CN114100331B - Volatile organic matter treatment material and preparation method and application thereof - Google Patents
Volatile organic matter treatment material and preparation method and application thereof Download PDFInfo
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- CN114100331B CN114100331B CN202010895466.8A CN202010895466A CN114100331B CN 114100331 B CN114100331 B CN 114100331B CN 202010895466 A CN202010895466 A CN 202010895466A CN 114100331 B CN114100331 B CN 114100331B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- 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
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
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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
- B01J20/28—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
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
- B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention relates to the field of air pollution treatment, and discloses a volatile organic matter treatment material, a preparation method and application thereof. The material has good collection and adsorption properties on volatile organic compounds, and can decompose the adsorbed organic compounds at the same time. The material is biodegradable, does not cause secondary pollution and has environmental protection.
Description
Technical Field
The invention relates to the field of atmospheric pollution treatment, in particular to a volatile organic matter treatment material and a preparation method and application thereof.
Background
Atmospheric pollution is one of the most outstanding environmental problems in China at present, and industrial waste gas is an important source of atmospheric pollutants and has the characteristics of high emission intensity, high concentration, multiple pollutant types, long duration and the like. The rapid development of industries such as petroleum, chemical engineering, printing and the like causes a large amount of volatile organic waste gases (VOCs) to be discharged into the atmosphere, which leads to the reduction of the quality of the atmospheric environment. Most of the organic substances have toxicity, and some of the organic substances are already listed as carcinogens, such as chloroethylene, benzene, polycyclic aromatic hydrocarbon and the like.
At present, the treatment technology of industrial organic waste gas mainly comprises two types, one is non-recovery method, such as combustion method and catalytic combustion method, and the other is recovery method, such as condensation method, adsorption method and absorption method. The adsorption method for purifying the gaseous pollutants refers to a method for separating a gas mixture by utilizing different adsorption selectivity of a solid phase adsorbent on each component in the gas mixture. As the most classical and commonly used gas purification technology, adsorption technology is also one of the mainstream technologies for the treatment of industrial VOCs at present, and activated carbon is the most commonly used adsorption material at present due to its extremely large specific surface area and adsorption capacity. However, the activated carbon has a small adsorption amount and a low adsorption selectivity, and only transfers toxic and harmful gases, rather than decomposes them, and may cause secondary pollution.
With the development of industry, the types of pollutants related to the VOCs are gradually increased, and the properties of the pollutants are different, so that higher requirements are made on adsorption materials and adsorption methods. The VOCs treatment technology is continuously innovated and developed towards a combined treatment process, so that various technologies can synergistically break through respective limits while exerting advantages of the technologies, efficiency is improved, and secondary pollution is reduced.
Disclosure of Invention
The invention aims to solve the problems of low efficiency and secondary pollution in VOCs treatment in the prior art, and provides a volatile organic compound treatment material and a preparation method and application thereof. The material has good collection and adsorption properties on volatile organic compounds, and can decompose the adsorbed organic compounds at the same time. The material is biodegradable, does not cause secondary pollution and has environmental protection.
In order to achieve the above object, a first aspect of the present invention provides a volatile organic compound-treating material comprising a crosslinked polymer containing a cyclodextrin-based compound structural unit and an epichlorohydrin structural unit, and titanium dioxide distributed in the crosslinked polymer.
Preferably, the material has a content of the crosslinked polymer of 90 to 99.9 wt% and a content of the titanium dioxide of 0.1 to 10 wt%.
Preferably, the volatile organic compound-treating material is in the form of a film.
In a second aspect, the invention provides a method of preparing a volatile organic treatment material, the method comprising:
(1) Carrying out polymerization reaction on an alkali solution of a cyclodextrin compound and epichlorohydrin to obtain a component A;
(2) Sequentially performing acid hydrolysis and alkali precipitation on titanium tetrachloride to obtain a precipitate, and then performing first contact on the precipitate and an oxidant to obtain a component B;
(3) And carrying out second contact on the component A and the component B to obtain the volatile organic compound treatment material.
In a third aspect, the invention provides a volatile organic compound-treating material prepared by the method as described above.
