CN109603780B - Sponge composite organic solvent absorbent and preparation method thereof - Google Patents
Sponge composite organic solvent absorbent and preparation method thereof Download PDFInfo
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- CN109603780B CN109603780B CN201910022059.3A CN201910022059A CN109603780B CN 109603780 B CN109603780 B CN 109603780B CN 201910022059 A CN201910022059 A CN 201910022059A CN 109603780 B CN109603780 B CN 109603780B
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- 230000002745 absorbent Effects 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 239000003960 organic solvent Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000004814 polyurethane Substances 0.000 claims abstract description 71
- 229920002635 polyurethane Polymers 0.000 claims abstract description 71
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- 239000000243 solution Substances 0.000 claims abstract description 36
- 238000001035 drying Methods 0.000 claims abstract description 30
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- 239000013078 crystal Substances 0.000 claims abstract description 13
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 11
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
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- XKKVXDJVQGBBFQ-UHFFFAOYSA-L zinc ethanol diacetate Chemical compound C(C)O.C(C)(=O)[O-].[Zn+2].C(C)(=O)[O-] XKKVXDJVQGBBFQ-UHFFFAOYSA-L 0.000 claims abstract description 9
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 6
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 20
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
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- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- UNYOJUYSNFGNDV-UHFFFAOYSA-M magnesium monohydroxide Chemical compound [Mg]O UNYOJUYSNFGNDV-UHFFFAOYSA-M 0.000 description 1
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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
- B01J20/26—Synthetic macromolecular compounds
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- 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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (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 sponge compound organic solvent absorbent and a preparation method thereof, wherein the preparation process comprises the following steps: firstly, treating polyurethane sponge with alkaline aqueous solution, then coating acrylic resin emulsion on the polyurethane sponge treated with alkaline solution, curing to obtain acrylic resin/polyurethane sponge composite material, growing ZnO seed crystal in zinc acetate ethanol solution of the acrylic resin/polyurethane sponge composite material, then placing the acrylic resin/polyurethane sponge composite material in aqueous solution containing zinc ions and hexamethylenetetramine to grow ZnO nano particles, and drying to obtain the sponge composite organic solvent absorbent. The composite absorbent prepared by the invention not only retains the macroporous structure of polyurethane sponge, but also obtains the high oil absorption capacity of oil absorption resin, improves the surface hydrophobic oleophylic property by introducing ZnO nanoparticles, can effectively intercept trace organic solvent in an oil-water mixture, and can be applied to the continuous treatment of solvent-containing wastewater.
Description
Technical Field
The invention belongs to the field of adsorption and absorption functional materials, and particularly relates to a sponge compound organic solvent absorbent and a preparation method thereof.
Background
One type of pollutant often contained in industrial wastewater is Volatile Organic Compounds (VOCs), such as benzene, ester, ketone, halogenated hydrocarbon and other organic solvents, which have great influence on human health, can harm human liver, kidney, brain and nervous system, cause serious consequences such as memory deterioration and even possibly cause cancer. The common treatment method for VOCs in wastewater comprises the following steps: the absorption method comprises an adsorption absorption method, a biodegradation method, a gas stripping method, a pervaporation method, an extraction method, an ultrasonic method, a hydrolysis method, a photodegradation method and the like, wherein the absorbent is an important means for treating the VOCs due to the advantages of large absorption capacity, recyclability, high absorption rate and the like.
