CN113698659A - Palygorskite-double-network gel sponge with oil repellency and water absorption functions as well as preparation method and application thereof - Google Patents
Palygorskite-double-network gel sponge with oil repellency and water absorption functions as well as preparation method and application thereof Download PDFInfo
- Publication number
- CN113698659A CN113698659A CN202110998671.1A CN202110998671A CN113698659A CN 113698659 A CN113698659 A CN 113698659A CN 202110998671 A CN202110998671 A CN 202110998671A CN 113698659 A CN113698659 A CN 113698659A
- Authority
- CN
- China
- Prior art keywords
- palygorskite
- water
- dispersion liquid
- oil
- modified
- 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.)
- Granted
Links
Images
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
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
- C08J9/286—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/12—Naturally occurring clays or bleaching earth
-
- 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
-
- 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
- B01J20/28047—Gels
-
- 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
- C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
-
- 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
- C08J9/009—Use of pretreated compounding ingredients
-
- 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
- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/24—Homopolymers or copolymers of amides or imides
- C08J2333/26—Homopolymers or copolymers of acrylamide or methacrylamide
-
- 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
- C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
- C08J2405/04—Alginic acid; Derivatives thereof
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/20—Controlling water pollution; Waste water treatment
- Y02A20/204—Keeping clear the surface of open water from oil spills
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses an oil-repellent water-absorbent palygorskite-double-network gel sponge, a preparation method and application thereof, wherein polyacrylamide hydrochloride solution and palygorskite dispersion liquid are mixed and centrifugally dried to obtain polyacrylamide modified palygorskite powder; uniformly dispersing polyacrylamide modified palygorskite powder in water to obtain polyacrylamide modified palygorskite dispersion liquid; mixing and reacting the polyacrylamide modified palygorskite dispersion liquid with a sodium perfluorooctanoate solution, and performing centrifugal drying treatment to obtain modified palygorskite powder; uniformly dispersing modified palygorskite powder in water to obtain modified palygorskite dispersion liquid; adding acrylamide and sodium alginate into the modified palygorskite dispersion liquid, adding potassium persulfate and N, N' -methylene-bis-lactam after dissolving, adding tetramethylethylenediamine after dissolving, and stirring until the solution is converted into gel; and (3) soaking the gel in a calcium chloride solution, and performing freeze drying treatment to obtain the palygorskite-double-network gel sponge. The invention can realize the purification treatment of oil substances.
Description
Technical Field
The invention belongs to the technical field of oil-water separation, and particularly relates to an oil-repellent and water-absorbent palygorskite-double-network gel sponge, and a preparation method and application thereof.
Background
The presence of water in the oil-like substance often causes adverse effects. For example, in production and life, edible oil can be deteriorated rapidly when meeting water; in oil production, the presence of water in the oil will reduce the quality of the oil; the organic solvent contains water, which may cause failure of the chemical reaction or decrease in the purity of the product. Therefore, it is very necessary to remove the moisture in the oil-based materials to the maximum extent.
The water exists in oil substances mainly in the form of physical blending and water-in-oil emulsion. When the moisture exists in the oil substances in a simple physical blending mode, the two can be separated in a liquid separation mode to achieve the purpose of coarse separation. Further reduction of the water content requires the use of a desiccant or distillation. For the emulsion, the oil-water separation is usually carried out by oscillation, electric separation, or the like. Both methods have the problems of higher separation cost, higher separation difficulty and poorer separation effect.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an oil-repellent water-absorbent palygorskite-double-network gel sponge, a preparation method and application thereof, which can quickly and efficiently separate an emulsion type oil-water mixture containing a small amount of water or adsorb a small amount of water in oil substances without additional energy, thereby realizing the purification treatment of the oil substances.
In order to solve the technical problems, the invention is realized by the following technical scheme:
a preparation method of the paligorskite-double-network gel sponge with oil repellency and water absorption comprises the following steps:
mixing a polyacrylamide hydrochloride solution with a palygorskite dispersion liquid, centrifuging, and drying a centrifuged precipitate to obtain polyacrylamide modified palygorskite powder;
uniformly dispersing the polyacrylamide modified palygorskite powder in water to obtain a polyacrylamide modified palygorskite dispersion liquid;
mixing and reacting the polyacrylamide modified palygorskite dispersion liquid with a sodium perfluorooctanoate solution, centrifuging, and drying the centrifuged precipitate to obtain modified palygorskite powder;
uniformly dispersing the modified palygorskite powder in water to obtain a modified palygorskite dispersion liquid;
adding acrylamide and sodium alginate into the modified palygorskite dispersion liquid, adding potassium persulfate and N, N' -methylene-bis-lactam after the modified palygorskite dispersion liquid is fully dissolved, adding tetramethylethylenediamine after the modified palygorskite dispersion liquid is fully dissolved, and stirring until the solution is converted into gel;
and (3) soaking the gel in a calcium chloride solution for a certain time, and then carrying out freeze drying treatment on the soaked gel to obtain the palygorskite-double-network gel sponge.
Further, the mass concentration of the polyacrylamide hydrochloride solution is 2.5-5 mg/mL, and the mass fraction of the palygorskite dispersion liquid is 1-3 wt%.
