CN108976468B - Hydrophobic modification method of sodium alginate sponge, product and application thereof - Google Patents
Hydrophobic modification method of sodium alginate sponge, product and application thereof Download PDFInfo
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 75
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 74
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 74
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 30
- 238000002715 modification method Methods 0.000 title claims abstract description 17
- 239000003921 oil Substances 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 53
- 235000019198 oils Nutrition 0.000 claims description 35
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 17
- 238000002791 soaking Methods 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 235000012424 soybean oil Nutrition 0.000 claims description 12
- 239000003549 soybean oil Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000003463 adsorbent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- 238000009736 wetting Methods 0.000 claims description 8
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 7
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- 239000000203 mixture Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims 1
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- 230000009286 beneficial effect Effects 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- -1 polysiloxane Polymers 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 229910021389 graphene Inorganic materials 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract description 2
- 239000003960 organic solvent Substances 0.000 abstract description 2
- 125000005375 organosiloxane group Chemical group 0.000 abstract description 2
- 229920001296 polysiloxane Polymers 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 241000243142 Porifera Species 0.000 description 110
- 229910052726 zirconium Inorganic materials 0.000 description 37
- 229910052708 sodium Inorganic materials 0.000 description 31
- 239000011734 sodium Substances 0.000 description 31
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 30
- 150000003385 sodium Chemical class 0.000 description 19
- 239000011575 calcium Substances 0.000 description 13
- 229910052791 calcium Inorganic materials 0.000 description 12
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- 229910001628 calcium chloride Inorganic materials 0.000 description 7
- 238000004108 freeze drying Methods 0.000 description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 4
- NPGIHFRTRXVWOY-UHFFFAOYSA-N Oil red O Chemical compound Cc1ccc(C)c(c1)N=Nc1cc(C)c(cc1C)N=Nc1c(O)ccc2ccccc12 NPGIHFRTRXVWOY-UHFFFAOYSA-N 0.000 description 4
- 229910006213 ZrOCl2 Inorganic materials 0.000 description 4
- 229910001424 calcium ion Inorganic materials 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 150000004676 glycans Chemical class 0.000 description 3
- 229920001282 polysaccharide Polymers 0.000 description 3
- 239000005017 polysaccharide Substances 0.000 description 3
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
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- 229960000907 methylthioninium chloride Drugs 0.000 description 2
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- 239000000758 substrate Substances 0.000 description 2
- AEMOLEFTQBMNLQ-AZLKCVHYSA-N (2r,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-AZLKCVHYSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-SYJWYVCOSA-N (2s,3s,4s,5s,6r)-3,4,5,6-tetrahydroxyoxane-2-carboxylic acid Chemical compound O[C@@H]1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@@H]1O AEMOLEFTQBMNLQ-SYJWYVCOSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241001346815 Spongia officinalis Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 229920001577 copolymer Polymers 0.000 description 1
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- 238000005265 energy consumption Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Images
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- 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
- 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
-
- 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
- B01J20/28042—Shaped bodies; Monolithic structures
- B01J20/28045—Honeycomb or cellular structures; Solid foams or sponges
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a hydrophobic modification method of sodium alginate sponge, and a product and application thereof. Compared with the method for performing hydrophobic modification on the sodium alginate sponge by using materials such as graphene, polysiloxane, organosiloxane and metal organic framework (the modifiers are high in price and toxic, complex in synthesis process and not beneficial to large-scale production and application), the porous sodium alginate sponge prepared by the method is simple in method, green and environment-friendly and easy to produce on a large scale. And sodium alginate is abundant in natural resources, can replace petroleum-based sponge, and solves the problem of lack of petroleum resources at present. And then, the hydrophobic three-dimensional porous sodium alginate sponge has a good adsorption effect on various oils or organic solvents, is easy to desorb and can be repeatedly recycled.
Description
Technical Field
The invention belongs to the technical field of adsorption separation materials, and particularly relates to a hydrophobic modification method of sodium alginate sponge, and a product and application thereof.
Background
At present, the discharge amount of oily sewage in petrochemical industry, textile industry, food industry, steel industry and the like is increasing day by day, and the frequent accidents of oil leakage cause long-term harm to human bodies, animals, plants and ecological environment. The one-dimensional oil absorption material is not easy to recover, and the adsorption capacity is low; the two-dimensional film material is easy to pollute, high in energy consumption and low in efficiency. At present, the widely used three-dimensional oil absorption material takes commercial sponge as a porous substrate, and the surface of the porous substrate is modified for oil-water separation. At present, petroleum resources are exhausted, but natural high molecular polysaccharide materials are abundant, so that the development of three-dimensional bio-based porous adsorption materials is urgently needed to solve the problems.
