CN116272904A - MOFs composite VOCs adsorbent and preparation method thereof - Google Patents
MOFs composite VOCs adsorbent and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a MOFs composite material VOCs adsorbent and a preparation method thereof. The beneficial effects of the invention are as follows: compared with the traditional activated carbon adsorbent, the MOFs composite material synthesized by the method has higher specific surface area, higher adsorption capacity and higher selectivity on adsorption substances.
Description
Technical Field
The invention relates to the technical field related to volatile organic waste gas treatment, in particular to a MOFs composite material VOCs adsorbent and a preparation method thereof.
Background
Organic waste gas VOCs, i.e. volatile organic compounds VOCs (volatile organic compounds), are various organic compounds with boiling points of 50 ℃ to 260 ℃ at normal temperature, according to the World Health Organization (WHO) definition. In China, the organic compound with saturated vapor pressure higher than 70Pa at normal temperature and boiling point lower than 260 ℃ at normal pressure or all organic compounds with corresponding volatility with vapor pressure higher than or equal to 10Pa at 20 ℃ are generally referred to. The active volatile organic compounds are specified in the environmental protection meaning that the volatile organic compounds can participate in the atmospheric photochemical reaction to generate harm, and can be further divided into eight categories according to the chemical structure of the volatile organic compounds: alkanes, aromatic hydrocarbons, alkenes, halocarbons, esters, aldehydes, ketones, and others. The main components of VOCs are: hydrocarbons, halogenated hydrocarbons, oxygenated and nitrided hydrocarbons, including benzene series, organic chlorides, freon series, organic ketones, amines, alcohols, ethers, esters, acids, and petroleum hydrocarbon compounds, etc., have been identified as 300 or more. The most common are benzene, toluene, xylene, styrene, trichloroethylene, trichloromethane, trichloroethane, diisocyanate (TDI), diisocyanatotoluene, and the like.
Sources of VOCs include natural sources and artificial sources, and in cities, the natural sources of VOCs are mainly green vegetation and basically belong to uncontrollable sources; the artificial sources mainly comprise incomplete combustion behavior, solvent use, industrial processes, oil volatilization, biological action and the like. At present, the emission of VOCs in China mainly comes from fixed source combustion, road traffic, solvent product use and industrial processes. Among the many man-made sources, industrial sources are the main sources of VOCs pollution, and have the characteristics of concentrated emission, high emission intensity, high concentration and complex components.
The outdoor VOCs are mainly from outdoor industrial gas, namely gas emitted by industrial production or various machines, and have a wider range, including gas volatilized in the industrial production process, automobile tail gas, photochemical smog and the like. The indoor smoke mainly comes from combustion products such as fire coal, natural gas and the like, smoking, heating, cooking and the like, and the emission of building and decorative materials, furniture, household appliances, cleaning agents, human bodies and the like.
The sources of organic waste gas VOCs are various, and the generation mode and the emission mode are different, so that the treatment method of the organic waste gas VOCs needs to be selected according to the actual conditions in the actual production process. The existing treatment methods of organic waste gas VOCs mainly comprise a condensation recovery method, a liquid absorption method, a membrane separation method, a combustion method, an active carbon adsorption method, a low-temperature ionic liquid method, a biological treatment method and the like, and various process combinations are adopted.
The condensation method is a method of recovering the waste gas after the waste gas is cooled to below the dew point of the VOCs component and condensed into a liquid state. The method is mostly suitable for the treatment of the VOCs with high concentration (the concentration of the VOCs is more than or equal to 5000 ppm) and single component with recovery value, the treatment efficiency is between 50 and 85 percent, and when the concentration of the VOCs is more than or equal to 1 percent, the recovery rate can reach 90 percent. The advantages are high efficiency and recoverable components; the defects are high cost and high energy consumption. Condensation is often used in conjunction with other techniques, such as adsorption, washing, etc., as a pretreatment step.
The absorption method is a method of removing VOCs by contacting the exhaust gas with a scrubbing liquid, and then neutralizing, oxidizing or reacting the VOCs with a chemical agent. Is suitable for VOCs with high water solubility and is not suitable for low-concentration gas. The removal rate of VOCs can reach 80% -90%. The method has the advantages that the method can remove gaseous VOCs and particulate matters, has high mass transfer efficiency, and can remove acid gas with high efficiency; the defect is that the subsequent wastewater treatment is carried out, and the maintenance cost is high.