The absorbent for treating VOCs in the wastewater is various in types, wherein inorganic absorbents such as activated carbon and diatomite and natural organic absorbents such as wood fiber, wheat straw and sponge have a common defect of absorbing oil and water; the chemical synthetic materials such as polypropylene fiber, polyurethane foam, acrylic resin and the like are the main research directions of oil absorption materials due to high absorption speed and large absorption capacity, and are widely applied to the treatment of oily wastewater, wherein the acrylic high-oil-absorption resin has a three-dimensional cross-linked network structure, is easy to be occluded by an organic solvent, has the characteristics of no water absorption after oil absorption, multiple oil absorption types, good oil retention performance and the like, and becomes the focus of attention at home and abroad. However, the oil-absorbing resin has the defects of poor mechanical property, device blockage and the like after oil absorption and swelling in the using process, and is not beneficial to the continuous treatment of oily wastewater. Chinese patent 201710230193.3 discloses a sponge-supported organic solvent absorbent and a preparation method thereof, wherein an emulsion polymerization method is adopted to prepare an emulsion oil-absorbing resin containing epoxy functional groups, and polyurethane sponge is chemically modified, and the epoxy resin and the polyurethane sponge are grafted and compounded by forming chemical bonds to prepare the sponge-supported organic solvent absorbent. The absorbent has the characteristics of polyurethane sponge and oil-absorbing resin, has good absorption performance, can not deform obviously after being absorbed, has certain mechanical strength and flexibility, has small permeation resistance in practical application due to the special high-porosity framework structure of the polyurethane sponge, can keep a through hole structure after being absorbed, and is beneficial to full contact between waste water and waste liquid and the absorbent. However, the absorbent is complicated in preparation process and is not suitable for treating trace amounts of organic solvents in wastewater.
Disclosure of Invention
The invention aims to provide a preparation method of a sponge compound type organic solvent absorbent aiming at the defects of the prior art, so that the compounding process of high oil absorption resin and polyurethane sponge is simplified, the absorption speed of the sponge compound type absorbent on organic solvent is obviously accelerated, and trace organic solvent in water can be effectively removed.
In order to achieve the purpose, the invention adopts the technical scheme that:
a sponge compound organic solvent absorbent and a preparation method thereof comprise the following steps:
(1) immersing polyurethane sponge by using an alkaline solution, heating for 0.5-1.5h at 40-60 ℃, washing by using deionized water and drying for later use;
(2) immersing the polyurethane sponge subjected to alkali treatment in the step (1) in acrylic resin emulsion, taking out after 0.5-1.5h, naturally drying at room temperature, and repeating the process for 2-3 times;
(3) placing the polyurethane sponge loaded with the acrylic resin in the step (2) in a constant-temperature drying oven at 50-150 ℃ for curing for 1-4h to obtain an acrylic resin/polyurethane sponge composite material;
(4) dipping the acrylic resin/polyurethane sponge composite material by using a zinc acetate ethanol solution, and drying to obtain a ZnO seed crystal/acrylic resin/polyurethane sponge composite material;
(5) respectively preparing a zinc ion aqueous solution and a hexamethylenetetramine aqueous solution, uniformly mixing the two solutions, then immersing the ZnO seed crystal/acrylic resin/polyurethane sponge composite material in the obtained mixed solution for 5-10h to grow ZnO nano particles, and drying to obtain the sponge composite organic solvent absorbent.
In order to simplify the process of compounding the high oil absorption resin and the polyurethane sponge, the polyurethane sponge is directly treated by the alkaline solution, so that more-OH is introduced to facilitate crosslinking with the high oil absorption resin, the prepared oil absorption resin/sponge composite material not only keeps the macroporous structure of the polyurethane sponge and facilitates water circulation, but also obtains the oil absorption capacity of the high oil absorption resin, captured oil is stored in the three-dimensional network structure of the high oil absorption resin, and meanwhile, due to the supporting effect of the polyurethane sponge, the high oil absorption resin can not block pore passages even if being swelled after absorbing oil; in order to improve the absorption speed and removal rate of the composite absorbent, ZnO nanoparticles are deposited on the surface of the oil absorption resin/sponge composite material to construct a surface micro-nano structure, so that the roughness of the surface of the composite material is obviously increased, the hydrophobicity and lipophilicity and the oil-water selectivity of the composite material are further improved, the absorption speed of the prepared sponge composite absorbent on an organic solvent is obviously accelerated, and the removal rate of trace organic solvents in water can reach more than 80%.