Preferably, the volatile organic compound treatment material is in the form of a film.
A fourth aspect of the invention provides the use of a volatile organic compound treating material as described above in the treatment of atmospheric pollution.
The volatile organic compound treatment material can efficiently adsorb volatile organic compounds, can quickly decompose adsorbed organic compounds, does not cause secondary pollution, and is a very practical volatile organic compound treatment material.
Drawings
FIG. 1 shows a film-like volatile organic compound-treating material produced in example 1 of the present invention.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The first aspect of the present invention provides a volatile organic compound treatment material comprising a crosslinked polymer containing a cyclodextrin-based compound structural unit and an epichlorohydrin structural unit, and titanium dioxide distributed in the crosslinked polymer.
In the present invention, the components of the volatile organic compound treatment material can be selected from a wide range, and preferably, the content of the crosslinked polymer in the material is 90 to 99.9 wt%, such as 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 99.3, 99.6, 99.9 wt% and any range of composition between any two values, and more preferably 95 to 99.5 wt%; the titanium dioxide may be present in an amount of 0.1 to 10 wt%, such as 0.1, 0.4, 0.7, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 wt% and any range between any two values, more preferably 0.5 to 5 wt%. Within the preferred range, the effect of the material in adsorbing and decomposing volatile organic compounds can be enhanced.
Preferably, the weight ratio of the cyclodextrin compound structural unit to the epichlorohydrin structural unit in the crosslinked polymer is 1:0.2 to 5, for example 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1. 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1: 2. 1: 3. 1: 4. 1:5 and any range between any two values, more preferably 1:0.8-2. Within the preferred range, the effect of the material on treating VOC can be improved.
In order to better achieve the effect of adsorbing and decomposing volatile organic compounds by the material, it is preferable that the volatile organic compound treatment material is in the form of a film. The thickness and size of the material can be selected by one skilled in the art as desired.
In the present invention, the method for preparing the crosslinked polymer preferably comprises: and carrying out polymerization reaction on the alkali solution of the cyclodextrin compound and epoxy chloropropane to obtain the cross-linked polymer.
In the present invention, the preparation method of the alkali solution of the cyclodextrin compound may be a preparation method that is conventional in the art, and preferably, the preparation method of the alkali solution of the cyclodextrin compound comprises: mixing the cyclodextrin compound with an alkali solution to dissolve the cyclodextrin compound in the alkali solution to obtain the alkali solution of the cyclodextrin compound.
In order to accelerate the dissolution speed, the mixture of the cyclodextrin compound and the alkali solution can be treated by heating, stirring, ultrasound and the like, and the operation method and conditions can be selected by those skilled in the art according to needs.
Preferably, the alkali solution is at least one of a sodium hydroxide solution and a potassium hydroxide solution.
In the present invention, the concentration of the alkali solution can be selected within a wide range, and preferably, the concentration of the alkali solution is 1 to 10 wt%, such as 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 wt%, and any range of composition between any two values.
In the present invention, the amount of the cyclodextrin compound to be used may be selected from a wide range, and preferably the alkali solution of the cyclodextrin compound contains 10 to 25 wt% of the cyclodextrin compound, for example, 10, 12, 14, 16, 18, 20, 22, 25 wt% and any range between any two values.
In the present invention, the cyclodextrin compound may be any one of existing cyclodextrin compounds, and preferably, the cyclodextrin compound is selected from cyclodextrin and/or cyclodextrin ether derivatives.
The cyclodextrin includes, but is not limited to, alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin.
Among them, the substituent in the cyclodextrin ether derivative includes, but is not limited to, alkyl, hydroxyalkyl or sulfoalkyl. The cyclodextrin ether derivatives may be hydroxypropyl-beta-cyclodextrin, randomly methylated-beta-cyclodextrin and sulfobutyl-beta-cyclodextrin.
Among them, randomly methylated- β -Cyclodextrin (random methylated- β -Cyclodextrin, RM- β -CD) is commercially available.