The membrane separation technology is to utilize artificial synthetic membrane, and commonly used porous glassy polymer material forms a molecular sieve membrane to recover volatile components. Is suitable for separating high-concentration VOCs, and the recovery efficiency can reach 90% -99%. The method has the advantages of high efficiency, high definition degree, recoverable components and integration of other technologies; the disadvantages are high cost, membrane pollution, poor stability of the membrane, and small flux of the membrane.
The combustion method is a purification method for directly burning and removing the exhaust gas VOCs, and can be classified into a direct combustion method, a thermal combustion method and a catalytic combustion method according to different combustion equipment and materials used. The thermal combustion method needs to fully mix the organic waste gas and the fuel gas at high temperature to realize complete combustion. The method is suitable for treating high-concentration and small-gas-amount combustible gas, has high purification efficiency, and thoroughly oxidizes and decomposes organic waste gas, and has the defects that: equipment is easy to corrode, the treatment cost is high, and secondary pollution is easy to form; the catalytic combustion method needs to quickly oxidize hydrocarbon in the organic waste gas into water and carbon dioxide under the condition of low temperature under the action of a catalyst, so as to achieve the aim of treatment. Disadvantages: the catalyst is easy to poison, and the input cost is high;
the biodegradation method is to utilize microorganisms to digest and metabolize pollutants in the waste gas and convert the pollutants into harmless water, carbon dioxide or other inorganic salts. The biodegradation method is suitable for hydrophilic organic matters which can be decomposed by microorganisms, and comprises various organic matters consisting of hydrocarbon and oxygen, simple organic sulfide, organic nitride, inorganic matters such as hydrogen sulfide or ammonia gas and the like. Is suitable for removing VOCs with medium, low concentration and medium air quantity, and the removal rate can reach 90 percent. The method has the advantages of mild conditions, normal temperature and normal pressure, simple equipment, convenient maintenance and no secondary pollution; the defects are that the occupied area is large, the influence of climate is large, the influence of working condition change is large, the early debugging time is long, and pollutants cannot be recovered.
The photocatalytic oxidation method is to use photocatalytic nano particles to generate electron hole pairs under the condition of illumination with a certain wavelength (usually ultraviolet light), decompose water adsorbed on the surface of a catalyst into hydroxyl groups, reduce surrounding oxygen into active oxygen by electrons, and oxidize surrounding organic waste gas by the aid of the strong oxidation-reduction capability of the photocatalytic nano particles and the active oxygen, so that a pollutant degradation effect is achieved. The method is suitable for treating the organic waste gas with low concentration (generally less than 1000mg/m < 3 >) and large air quantity. The method has the advantages of low energy consumption, low initial investment and operation cost and complete oxidation; the disadvantage is that the waste gas needs to be pretreated, so that the catalyst is prevented from being deactivated by covering TiO2, an ultraviolet light source is needed, and the energy utilization rate is required to be improved. The removal rate of VOCs is generally 50% -70%.
The plasma technology is that under strong electric field, gas is discharged to form high-energy electrons, ions, excited atoms and free radicals, and finally forms excited oxygen plasmas and ozone at all levels, which act on VOCs to oxidize and dissociate the VOCs into small molecular substances such as CO2, CO, H2O and the like. The method is suitable for purifying organic matters with low concentration (generally less than 500mg/m < 3 >) and large air quantity, and can also purify indoor air. The device has the advantages of capability of removing VOCs at low temperature, easy operation and maintenance, simple device and convenient opening; the disadvantage is that the power supply determines the electron energy and the final treatment effect, the exhaust gas is pre-treated and the discharge safety is noted. The VOCs removal rate is generally about 50%. In general, a proper treatment technology or a proper combination of technologies should be selected according to the requirements of the concentration, the flow rate, the type of the characteristic pollutants and the removal rate of the waste gas. Meanwhile, the factors such as equipment cost, operation cost, maintenance cost and the like should be comprehensively considered.