Sodium alginate is a natural polysaccharide which is low in price, non-toxic and easy to degrade, a chain of the natural polysaccharide contains sodium carboxylate and hydroxyl active groups, and three-dimensional porous sponge can be prepared through freeze drying and ionic crosslinking. However, the amphoteric sodium alginate-based sponge has high adsorption capacity for water and oil at the same time, and does not have the characteristic of oil-water selective separation. Therefore, a simple, efficient, cheap and environment-friendly modification method needs to be developed to perform hydrophobic modification on amphoteric sodium alginate sponge so as to achieve the purpose of oil-water separation.
Disclosure of Invention
This section is for the purpose of summarizing some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. In this section, as well as in the abstract and the title of the invention of this application, simplifications or omissions may be made to avoid obscuring the purpose of the section, the abstract and the title, and such simplifications or omissions are not intended to limit the scope of the invention.
The present invention has been made in view of the above-mentioned technical drawbacks.
Therefore, as one aspect of the invention, the invention overcomes the defects in the prior art and provides a method for hydrophobically modifying sodium alginate sponge.
In order to solve the technical problems, the invention provides the following technical scheme: a hydrophobic modification method of sodium alginate sponge comprises the steps of firstly soaking the sodium alginate sponge in a calcium ion solution and then soaking the sodium alginate sponge in a zirconium ion solution to obtain the modified sodium alginate sponge.
As a preferred scheme of the hydrophobic modification method of the sodium alginate sponge, the method comprises the following steps: the sodium alginate sponge is prepared by dissolving 1g sodium alginate solution in 25mL water, pouring the solution into 1.0 × 1.0 × 1.0cm3And (4) preparing the module.
As a preferred scheme of the hydrophobic modification method of the sodium alginate sponge, the method comprises the following steps: the zirconium ions comprise zirconium oxychloride, and are soaked in the zirconium ion solution for 2-8 hours.
As a preferred scheme of the hydrophobic modification method of the sodium alginate sponge, the method comprises the following steps: the concentration of the zirconium oxychloride is 1 wt% -5 wt%.
As a preferred scheme of the hydrophobic modification method of the sodium alginate sponge, the method comprises the following steps: the calcium ions comprise calcium chloride, and the concentration of the calcium chloride is 1-5 wt%.
As a preferred scheme of the hydrophobic modification method of the sodium alginate sponge, the method comprises the following steps: and soaking in a calcium ion solution for 2-8 h.
As a preferred scheme of the hydrophobic modification method of the sodium alginate sponge, the method comprises the following steps: soaking in a zirconium ion solution, washing and drying to obtain modified sodium alginate sponge; and drying at the temperature of 60-100 ℃.
As another aspect of the invention, the invention overcomes the defects in the prior art and provides the sodium alginate sponge obtained by the hydrophobic modification method of the sodium alginate sponge.
In order to solve the technical problems, the invention provides the following technical scheme: the sodium alginate sponge is obtained by a hydrophobic modification method of the sodium alginate sponge, wherein the water wetting angle of the sodium alginate sponge is 138.2-143.8 degrees, and the porosity is 81.8 percent.
As another aspect of the invention, the invention overcomes the defects in the prior art and provides the application of the sodium alginate sponge as an oil adsorbent or an oil-water separation material.
In order to solve the technical problems, the invention provides the following technical scheme: the sodium alginate sponge is applied as an oil adsorbent or an oil-water separation material.
As a preferred scheme of the application of the sodium alginate sponge as an oil adsorbent or an oil-water separation material, the sodium alginate sponge comprises the following steps: the oil adsorbent comprises oil, oil and an oil water adsorbent, wherein the oil comprises one or more of n-hexane, cyclohexane, toluene, acetone, paraffin oil, soybean oil, chloroform, dimethylformamide, carbon tetrachloride or ethanol, and the oil comprises one or more of n-hexane, cyclohexane, toluene, acetone, paraffin oil, soybean oil, chloroform, dimethylformamide, carbon tetrachloride or ethanol.