In a preferred embodiment of the present invention, the cyclodextrin is selected from at least one of α -cyclodextrin, β -cyclodextrin, γ -cyclodextrin, hydroxypropyl- β -cyclodextrin, randomly methylated- β -cyclodextrin and sulfobutyl- β -cyclodextrin, more preferably from at least one of β -cyclodextrin, hydroxypropyl- β -cyclodextrin, randomly methylated- β -cyclodextrin and sulfobutyl- β -cyclodextrin. In the above preferable aspect, the VOC treatment effect of the volatile organic compound-treating material can be further improved.
In the present invention, the amount of epichlorohydrin may be selected from a wide range, and preferably, the ratio of the amount of cyclodextrin compound to the amount of epichlorohydrin is 1:0.2 to 5, for example 1:0.2, 1:0.4, 1:0.6, 1:0.8, 1:1. 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1: 2. 1: 3. 1: 4. 1:5 and any range between any two values, more preferably 1:0.8-2.
In the present invention, the rate of addition of the epichlorohydrin may be selected within a wide range, and preferably, the rate of addition of the epichlorohydrin is 0.5 to 10 parts by volume/min with respect to 100 parts by volume of the alkali solution of the cyclodextrin-based compound.
In the present invention, the method for adding the epichlorohydrin may not be particularly limited, and is preferably added by dropwise addition.
In the present invention, preferably, the polymerization conditions include: the temperature is 20-80 ℃ and the time is 0.5-4h.
In a second aspect, the invention provides a method of preparing a volatile organic treatment material, the method comprising:
(1) Performing polymerization reaction on alkali solution of cyclodextrin compounds and epoxy chloropropane to obtain a component A;
(2) Sequentially performing acid hydrolysis and alkali precipitation on titanium tetrachloride to obtain a precipitate, and then performing first contact on the precipitate and an oxidant to obtain a component B;
(3) And carrying out second contact on the component A and the component B to obtain the volatile organic compound treatment material.
In the present invention, specific methods and conditions for preparing component A in step (1) can be referred to the preparation method of the crosslinked polymer of the first aspect, and will not be described herein.
In the present invention, component A obtained by polymerization is present in the form of a liquid in the above-mentioned method and corresponding conditions.
The kind of the cyclodextrin compound is as described in the first aspect.
In the present invention, the liquid component B containing titanium dioxide is prepared according to the method described in the step (2).
In the present invention, the liquid state may refer to a state of a solution, a gel state, or a suspension, and not a state existing in a gas state or a solid state.
In the present invention, the amount of titanium tetrachloride may be selected within a wide range, and preferably, the amount of titanium tetrachloride is such that the content of titanium dioxide in the volatile organic compound-treated material is 1 to 10% by weight.
In the present invention, the acid hydrolysis method preferably includes: titanium tetrachloride is hydrolyzed using an acid solution. The acid solution may be any acid solution conventionally used in the art, such as a hydrochloric acid solution, a sulfuric acid solution, or a nitric acid solution.
Wherein the concentration of the acid solution can be selected within a wide range, preferably the concentration of the acid solution is 2-6M.
In the present invention, the amount ratio of titanium tetrachloride to acid solution can be selected within a wide range, and it is preferable that the weight ratio of titanium tetrachloride to acid solution is 1:1-10.
In the present invention, the product of the acid hydrolysis is precipitated under alkaline conditions, which may be achieved by adding an alkaline solution or other means providing alkaline conditions, preferably by adding an alkaline solution.
In a preferred embodiment of the present invention, the manner of alkali precipitation comprises: an alkaline solution was added to the product of the acid hydrolysis so that the pH of the reaction system was 7.5 to 10, to obtain a precipitate.
The alkaline solution may be ammonia water, sodium hydroxide solution, potassium hydroxide solution, etc., and preferably ammonia water.
The concentration of the alkaline solution can be selected from a wide range, for example, the concentration of the weak alkaline aqueous ammonia can be 5-15 wt%. The concentration of the strong base (e.g., sodium hydroxide solution or potassium hydroxide solution) may be 1-5M.
In the present invention, the addition rate of the alkaline solution can be selected within a wide range, and preferably, the addition rate of the alkaline solution is 0.5 to 10 parts by volume/min with respect to 100 parts by volume of the product of the acid hydrolysis.
