CN107999030B - Preparation method of composite oil-water separating agent - Google Patents

Preparation method of composite oil-water separating agent Download PDF

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CN107999030B
CN107999030B CN201711132831.4A CN201711132831A CN107999030B CN 107999030 B CN107999030 B CN 107999030B CN 201711132831 A CN201711132831 A CN 201711132831A CN 107999030 B CN107999030 B CN 107999030B
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water
oil
bamboo fiber
separating agent
bamboo
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CN107999030A (en
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刘俊稚
葛亚明
陈庆国
穆军
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Zhejiang Ocean University ZJOU
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • 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
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • 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
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Abstract

The invention relates to the technical field of oily wastewater treatment and oil spill pollution remediation, in particular to a preparation method of a composite oil-water separating agent, which comprises the steps of firstly mixing protein powder, calcium carbonate and phosphoric acid in a water glass solution to form a mixture, then adding bamboo fiber nanoparticles and modified chitosan, drying, hardening and cleaning to obtain the composite oil-water separating agent, wherein the bamboo fiber nanoparticles are loaded with nano silica aerogel and then used, and the modified chitosan is obtained by mixing chitosan with a low-concentration sodium fluoride solution in an acetic acid/sodium acetate buffer solution with the pH value of 4-5. The bamboo fiber nano particles, the modified chitosan, the calcium phosphate and the protein hydrolysis mixture are loaded on the silica gel to form a multi-dimensional space network structure, so that the oil-water separating agent has super-strong hydrophilicity, water absorption capacity and water storage capacity, the water absorption speed is high, the efficiency of separating and recovering water from oil-contaminated water is high, and the stability and the strength of the oil-water separating agent are good.

Description

Preparation method of composite oil-water separating agent
Technical Field
The invention relates to the technical field of oily wastewater treatment and oil spill pollution remediation, in particular to a preparation method of a composite oil-water separating agent.
Background
In recent years, along with the prosperous development of modern industry, the production amount of oily wastewater and the risk of oil spill pollution accidents are increased, if the oily wastewater is not properly treated or directly discharged, nearby water bodies can be polluted, aquatic ecosystems can be damaged, irreversible damage can be caused to human health and ecological environment by polluting soil, air and the like, if the oily wastewater permeates into soil, soil hardening can be caused, and volatilized organic waste gas can threaten human health. At present, various hydrophilic and oleophobic materials exist in the market for separating oil and water, but the problems of low separation efficiency and small saturated adsorption capacity to water exist.
Disclosure of Invention
Aiming at the problems of the existing water-absorbing material, the invention aims to provide a preparation method of a composite oil-water separating agent, the oil-water separating agent prepared by the method has a larger oil-repelling angle and stronger hydrophilic water-absorbing capacity, and the oil-water separating agent can successfully isolate high-viscosity oil such as crude oil, heavy oil and the like from water molecules by coating the oil-water separating agent on a biopolymer membrane.
The invention provides the following technical scheme:
a preparation method of a compound oil-water separating agent comprises the following steps:
(1) mixing protein powder, calcium carbonate and phosphoric acid with the mass volume ratio of 80%, wherein the mass ratio of the protein powder to the calcium carbonate to the phosphoric acid is 0.2:1: 5-7, and then adding the mixture into 2-3 wt% of water glass solution for ultrasonic auxiliary reaction to obtain a mixture, wherein the volume ratio of the water glass solution to the phosphoric acid is 2-3: 1;
(2) adding 10-30 parts by weight of bamboo fiber nanoparticles and 15-23 parts by weight of modified chitosan into 50-70 parts by weight of the mixture obtained in the step (1), uniformly stirring, and keeping at 20-28 ℃ for 2-5 hours to obtain a viscous jelly;
(3) vacuum drying the viscous jelly to water content of 25-35 wt% to obtain solid powder, and adding CO2Hardening in an atmosphere;
(4) and cleaning the hardened solid powder for 2-5 times by using deionized water, and then drying in vacuum to obtain the composite oil-water separating agent.