The invention has the beneficial effects that: the sodium alginate-calcium-zirconium sponge has a three-dimensional porous structure, and the hydrophobic modification method is simple, cheap, environment-friendly, easy to operate and capable of realizing large-scale production; the modified sodium alginate-calcium-zirconium sponge has higher hydrophobicity and lipophilicity and can be used for oil-water separation; the modified sodium alginate-calcium-zirconium sponge has high porosity, and is favorable for the sponge to directly adsorb various oils and organic pollutants; the modified sodium alginate-calcium-zirconium sponge has good stability and durability; the modified sodium alginate-calcium-zirconium sponge has high plasticity, can be made into sponges with different sizes and shapes according to requirements, and can also be used as a hydrophobic coating to be suitable for various occasions.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is an apparent morphology chart of sodium alginate before and after modification in example 1.
FIG. 2 is a graph showing the oil-water adsorption properties of sodium alginate sponge before and after modification in example 1.
FIG. 3 is an SEM image of example 1 on a sodium alginate sponge before modification.
FIG. 4 is a diagram showing the application of the modified sodium alginate-calcium-zirconium sponge in oil-water separation in example 1.
FIG. 5 is a graph showing the hydrophobic and oleophilic nature of the modified sodium alginate-calcium-zirconium sponge of example 8.
FIG. 6 is a graph showing the hydrophobic and oleophilic nature of the modified sodium alginate-zirconium sponge of example 9.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Furthermore, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment is included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1:
1g of sodium alginate was dissolved in 25mL of water, and the solution was poured into 1.0X 1.0cm3Preparing sodium alginate sponge in the module, soaking 1g of sodium alginate sponge in 200mL of 5 wt% CaCl2Preparing sodium alginate-calcium sponge after being put in the solution for 4 hours, washing and soaking in 200mL of 3 wt% ZrOCl2·8H20 solution for 4 hours, washing, freeze-drying and drying at 80 ℃ to obtain the sodium alginate-calcium-zirconium sponge.
The water wetting angle of the modified sodium alginate sponge, sodium alginate-calcium-zirconium sponge, is 138.2-143.8 degrees. The porosity of sodium alginate-calcium-zirconium is 81.8%.
The surface observation of the hydrophobic and oleophilic properties before and after modification is shown in fig. 2. FIG. 2 is the observation of oil and water adsorption of sodium alginate sponge before and after modification in example 1, wherein, FIG. 2(a) is sodium alginate-calcium sponge before modification, on the surface of which water and soybean oil are dropped, for the convenience of observation, wherein, the water is dyed by methylene blue solution, the soybean oil is dyed by oil red O (the same below), and the soybean oil and the water are both infiltrated into the sponge, which represents the hydrophilic oleophylic property of the unmodified sodium alginate-calcium sponge; FIG. 2(b) shows that the outer surface of the modified sodium alginate-calcium-zirconium sponge is hydrophobic and oleophilic, water drops do not penetrate into the sponge and are spherical on the surface, and oil drops are adsorbed by the sponge; fig. 2(c) shows the hydrophobicity and lipophilicity inside the modified sodium alginate-calcium-zirconium sponge, oil drops are adsorbed, and the water drops are spherical on the surface of the sponge, which explains the uniformity of the hydrophobicity modification of the sodium alginate-calcium-zirconium sponge; FIG. 2(d) is a water wetting angle test, with observable drops in spherical form and water wetting angles of 138.2 ° -143.8 °; FIG. 2(e) shows that the modified sodium alginate-calcium-zirconium sponge can float on the water surface and the sodium alginate-calcium sponge before modification sinks under the water surface; FIG. 2(f) shows the mirror image phenomenon (a large number of bubbles gather on the surface) of the modified sodium alginate-calcium-zirconium sponge after being immersed in water; in addition, the sodium alginate-zirconium sponge is hydrophobic and oleophilic, and the water wetting angle is 138.2-143.8 degrees.
The molecular formula of sodium alginate is a copolymer consisting of beta-D-mannuronic acid (M unit) and alpha-L-guluronic acid (G unit), and units of-GMGMGM, -MMM-and-GGGGG-in different proportions. When the sodium alginate sponge is soaked in calcium chloride solution, the groups-COONa and Ca in the chain segment-GGGGG-unit of the sodium alginate2+The water-insoluble sodium alginate-calcium sponge is prepared by the cross-linking reaction of ion exchange. Soaking in ZrOCl2·8H2In O solution, Zr4+Cross-linking with a group-COONa in the M unit, Ca2+And Zr4+Oxygen-containing groups (-COONa and-OH) in the sodium alginate are consumed under the synergistic effect, the hydrophobicity is improved, and the sodium alginate sponge structure is porous and fluffy, is beneficial to adsorption and has excellent adsorption performance.