The adsorption method utilizes the adsorbent to adsorb the organic waste gas, and is suitable for treating the low-concentration organic waste gas. High purifying efficiency and low cost. The adsorption method utilizes physical combination or chemical reaction of the adsorbent and pollutants (VOCs) to remove the pollutants, is suitable for purifying the VOCs with medium and low concentrations, has high universality and easy operation, is not suitable for organic gases with high concentration, high temperature and high humidity, has poor regeneration capacity of the adsorption material, and the adsorption capacity is continuously reduced along with the regeneration times, so that the adsorption material needs to be replaced regularly, and the removal rate of the VOCs is changed along with the service time of the adsorbent and is generally between 30 and 90 percent.
In combination, the adsorption method has the advantages of high efficiency, low energy consumption, simple operation, recoverability and the like, so that the adsorption method becomes a common effective technical means for removing VOCs, and the existing adsorbents for VOCs adsorption mainly comprise activated carbon, activated carbon fiber, diatomite, molecular sieve, metal organic framework material, organic adsorbent and the like.
The activated carbon and the activated carbon fiber belong to carbon-based porous materials, have large adsorption capacity, acid and alkali resistance and low cost, are the adsorbent materials with the most wide application, but the abundant surface groups of the activated carbon and the activated carbon fiber are easy to chemically adsorb with VOCs molecules or form stable hydrogen bonds, the desorption/desorption is not thorough, and the regeneration is difficult due to the fact that the carbon-based material is not resistant to high temperature; the diatomite is a diatomite shell composed of amorphous hydrated silicon dioxide, has poor hydrothermal stability and is mainly of a macroporous structure, and is not beneficial to VOCs gas adsorption under low concentration; mesoporous silica is also limited by mesoporous channels with larger self, has relatively weak adsorption binding force on VOCs molecules with smaller kinetic diameters, and has poor capability of enriching low-concentration VOCs gas; molecular sieves have the advantages of large specific surface area (500-1000 m < 2 >/g), recycling, high adsorption capacity, high temperature resistance, good hydrophobicity and the like, and are widely applied to the adsorption of VOCs, but the pore structures of common molecular sieves (MCM-14, beta-1, X molecular sieves and Y molecular sieves) are relatively fixed (micropores or mesopores), so that the simple non-differentiated adsorption can be carried out on some VOCs, and the adsorption effect on some large VOCs is poor, so that the actual condition of the adsorption of complex components of VOCs is difficult to meet. The Metal-organic framework material (Metal-OrganicFrameworks, MOFs) is an ordered network structure formed by coordination of organic bridging ligands and inorganic Metal ions. MOFs material has the advantages of ultrahigh specific surface area, lower crystal density, pore size, functional adjustability and the like, and has good application prospect in the fields of VOCs adsorption separation and the like.
Because MOFs materials have low atomic density and cannot provide enough dispersion force to capture small molecular substances, the MOFs materials are generally prepared into composite materials to overcome or weaken the defects, so that the adsorption performance of MOFs materials is improved. The MOFs crystal usually exists in a powder form, is not easy to process and recycle in practical application, and even can cause powder pollution, so that the shaping treatment of the MOFs is beneficial to improving the utilization efficiency and widening the application range of the MOFs. CN104226255a discloses a preparation method of a metal-organic framework-graphene oxide composite material, by stripping graphite oxide to obtain thinner and more flexible graphene oxide, and by changing the synthesis conditions of MILs-53 to control the crystal form of the graphene oxide, graphene oxide (GrO) and MILs-53 material can be compounded by utilizing the advantage that graphene oxide (GrO) has rich oxygen-containing functional groups, and a new material with large specific surface area and higher atomic density can be prepared, so that the CO2 adsorption performance of the material can be obviously improved, but the adsorption capacity of the material is improved, the specific surface area is not improved, the adsorption capacity and selectivity for other gases are still insufficient, and the organic waste gas VOCs can not be effectively treated.
Disclosure of Invention
Aiming at the problems that the traditional adsorbent is insufficient in adsorption capacity of active carbon, poor in selectivity and difficult to desorb part of substances in the treatment of organic waste gas in the prior art, the invention provides a MOFs composite material. Compared with the traditional adsorbent, the adsorbent synthesized by the invention has the advantages of stronger adsorption capacity, higher selectivity, good product stability, convenience in molding and the like.