The method comprises the steps of mixing protein powder, calcium carbonate and phosphoric acid in a water glass solution to form a viscous system, adding bamboo fiber nanoparticles and modified chitosan, drying, hardening and cleaning to obtain the composite oil-water separating agent, wherein the protein powder, the calcium carbonate and the phosphoric acid are mixed to form hydrophilic calcium phosphate and amino acid, and the calcium phosphate plays a role of a binder and forms a hydrophilic cross-linked network together with the water glass. The bamboo fiber has an abundant capillary structure inside, so that the bamboo fiber has an ultrastrong water absorption performance and an instant water absorption capacity, chitosan is straight-chain polysaccharide which is formed by connecting 2-amino-glucose and N-2-acetyl-2-amino-glucose through beta-1, 4 glycosidic bonds and has no side chain, and is rich in abundant hydrophilic groups including hydroxyl, amino, carbonyl, acetyl and the like, so that bamboo fiber nanoparticles and modified chitosan are added into the cross-linked network to form a composite system with an ultrastrong water absorption capacity. Drying the obtained viscous jelly, and subjecting to CO2Hardening, gradually changing water glass into a sodium carbonate and silica gel skeleton, washing with deionized water to remove the sodium carbonate, and loading protein powder, amino acid hydrolyzed into the protein powder, calcium phosphate, bamboo fiber nano particles and modified chitosan on the silica gel skeleton to form a multi-dimensional hydrophilic, water-absorbing and water-storing network structure, so that the obtained composite oil-water separating agent has super-strong hydrophilic and water-absorbing capacity.
As an improvement of the method, the bamboo fiber nano-particles are prepared by the following steps: processing bamboo material into bamboo fiber by conventional bamboo chip preparation, boiling, crushing decomposition, bamboo filament cooking, and biological enzyme degumming, and introducing CO into bamboo fiber2In an aging furnace, adjusting CO2The flow rate is 100-150 mL/min, the aging furnace is heated at the speed of 5-8 ℃/min and kept at 400-500 ℃ for 3-6 h, and then CO is adjusted2The flow rate is 300-360 mL/min, the aging furnace is heated at the speed of 1-2 ℃/min and kept at 800-900 ℃ for 2-3 h, and CO is stopped2And introducing and adding deionized water steam into the aging furnace for spraying for 2-3 min, wherein the volume ratio of the deionized water steam to the aging furnace is 0.6-0.7: 1, then, cooling to obtain carbonized bamboo fibers, and grinding to obtain bamboo fiber nanoparticles with the particle size of 10-20 nm. The natural bamboo fiber prepared by the conventional process is placed in an oxygen-isolated environment and carbonized at high temperature to form biochar, so that the strength of the bamboo fiber is enhanced, and internal organic impurities are removed. In the carbonization process, the temperature is raised in stages and CO is regulated2The flow mode is that firstly the temperature rise rate of the low-temperature calcination stage is high, and CO is continuously introduced2To promote the formation of a mesoporous structure in the bamboo fiber, and CO2The stability of the C-O skeleton and the formation of-COO-of the biochar can be enhanced by the acidic atmosphere formed by the water released in carbonization, and then the temperature is slowly increased to a higher calcining temperature so as to enhance the strength of the biochar skeleton and the pore structure and increase the stability of the bamboo charcoal in a water body. After high-temperature calcination, deionized water steam spray is added to rapidly cool the bamboo fibers to extinguish fire, complex porous structures are generated in the bamboo fibers, the surface area is increased by multiple times, the water absorption capacity is greatly improved, and the bamboo fiber nanoparticles prepared by the treatment process have large water absorption capacity and high water absorption rateFast and high strength.
As an improvement of the method, the bamboo fiber nanoparticles are used after being treated by the following steps: mixing bamboo fiber nanoparticles and nano-silica aerogel in a mass ratio of 1: 0.2-0.5, adjusting pressure and temperature to enable the titanium dioxide aerogel to be in a supercritical state, oscillating at 100-120 rpm/min for 30-60 min, and immediately reducing pressure to enable the nano-silica aerogel to be loaded on the bamboo fiber nanoparticles. Silicon hydroxyl in the silicon dioxide aerogel can form hydrogen bonds with water, and the silicon dioxide aerogel has strong water absorption capacity, and meanwhile, the silicon dioxide aerogel is rich in internal pore structure and strong in water storage capacity, so that the silicon dioxide aerogel is loaded on the bamboo fiber nanoparticles to enable pore structures of the aerogel and the bamboo fiber nanoparticles to be staggered, the comprehensive water storage capacity is superior to respective water storage effects of the aerogel and the bamboo fiber nanoparticles, the silicon dioxide aerogel and a silicon dioxide gel framework are good in compatibility, and the stability of the oil-water separating agent can be enhanced.