The acrylic resin selected by the invention is a high oil-absorbing resin, has the characteristic of only absorbing oil and not absorbing water, and the selectivity is particularly combined with the requirement of the patent. The acrylic resin has the advantages of fast absorption, high oil absorption rate and strong oil retention, can completely retain the high oil absorption performance of the acrylic resin by being compounded with the polyurethane sponge, obtains a loose porous structure of the polyurethane sponge, and is beneficial to oil-water separation.
In the step (1), the concentration of the alkaline solution is 5-15% (wt), and the alkaline solution is one of a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution.
The concentration of the alkaline solution influences the treatment effect of the alkaline solution, the polyurethane sponge framework can be excessively corroded due to overhigh concentration, the framework becomes thin, the load rate of the high oil absorption resin is reduced, and the absorption rate of the organic solvent are influenced.
In the step (2), the solid content of the acrylic resin emulsion is 40-50%, and the absorption rate of the resin to butyl acetate is 10-12 times.
In the step (4), the concentration of the zinc acetate ethanol solution is 5-15 mmol/L.
In the step (5), the concentration of the zinc ion solution is 50-150mmol/L, and the zinc ion solution is one of zinc nitrate aqueous solution and zinc sulfate aqueous solution; the concentration of the hexamethylenetetramine solution is 25-75 mmol/L.
In the step (1), the used polyurethane sponge has a developed pore structure, and the size of the pores is 15-25 ppi.
Compared with the prior art, the invention has the following advantages:
(1) the polyurethane sponge modification method adopted by the invention is simple, convenient to operate and low in cost, and increases the surface roughness of the framework on the basis of not damaging the framework.
(2) The composite absorbent synthesized by the invention overcomes the defect of low oil-water selectivity of the traditional sponge, and solves the problem of blockage caused by easy expansion after the traditional oil-absorbing resin absorbs oil.
(3) According to the invention, ZnO nanoparticles are deposited on the surface of the resin to construct a micro-nano structure, so that the surface hydrophobicity and lipophilicity and the oil-water selectivity of the composite absorbent are further improved.
(4) The composite absorbent can be used for treating trace organic solvents in wastewater, has wider application range and higher practicability.
Drawings
FIG. 1 is a scanning electron micrograph of a sponge composite organic solvent absorbent of example 1;
FIG. 2 is a scanning electron microscope image of the oil-absorbing resin/sponge composite prepared in comparative example 1;
FIG. 3 is a graph showing absorption kinetics of the sponge composite type organic solvent absorbent of example 1;
FIG. 4 is a graph showing the absorption kinetics of the oil absorbent resin/sponge composite obtained in comparative example 1.
Detailed Description
In order to make the present invention easier to understand, the following examples will further illustrate the present invention, but the scope of the present invention is not limited to these examples.
The invention judges the absorption effect of the composite absorbent through the absorption rate and the relative absorption rate of the composite absorbent to the organic solvent, and the specific measurement method comprises the following steps: weighing a proper amount of dry absorbent, immersing the absorbent in a sufficient amount of organic solvent, taking out the absorbent after absorbing for a period of time, weighing the mass of the absorbent, calculating the absorption capacity according to the formula (1), and calculating the relative absorption rate according to the formula (2):
in the formula:Q-the absorption capacity of the absorbent to the organic solvent, g/g;m 1 -mass of the absorbent before absorption of the organic solvent, g; m2 absorbentAbsorbing the mass, g, of the saturated organic solvent;ɳ-the relative absorption rate of the absorbent for the organic solvent;Q 0.5 -absorption capacity at 0.5h of absorbent, g/g.
The method judges the actual application effect of the composite absorbent through the removal rate of the composite absorbent to trace organic solvents in water, and comprises the following specific measurement methods:
(1) and (4) measuring the content of trace butyl acetate in the aqueous solution.