Further, the mass fraction of the polyacrylamide modified palygorskite dispersion liquid is 1.5 wt% -3 wt%.
Furthermore, the molar concentration of the sodium perfluorooctanoate solution is 0.1-0.5 mol/L.
Further, the modified palygorskite dispersion liquid is 2-5 wt% in mass fraction.
Further, the mass fraction of the acrylamide is 3 wt% -6 wt%, the mass fraction of the sodium alginate is 0.3 wt% -1.0 wt%, the mass fraction of the potassium persulfate is 0.04 wt% -0.08 wt%, the mass fraction of the N, N' -methylene-bis-lactam is 0.03 wt% -0.06 wt%, and the adding amount of the tetramethyl-ethylenediamine is 0.62 mg/mL-1.55 mg/mL.
Further, the mass fraction of the calcium chloride solution is 0.3 wt% to 0.5 wt%.
Further, the soaking time is 12-24 h, and the freeze-drying time is 24-48 h.
An oil-repellent and water-absorbent palygorskite-double-network gel sponge prepared by the preparation method.
An application of paligorskite-double-network gel sponge as membrane separating material for oil-water separation and water adsorbent for removing water from oil substances is disclosed.
Compared with the prior art, the invention has at least the following beneficial effects:
the principle of oil repellency and water absorption of the prepared palygorskite-double-network gel sponge comprises the following steps: the palygorskite is natural nano mineral clay with larger specific surface area, the surface of the palygorskite is rich in negative charges, the polyacrylamide is a common cationic polymer, and the surface of the palygorskite firstly adsorbs the polyacrylamide and then adsorbs perfluoro caprylic acid groups with negative charges by utilizing the adsorption effect of the charges twice, namely the surface of the palygorskite is provided with a charge layer and fluorine-containing oil repellent groups. The electrostatic layer is used for adsorbing water molecules, when the modified palygorskite is contacted with oil, nonpolar oil molecules are blocked by fluorine-containing groups with low surface energy, and water molecules with polarity can penetrate through the fluorine-containing layer and be adsorbed on the surface of the palygorskite under the action of the electrostatic layer. And the polyacrylamide and the sodium alginate are hydrophilic polymers, and when water molecules are captured by the palygorskite, the water molecules are absorbed by the acrylamide and the sodium alginate and stored in a polymer network, so that the water is prevented from reentering the oil.
In order to make the aforementioned and other objects, features and advantages of the present invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is the reaction principle of modified palygorskite in the preparation method of oil-repellent and water-absorbent palygorskite-double-network gel sponge of the invention.
FIG. 2 is a graph showing the change before and after application of an oil-repellent, water-absorbent palygorskite-double network gel sponge in example 1 in aqueous hexadecane.
FIGS. 3a and 3b are optical micrographs of the mixed solution before and after the water adsorption removal in the water-in-toluene emulsion using the prepared palygorskite-double network gel sponge having oil-repellent and water-absorbent properties in example 5.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As a specific embodiment of the present invention, a method for preparing an oil-repellent and water-absorbent palygorskite-double-network gel sponge specifically comprises the following steps:
step 1: grinding and sieving palygorskite raw stones serving as raw materials, dispersing a certain amount of palygorskite powder in water, purifying with sulfuric acid, centrifuging the dispersion liquid, and drying the centrifuged precipitate to obtain purified palygorskite powder;
preferably, the centrifugal speed is 3500rpm to 5000 rpm.
Step 2: dissolving a certain amount of polyacrylamide hydrochloride in water to prepare a polyacrylamide hydrochloride solution for later use;
preferably, the mass concentration of the polyacrylamide hydrochloride solution is 2.5 mg/mL-5 mg/mL.
And step 3: dispersing the purified palygorskite powder obtained in the step 1 in water, stirring and carrying out ultrasonic treatment until the purified palygorskite powder is uniformly dispersed to obtain a palygorskite dispersion liquid, adding the polyacrylamide hydrochloride solution obtained in the step 2 into the palygorskite dispersion liquid, carrying out centrifugal cleaning after uniform stirring, and drying the centrifuged precipitate to obtain powder named as polyallylamine modified palygorskite powder;
preferably, the mass fraction of the palygorskite dispersion liquid is 1 wt% -3 wt%, and the centrifugal rotation speed is 3500 rpm-5000 rpm.
And 4, step 4: dissolving a certain amount of perfluorooctanoic acid in a sodium hydroxide solution, and stirring until the solution is clear and transparent for later use, namely, a sodium perfluorooctanoate solution;
preferably, the molar concentration of the sodium perfluorooctanoate solution is 0.1mol/L to 0.5 mol/L.
And 5: dispersing the polyacrylamide modified palygorskite powder obtained in the step (3) in water, uniformly stirring to obtain a polyacrylamide modified palygorskite dispersion liquid, adding the sodium perfluorooctanoate solution obtained in the step (4) into the polyacrylamide modified palygorskite dispersion liquid, stirring until precipitation occurs, centrifugally cleaning, drying the centrifuged precipitate for later use, and naming the obtained powder as modified palygorskite;
preferably, the mass fraction of the polyacrylamide modified palygorskite dispersion liquid is 1.5 wt% -3 wt%, and the centrifugal rotating speed is 4000 rpm-6000 rpm.