As an improvement of the method, the modified chitosan is prepared by the following steps: placing chitosan in acetic acid/sodium acetate buffer solution with the pH value of 4-5, uniformly mixing, adding sodium fluoride solution, uniformly stirring, and then keeping the mixture at the temperature of 23-28 ℃ for 2-3 hours to obtain a mixed system; and (3) drying the mixed system in a vacuum environment, and washing for 2-5 times by using deionized water to obtain the modified chitosan. The chitosan is placed in a low-concentration sodium fluoride solution, the pH value is adjusted to be 4-5, amino groups on the chitosan are positively ionized to form amino ions, and therefore fluorine ions are combined, an-F end group is formed in the chitosan, the chitosan has the capability of forming hydrogen bonds with water, and the water absorption capability of the modified chitosan is improved by 15% -20% compared with that of the chitosan.
As an improvement of the method, the concentration of the sodium fluoride solution is 0.1-0.2 mol/L, the volume ratio of the acetic acid/sodium acetate buffer solution to the sodium fluoride solution is 3-7: 1, and the mass ratio of the sodium fluoride to the chitosan is 1: 6-9. And controlling a proper ratio to ensure that the pH value of the solution is 4-5 in the whole modification process, so that the chitosan amino group is positively ionized, and sodium ions in the sodium fluoride fully enter an acetic acid/sodium acetate buffer solution system to release fluoride ions.
As a modification of the method of the present invention, the hardening process in step (3) is as follows: introducing solid powder into a reactor containing CO2The air duct is blown away to adjust CO2The flow rate of the gas is 50-70 mL/min and is kept for 60-90 min, and then CO is added2The flow rate is 150-200 mL/min and kept for 120-180 min. The CO2 wind flow is changed in the wind channel in a stage shape, so that the water glass is fully hardened and the silica gel framework is ensured to be intact.
As an improvement of the method, the temperature of vacuum drying is 15-28 ℃. The low temperature vacuum drying protects the integrity of the multidimensional network structure.
The invention has the following beneficial effects:
in the compound oil-water separating agent prepared by the method, bamboo fiber nanoparticles, modified chitosan, calcium phosphate and a protein hydrolysis mixture are loaded on silica gel to form a multi-dimensional space network structure, so that the oil-water separating agent has super-strong hydrophilicity, water absorption capacity and water storage capacity, high water absorption speed, high efficiency of separating and recovering water from oily water, and good stability and strength.
Detailed Description
The following further describes the embodiments of the present invention.
The starting materials used in the present invention are commercially available or commonly used in the art, unless otherwise specified, and the methods in the following examples are conventional in the art, unless otherwise specified.
Example 1
A preparation method of a compound oil-water separating agent comprises the following steps:
(1) mixing albumen powder, calcium carbonate and phosphoric acid with the mass volume ratio of 80% according to the mass ratio of 0.2:1:5, then putting the mixture into 2 wt% of water glass solution for ultrasonic auxiliary reaction to obtain a mixture, wherein the volume ratio of the water glass solution to the 80% phosphoric acid is 2: 1;
(2) adding 10g of bamboo fiber nanoparticles and 15g of modified chitosan into 50g of the mixture obtained in the step (1), uniformly stirring, and keeping at 20 ℃ for 2 hours to obtain a viscous jelly;
(3) vacuum drying the viscous gel at 15 deg.C to water content of 35 wt% to obtain solid powder, and adding CO2Hardening in atmosphere, wherein the hardening process is as follows: introducing solid powder into a reactor containing CO2The air duct is blown away to adjust CO2At a flow rate of 50mL/min for 60min, and then increasing CO2The flow rate of the flow is 150mL/min and is kept for 120 min;
(4) and cleaning the hardened solid powder for 2 times by using deionized water, and then drying in vacuum at 15 ℃ to obtain the compound oil-water separating agent.