Accurately transferring 10 mL of 1 mol/L NaOH solution and 10 mL of neutral ethanol by using a pipette, placing the NaOH solution and the neutral ethanol in a 150 mL conical flask, accurately measuring 5 mL of butyl acetate aqueous solution sample, adding the butyl acetate aqueous solution sample into the conical flask, fully oscillating, standing at normal temperature for 180min, using phenolphthalein as an indicator, titrating by using 0.5 mol/L hydrochloric acid standard solution until the solution is colorless from red, and reading the volume of the consumed hydrochloric acid standard solution. And simultaneously performing a blank test. The content C (mg/mL) of the trace butyl acetate in the aqueous solution is calculated according to the formula (3):
in the formula:Vvolume of sample, mL;V 0 -the blank consumes the volume of HCl titrant, mL;V 1 -the sample consumes the volume of HCl titrant, mL;M HCl -the molar concentration of standard hydrochloric acid, mol/L;
116.2-molar mass of butyl acetate, g/mol.
(2) Removing rate of trace butyl acetate in water solution.
Removal rate of micro butyl acetate in aqueous solution by composite absorbentP(%) calculated according to formula (4):
in the formula:Pthe removal rate of the composite absorbent to trace butyl acetate in the aqueous solution is percent;C-compoundingThe content of trace butyl acetate in the water solution after absorption by the absorbent is g/L;C 0 the initial content of trace butyl acetate in the aqueous solution, g/L.
Example 1
A preparation method of a sponge compound organic solvent absorbent comprises the following steps:
(1) immersing polyurethane sponge by using NaOH (10 wt%) aqueous solution, heating for 1.5h at 60 ℃, then washing by using deionized water and drying for later use;
(2) immersing the polyurethane sponge subjected to alkali treatment in the step (1) in the acrylic resin emulsion for 1.5h, taking out the polyurethane sponge, naturally drying the polyurethane sponge at room temperature, and repeating the process for 2 times;
(3) placing the polyurethane sponge loaded with the acrylic resin in the step (2) in a constant-temperature drying oven at 150 ℃ for curing for 2h to obtain an acrylic resin/polyurethane sponge composite material;
(4) the acrylic resin/polyurethane sponge composite material is added at a ratio of 5mmol/L-1Dipping the zinc acetate ethanol solution, and drying to obtain a ZnO seed crystal/acrylic resin/polyurethane sponge composite material;
(5) respectively prepare 50mmol/L-1Aqueous zinc nitrate solution and 25mmol/L-1And uniformly mixing the two solutions, then immersing the ZnO seed crystal/acrylic resin/polyurethane sponge composite material in the obtained mixed solution for 10 hours to grow ZnO nano particles, and drying to obtain the sponge composite organic solvent absorbent.
The absorption rate of the absorbent to toluene is 6.2g/g, and the relative absorption rate is 0.63; the absorption capacity to butyl acetate is 5.6g/g, and the relative absorption rate is 0.63; the absorption capacity for acetone was 2.8g/g, and the relative absorption rate was 0.61. The absorbent has a removal rate of 82% to 6g/L butyl acetate aqueous solution.
Comparative example 1
The difference from example 1 is that: step (4) and step (5) in example 1 were not included, and the other steps were the same as in example 1, so that comparative example 1 yielded an oil-absorbent resin/sponge composite. The composite material has the absorption capacity to toluene of 6.1g/g and the relative absorption rate of 0.34; the absorption capacity to butyl acetate is 5.5g/g, and the relative absorption rate is 0.35; the absorption capacity for acetone was 2.7g/g, and the relative absorption rate was 0.35. The absorbent has a removal rate of 50% to 6g/L butyl acetate aqueous solution.
As can be seen from fig. 1 and 2, the surface of the sponge composite organic solvent absorbent prepared in example 1 is accumulated with micro-nano particles with irregular shapes, so that the surface roughness of the absorbent is obviously improved, while the surface of the oil-absorbing resin/sponge composite material prepared in comparative example 1 is smooth; as can be seen from fig. 3 and 4, the absorption rate of the organic solvent by the sponge composite absorbent prepared in example 1 is significantly higher than that of comparative example 1, and the sponge composite absorbent of example 1 has the same saturated absorption capacity as that of the oil absorbent resin/sponge composite of comparative example 1.
Comparative example 2
The difference from example 1 is that: MgOH is adopted to replace NaOH.