The invention provides the following technical scheme:
a preparation method of MOFs composite VOCs adsorbent comprises the following steps:
firstly, preparing modified activated carbon, washing the activated carbon with deionized water, soaking, standing, removing upper impurities, ash and supernatant, and drying; adding dried asphalt-based activated carbon into HNO3 solution, stirring for reaction, stirring at room temperature for 3h, filtering to obtain solid, washing with water to neutrality, drying at constant temperature, and performing ozone oxidation on the product again to increase carboxyl content of the oxidized activated carbon to obtain modified activated carbon C Ⅰ ；
Second step, modified activated carbon C Ⅰ Adding into metal salt aqueous solution, stirring and mixing for 2h at room temperature, centrifuging to separate solid, and drying at constant temperature to obtain modified activated carbon C Ⅱ ；
Thirdly, taking organic ligand solution and activated carbon C Ⅱ Adding an organic alkali reagent into deionized water solution of metal salt, stirring and mixing for 30min at room temperature, placing the mixture into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃ for 30min, reacting at constant temperature for 24h, washing the product with ethanol and deionized water for 2-3 times after the reaction is finished, and removing a template agent to obtain the composite material of the target product activated carbon and MOFs.
Further, the activated carbon selected in the first step is one of coconut shell activated carbon, fruit shell activated carbon, wood column activated carbon and wood powder activated carbon, and preferably is coconut shell activated carbon.
Further, the nitric acid concentration used in the first reaction step is 6 to 9mol/L, preferably 8 mol/L.
Further, the temperature of the first reaction using ozone oxidation is 20-25 ℃.
Further, the metal salt used in the second reaction and the third reaction is zinc chloride, zinc nitrate or zinc sulfate.
Further, the organic ligand used in the third step of reaction is ethanol solution of one of terephthalic acid, trimesic acid, oxalic acid, succinic acid and other organic acids.
Further, the organic base reagent used in the third reaction step is one of Triethylamine (TEA), N-Dimethylformamide (DMF), N-Diethylformamide (DEF) and N-methylpyrrolidone, preferably N, N-Diethylformamide (DEF), and the dosage molar ratio of the organic ligand to the organic base reagent is 1:4-6.
Further, the molar ratio of the metal salt and the organic ligand required by the third reaction is 1:2.9-3.5, preferably 3.2.
Further, the volume ratio of the metal ion aqueous solution to the organic ligand ethanol solution used in the third step of reaction is 1:1.
Further, according to the adsorbent prepared by the preparation method, the adsorbent is formed by compositing activated carbon and an organic metal framework, the activated carbon is oxidatively modified activated carbon, the organic metal framework is attached to the surface of the activated carbon through the surface carboxyl of the activated carbon, and the molar ratio of the organic metal framework to the carbon in the adsorbent is 1:150-200.
The beneficial effects of the invention are as follows: 1. compared with the traditional activated carbon catalyst, the MOFs composite material synthesized by the method has higher specific surface area, stronger adsorption capacity and higher selectivity for adsorbed substances. 2. According to the invention, the MOFs material is compounded with carbon, so that the stability of the adsorbent is effectively improved, and the MOFs material is easy to process and form.
Drawings
FIG. 1 is a table showing the performance data of the synthesis of various MOFs composites and conventional adsorbent materials according to the present invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the embodiments of the present invention and the accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
In the first step, 100g of coconutWashing the shell activated carbon with deionized water, soaking, standing, removing upper impurities, ash and supernatant, and drying at 105 ℃ for 24 hours; adding 10g of dried active carbon into 50ml of 8mol/L HNO3 solution, stirring for reaction at 300r/min, stirring at room temperature for 3h, filtering to obtain solid, washing with water to neutrality, drying at 110 ℃ at constant temperature, introducing ozone at room temperature (25 ℃) for 3h to obtain oxidized active carbon, and marking as C Ⅰ0 ；
Second, 10g of modified activated carbon C obtained in the first step is treated Ⅰ0 Adding 250ml of 0.1mol/L zinc chloride aqueous solution, stirring and mixing at room temperature for 2h at 300r/min, centrifuging to separate solid, and drying at 100deg.C to obtain modified active carbon, denoted C Ⅱ0 ；
In the third step, 50ml of 0.3mol/L terephthalic acid ethanol solution is taken and 10g of activated carbon C is added Ⅱ0 15.6ml of 0.3mol/L zinc chloride deionized water solution, 5ml of organic alkali reagent 5ml of N, N-Dimethylformamide (DMF) are added, stirring and mixing are carried out for 30min at room temperature, the mixture is placed into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, the temperature is increased to 120 ℃ for 30min, the constant temperature reaction is carried out for 24h, after the reaction is finished, the product is washed for 2-3 times by ethanol and deionized water, the template agent is removed, and the active carbon and MOFs composite material is obtained and is marked as Zn@ -MOFs-A.