Step 6: dispersing the modified palygorskite obtained in the step 5 in water to obtain a modified palygorskite dispersion liquid, then adding a certain amount of acrylamide and sodium alginate, after fully dissolving, adding a certain amount of potassium persulfate and N, N' -methylene-bis-lactam, continuously stirring and dissolving, dropwise adding a small amount of tetramethylethylenediamine, stirring until the solution is converted into gel, soaking the shaped gel in a calcium chloride solution for several hours, and freezing and vacuum drying the soaked gel by using a freeze dryer to obtain the palygorskite-double-network gel sponge.
Preferably, the modified palygorskite dispersion liquid is 2-5 wt%, the sodium alginate is 0.3-1.0 wt%, the acrylamide is 3-6 wt%, the potassium persulfate is 0.04-0.08 wt%, the N, N' -methylene-bis-lactam is 0.03-0.06 wt%, the tetramethylethylenediamine is 0.62-1.55 mg/mL, the centrifugal speed is 4000-6000 rpm, the calcium chloride solution is 0.3-0.5 wt%, the soaking time is 12-24 h, and the freeze-drying time is 24-48 h.
The palygorskite-double-network gel sponge material with the oil repellency and water absorption properties prepared by the preparation method of the palygorskite-double-network gel sponge material is used as an adsorbent and a membrane separation intermediate layer for oil-water separation, and the specific application method is as follows:
direct adsorption of small, non-emulsified water droplets at the bottom of the oil mass: the palygorskite-double-network gel sponge material with oil repelling and water absorbing properties can directly adsorb and remove water drops in oil substances through an oil layer.
Performing water removal and separation on the water-in-oil emulsion as a filter layer: palygorskite-double-network gel sponge material with oil-repelling and water-absorbing properties is filled in a filter column, then water-in-oil emulsion is poured from top to bottom, a filter layer adsorbs water in the water-in-oil emulsion, oil in the water-in-oil emulsion penetrates through the filter layer under the action of gravity, oil-water separation is realized, and trace moisture in the water-in-oil emulsion is removed. Preferably, the thickness of the filter membrane is 5mm to 10 mm.
Example 1:
a preparation method of the paligorskite-double-network gel sponge with oil repellency and water absorption comprises the following steps:
step 1: grinding and sieving palygorskite raw stones serving as raw materials, dispersing a certain amount of palygorskite powder in water, purifying with sulfuric acid, centrifuging the dispersion liquid, and drying the centrifuged precipitate to obtain purified palygorskite powder, wherein the centrifugation speed is 3500 rpm;
step 2: dissolving a certain amount of polyacrylamide hydrochloride in water to prepare a polyacrylamide hydrochloride solution for later use, wherein the mass concentration of the polyacrylamide hydrochloride solution is 2.5 mg/mL;
and step 3: dispersing the purified palygorskite powder obtained in the step 1 in water, stirring and ultrasonically treating until the palygorskite powder is uniformly dispersed to obtain a palygorskite dispersion liquid, wherein the mass fraction of the palygorskite dispersion liquid is 3 wt%; adding the polyacrylamide hydrochloride solution obtained in the step (2) into the palygorskite dispersion liquid, stirring uniformly, then carrying out centrifugal cleaning, drying the precipitate after centrifugation, and naming the obtained powder as polyacrylamide modified palygorskite powder, wherein the centrifugal speed is 4000 rpm;
and 4, step 4: dissolving a certain amount of perfluorooctanoic acid in a sodium hydroxide solution, stirring until the solution is clear and transparent for later use, and naming the solution as a sodium perfluorooctanoate solution, wherein the molar concentration of the sodium perfluorooctanoate solution is 0.5 mol/L;
and 5: dispersing the polyacrylamide modified palygorskite powder obtained in the step (3) in water, uniformly stirring to obtain a polyacrylamide modified palygorskite dispersion liquid, adding the sodium perfluorooctanoate solution obtained in the step (4) into the polyacrylamide modified palygorskite dispersion liquid, stirring until precipitation occurs, centrifugally cleaning, drying the centrifuged precipitate for later use, and naming the obtained powder as modified palygorskite;
wherein the mass fraction of the polyacrylamide modified palygorskite dispersion liquid is 1.5 wt%, the centrifugal speed is 4000rpm, and the modification mechanism is shown in figure 1.
Step 6: dispersing the modified palygorskite obtained in the step 5 in water to obtain a modified palygorskite dispersion liquid, then adding a certain amount of acrylamide and sodium alginate, after fully dissolving, adding a certain amount of potassium persulfate and N, N' -methylene-bis-lactam, continuously stirring and dissolving, dropwise adding a small amount of tetramethylethylenediamine, stirring until the solution is converted into gel, soaking the shaped gel in a calcium chloride solution for several hours, and freezing and vacuum drying the soaked gel by using a freeze dryer to obtain the palygorskite-double-network gel sponge.