In the present invention, the amount of the alkaline solution to be added may not be particularly limited as long as the reaction system can be brought to a pH of 7.5 to 10.
In order to enable the precipitation reaction to proceed better, it is preferable to obtain the precipitate by dropping aqueous ammonia.
In the present invention, the obtained precipitate may be separated by a conventional method, such as centrifugation or filtration, and the obtained precipitate may be washed with water.
Preferably, in step (2), the first contacting comprises: dissolving the precipitate in the oxidant, and reacting the obtained material at 100-120 ℃ for 16-24h to obtain the component B.
In the present invention, the kind of the oxidizing agent may be an oxidizing agent conventional in the art, and preferably, the oxidizing agent is hydrogen peroxide.
In the present invention, the oxidizing agent is preferably used in an amount of 20 to 200 parts by weight, for example, 20, 40, 60, 80, 100, 120, 140, 160, 180, 200% by weight and any range between any two values, on a pure substance basis, with respect to 100 parts by weight of the precipitate.
In the present invention, preferably, the oxidizing agent is present in the form of a solution. The concentration of the oxidizing agent can be selected within wide limits, preferably the concentration of the oxidizing agent in the oxidizing agent solution is from 10 to 40% by weight.
In the present invention, the content of titanium dioxide in component B is preferably 1 to 30% by weight, and may be, for example, 1, 5, 10, 15, 20, 25, 30% by weight and any range of composition between any two values, more preferably 5 to 10% by weight, and still more preferably 5 to 7% by weight. Within the preferred range, the effect of the material in adsorbing and decomposing volatile organic compounds can be enhanced.
It is to be understood that when the concentration of the oxidizing agent is such that the content of titanium element in component B is within the above range, the concentration adjustment may not be performed, and when the concentration of the oxidizing agent is not high enough to make the content of titanium element in component B within the above range, the content of titanium element in component B may be adjusted by dilution.
The dilution can be carried out before or after the reaction of the precipitate and the oxidant, and preferably, in the step (2), the obtained material is diluted by water before reacting for 16-24h at 100-120 ℃, and the dilution is carried out by a factor of 1-30 wt% of the titanium dioxide content in the component B.
In the invention, the component A and the component B are subjected to second contact, so that the component A and the component B are mixed, and further, the titanium dioxide is distributed in the cross-linked polymer containing the cyclodextrin compound structural unit and the epichlorohydrin structural unit.
Wherein the conditions of the second contacting preferably include: the temperature is 40-90 ℃ and the time is 0.5-4h.
In order to enable the titanium dioxide to be more uniformly distributed in the crosslinked polymer containing the cyclodextrin compound structural unit and the epichlorohydrin structural unit, the mixing can be promoted in the second contact process by stirring, ultrasound and the like.
In the present invention, preferably, the method further comprises: and carrying out post-treatment on the obtained volatile organic compound treatment material to obtain a film-shaped volatile organic compound treatment material.
The post-treatment method may be a method conventionally employed in the art, and preferably includes at least one of deaeration, molding, and drying.
In the present invention, defoaming can be performed by a defoaming method which is conventional in the art, and defoaming can be performed by, for example, a still standing or defoaming apparatus.
In the present invention, one skilled in the art can prepare products with different shapes according to needs by using a conventional forming method in the art, and details of the specific forming method are not described.
In the present invention, the drying conditions may not be particularly limited, and may be adjusted by those skilled in the art according to circumstances.
In a third aspect, the invention provides a volatile organic compound-treating material prepared by the method as described above.
Preferably, the volatile organic compound treatment material is in the form of a film.
A fourth aspect of the invention provides the use of a volatile organic compound treating material as described above in the treatment of atmospheric pollution.
Preferably, the volatile organic treatment material as described above has application in adsorbing and/or decomposing volatile organic compounds.
For example, when the voc treatment material is in the form of a film, it can be used to cover soil contaminated with voc for adsorbing and decomposing the voc, thereby blocking the voc from volatilizing from the soil into the atmosphere.
The present invention will be described in detail below by way of examples.