The absorption rate of the obtained absorbent to toluene is 5.9g/g, and the relative absorption rate is 0.43; the absorption capacity to butyl acetate is 5.2g/g, and the relative absorption rate is 0.33; the absorption capacity for acetone was 2.3g/g, and the relative absorption rate was 0.35. The absorbent has 48 percent of removal rate of 6g/L butyl acetate aqueous solution.
Comparative example 3
The difference from example 1 is that: the NaOH concentration was 20 wt%.
The absorption rate of the obtained absorbent to toluene is 4.8g/g, and the relative absorption rate is 0.38; the absorption capacity to butyl acetate is 4.2g/g, and the relative absorption rate is 0.33; the absorption capacity for acetone was 1.9g/g, and the relative absorption rate was 0.31. The absorbent has a removal rate of 45% to 6g/L butyl acetate aqueous solution.
Example 2
A preparation method of a sponge compound organic solvent absorbent comprises the following steps:
(1) immersing polyurethane sponge by KOH (5 wt%) water solution, heating for 1h at 55 ℃, washing by deionized water and drying for later use;
(2) immersing the polyurethane sponge subjected to alkali treatment in the step (1) in the acrylic resin emulsion for 1.5h, taking out the polyurethane sponge, naturally drying the polyurethane sponge at room temperature, and repeating the process for 3 times;
(3) placing the polyurethane sponge loaded with the acrylic resin in the step (2) in a constant-temperature drying oven at 120 ℃ for curing for 2.5 hours to obtain an acrylic resin/polyurethane sponge composite material;
(4) mixing acrylic resin/polyurethane sponge composite material at a ratio of 15mmol/L-1Dipping the zinc acetate ethanol solution, and drying to obtain a ZnO seed crystal/acrylic resin/polyurethane sponge composite material;
(5) respectively prepare 150mmol/L-1ZnSO4Aqueous zinc nitrate solution and 75mmol/L-1And uniformly mixing the two solutions, then immersing the ZnO seed crystal/acrylic resin/polyurethane sponge composite material in the obtained mixed solution for 6 hours to grow ZnO nano particles, and drying to obtain the sponge composite organic solvent absorbent.
The absorption rate of the absorbent to toluene is 6.3g/g, and the relative absorption rate is 0.61; the absorption capacity to butyl acetate is 5.8g/g, and the relative absorption rate is 0.63; the absorption capacity for acetone was 2.6g/g, and the relative absorption rate was 0.63. The absorbent has a removal rate of 84% to 6g/L butyl acetate aqueous solution.
Example 3
A preparation method of a sponge compound organic solvent absorbent comprises the following steps:
(1) immersing polyurethane sponge by KOH (15 wt%) water solution, heating at 45 ℃ for 0.5h, washing by deionized water and drying for later use;
(2) immersing the polyurethane sponge subjected to alkali treatment in the step (1) in the acrylic resin emulsion for 1h, taking out the polyurethane sponge, naturally drying the polyurethane sponge at room temperature, and repeating the process for 2 times;
(3) placing the polyurethane sponge loaded with the acrylic resin in the step (2) in a constant-temperature drying oven at 100 ℃ for curing for 1.5h to obtain an acrylic resin/polyurethane sponge composite material;
(4) mixing acrylic resin/polyurethane sponge composite material at a ratio of 9mmol/L-1Zinc acetate ethanol solution impregnationDrying to obtain a ZnO seed crystal/acrylic resin/polyurethane sponge composite material;
(5) respectively prepare 90mmol/L-1ZnSO4Aqueous zinc nitrate solution and 45mmol/L-1And uniformly mixing the two solutions, then immersing the ZnO seed crystal/acrylic resin/polyurethane sponge composite material in the obtained mixed solution for 8 hours to grow ZnO nano particles, and drying to obtain the sponge composite organic solvent absorbent.
Example 4
A preparation method of a sponge compound organic solvent absorbent comprises the following steps:
(1) immersing polyurethane sponge by using NaOH (12 wt%) aqueous solution, heating for 1.5h at 40 ℃, washing by using deionized water and drying for later use;
(2) immersing the polyurethane sponge subjected to alkali treatment in the step (1) in the acrylic resin emulsion for 1.5h, taking out the polyurethane sponge, naturally drying the polyurethane sponge at room temperature, and repeating the process for 3 times;
(3) placing the polyurethane sponge loaded with the acrylic resin in the step (2) in a constant-temperature drying oven at 90 ℃ for curing for 4h to obtain an acrylic resin/polyurethane sponge composite material;
(4) mixing acrylic resin/polyurethane sponge composite material at a ratio of 12mmol/L-1Dipping the zinc acetate ethanol solution, and drying to obtain a ZnO seed crystal/acrylic resin/polyurethane sponge composite material;
(5) respectively prepare 120mmol/L-1ZnSO4Aqueous zinc nitrate solution and 60mmol/L-1And uniformly mixing the two solutions, then immersing the ZnO seed crystal/acrylic resin/polyurethane sponge composite material in the obtained mixed solution for 9 hours to grow ZnO nano particles, and drying to obtain the sponge composite organic solvent absorbent.
The absorption rate of the absorbent to toluene is 6.4g/g, and the relative absorption rate is 0.63; the absorption capacity to butyl acetate is 5.6g/g, and the relative absorption rate is 0.62; the absorption capacity for acetone was 2.9g/g, and the relative absorption rate was 0.62. The absorbent has a removal rate of 82% to 6g/L butyl acetate aqueous solution.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
1. A preparation method of a sponge compound organic solvent absorbent is characterized by comprising the following steps: the method comprises the following steps:
(1) immersing polyurethane sponge by using an alkaline solution, heating for 0.5-1.5h at 40-60 ℃, washing by using deionized water and drying for later use; the alkaline solution is one of a sodium hydroxide aqueous solution and a potassium hydroxide aqueous solution; the concentration of the alkaline solution is 5-15 wt%;
(2) immersing the polyurethane sponge subjected to alkali treatment in the step (1) in acrylic resin emulsion, taking out and drying after 0.5-1.5h, and repeating the process for 2-3 times;
(3) placing the polyurethane sponge loaded with the acrylic resin in the step (2) in a constant-temperature drying oven at 50-150 ℃ for curing for 1-4h to obtain an acrylic resin/polyurethane sponge composite material;
(4) dipping the acrylic resin/polyurethane sponge composite material by using a zinc acetate ethanol solution, and drying to obtain a ZnO seed crystal/acrylic resin/polyurethane sponge composite material;
(5) respectively preparing a zinc ion solution and a hexamethylenetetramine solution, uniformly mixing the two solutions, immersing the ZnO seed crystal/acrylic resin/polyurethane sponge composite material in the obtained mixed solution for 5-10h to grow ZnO nanoparticles, and drying to obtain the sponge composite organic solvent absorbent.
2. The preparation method of the sponge compound type organic solvent absorbent according to claim 1, which is characterized in that: in the step (2), the solid content of the acrylic resin emulsion is 40-50%.
3. The preparation method of the sponge compound type organic solvent absorbent according to claim 1, which is characterized in that: in the step (4), the concentration of the zinc acetate ethanol solution is 5-15 mmol/L.
4. The preparation method of the sponge compound type organic solvent absorbent according to claim 1, which is characterized in that: in the step (5), the concentration of the zinc ion solution is 50-150mmol/L, and the zinc ion solution is one of zinc nitrate aqueous solution and zinc sulfate aqueous solution; the concentration of the hexamethylenetetramine solution is 25-75 mmol/L.
5. The preparation method of the sponge compound type organic solvent absorbent according to claim 1, which is characterized in that: and (5) mixing the zinc ion solution and the hexamethylenetetramine solution according to the molar concentration ratio of 2: 1.
6. The preparation method of the sponge compound type organic solvent absorbent according to claim 1, which is characterized in that: in the step (1), the pore size of the used polyurethane sponge is 15-25 ppi.
7. A sponge composite type organic solvent absorbent obtained by the preparation method according to any one of claims 1 to 6.
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