The modified palygorskite dispersion liquid comprises, by mass, 5% of modified palygorskite dispersion liquid, 0.3% of sodium alginate, 3% of acrylamide, 0.08% of potassium persulfate, 0.04% of N, N' -methylene-bis-lactam, 0.93mg/mL of tetramethylethylenediamine, 6000rpm of centrifugal rotation speed, 0.5% of calcium chloride solution, 24 hours of soaking time and 24 hours of freeze drying time.
The palygorskite-double-network gel sponge material with the oil-repellent and water-absorbent properties prepared by the embodiment is used for carrying out water removal treatment on hydrous hexadecane, and the specific steps are as follows:
respectively adding 10mL of hexadecane, toluene and chloroform into a culture dish, and then dropwise adding 0.5mL of methyl blue dyeing water into the culture dish;
the palygorskite-double-network gel sponge material is stretched into hexadecane liquid by using forceps, the blue water drops are contacted for 20s, then the water drops are completely absorbed, and then the water content in the oil is tested, and the absorption efficiency is calculated, so that the result is shown in figure 2.
The aqueous hexadecane, toluene and chloroform treated in this example had no visible water droplets and maintained high separation efficiency. Therefore, the surface of the gel sponge is not polluted by three oils to lose the effect, a large amount of water is absorbed by the palygorskite-double-network gel sponge, the gel sponge is not broken, and no water overflows to cause secondary pollution.
Example 2:
a preparation method of the paligorskite-double-network gel sponge with oil repellency and water absorption comprises the following steps:
step 1: grinding and sieving raw palygorskite serving as a raw material, dispersing a certain amount of palygorskite powder in water, purifying with sulfuric acid, centrifuging the dispersion liquid, and drying the centrifuged precipitate to obtain purified palygorskite powder, wherein the centrifugation speed is 4000 rpm;
step 2: dissolving a certain amount of polyacrylamide hydrochloride in water to prepare a polyacrylamide hydrochloride solution for later use, wherein the mass concentration of the polyacrylamide hydrochloride solution is 3 mg/mL;
and step 3: dispersing the purified palygorskite powder obtained in the step 1 in water, stirring and ultrasonically treating until the palygorskite powder is uniformly dispersed to obtain a palygorskite dispersion liquid, wherein the mass fraction of the palygorskite dispersion liquid is 3 wt%; adding the polyacrylamide hydrochloride solution obtained in the step (2) into the palygorskite dispersion liquid, stirring uniformly, then carrying out centrifugal cleaning, drying the precipitate after centrifugation, and naming the obtained powder as polyacrylamide modified palygorskite powder, wherein the centrifugation speed is 4500 rpm;
and 4, step 4: dissolving a certain amount of perfluorooctanoic acid in a sodium hydroxide solution, stirring until the solution is clear and transparent for later use, and naming the solution as a sodium perfluorooctanoate solution, wherein the molar concentration of the sodium perfluorooctanoate solution is 0.4 mol/L;
and 5: dispersing the polyacrylamide modified palygorskite powder obtained in the step (3) in water, uniformly stirring to obtain a polyacrylamide modified palygorskite dispersion liquid, adding the sodium perfluorooctanoate solution obtained in the step (4) into the polyacrylamide modified palygorskite dispersion liquid, stirring until precipitation occurs, centrifugally cleaning, drying the centrifuged precipitate for later use, and naming the obtained powder as modified palygorskite;
wherein the mass fraction of the polyacrylamide modified palygorskite dispersion liquid is 2 wt%, and the centrifugal speed is 4500 rpm.
Step 6: dispersing the modified palygorskite obtained in the step 5 in water to obtain a modified palygorskite dispersion liquid, then adding a certain amount of acrylamide and sodium alginate, after fully dissolving, adding a certain amount of potassium persulfate and N, N' -methylene-bis-lactam, continuously stirring and dissolving, dropwise adding a small amount of tetramethylethylenediamine, stirring until the solution is converted into gel, soaking the shaped gel in a calcium chloride solution for several hours, and freezing and vacuum drying the soaked gel by using a freeze dryer to obtain the palygorskite-double-network gel sponge.
The modified palygorskite dispersion liquid comprises, by mass, 4% of modified palygorskite dispersion liquid, 0.5% of sodium alginate, 3.5% of acrylamide, 0.07% of potassium persulfate, 0.05% of N, N' -methylene-bis-lactam, 1.24mg/mL of tetramethylethylenediamine, 5000rpm of centrifugal speed, 0.5% of calcium chloride solution, 24 hours of soaking and 36 hours of freeze-drying.
The paligorskite-double network gel sponge material with the oil-repellent and water-absorbent properties prepared in the embodiment is used for carrying out water removal treatment on the water-containing toluene.