Example 2
The first step of reaction, 100g of wood activated carbon powder is washed by deionized water, soaked, kept stand, and then upper impurities, ash and supernatant are removed, and the mixture is dried for 24 hours at a constant temperature of 105 ℃; adding 10g of dried active carbon into 50ml of 8mol/L HNO3 solution, stirring for reaction at 300r/min, stirring at room temperature for 3h, filtering to obtain solid, washing with water to neutrality, drying at 110 ℃ at constant temperature, introducing ozone at room temperature (25 ℃) for 3h to obtain oxidized active carbon, and marking as C Ⅰ1 ；
In the second step, 10g of modified activated carbon C Ⅰ1 Adding 250ml of 0.1mol/L zinc chloride aqueous solution, stirring and mixing at room temperature for 2h at 300r/min, centrifuging to separate solid, and drying at 100deg.C to obtain modified active carbon, denoted C Ⅱ1 ；
In the third step, 50ml of 0.3mol/L terephthalic acid ethanol solution is taken and 10g of active carbon is addedC Ⅱ1 15.6ml of 0.3mol/L zinc chloride deionized water solution, 5ml of organic alkali reagent 5ml of N, N-Dimethylformamide (DMF) are added, stirring and mixing are carried out for 30min at room temperature, the mixture is placed into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, the temperature is increased to 120 ℃ for 30min, the constant temperature reaction is carried out for 24h, after the reaction is finished, the product is washed for 2-3 times by ethanol and deionized water, the template agent is removed, and the active carbon and MOFs composite material is obtained and is marked as Zn@ -MOFs-B.
Example 3
The first step of reaction, washing 100g of coconut shell activated carbon with deionized water, soaking, standing, removing upper impurities, ash and supernatant, and drying at a constant temperature of 105 ℃ for 24 hours; adding 10g of dried active carbon into 50ml of 8mol/L HNO3 solution, stirring for reaction at 300r/min, stirring at room temperature for 3h, filtering to obtain solid, washing with water to neutrality, drying at 110 ℃ at constant temperature, introducing ozone at room temperature (25 ℃) for 3h to obtain oxidized active carbon, and marking as C Ⅰ2 ；
In the second step, 10g of modified activated carbon C Ⅰ2 Adding 250ml of 0.1mol/L zinc nitrate aqueous solution, stirring and mixing at room temperature for 2h at 300r/min, centrifuging to separate solid, and drying at 100deg.C to obtain modified active carbon, denoted C Ⅱ2 ；
In the third step, 50ml of 0.3mol/L terephthalic acid ethanol solution is taken and 10g of activated carbon C is added Ⅱ2 15.6ml of 0.3mol/L zinc nitrate deionized water solution, 5ml of organic alkali reagent 5ml of N, N-Dimethylformamide (DMF) are added, stirring and mixing are carried out for 30min at room temperature, the mixture is placed into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, the temperature is increased to 120 ℃ for 30min, the constant temperature reaction is carried out for 24h, after the reaction is finished, the product is washed for 2-3 times by ethanol and deionized water, the template agent is removed, and the active carbon and MOFs composite material is obtained and is marked as Zn@ -MOFs-C.