Example 2:
taking n-hexane as an example, the sample sodium alginate-calcium-zirconium sponge in the example 1 is soaked in the n-hexane for 1 to 2 minutes, then taken out and weighed, and the initial mass is the oil absorption of the sample according to the calculation of the oil absorption by the mass difference before and after oil absorption. After each oil absorption, the mixture is gently squeezed for a plurality of times, eluted by ethanol and dried at 80 ℃ for later use. The adsorption capacity of the first five times is respectively 10.21, 7.3, 7.1, 6.5 and 6.9g/g, and excellent recycling performance is shown.
Taking chloroform as an example, the sample sodium alginate-calcium-zirconium sponge in the example 1 is soaked in chloroform for 1-2 minutes, then is taken out and weighed, and the oil absorption is calculated by comparing the mass difference before and after oil absorption with the initial mass, namely the oil absorption of the sample. After each oil absorption, the mixture is gently squeezed for a plurality of times, eluted by ethanol and dried at 80 ℃ for later use. The adsorption capacity of the first five times is 25.3, 19.6, 15.9, 13 and 11.9g/g respectively, and excellent recycling performance is shown.
Example 3:
the modified sodium alginate-calcium-zirconium sponge was tested for its application in oil-water separation, using light oil soybean oil/water as an example (fig. 4 a). For convenient observation, the soybean oil was stained with oil red O, and the sample sodium alginate-calcium-zirconium sponge of example 1 was placed on the water surface containing oil stains, and the oil slick on the water surface was completely removed in only 30 seconds from the start to the end of the adsorption. Exhibit excellent oil-water separation performance.
The modified sodium alginate-calcium-zirconium sponge was tested for its use in oil-water separation (fig. 4b), using heavy oil chloroform/water as an example. To facilitate observation of chloroform stained with oil red O, the sample sodium alginate-calcium-zirconium sponge of example 1 was immersed in the water bottom with tweezers, and it took only 10 seconds from the start to the end of adsorption to completely remove oil droplets from the water bottom. Exhibit excellent oil-water separation performance.
Example 4:
the sample sodium alginate-calcium-zirconium sponge in example 1 was soaked in toluene and chloroform solution for 10 days, washed with ethanol and dried, and the water wetting angle was measured to be 128-.
Example 5:
1g of sodium alginate solution is dissolved in 25mL of water and the solution is poured into 1.0X 1.0cm3Preparing sodium alginate sponge in the module, soaking 1g of sodium alginate sponge in 200mL of 1 wt% CaCl2Preparing sodium alginate-calcium sponge after being put in the solution for 4 hours, washing and soaking in 200mL of 5 wt% ZrOCl2·8H20 solution for 4 hours, washing, freeze-drying and drying at 80 ℃ to obtain the sodium alginate-calcium-zirconium sponge.
Example 6:
mixing 1g sodium alginateThe solution was dissolved in 25mL of water, and the solution was poured into 1.0X 1.0cm3Preparing sodium alginate sponge in the module, soaking 1g of sodium alginate sponge in 200mL of 3 wt% CaCl2Preparing sodium alginate-calcium sponge after being put in the solution for 4 hours, washing and soaking in 200mL of 1 wt% ZrOCl2·8H20 solution for 4 hours, washing, freeze-drying and drying at 80 ℃ to obtain the sodium alginate-calcium-zirconium sponge.
Example 7:
1g of sodium alginate solution is dissolved in 25mL of water and the solution is poured into 1.0X 1.0cm3Preparing sodium alginate sponge in the module, soaking 1g of sodium alginate sponge in 200mL of 5 wt% CaCl2And (3) preparing the sodium alginate-calcium sponge after the solution is put for 4 hours, washing, freeze-drying and drying at the temperature of 80 ℃ to prepare the sodium alginate-calcium sponge.
Fig. 1 is an apparent morphology of sodium alginate before and after modification in example 1, and an unmodified sodium alginate sponge negative control, sodium alginate-calcium sponge prepared in example 7, and sodium alginate-calcium-zirconium sponge prepared in example 1 are sequentially arranged from left to right, wherein the porosity of the sodium alginate-calcium-zirconium in example 1 is 81.8%, and the water wetting angle is 138.2 ° to 143.8 °.
Fig. 3 is SEM observations of example 1 on sodium alginate sponge before modification, where fig. 3(a) and 3(d) are SEM morphologies of unmodified sodium alginate sponge, (b) and (e) are sodium alginate-calcium sponge, and (c) and (f) are SEM morphologies of sodium alginate-calcium-zirconium sponge. The modified sodium alginate sponge still maintains the porous structure, but the surface becomes rougher (f).