Example 3:
a preparation method of palygorskite-double-network gel sponge material with oil-repellent and water-absorbent properties comprises the following steps:
step 1: grinding and sieving palygorskite raw stones serving as raw materials, dispersing a certain amount of palygorskite powder in water, purifying with sulfuric acid, centrifuging the dispersion liquid, and drying the centrifuged precipitate to obtain purified palygorskite powder, wherein the centrifugation speed is 5000 rpm;
step 2: dissolving a certain amount of polyacrylamide hydrochloride in water to prepare a polyacrylamide hydrochloride solution for later use, wherein the mass concentration of the polyacrylamide hydrochloride solution is 3.5 mg/mL;
and step 3: dispersing the purified palygorskite powder obtained in the step 1 in water, stirring and ultrasonically treating until the palygorskite powder is uniformly dispersed to obtain a palygorskite dispersion liquid, wherein the mass fraction of the palygorskite dispersion liquid is 2%; adding the polyacrylamide hydrochloride solution obtained in the step (2) into the palygorskite dispersion liquid, stirring uniformly, then carrying out centrifugal cleaning, drying the precipitate after centrifugation, and naming the obtained powder as polyacrylamide modified palygorskite powder, wherein the centrifugal speed is 5000 rpm;
and 4, step 4: dissolving a certain amount of perfluorooctanoic acid in a sodium hydroxide solution, stirring until the solution is clear and transparent for later use, and naming the solution as a sodium perfluorooctanoate solution, wherein the molar concentration of the sodium perfluorooctanoate solution is 0.3 mol/L;
and 5: dispersing the polyacrylamide modified palygorskite powder obtained in the step (3) in water, uniformly stirring to obtain a polyacrylamide modified palygorskite dispersion liquid, adding the sodium perfluorooctanoate solution obtained in the step (4) into the polyacrylamide modified palygorskite dispersion liquid, stirring until precipitation occurs, centrifugally cleaning, drying the centrifuged precipitate for later use, and naming the obtained powder as modified palygorskite;
wherein the mass fraction of the polyacrylamide modified palygorskite dispersion liquid is 2.5 wt%, and the centrifugal rotating speed is 5000 rpm.
Step 6: dispersing the modified palygorskite obtained in the step 5 in water to obtain a modified palygorskite dispersion liquid, then adding a certain amount of acrylamide and sodium alginate, after fully dissolving, adding a certain amount of potassium persulfate and N, N' -methylene-bis-lactam, continuously stirring for dissolving, dropwise adding a small amount of tetramethyl ethylenediamine, and stirring until the solution is converted into gel. And (3) soaking the shaped gel in a calcium chloride solution for several hours, and freezing and vacuum-drying the soaked gel by using a freeze dryer to obtain the palygorskite-double-network gel sponge.
The modified palygorskite dispersion liquid comprises, by weight, 4% of modified palygorskite dispersion liquid, 0.6% of sodium alginate, 4% of acrylamide, 0.06% of potassium persulfate, 0.06% of N, N' -methylene-bis-lactam, 1.24mg/mL of tetramethylethylenediamine, 4000rpm of centrifugal speed, 0.4% of calcium chloride solution, 18h of soaking time and 36h of freeze-drying time.
The palygorskite-double-network gel sponge material with the oil-repellent and water-absorbent properties prepared in the embodiment is used for carrying out water absorption treatment on aqueous chloroform.
Example 4:
a preparation method of palygorskite-double-network gel sponge material with oil-repellent and water-absorbent properties comprises the following steps:
step 1: grinding and sieving palygorskite raw stones serving as raw materials, dispersing a certain amount of palygorskite powder in water, purifying with sulfuric acid, centrifuging the dispersion liquid, and drying the centrifuged precipitate to obtain purified palygorskite powder, wherein the centrifugation speed is 5000 rpm;
step 2: dissolving a certain amount of polyacrylamide hydrochloride in water to prepare a polyacrylamide hydrochloride solution for later use, wherein the mass concentration of the polyacrylamide hydrochloride solution is 4 mg/mL;
and step 3: dispersing the purified palygorskite powder obtained in the step 1 in water, stirring and ultrasonically treating until the palygorskite powder is uniformly dispersed to obtain a palygorskite dispersion liquid, wherein the mass fraction of the palygorskite dispersion liquid is 2 wt%; adding the polyacrylamide hydrochloride solution obtained in the step (2) into the palygorskite dispersion liquid, stirring uniformly, then carrying out centrifugal cleaning, drying the precipitate after centrifugation, and naming the obtained powder as polyacrylamide modified palygorskite powder, wherein the centrifugal speed is 5000 rpm;
and 4, step 4: dissolving a certain amount of perfluorooctanoic acid in a sodium hydroxide solution, stirring until the solution is clear and transparent for later use, and naming the solution as a sodium perfluorooctanoate solution, wherein the molar concentration of the sodium perfluorooctanoate solution is 0.2 mol/L;
and 5: dispersing the polyacrylamide modified palygorskite powder obtained in the step (3) in water, uniformly stirring to obtain a polyacrylamide modified palygorskite dispersion liquid, adding the sodium perfluorooctanoate solution obtained in the step (4) into the polyacrylamide modified palygorskite dispersion liquid, stirring until precipitation occurs, centrifugally cleaning, drying the centrifuged precipitate for later use, and naming the obtained powder as modified palygorskite;
wherein the mass fraction of the polyacrylamide modified palygorskite dispersion liquid is 2.5 wt%, and the centrifugal rotating speed is 5000 rpm.