Example 4
The first step of reaction, washing 100g of coconut shell activated carbon with deionized water, soaking, standing, removing upper impurities, ash and supernatant, and drying at a constant temperature of 105 ℃ for 24 hours; adding 10g of dried active carbon into 50ml of 8mol/L HNO3 solution, stirring for reaction at 300r/min, stirring for 3h at room temperature, filtering to obtain solid, washing with water to neutrality, and stirring at 110deg.CDrying at constant temperature, introducing ozone at room temperature (25deg.C) for 3 hr, and recording as C Ⅰ3 ；
In the second step, 10g of modified activated carbon C Ⅰ3 Adding 250ml of 0.1mol/L zinc chloride aqueous solution, stirring and mixing at room temperature for 2h at 300r/min, centrifuging to separate solid, and drying at 100deg.C to obtain modified active carbon, denoted C Ⅱ3 ；
In the third step, 50ml of 0.3mol/L terephthalic acid ethanol solution is taken and 10g of activated carbon C is added Ⅱ3 15.6ml of 0.3mol/L zinc chloride deionized water solution, 10ml of triethylamine (DMF) as an organic alkali reagent, stirring and mixing for 30min at room temperature, placing the mixture into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃ for 30min, reacting at constant temperature for 24h, washing the product with ethanol and deionized water for 2-3 times after the reaction is finished, and removing a template agent to obtain the active carbon and MOFs composite material which is marked as Zn@ -MOFs-D.
Example 5
The first step of reaction, washing 100g of coconut shell activated carbon with deionized water, soaking, standing, removing upper impurities, ash and supernatant, and drying at a constant temperature of 105 ℃ for 24 hours; adding 10g of dried active carbon into 50ml of 8mol/L HNO3 solution, stirring for reaction at 300r/min, stirring at room temperature for 3h, filtering to obtain solid, washing with water to neutrality, drying at 110 ℃ at constant temperature, introducing ozone at room temperature (25 ℃) for 3h, and marking as C Ⅰ4 ；
In the second step, 10g of modified activated carbon C Ⅰ Adding 250ml of 0.1mol/L zinc chloride aqueous solution, stirring and mixing at room temperature for 2h at 300r/min, centrifuging to separate solid, and drying at 100deg.C to obtain modified active carbon, denoted C Ⅱ4 ；
In the third step, 50ml of 0.3mol/L trimesic acid ethanol solution is taken and 10g of activated carbon C is added Ⅱ4 15.6ml of 0.3mol/L zinc chloride deionized water solution, 5ml of organic alkali reagent 5ml of N, N-Dimethylformamide (DMF) are added, stirring and mixing are carried out for 30min at room temperature, the mixture is placed into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, the temperature is increased to 120 ℃ for 30min, the constant temperature reaction is carried out for 24h, after the reaction is finished, the product is washed for 2-3 times by ethanol and deionized water, and the template agent is removed, thus obtaining the activityThe carbon and MOFs composite was designated Zn@ -MOFs-E.
Example 6
The first step of reaction, washing 100g of coconut shell activated carbon with deionized water, soaking, standing, removing upper impurities, ash and supernatant, and drying at a constant temperature of 105 ℃ for 24 hours; adding 10g of dried active carbon into 50ml of 8mol/L HNO3 solution, stirring for reaction at 300r/min, stirring at room temperature for 3h, filtering to obtain solid, washing with water to neutrality, drying at 110 ℃ at constant temperature for standby, introducing ozone at room temperature (25 ℃) for 3h, and marking as C Ⅰ5 ；
In the second step, 10g of modified activated carbon C Ⅰ5 Adding 250ml of 0.1mol/L zinc chloride aqueous solution, stirring and mixing at room temperature for 2h at 300r/min, centrifuging to separate solid, and drying at 100deg.C to obtain modified active carbon, denoted C Ⅱ5 ；
In the third step, 50ml of 0.3mol/L terephthalic acid ethanol solution is taken and 10g of activated carbon C is added Ⅱ5 14.3ml of 0.3mol/L zinc chloride deionized water solution, 5ml of organic alkali reagent 5ml of N, N-Dimethylformamide (DMF), stirring and mixing for 30min at room temperature, placing the mixture into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining, heating to 120 ℃ for 30min, reacting at constant temperature for 24h, washing the product with ethanol and deionized water for 2-3 times after the reaction is finished, and removing a template agent to obtain the active carbon and MOFs composite material which is marked as Zn@ -MOFs-F. The comparison of the specific surface area, pore volume and VOCs adsorption capacity of the invention with the traditional adsorption material is shown in the following table one:
comparison of specific surface area, pore volume and VOCs adsorption capacity of different adsorption materials
In summary, the adsorption capacity of the adsorbent VOCs synthesized by the technical scheme disclosed by the invention is far higher than that of the traditional adsorbent, particularly the adsorption capacity of benzene and methyl chloride is far higher than that of other traditional adsorbents, and the adsorbent can be used for selectively separating and purifying the mixture gas of benzene compounds, chlorinated alkane and other hydrocarbon compounds.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a separate embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to the embodiments described in detail below, and that the embodiments described in the examples may be combined as appropriate to form other embodiments that will be apparent to those skilled in the art.