In the following examples, reagents and materials used are commercially available unless otherwise specified.
In the following examples, the concentration of dilute hydrochloric acid was 1mol/L.
By NH 3 The concentration of ammonia was 10% by weight.
Example 1
This example illustrates the preparation of a volatile organic compound-treating material according to the present invention
(1) Adding 100g of beta-cyclodextrin into 400g of 1 weight percent sodium hydroxide solution, heating and stirring in an oil bath at 50 ℃ until the cyclodextrin is completely dissolved, dropwise adding 120g of epoxy chloropropane, and reacting at 80 ℃ for 1 hour to obtain the component A. The detection shows that the beta-cyclodextrin and the epichlorohydrin are not remained basically, which indicates that the reactant is basically and completely participated in the reaction.
(2) 10g of titanium tetrachloride was hydrolyzed in 20mL of dilute hydrochloric acid, and after the hydrolysis, ammonia water was added dropwise thereto to a pH of 9, and a white precipitate appeared. Filtering, washing with water, collecting precipitate, adding the precipitate into 6g of 30 wt% hydrogen peroxide, stirring until the precipitate is clear, adding 60g of deionized water, and reacting the obtained aqueous solution in an oil bath at 120 ℃ for 24 hours to obtain a component B.
(3) The component A and the component B were mixed and then reacted at 80 ℃ for 1 hour. And placing the product after the reaction in a glass flat-bottom culture dish, standing for defoaming, placing the culture dish in an oven for drying, washing the culture dish for many times by using deionized water, and drying to obtain the membranous volatile organic compound treatment material (see figure 1).
Example 2
This example illustrates the preparation of a volatile organic compound-treating material according to the present invention
(1) Adding 100g of beta-cyclodextrin into 400g of 5 wt% sodium hydroxide solution, heating and stirring in an oil bath at 50 ℃ until the cyclodextrin is completely dissolved, dropwise adding 160g of epoxy chloropropane, and reacting at 80 ℃ for 1 hour to obtain the component A. The detection shows that the beta-cyclodextrin and the epichlorohydrin are not remained basically, which indicates that the reactant is basically and completely participated in the reaction.
(2) 25g of titanium tetrachloride was hydrolyzed in 50mL of dilute hydrochloric acid, and after completion of the hydrolysis, ammonia was added dropwise to a pH of 9, and a white precipitate appeared. And filtering, washing and collecting precipitate, adding the precipitate into 14g 30 wt% hydrogen peroxide, stirring until the precipitate is clear, adding 140g deionized water, and reacting the obtained aqueous solution in an oil bath at 120 ℃ for 24 hours to obtain a component B.
(3) The component A and the component B are fully mixed and reacted for 1 hour at the temperature of 80 ℃. And placing the reacted product in a glass flat-bottom culture dish, standing for defoaming, placing the culture dish in an oven for drying, washing the culture dish for many times by using deionized water, and drying to obtain the membranous volatile organic compound treatment material.
Example 3
This example illustrates the preparation of a volatile organic compound treating material according to the present invention
(1) Adding 100g of beta-cyclodextrin into 400g of 5 weight percent sodium hydroxide solution, heating and stirring in an oil bath at 50 ℃ until the cyclodextrin is completely dissolved, dropwise adding 160g of epoxy chloropropane, and reacting at 80 ℃ for 1 hour to obtain the component A. The detection shows that the beta-cyclodextrin and the epichlorohydrin are not remained basically, which indicates that the reactant is basically and completely participated in the reaction.
(2) 5g of titanium tetrachloride was hydrolyzed in 10mL of dilute hydrochloric acid, and after completion of the hydrolysis, ammonia was added dropwise to a pH of 9, and a white precipitate appeared. Filtering, washing with water, collecting precipitate, adding the precipitate into 3g of 30 wt% hydrogen peroxide, stirring until the precipitate is clear, adding 30g of deionized water, and reacting the obtained aqueous solution in an oil bath at 120 ℃ for 24 hours to obtain a component B.