Step 6: dispersing the modified palygorskite obtained in the step 5 in water to obtain a modified palygorskite dispersion liquid, then adding a certain amount of acrylamide and sodium alginate, after fully dissolving, adding a certain amount of potassium persulfate and N, N' -methylene-bis-lactam, continuously stirring for dissolving, dropwise adding a small amount of tetramethyl ethylenediamine, and stirring until the solution is converted into gel. And (3) soaking the shaped gel in a calcium chloride solution for several hours, and freezing and vacuum-drying the soaked gel by using a freeze dryer to obtain the palygorskite-double-network gel sponge.
Wherein the modified palygorskite dispersion liquid is 3.0 wt%, the sodium alginate is 0.8 wt%, the acrylamide is 5 wt%, the potassium persulfate is 0.05 wt%, the N, N' -methylenebislactam is 0.02 wt%, the tetramethylethylenediamine is 1.55mg/mL, the centrifugal speed is 4000rpm, the calcium chloride solution is 0.3 wt%, the soaking time is 16h, and the freeze-drying time is 48 h.
The palygorskite-double-network gel sponge material with the oil-repellent and water-absorbent properties prepared in the embodiment is used for carrying out water absorption treatment on aqueous chloroform.
Example 5:
a preparation method of palygorskite-double-network gel sponge material with oil-repellent and water-absorbent properties comprises the following steps:
step 1: grinding and sieving palygorskite raw stones serving as raw materials, dispersing a certain amount of palygorskite powder in water, purifying with sulfuric acid, centrifuging the dispersion liquid, and drying the centrifuged precipitate to obtain purified palygorskite powder, wherein the centrifugation speed is 5000 rpm;
step 2: dissolving a certain amount of polyacrylamide hydrochloride in water to prepare a polyacrylamide hydrochloride solution for later use, wherein the mass concentration of the polyacrylamide hydrochloride solution is 5 mg/mL;
and step 3: dispersing the purified palygorskite powder obtained in the step 1 in water, stirring and carrying out ultrasonic treatment until the purified palygorskite powder is uniformly dispersed to obtain a palygorskite dispersion liquid with the mass fraction of 1 wt%, adding the polyacrylamide hydrochloride solution obtained in the step 2 into the palygorskite dispersion liquid, carrying out centrifugal cleaning after uniform stirring, drying the centrifuged precipitate, and naming the obtained powder as the polyallylamine modified palygorskite powder with the centrifugal speed of 5000 rpm;
and 4, step 4: dissolving a certain amount of perfluorooctanoic acid in a sodium hydroxide solution, stirring until the solution is clear and transparent for later use, and naming the solution as a sodium perfluorooctanoate solution, wherein the molar concentration of the sodium perfluorooctanoate solution is 0.1 mol/L;
and 5: dispersing the polyacrylamide modified palygorskite powder obtained in the step (3) in water, uniformly stirring to obtain a polyacrylamide modified palygorskite dispersion liquid, adding the sodium perfluorooctanoate solution obtained in the step (4) into the polyacrylamide modified palygorskite dispersion liquid, stirring until precipitation occurs, centrifugally cleaning, drying the centrifuged precipitate for later use, and naming the obtained powder as modified palygorskite;
wherein the mass fraction of the polyacrylamide modified palygorskite dispersion liquid is 3 wt%, and the centrifugal speed is 5000 rpm.
Step 6: dispersing the modified palygorskite obtained in the step 5 in water to obtain a modified palygorskite dispersion liquid, then adding a certain amount of acrylamide and sodium alginate, after fully dissolving, adding a certain amount of potassium persulfate and N, N' -methylene-bis-lactam, continuously stirring and dissolving, dropwise adding a small amount of tetramethylethylenediamine, stirring until the solution is converted into gel, soaking the shaped gel in a calcium chloride solution for several hours, and freezing and vacuum drying the soaked gel by using a freeze dryer to obtain the palygorskite-double-network gel sponge.
Wherein the modified palygorskite dispersion liquid is 2 wt%, the sodium alginate is 1 wt%, the acrylamide is 6 wt%, the potassium persulfate is 0.04 wt%, the N, N' -methylene-bis-lactam is 0.03 wt%, the tetramethylethylenediamine is 0.62mg/mL, the centrifugal speed is 6000rpm, the calcium chloride solution is 0.3 wt%, the soaking time is 12h, and the freeze-drying time is 48 h.
The paligorskite-double-network gel sponge material with the oil-repelling and water-absorbing properties prepared in the embodiment is used for carrying out oil-water separation on the water-in-toluene emulsion.
The water-in-toluene emulsion is prepared according to the oil/water volume ratio of 100:1, and the preparation method of the emulsion is described by taking the water-in-toluene emulsion as an example. Firstly, adding 100mL of toluene into a round-bottom flask, and then adding a certain amount of 1mg/L of nonionic surfactant (span-80) aqueous solution; and (3) after mechanically stirring for 30min, dropwise adding 1mL of deionized water into the flask, and continuously mechanically stirring at a high speed for 12h until a stable milky emulsion is formed.
Filling the palygorskite-double-network gel sponge into a separation column, and pouring the toluene-in-water emulsion into the separation column; the filtered toluene liquid was collected and compared under an optical microscope for the liquid state before and after separation, see fig. 3a (before separation) and fig. 3b (after separation).
