
| CN103446897A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Chemical and ionic cross-linked alginate hydrogel flat membrane for filtration and preparation method thereof |
| CN104787772A (en) * | 2015-03-23 | 2015-07-22 | 河北金纳科技有限公司 | Preparation method of hydrophobic nano-aerogel composite material |
| CN105924686A (en) * | 2016-04-13 | 2016-09-07 | 四川大学 | Biology base polymer aerogel oil absorption material and preparation method thereof |
-
2019
- 2019-10-10 CN CN201910960877.8A patent/CN110698722A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013129413A1 (en) * | 2012-02-29 | 2013-09-06 | 株式会社メディオン・リサーチ・ラボラトリーズ | Kit for preparing carbon-dioxide-containing composition |
| CN103446897A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Chemical and ionic cross-linked alginate hydrogel flat membrane for filtration and preparation method thereof |
| CN104787772A (en) * | 2015-03-23 | 2015-07-22 | 河北金纳科技有限公司 | Preparation method of hydrophobic nano-aerogel composite material |
| CN105924686A (en) * | 2016-04-13 | 2016-09-07 | 四川大学 | Biology base polymer aerogel oil absorption material and preparation method thereof |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437404A (en) * | 2022-03-01 | 2022-05-06 | 浙江大学 | Preparation method of calcium alginate porous hydrogel |
| CN114437404B (en) * | 2022-03-01 | 2022-10-21 | 浙江大学 | Preparation method of calcium alginate porous hydrogel |
| CN115058039A (en) * | 2022-05-19 | 2022-09-16 | 珠海钛然科技有限公司 | Biomass-based transparent super-hydrophobic composite membrane and preparation method thereof |
| CN115058039B (en) * | 2022-05-19 | 2023-08-25 | 珠海钛然科技有限公司 | Biomass-based transparent super-hydrophobic composite membrane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jiang et al. | Superhydrophobic aerogel membrane with integrated functions of biopolymers for efficient oil/water separation | |
| CN107857893B (en) | Preparation method of oil absorption material with hierarchical pore structure | |
| CN110698722A (en) | Preparation method of oil-water separation type alginate aerogel with nano-micron gradient hierarchical pore structure | |
| Dong et al. | Biomass poplar catkin fiber-based superhydrophobic aerogel with tubular-lamellar interweaved neurons-like structure | |
| CN106853296A (en) | A kind of oil water separation type sodium alginate/graphene oxide composite aerogel and preparation method thereof | |
| CN107051377A (en) | It is a kind of to be used for synchronous nano composite material for removing carbon nitrogen phosphorus and preparation method thereof | |
| CN104804140A (en) | Water-retention and sand-fixing liquid mulching film and preparation method thereof | |
| CN108031447B (en) | Cellulose/silicon oxide composite aerogel elastomer, preparation method and application thereof in oil-water separation field | |
| CN105688871A (en) | Preparing method and application of dephosphorization adsorbent carrying nano particle foamed carbon particles | |
| CN106955671B (en) | Three-dimensional porous structure graphene oxide composite diatomite adsorption microspheres and preparation method | |
| CN104056607B (en) | A kind of Enteromorpha gel oil absorption material and preparation method thereof | |
| CN103111266B (en) | Preparation method of granular adsorbent for removing antibiotics in water, prepared adsorbent and application thereof | |
| CN103159891B (en) | Magnetic amino-modified superhighly-crosslinked resin and preparation method thereof | |
| CN102489268B (en) | Amine-modified fibrous emergent absorbing material and preparation method thereof | |
| CN102728328A (en) | Renewable asphalt mixture modifier for absorbing automobile exhaust and preparation method thereof | |
| CN104151600B (en) | Preparation method of super-hydrophobic magnetic sponge | |
| CN104017236A (en) | Preparation method of organic-inorganic hybrid super hydrophobic modified bacterial cellulose aerogel oil absorption material | |
| Jianliang et al. | Durable hydrophobic Enteromorpha design for controlling oil spills in marine environment prepared by organosilane modification for efficient oil-water separation | |
| CN104817413A (en) | Environment-friendly water-soil conserving soil modifier formula | |
| CN108905983A (en) | A kind of preparation method of the Beta-cyclodextrin-based material of sodium alginate-for handling intermetallic composite coating waste water | |
| Yin et al. | Resource recovery of Eichhornia crassipes as oil superabsorbent | |
| CN108794799A (en) | A kind of preparation method of porous absorption oil absorption material | |
| Chen et al. | Oleophilic pitch derived porous carbon loading with microbials for selective absorption and efficient degradation of petroleum pollutions | |
| CN105618006A (en) | Preparation method for straw hydrogel composite material special for sewage treatment | |
| Xu et al. | Lipophilic, nanocellulose based macroporous sponge loaded with mixed microorganisms for efficient elimination of petroleum hydrocarbon pollution in water |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200117 |
|
| WD01 | Invention patent application deemed withdrawn after publication |