Wherein, the bamboo fiber nano particles in the step (2) are prepared by the following processes: processing bamboo material into bamboo fiber by conventional bamboo chip preparation, boiling, crushing decomposition, bamboo filament cooking, and biological enzyme degumming, and introducing CO into bamboo fiber2In an aging furnace, adjusting CO2The flow rate is 100mL/min, the aging furnace is heated at the speed of 5 ℃/min and kept at 400 ℃ for 6h, and then CO is regulated2The flow rate is 300mL/min, the temperature is increased to 800 ℃ at the speed of 1 ℃/min and is kept for 2-3 h, and the introduction of CO is stopped2And adding deionized water steam into the aging furnace for spraying for 2min, wherein the volume ratio of the deionized water steam to the aging furnace is 0.6:1, then cooling to obtain carbonized bamboo fibers, and grinding to obtain bamboo fiber nanoparticles with the particle size of 10 nm.
The modified chitosan in the step (2) is prepared by the following processes: putting chitosan into acetic acid/sodium acetate buffer solution with the pH value of 4, uniformly mixing, adding 0.1mol/L sodium fluoride solution, uniformly stirring, wherein the volume ratio of the acetic acid/sodium acetate buffer solution to the sodium fluoride solution is 3:1, and the mass ratio of the sodium fluoride to the chitosan is 1:6, and then keeping for 2 hours at 23 ℃ to obtain a mixed system; and drying the mixed system in a vacuum environment at 15 ℃, and washing for 2 times by using deionized water to obtain the modified chitosan.
Example 2
A preparation method of a compound oil-water separating agent comprises the following steps:
(1) mixing albumen powder, calcium carbonate and phosphoric acid with the mass volume ratio of 80% according to the mass ratio of 0.2:1:6, and then putting the mixture into 2.5 wt% of water glass solution to perform ultrasonic auxiliary reaction to obtain a mixture, wherein the volume ratio of the water glass solution to the 80% phosphoric acid is 2.5: 1;
(2) adding 20g of bamboo fiber nanoparticles and 19g of modified chitosan into 60g of the mixture obtained in the step (1), uniformly stirring, and keeping at 24 ℃ for 3.5 hours to obtain a viscous jelly;
(3) vacuum drying the viscous gel at 23 deg.C to water content of 30 wt% to obtain solid powder, and adding CO2Hardening in atmosphere, wherein the hardening process is as follows: introducing solid powder into a reactor containing CO2The air duct is blown away to adjust CO2At a flow rate of 60mL/min for 75min, then increasing CO2The flow rate of the flow is 170mL/min and is kept for 150 min;
(4) and cleaning the hardened solid powder for 4 times by using deionized water, and then drying in vacuum at 24 ℃ to obtain the compound oil-water separating agent.
Wherein, the bamboo fiber nano particles in the step (2) are prepared by the following processes: processing bamboo material into bamboo fiber by conventional bamboo chip preparation, boiling, crushing decomposition, bamboo filament cooking, and biological enzyme degumming, and introducing CO into bamboo fiber2In an aging furnace, adjusting CO2The flow rate is 120mL/min, the aging furnace is heated at the speed of 7 ℃/min and is kept at 450 ℃ for 4h, and then CO is regulated2The flow rate is 330mL/min, the temperature is raised to 850 ℃ at the speed of 1.5 ℃/min and kept for 2.5h, and the CO is stopped2Introducing and adding deionized water steam into the aging furnace for spraying for 2.5min, wherein the volume ratio of the deionized water steam to the aging furnace is 0.65:1, then cooling to obtain carbonized bamboo fibers, and grinding to obtain bamboo fiber nanoparticles with the particle size of 15 nm.
The modified chitosan in the step (2) is prepared by the following processes: putting chitosan into acetic acid/sodium acetate buffer solution with the pH value of 4.5, uniformly mixing, adding 0.15mol/L sodium fluoride solution, uniformly stirring, wherein the volume ratio of the acetic acid/sodium acetate buffer solution to the sodium fluoride solution is 5:1, and the mass ratio of the sodium fluoride to the chitosan is 1:7.5, and then keeping for 2.5 hours at 25 ℃ to obtain a mixed system; and (3) drying the mixed system in a vacuum environment at 23 ℃, and washing for 4 times by using deionized water to obtain the modified chitosan.