Example 8:
1g of sodium alginate solution is dissolved in 25mL of water and the solution is poured into 1.0X 1.0cm3Preparing sodium alginate sponge in the module, soaking 1g of sodium alginate sponge in 200mL of 5 wt% CaCl2The sodium alginate-calcium sponge is prepared after being put in the solution for 4 hours, and is soaked in 200mL of 3wt percent ZrO after being washed2And (4) soaking in the solution for 4 hours, washing, freeze-drying, and drying at 80 ℃ to obtain the sodium alginate-calcium-zirconium sponge.
The hydrophobic and oleophilic property of the modified sodium alginate sponge in the embodiment is observed on the surface, and the experimental result is shown in figure 5. Fig. 5 shows the modified sodium alginate-calcium-zirconium sponge of this example, on the surface of which water and soybean oil are dropped, for easy observation, wherein the water is dyed with methylene blue solution, the soybean oil is dyed with oil red O, and both the soybean oil and the water penetrate into the sodium alginate sponge, which represents that the modified sodium alginate composite sponge is hydrophilic and oleophilic and has no oil-water separation characteristic.
Example 9:
1g of sodium alginate solution is dissolved in 25mL of water and the solution is poured into 1.0X 1.0cm3Preparing sodium alginate sponge in the module, soaking 1g of sodium alginate sponge in 200mL of 3 wt% ZrO2In the solution, the experimental results are shown in fig. 6, and sodium alginate is dissolved after a period of time (1 hour), so that hydrophobic modification cannot be carried out.
In conclusion, the sodium alginate-calcium-zirconium sponge has a three-dimensional porous structure, and the hydrophobic modification method is simple, cheap, environment-friendly, easy to operate and capable of realizing large-scale production; the modified sodium alginate-calcium-zirconium sponge has higher hydrophobicity and lipophilicity and can be used for oil-water separation; the modified sodium alginate-calcium-zirconium sponge has high porosity, and is favorable for the sponge to directly adsorb various oils and organic pollutants; the modified sodium alginate-calcium-zirconium sponge has good stability and durability; the modified sodium alginate-calcium-zirconium sponge has high plasticity, can be made into sponges with different sizes and shapes according to requirements, and can also be used as a hydrophobic coating to be suitable for various occasions.
Compared with the method for performing hydrophobic modification on the sodium alginate sponge by using materials such as graphene, polysiloxane, organosiloxane and metal organic framework (the modifiers are high in price and toxic, complex in synthesis process and not beneficial to large-scale production and application), the porous sodium alginate sponge prepared by the method is simple in method, green and environment-friendly and easy to produce on a large scale. And sodium alginate is abundant in natural resources, can replace petroleum-based sponge, and solves the problem of lack of petroleum resources at present. And then, the hydrophobic three-dimensional porous sodium alginate sponge has a good adsorption effect on various oils or organic solvents, is easy to desorb and can be repeatedly recycled.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (5)
1. A hydrophobic modification method of sodium alginate sponge is characterized in that: comprises the steps of (a) preparing a mixture of a plurality of raw materials,
soaking sodium alginate sponge in 1-5 wt% calcium chloride solution for 4 hr, soaking in 1-5 wt% zirconium oxychloride solution for 4 hr, washing and stoving to obtain modified sodium alginate sponge;
and drying at the temperature of 60-100 ℃.
2. The method for hydrophobically modifying sodium alginate sponge as claimed in claim 1, wherein: the sodium alginate sponge is prepared by dissolving 1g sodium alginate solution in 25mL water, pouring the solution into 1.0 × 1.0 × 1.0cm3And (4) preparing the module.
3. The sodium alginate sponge obtained by the method for hydrophobically modifying the sodium alginate sponge as claimed in claim 1 or 2, wherein: the water wetting angle of the sodium alginate sponge is 138.2-143.8 degrees, and the porosity is 81.8 percent.
4. Use of the sodium alginate sponge of claim 3 as an oil adsorbent or oil-water separation material.
5. The use of claim 4, wherein: the oil adsorbent is characterized in that the oil adsorbent comprises one or more of n-hexane, cyclohexane, toluene, acetone, paraffin oil, soybean oil, chloroform, dimethylformamide, carbon tetrachloride or ethanol; the oil-water separation material is characterized in that the oil comprises one or more of n-hexane, cyclohexane, toluene, acetone, paraffin oil, soybean oil, chloroform, dimethylformamide, carbon tetrachloride or ethanol.
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