Claims (10)
1. A preparation method of MOFs composite VOCs adsorbent is characterized by comprising the following steps:
firstly, preparing modified activated carbon, washing the activated carbon with deionized water, soaking, standing, removing upper impurities, ash and supernatant, and drying; adding dried asphalt-based activated carbon into HNO3 solution, stirring for reaction, stirring at room temperature for 3h, filtering to obtain solid, washing with water to neutrality, drying at constant temperature, and performing ozone oxidation on the product again to increase carboxyl content of the oxidized activated carbon to obtain modified activated carbon C Ⅰ ；
Second step, modified activated carbon C Ⅰ Adding into metal salt aqueous solution, stirring and mixing for 2h at room temperature, centrifuging to separate solid, and drying at constant temperature to obtain modified activated carbon C Ⅱ ；
Thirdly, taking organic ligand solution and activated carbon C Ⅱ Adding organic alkali reagent into deionized water solution of metal salt, stirring and mixing at room temperature for 3 timesAnd (3) placing the mixture into a hydrothermal synthesis reaction kettle with a polytetrafluoroethylene lining for 0min, heating to 120 ℃ for 30min, reacting at constant temperature for 24h, washing the product with ethanol and deionized water for 2-3 times after the reaction is finished, and removing a template agent to obtain the composite material of the target product activated carbon and MOFs.
2. The method for preparing the MOFs composite VOCs adsorbent, according to claim 1, is characterized in that: the activated carbon selected in the first step is one of coconut shell activated carbon, fruit shell activated carbon, wood columnar activated carbon and wood powder activated carbon.
3. The method for preparing the MOFs composite VOCs adsorbent, according to claim 1, is characterized in that: the concentration of nitric acid used in the first step reaction is 6-9 mol/L.
4. The method for preparing the MOFs composite VOCs adsorbent, according to claim 1, is characterized in that: the temperature of the first step reaction using ozone oxidation is 20-25 ℃.
5. The method for preparing the MOFs composite VOCs adsorbent, according to claim 1, is characterized in that: the metal salt used in the second reaction and the third reaction is zinc chloride, zinc nitrate or zinc sulfate.
6. The method for preparing the MOFs composite VOCs adsorbent, according to claim 1, is characterized in that: the organic ligand used in the third step is ethanol solution of terephthalic acid.
7. The method for preparing the MOFs composite VOCs adsorbent, according to claim 1, is characterized in that: the organic base reagent used in the third reaction step is one of Triethylamine (TEA), N-Dimethylformamide (DMF), N-Diethylformamide (DEF) and N-methylpyrrolidone, preferably N, N-Diethylformamide (DEF), and the dosage molar ratio of the organic ligand to the organic base reagent is 1:4-6.
8. The method for preparing the MOFs composite VOCs adsorbent, according to claim 1, is characterized in that: the molar ratio of the metal salt to the organic ligand required by the third step of reaction is 1:2.9-3.5.
9. The method for preparing the MOFs composite VOCs adsorbent, according to claim 1, is characterized in that: the volume ratio of the metal ion aqueous solution to the organic ligand ethanol solution used in the third step of reaction is 1:1.
10. The adsorbent produced by the production process according to claim 1 to 8, characterized in that: the adsorbent is formed by compounding activated carbon and an organic metal framework, the activated carbon is oxidatively modified activated carbon, the organic metal framework is attached to the surface of the activated carbon through carboxyl on the surface of the activated carbon, and the molar ratio of the organic metal framework to the carbon in the adsorbent is 1:150-200.
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