Example 3
A preparation method of a compound oil-water separating agent comprises the following steps:
(1) mixing albumen powder, calcium carbonate and phosphoric acid with the mass volume ratio of 80% according to the mass ratio of 0.2:1:7, then putting the mixture into 3 wt% of water glass solution for ultrasonic auxiliary reaction to obtain a mixture, wherein the volume ratio of the water glass solution to the 80% phosphoric acid is 3: 1;
(2) adding 30g of bamboo fiber nanoparticles and 23g of modified chitosan into 70g of the mixture obtained in the step (1), uniformly stirring, and keeping at 28 ℃ for 5 hours to obtain a viscous jelly;
(3) vacuum drying the sticky gum at 28 deg.C to a water content of 25 wt% to obtain a solid powder, and adding CO2Hardening in atmosphere, wherein the hardening process is as follows: introducing solid powder into a reactor containing CO2The air duct is blown away to adjust CO2At a flow rate of 70mL/min for 90min, and then increasing CO2The flow rate of the flow is up to 200mL/min and kept for 180 min;
(4) and cleaning the hardened solid powder for 5 times by using deionized water, and then drying in vacuum at 28 ℃ to obtain the compound oil-water separating agent.
Wherein, the bamboo fiber nano particles in the step (2) are prepared by the following processes: processing bamboo material into bamboo fiber by conventional bamboo chip preparation, boiling, crushing decomposition, bamboo filament cooking, and biological enzyme degumming, and introducing CO into bamboo fiber2In an aging furnace, adjusting CO2The flow rate is 150mL/min, the aging furnace is heated at the speed of 8 ℃/min and kept at 500 ℃ for 6h, and then CO is regulated2The flow rate is 360mL/min, the temperature is increased to 900 ℃ at the speed of 2 ℃/min and is kept for 3h, and CO is stopped2Introducing and adding deionized water steam into the aging furnace for spraying for 3min, wherein the volume ratio of the deionized water steam to the aging furnace is 0.7:1, then cooling to obtain carbonized bamboo fibers, and grinding to obtain bamboo fiber nanoparticles with the particle size of 20 nm.
The modified chitosan in the step (2) is prepared by the following processes: putting chitosan into acetic acid/sodium acetate buffer solution with the pH value of 5, uniformly mixing, adding 0.2mol/L sodium fluoride solution, uniformly stirring, wherein the volume ratio of the acetic acid/sodium acetate buffer solution to the sodium fluoride solution is 7:1, and the mass ratio of the sodium fluoride to the chitosan is 1:9, and then keeping for 3 hours at 28 ℃ to obtain a mixed system; and drying the mixed system in a vacuum environment, and washing for 5 times by using deionized water to obtain the modified chitosan.
Example 4
The preparation method of the compound oil-water separating agent is different from the embodiment 1 in that the bamboo fiber nanoparticles in the step (2) are prepared by the process and then are used after being treated by the following steps: mixing the bamboo fiber nanoparticles and the nano-silica aerogel in a mass ratio of 1:0.2, adjusting the pressure and the temperature to enable the titanium dioxide aerogel to be in a supercritical state, oscillating at 100rpm/min for 60min, and immediately reducing the pressure to enable the nano-silica aerogel to be loaded on the bamboo fiber nanoparticles.
Example 5
The preparation method of the compound oil-water separating agent is different from the embodiment 1 in that the bamboo fiber nanoparticles in the step (2) are prepared by the process and then are used after being treated by the following steps: mixing the bamboo fiber nanoparticles and the nano-silica aerogel in a mass ratio of 1:0.4, adjusting the pressure and the temperature to enable the titanium dioxide aerogel to be in a supercritical state, oscillating at 110rpm/min for 45min, and immediately reducing the pressure to enable the nano-silica aerogel to be loaded on the bamboo fiber nanoparticles.
Example 6
The preparation method of the compound oil-water separating agent is different from the embodiment 1 in that the bamboo fiber nanoparticles in the step (2) are prepared by the process and then are used after being treated by the following steps: mixing the bamboo fiber nanoparticles and the nano-silica aerogel in a mass ratio of 1:0.5, adjusting the pressure and the temperature to enable the titanium dioxide aerogel to be in a supercritical state, oscillating at 120rpm/min for 60min, and immediately reducing the pressure to enable the nano-silica aerogel to be loaded on the bamboo fiber nanoparticles.
Hydrophilic oleophobic Property test
1. Water absorption capacity test: 2g of each of the oil-water separating agents obtained in examples 6 was taken, and then placed in a beaker containing 100g of water, and left to stand at 23. + -. 2 ℃ for 48 hours, and then the weight was taken out and weighed, and the difference between the two masses was calculated as the water absorption capacity, and the water absorption capacity was calculated as the percentage of the water absorption capacity to 2g, and the results are shown in Table 1.