(3) The component A and the component B are fully mixed and reacted for 1 hour at the temperature of 80 ℃. And placing the reacted product in a glass flat-bottom culture dish, standing for defoaming, placing the culture dish in an oven for drying, washing the culture dish for many times by using deionized water, and drying to obtain the membranous volatile organic compound treatment material.
Example 4
This example illustrates the preparation of a volatile organic compound treating material according to the present invention
(1) 100g of beta-cyclodextrin is added into 400g of 5 weight percent sodium hydroxide solution, heated and stirred in an oil bath at 50 ℃ until the cyclodextrin is completely dissolved, 200g of epoxy chloropropane is added drop by drop, and the reaction is carried out for 1 hour at 80 ℃ to obtain the component A. Detection shows that the beta-cyclodextrin and the epichlorohydrin are basically not remained, which indicates that the reactant is basically and completely participated in the reaction.
(2) 6g of titanium tetrachloride was hydrolyzed in 10mL of dilute hydrochloric acid, and after completion of the hydrolysis, ammonia was added dropwise to a pH of 9, and a white precipitate appeared. Filtering, washing and collecting precipitate, adding the precipitate into 4g of 30 wt% hydrogen peroxide, stirring until the precipitate is clear, adding 30g of deionized water, and reacting the obtained aqueous solution in an oil bath at 120 ℃ for 24 hours to obtain a component B.
(3) The component A and the component B are fully mixed and reacted for 1 hour at the temperature of 80 ℃. And placing the reacted product in a glass flat-bottom culture dish, standing for defoaming, placing the culture dish in an oven for drying, washing the culture dish for many times by using deionized water, and drying to obtain the membranous volatile organic compound treatment material.
Example 5
This example illustrates the preparation of a volatile organic compound treating material according to the present invention
The procedure was as described in example 3, except that equal mass of hydroxypropyl- β -cyclodextrin was used instead of β -cyclodextrin.
Example 6
This example illustrates the preparation of a volatile organic compound treating material according to the present invention
The procedure was followed as described in example 3, except that an equal mass of randomly methylated-beta-cyclodextrin was used instead of beta-cyclodextrin.
Example 7
This example illustrates the preparation of a volatile organic compound treating material according to the present invention
The procedure was followed as described in example 3, except that an equal mass of sulfobutyl-beta-cyclodextrin was used instead of beta-cyclodextrin.
Example 8
This example illustrates the preparation of a volatile organic compound-treating material according to the present invention
The procedure was as in example 1, except that the amount of titanium tetrachloride used was 20g.
Example 9
This example illustrates the preparation of a volatile organic compound treating material according to the present invention
The procedure was as described in example 1, except that 5g of titanium tetrachloride was used.
Example 10
This example illustrates the preparation of a volatile organic compound treating material according to the present invention
The procedure was followed as described in example 1, except that 19g of titanium tetrachloride and 280g of epichlorohydrin were used.
Example 11
This example illustrates the preparation of a volatile organic compound treating material according to the present invention
The procedure was followed as described in example 1, except that the amount of titanium tetrachloride was 6g and the amount of epichlorohydrin was 60g.
Example 12
This example illustrates the preparation of a volatile organic compound treating material according to the present invention
The procedure was as described in example 1, except that in step (2), deionized water was not added after dissolving the precipitate in hydrogen peroxide, and the amount of component B added was 1g.
Test example
This test example is intended to demonstrate the ability of a volatile organic treatment material to adsorb volatile organic compounds
0.5mL of toluene was added to a 5mL triangular flask, the triangular flask mouths were covered with the films prepared in examples 1 to 15, respectively, and then the triangular flask with the closed mouth was put into a 5L jar, and the lid was closed, and the VOC value in the jar was measured at regular intervals.
0.5mL of toluene was added to a 5mL triangular flask, and the flask was directly placed in a 5L jar without sealing, and the VOC value in the jar was measured at regular intervals as a blank control.
The VOC values measured are shown in Table 1 (unit: ppm).