As can be seen from fig. 3a and 3b, the toluene after separation has no distinct spherical emulsion droplets; from the appearance, toluene changed from a white turbid state before separation to a clear transparent state. Therefore, the palygorskite-double network gel sponge prepared in the example can successfully separate oil from water in toluene emulsion.
The palygorskite used in the invention is a natural clay mineral material, has wide source and low price, and cannot damage the environment.
The sodium alginate and the acrylamide used in the invention are both high molecular materials which do not damage the environment and organisms after being turned into gel, and the sodium alginate and the acrylamide have hydrophilicity and are easy to degrade and recycle after being used.
The fluorine-containing chain segment adsorbed on the outermost layer of the modified palygorskite used in the invention can repel oil substances, and the cationic polymer polyacrylamide adsorbed on the surface can form a compact ionic electrostatic layer, adsorb water molecules with electric dipole moment and further enhance the repulsion to the oil substances. The palygorskite-double-network gel sponge used in the invention has rich pore channel structures, can store a large amount of water, and provides rich specific surface area for loading modified palygorskite.
Finally, it should be noted that: the above-mentioned embodiments are only specific embodiments of the present invention, which are used for illustrating the technical solutions of the present invention and not for limiting the same, and the protection scope of the present invention is not limited thereto, although the present invention is described in detail with reference to the foregoing embodiments, those skilled in the art should understand that: any person skilled in the art can modify or easily conceive the technical solutions described in the foregoing embodiments or equivalent substitutes for some technical features within the technical scope of the present disclosure; such modifications, changes or substitutions do not depart from the spirit and scope of the embodiments of the present invention, and they should be construed as being included therein. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (10)
1. A preparation method of the paligorskite-double-network gel sponge with oil repellency and water absorption is characterized by comprising the following steps:
mixing a polyacrylamide hydrochloride solution with a palygorskite dispersion liquid, centrifuging, and drying a centrifuged precipitate to obtain polyacrylamide modified palygorskite powder;
uniformly dispersing the polyacrylamide modified palygorskite powder in water to obtain a polyacrylamide modified palygorskite dispersion liquid;
mixing and reacting the polyacrylamide modified palygorskite dispersion liquid with a sodium perfluorooctanoate solution, centrifuging, and drying the centrifuged precipitate to obtain modified palygorskite powder;
uniformly dispersing the modified palygorskite powder in water to obtain a modified palygorskite dispersion liquid;
adding acrylamide and sodium alginate into the modified palygorskite dispersion liquid, adding potassium persulfate and N, N' -methylene-bis-lactam after the modified palygorskite dispersion liquid is fully dissolved, adding tetramethylethylenediamine after the modified palygorskite dispersion liquid is fully dissolved, and stirring until the solution is converted into gel;
and (3) soaking the gel in a calcium chloride solution for a certain time, and then carrying out freeze drying treatment on the soaked gel to obtain the palygorskite-double-network gel sponge.
2. The method for preparing the oil-repellent water-absorbent palygorskite-double-network gel sponge according to claim 1, wherein the mass concentration of the polyacrylamide hydrochloride solution is 2.5-5 mg/mL, and the mass fraction of the palygorskite dispersion is 1-3 wt%.
3. The method for preparing the oil-repellent water-absorbent palygorskite-double network gel sponge according to claim 1, wherein the mass fraction of the polyacrylamide modified palygorskite dispersion is 1.5-3 wt%.
4. The method of claim 1, wherein the molar concentration of the sodium perfluorooctanoate solution is 0.1mol/L to 0.5 mol/L.
5. The method for preparing the oil-repellent water-absorbent palygorskite-double network gel sponge according to claim 1, wherein the modified palygorskite dispersion liquid has a mass fraction of 2-5 wt%.
6. The method for preparing an oil-repellent and water-absorbent palygorskite-double network gel sponge as claimed in claim 1, wherein the mass fraction of acrylamide is 3-6 wt%, the mass fraction of sodium alginate is 0.3-1.0 wt%, the mass fraction of potassium persulfate is 0.04-0.08 wt%, the mass fraction of N, N' -methylene-bis-lactam is 0.03-0.06 wt%, and the addition amount of tetramethylethylenediamine is 0.62-1.55 mg/mL.
7. The method for preparing an oil-repellent and water-absorbent palygorskite-double network gel sponge according to claim 1, wherein the mass fraction of the calcium chloride solution is 0.3 wt% to 0.5 wt%.
8. The preparation method of the oil-repellent water-absorbent palygorskite-double-network gel sponge as claimed in claim 1, wherein the soaking time is 12-24 h, and the freeze-drying time is 24-48 h.
9. An oil-repellent water-absorbent palygorskite-double network gel sponge, characterized in that it is prepared by the preparation method according to any one of claims 1 to 8.