2. Testing of oleophobic property: the oil contact angles of the oil-water separating agents of examples 1 to 6 were measured by a contact angle measuring instrument, and the results are shown in Table 1
TABLE 1 test results
Experimental group Example 1 Example 2 Example 3 Example 4 Example 5 Example 6
Water absorption capacity/g 0.782 0.822 0.810 0.904 0.915 0.908
Water absorption/%) 39.1 41.1 40.5 45.2 45.8 45.4
Oil drain angle 82° 87° 84° 93° 95° 93°

Claims (6)

1. A preparation method of a compound oil-water separating agent comprises the following steps:
(1) mixing protein powder, calcium carbonate and 80% phosphoric acid in a mass-volume ratio of 0.2:1: 5-7, and then adding the mixture into 2-3 wt% of water glass solution to perform ultrasonic auxiliary reaction to obtain a mixture, wherein the volume ratio of the water glass solution to the phosphoric acid is 2-3: 1;
(2) adding 10-30 parts by weight of bamboo fiber nanoparticles and 15-23 parts by weight of modified chitosan into 50-70 parts by weight of the mixture obtained in the step (1), uniformly stirring, and keeping at 20-28 ℃ for 2-5 hours to obtain a viscous jelly;
(3) vacuum drying the viscous jelly to water content of 25-35 wt% to obtain solid powder, and adding CO2Hardening in an atmosphere;
(4) cleaning the hardened solid powder for 2-5 times by using deionized water, and then carrying out vacuum drying to obtain a composite oil-water separating agent;
the modified chitosan is prepared by the following steps: placing chitosan in acetic acid/sodium acetate buffer solution with the pH value of 4-5, uniformly mixing, adding sodium fluoride solution, uniformly stirring, keeping at 23-28 ℃ for 2-3 hours to obtain a mixed system, placing the mixed system in a vacuum environment, drying, and washing with deionized water for 2-5 times to obtain the modified chitosan.
2. The process for producing an oil-water separating agent according to claim 1, which comprisesCharacterized in that the bamboo fiber nano-particles are prepared by the following processes: processing bamboo material into bamboo fiber by conventional bamboo chip preparation, boiling, crushing decomposition, bamboo filament cooking, and biological enzyme degumming, and introducing CO into bamboo fiber2In an aging furnace, adjusting CO2The flow rate is 100-150 mL/min, the aging furnace is heated at the speed of 5-8 ℃/min and kept at 400-500 ℃ for 3-6 h, and then CO is adjusted2The flow rate is 300-360 mL/min, the aging furnace is heated at the speed of 1-2 ℃/min and kept at 800-900 ℃ for 2-3 h, and CO is stopped2And introducing and adding deionized water steam into the aging furnace for spraying for 2-3 min, wherein the volume ratio of the deionized water steam to the aging furnace is 0.6-0.7: 1, then, cooling to obtain carbonized bamboo fibers, and grinding to obtain bamboo fiber nanoparticles with the particle size of 10-20 nm.
3. The preparation method of the oil-water separating agent according to claim 1 or 2, wherein the bamboo fiber nanoparticles are used after being treated by the following steps: mixing bamboo fiber nanoparticles and nano-silica aerogel in a mass ratio of 1: 0.2-0.5, adjusting pressure and temperature to enable the titanium dioxide aerogel to be in a supercritical state, oscillating at 100-120 rpm/min for 30-60 min, and immediately reducing pressure to enable the nano-silica aerogel to be loaded on the bamboo fiber nanoparticles.
4. The method for preparing the oil-water separating agent according to claim 1, wherein the concentration of the sodium fluoride solution is 0.1-0.2 mol/L, the volume ratio of the acetic acid/sodium acetate buffer solution to the sodium fluoride solution is 3-7: 1, and the mass ratio of the sodium fluoride to the chitosan is 1: 6-9.
5. The method for producing an oil-water separating agent according to claim 1, wherein the hardening process in the step (3) is as follows: introducing solid powder into a reactor containing CO2The air duct is blown away to adjust CO2The flow rate of the gas is 50-70 mL/min and is kept for 60-90 min, and then CO is added2The flow rate is 150-200 mL/min and kept for 120-180 min.
6. The method for producing an oil-water separating agent according to claim 1, wherein the temperature of vacuum drying in the step (3) and the step (4) is 15 to 28 ℃.
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