TABLE 1
| Numbering | 0.5 hour | 1 hour (h) | 2 hours | 5 hours |
| Example 1 | 4.6 | 3.5 | 6.3 | 6.1 |
| Example 2 | 2.5 | 4.3 | 3.9 | 4.8 |
| Example 3 | 2.7 | 2.9 | 3.5 | 3.6 |
| Example 4 | 4.2 | 3.9 | 5.0 | 4.1 |
| Example 5 | 3.3 | 5.1 | 7.3 | 6.4 |
| Example 6 | 3.5 | 4.2 | 4.8 | 6.0 |
| Example 7 | 6.3 | 8.5 | 6.6 | 7.9 |
| Example 8 | 32.4 | 45.4 | 39.2 | 47.1 |
| Example 9 | 22.3 | 25.4 | 25.8 | 30.1 |
| Example 10 | 8.9 | 11.3 | 15.4 | 16.2 |
| Example 11 | 25.1 | 28.4 | 29.8 | 33.6 |
| Example 12 | 19.2 | 24.4 | 28.1 | 27.5 |
| Blank control | 3310 | 3239 | 3411 | 3385 |
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (14)
1. A method of preparing a volatile organic treatment material, the method comprising:
(1) Carrying out polymerization reaction on an alkali solution of a cyclodextrin compound and epichlorohydrin to obtain a component A;
(2) Sequentially performing acid hydrolysis and alkali precipitation on titanium tetrachloride to obtain a precipitate, and then performing first contact on the precipitate and an oxidant, wherein the first contact comprises the following steps: dissolving the precipitate in the oxidant, and reacting the obtained material at 100-120 ℃ for 16-24h to obtain a component B;
(3) Carrying out second contact on the component A and the component B, and carrying out post-treatment on the obtained product to obtain a film-shaped volatile organic compound treatment material;
the material comprises a cross-linked polymer containing a cyclodextrin compound structural unit and an epichlorohydrin structural unit and titanium dioxide distributed in the cross-linked polymer;
wherein, in the material, the content of the cross-linked polymer is 95 to 99.5 weight percent, and the content of the titanium dioxide is 0.5 to 5 weight percent; the weight ratio of the cyclodextrin compound structural unit to the epichlorohydrin structural unit in the crosslinked polymer is 1:0.8 to 2;
wherein the content of titanium dioxide in the component B is 5-10 wt%.
2. The method according to claim 1, wherein the cyclodextrin compound is cyclodextrin and/or a derivative thereof, and the alkali solution is at least one of a sodium hydroxide solution and a potassium hydroxide solution.
3. The method of claim 2, wherein the cyclodextrin is selected from at least one of a-cyclodextrin, β -cyclodextrin, and γ -cyclodextrin.
4. The method of claim 2, wherein the cyclodextrin ether derivative is selected from at least one of hydroxypropyl- β -cyclodextrin, methyl- β -cyclodextrin, randomly methylated- β -cyclodextrin, and sulfobutyl- β -cyclodextrin.
5. The method according to claim 2, wherein the cyclodextrin compound is selected from at least one of β -cyclodextrin, hydroxypropyl- β -cyclodextrin, randomly methylated- β -cyclodextrin, and sulfobutyl- β -cyclodextrin.
6. The method according to claim 1, wherein the alkali solution of the cyclodextrin compound contains the cyclodextrin compound in an amount of 10 to 25 wt%.
7. The process of claim 1, wherein in step (1), the polymerization conditions comprise: the temperature is 20-80 ℃ and the time is 0.5-4h.
8. The method of claim 1, wherein the oxidizing agent is hydrogen peroxide.
9. The method according to claim 8, wherein the oxidizing agent is used in an amount of 20 to 200 parts by weight on a pure basis with respect to 100 parts by weight of the precipitate.
10. The process of claim 1 wherein the titanium dioxide content of component B is from 5 to 7% by weight.
11. The method of claim 1, wherein the conditions of the second contacting comprise: the temperature is 40-90 ℃ and the time is 0.5-4h.
12. A volatile organic treatment material produced by the method of any one of claims 1 to 11.
13. Use of the volatile organic compound treatment material of claim 12 in the treatment of atmospheric pollution.
14. Use of the volatile organic treatment material of claim 12 to adsorb and/or decompose volatile organic compounds.
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