10. Use of an oil-repellent, water-absorbent palygorskite-double network gel sponge according to claim 9 as a membrane separation material for oil-water separation and as a water adsorbent for the removal of water from oil substances.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110998671.1A CN113698659B (en) | 2021-08-27 | 2021-08-27 | Palygorskite-double-network gel sponge with oil repellency and water absorption functions as well as preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110998671.1A CN113698659B (en) | 2021-08-27 | 2021-08-27 | Palygorskite-double-network gel sponge with oil repellency and water absorption functions as well as preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113698659A true CN113698659A (en) | 2021-11-26 |
| CN113698659B CN113698659B (en) | 2022-05-20 |
Family
ID=78656291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110998671.1A Active CN113698659B (en) | 2021-08-27 | 2021-08-27 | Palygorskite-double-network gel sponge with oil repellency and water absorption functions as well as preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113698659B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114011391A (en) * | 2021-12-23 | 2022-02-08 | 重庆大学 | Preparation method of double-network gel for adsorbing organic matters in wastewater |
| CN114160109A (en) * | 2021-12-23 | 2022-03-11 | 重庆大学 | Preparation method of coal ash doped gel for adsorbing inorganic ions in wastewater |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911381A (en) * | 2012-11-12 | 2013-02-06 | 天津工业大学 | Chemical/ionic/physical compounding cross linking hydrogel and preparation method thereof |
| CN103755897A (en) * | 2014-01-03 | 2014-04-30 | 西北师范大学 | Method for preparing palygorskite clay based salt-tolerance super water absorbency composite material |
-
2021
- 2021-08-27 CN CN202110998671.1A patent/CN113698659B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102911381A (en) * | 2012-11-12 | 2013-02-06 | 天津工业大学 | Chemical/ionic/physical compounding cross linking hydrogel and preparation method thereof |
| CN103755897A (en) * | 2014-01-03 | 2014-04-30 | 西北师范大学 | Method for preparing palygorskite clay based salt-tolerance super water absorbency composite material |
Non-Patent Citations (1)
| Title |
|---|
| MAO YU ET.AL.: "Reinforcement of Waterborne Polyurethane Films with Poly(acrylic acid)-Modified Palygorskite Fibers", 《FIBERS AND POLYMERS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114011391A (en) * | 2021-12-23 | 2022-02-08 | 重庆大学 | Preparation method of double-network gel for adsorbing organic matters in wastewater |
| CN114160109A (en) * | 2021-12-23 | 2022-03-11 | 重庆大学 | Preparation method of coal ash doped gel for adsorbing inorganic ions in wastewater |
| CN114011391B (en) * | 2021-12-23 | 2022-11-15 | 重庆大学 | Preparation method of double-network gel for adsorbing organic matters in wastewater |
| CN114160109B (en) * | 2021-12-23 | 2022-11-25 | 重庆大学 | Preparation method of coal ash doped gel for adsorbing inorganic ions in wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113698659B (en) | 2022-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113698659B (en) | Palygorskite-double-network gel sponge with oil repellency and water absorption functions as well as preparation method and application thereof | |
| Doshi et al. | A review of bio-based materials for oil spill treatment | |
| Phanthong et al. | Fabrication and evaluation of nanocellulose sponge for oil/water separation | |
| US9592488B2 (en) | Process for preparing lipid coated particles of plant material | |
| RU2653125C1 (en) | Polymeric sorbent, method of its production and use | |
| FI70923B (en) | FOERFARANDE FOER ATT SKOERDA ALGER | |
| Wang et al. | Adsorption of aqueous Hg (II) by sulfur-impregnated activated carbon | |
| CN1210754A (en) | Alginate gel based adsorbents for heavy metal removal | |
| Yang et al. | Graphene oxide/chitosan composite for methylene blue adsorption | |
| CN108043242A (en) | A kind of preparation method of the adjustable graphene oxide membrane of surface wettability energy | |
| Yi et al. | Scalable fabrication of sulfated silk fibroin nanofibrous membranes for efficient lipase adsorption and recovery | |
| Ye et al. | Amine functional cellulose derived from wastepaper toward oily wastewater treatment and its demulsification mechanism | |
| Men et al. | Preparation of heparin-functionalized microspheres and study on their adsorption characteristic for basic protein lysozyme | |
| CN113648978B (en) | Preparation method and application of aerogel with oriented neural network structure | |
| CN114733497A (en) | Light-reproducible metal-organic framework composite film and preparation method and application thereof | |
| Xu et al. | Preparation and optimization of porous regenerated cellulose microspheres from cellulose tetraethyl-ammonium/urea solution for adsorption of cationic methylene blue dy | |
| Akpomie et al. | Treatment of motor oil-contaminated water via sorption onto natural organic lignocellulosic waste: thermodynamics, kinetics, isotherm, recycling, and reuse | |
| US8628669B2 (en) | Methods to recover and reclaim hydrocarbons or hydrophobic substances in an aqueous environment | |
| RU2232633C2 (en) | Sorbent for cleaning water from hydrocarbons, method of production of sorbent and method of cleaning water | |
| CN112245975A (en) | Polymer modifier and oil-water adsorption material | |
| Fang et al. | Fabrication of superhydrophobic all-biomass aerogels with ultralight, elasticity and degradability for efficient oily wastewater treatment | |
| Jawad et al. | Removal of residual oil from palm oil mill effluent by novel adsorbent of alginate and mangrove composite beads coated by chitosan | |
| CN111821910A (en) | Amphiphilic surfactant, eluting agent and application thereof | |
| CN1062739A (en) | Improved cellulose chromatography support | |
| Adhikari et al. | Biosorption of Malathion by immobilized cells of Bacillus sp. S14 |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |