CN112892484B - VOCs adsorbent and preparation method thereof - Google Patents

VOCs adsorbent and preparation method thereof Download PDF

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CN112892484B
CN112892484B CN202110144832.0A CN202110144832A CN112892484B CN 112892484 B CN112892484 B CN 112892484B CN 202110144832 A CN202110144832 A CN 202110144832A CN 112892484 B CN112892484 B CN 112892484B
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CN112892484A (en
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陈勇
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Binzhou Zhongke Catalysis Technology Co ltd
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Abstract

The invention provides a VOCs adsorbent and a preparation method thereof, belonging to the field of gas purification. The adsorbent comprises an adsorbent parent body, a rough layer constructed on the surface of the adsorbent parent body and a hydrophobic layer constructed on the surface of the rough layer, wherein the adsorbent parent body comprises activated carbon, a molecular sieve and SiO 2 And at least one of ceramics, the rough layer comprises at least two of VIB group, VIIB group, VIII group, IB group or rare earth element phosphide, and the hydrophobic layer comprises hydrophobic polymer. The rough layer on the surface of the adsorbent parent body increases the surface area of the adsorbent, increases the contact area of the adsorbent and the VOCs, further increases the adsorption efficiency of the VOCs, and the hydrophobic layer on the surface of the rough layer can inhibit the influence of water in the VOCs on the adsorbent and prolong the service life of the adsorbent.

Description

VOCs adsorbent and preparation method thereof
Technical Field
The invention relates to the field of gas purification, and particularly relates to a VOCs adsorbent and a preparation method thereof.
Background
Volatile Organic Compounds (VOCs) are inevitably generated in the coal chemical industry, and the VOCs are various and complex in components, and mainly include non-methane hydrocarbons such as olefins, alkanes, alkynes, and aromatics, oxygen-containing organic compounds such as aldehydes, alcohols, ketones, ethers, and phenols, nitrogen-containing compounds, sulfur-containing compounds, and halogenated hydrocarbons. VOCs are recognized as leading causes of global warming, ozone layer destruction, photochemical smog, and acid rain. In addition, most VOCs have toxic and pungent odors, are easy to enter human bodies through skin, respiratory tract, digestive tract mucosa and other ways, affect the digestive system and central nerves of the human bodies, and are harmful to the physiological health of the human bodies.
The existing VOCs treatment method can be fundamentally divided into three levels of source control, process control and terminal treatment. Source control refers to the ability to alter or replace the properties of the original contaminated material from the source, and to control the production of VOCs by modifying the process and method. Process control refers to reducing emissions of VOCs by reducing unorganized emissions, changing the production process, using gas-skirt collection, and the like. The end treatment refers to a process of collecting, converting and treating the generated VOCs and then discharging the VOCs. As source and process control involves changes to the process and equipment, which are difficult, end management is currently the most adopted method.
In the end treatment, the adsorption technology is widely applied due to the advantages of convenient material availability, high efficiency, simple operation, regenerability of the adsorbent and the like, but the water content in the VOCs can significantly reduce the performance of the adsorbent and even cause the inactivation of the adsorbent, so the hydrophobic performance of the adsorbent needs to be improved. For example, the invention patent application with publication number CN111330543A discloses a hydrophobic activated carbon adsorbent for treating high-humidity VOCs and a preparation method thereof, wherein the preparation method specifically comprises the following steps: A. under the coexistence of protection gas and water vapor, heating the activated carbon to 300-800 ℃, and activating for 0.5-10 h to obtain activated carbon; B. mixing the activated carbon with a perfluoro-1-octanol solution, and stirring for reaction at 5-95 ℃ to obtain a modified activated carbon precursor; C. mixing the modified activated carbon precursor, glacial acetic acid, distilled water and absolute ethyl alcohol to obtain a modified activated carbon precursor solution; D. and mixing the modified activated carbon precursor solution with an alcoholic solution of tetrabutyl titanate, heating for reaction, and drying to obtain the hydrophobic activated carbon adsorbent for treating VOCs. The hydrophobic activated carbon adsorbent prepared by the method has excellent hydrophobic property and excellent adsorption effect on VOCs in a high-humidity environment.
Although the method effectively avoids the adverse effects of moisture on the service life of the adsorbent and the adsorption efficiency of the VOCs in the adsorption process, the further improvement of the adsorption efficiency of the VOCs is still limited by the limited surface area and the surface roughness of the activated carbon adsorbent.
Disclosure of Invention
The invention aims to solve the technical problem of how to effectively improve the hydrophobic property of the VOCs adsorbent and further improve the adsorption efficiency of the adsorbent.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
the hydrophobic VOCs adsorbent comprises an adsorbent parent body, wherein a rough layer is constructed on the surface of the adsorbent parent body, and a hydrophobic layer is constructed on the surface of the rough layer; the adsorbent matrix comprises activated carbon, molecular sieve and SiO 2 And ceramics; the above-mentionedThe rough layer comprises at least two of VIB group, VIIB group, VIII group, IB group or rare earth element phosphide; the hydrophobic layer is composed of a hydrophobic polymer.
According to the mass percentage, the adsorbent matrix comprises 15-25% of activated carbon, 15-35% of molecular sieve and 10-25% of SiO 2 And 25-40% of ceramic. Activated carbon, molecular sieve, SiO 2 And ceramics can be synthesized by the prior art method or directly selected from the commercial products.
According to the mass fraction ratio, the adsorbent parent body comprises 20% of activated carbon, 30% of molecular sieve and 20% of SiO 2 And 30% ceramic.
The silicon-aluminum ratio of the molecular sieve is more than 300.
The composition of the rough layer comprises Fe 3 P, CoP, NiP, MoP, LaP, CeP, PrP or Mn 3 P 2 At least two of them.
The hydrophobic polymer comprises at least one of polydimethylsiloxane, dodecyl trichlorosilane, octadecyl trichlorosilane, vinyl triethoxysilane or fluorosilane.
The invention also provides a preparation method of the VOCs adsorbent, which comprises the following steps:
(1) constructing a rough layer on the adsorbent parent body to obtain a rough adsorbent parent body;
(2) constructing a hydrophobic layer on the rough layer; the adsorbent matrix comprises activated carbon, molecular sieve and SiO 2 And ceramics; the rough layer comprises at least two of VIB group, VIIB group, VIII group, IB group or rare earth element phosphide; the hydrophobic layer is composed of a hydrophobic polymer.
The step (1) is specifically as follows:
A) mixing the adsorbent parent body with a solution a containing a phosphating agent and an auxiliary metal element M, stirring for 5-30 h, taking out, and then placing under an ultraviolet lamp for irradiating for 0.5-2 h to obtain an adsorbent precursor;
B) the roughened sorbent precursor is obtained after heat treatment of the precursor in an inert atmosphere.
And step A), mixing the adsorbent matrix with a solution a containing a phosphating agent and an auxiliary agent metal element M, stirring for 10-20 h, taking out, and then placing under an ultraviolet lamp for irradiating for 1-1.5 h to obtain an adsorbent precursor.
The phosphating agent comprises hypophosphite or phytic acid, and the auxiliary metal element M comprises at least two of VIB group, VIIB group, VIII group, IB group or rare earth elements, and is selected from VIB group, VIIB group, VIII group, IB group or rare earth element soluble salts.
The M comprises at least two of Fe, Co, Ni, Mo, La, Ce, Pr or Mn.
The concentration of P in the phosphating agent is 0.05-0.25M, the concentration of M is 0.01-0.15M, and the volume ratio of the adsorbent parent body to the solution a is 1: 2-4.
The temperature of the heat treatment in the step B) is 300-400 ℃, and the heat treatment time is 3-4 h.
The step (2) is specifically as follows: and spraying a solution b containing a hydrophobic polymer on the tiled roughened adsorbent matrix, drying, and repeating for 2-5 times to obtain the VOCs adsorbent.
In the step (2), the hydrophobic polymer comprises at least one of polydimethylsilane, dodecyl trichlorosilane, octadecyl trichlorosilane, vinyl triethoxysilane or fluorosilane.
The volume concentration of the hydrophobic polymer is 0.5-2%; the volume ratio of the roughened adsorbent parent body to the solution b is 1: 1.5-2.5.
The volume concentration of the hydrophobic polymer is 1-2%, and the volume ratio of the roughened adsorbent matrix to the solution b is 1: 2.
According to the mass percentage, the adsorbent matrix comprises 15-25% of activated carbon, 15-35% of molecular sieve and 10-25% of SiO 2 And 25-40% of ceramic.
The adsorbent matrix comprises 20% of activated carbon, 30% of molecular sieve and 20% of SiO 2 And 30% ceramic.
The silicon-aluminum ratio of the molecular sieve is more than 300.
The invention has the beneficial effects that:
(1) the rough layer on the surface of the adsorbent parent body can increase the surface area of the adsorbent, increase the contact area of the adsorbent and the VOCs, further increase the adsorption efficiency of the VOCs, and the hydrophobic layer on the surface of the rough layer can inhibit the influence of water in the VOCs on the adsorbent and prolong the service life of the adsorbent.
(2) The adsorbent parent material is selected from active carbon, molecular sieve and SiO 2 And ceramic, because each adsorbent has different pore characteristics, the prepared adsorbent finished product is suitable for various VOCs, wherein the hydrophobicity of the adsorbent can be further increased by selecting a molecular sieve with a large silica-alumina ratio.
(3) The metal phosphide has a catalytic conversion effect on sulfur-containing components, and the rough layer is composed of phosphide, so that part of sulfides in the rough layer can be converted into elemental sulfur firstly while VOCs are adsorbed, and the subsequent treatment is facilitated; the rough layer is composed of at least two metal phosphides, and the catalytic conversion efficiency can be further promoted by the synergistic effect of different metals.
(4) The irradiation of ultraviolet light is helpful to form more defects on the surface of the adsorbent precursor, so that the subsequently formed adsorbent finished product has better catalytic conversion performance on sulfides and the like in VOCs.
(5) The spraying method can control the amount of the hydrophobic polymer formed on the adsorbent, and compared with the dipping method, the method can effectively avoid the phenomenon that the adsorbent parent is excessively loaded with the hydrophobic polymer to block partial gaps of the adsorbent so as to reduce the adsorption capacity.
(6) The VOCs adsorbent with the rough layer and the hydrophobic layer prepared by the method has the hydrophobic performance obviously superior to that of an adsorbent without the hydrophobic layer, the static adsorption capacity for water can be less than 6%, and the static adsorption capacity for dimethyl sulfide is more than 44%.
Detailed Description
The present invention is described in further detail below with reference to specific examples.
Example 1
Preparation of VOCs adsorbent:
(1) prepared to contain 0.03M La 3+ 、0.03M Ce 3+ And 0.15M aqueous solution a of sodium hypophosphiteWherein the La source and the Ce source are selected from soluble salts thereof;
(2) according to the mass fraction percentage, 20 percent of activated carbon, 30 percent of molecular sieve and 20 percent of SiO 2 And 30% of ceramic is used as an adsorbent parent body, the adsorbent parent body is mixed with the aqueous solution a, the volume of the solution a is 3 times of that of the adsorbent parent body, the mixed solution is stirred for 15 hours, and the mixed solution is taken out, drained and irradiated under an ultraviolet lamp for 1 hour to obtain an adsorbent precursor;
(3) carrying out heat treatment on the adsorbent precursor for 3.5h at 350 ℃ in a nitrogen atmosphere to obtain a roughened adsorbent parent body; in this process, La adsorbed in the adsorbent matrix 3+ 、Ce 3+ React with P to form corresponding phosphide LaP and CeP, respectively.
(4) Preparing a toluene solution b of vinyl triethoxysilane with a volume concentration of 1.5%;
(5) spreading the roughened adsorbent parent body, uniformly spraying the solution b on the roughened adsorbent parent body by adopting a spraying method, wherein the volume of the solution b is 2 times that of the roughened adsorbent parent body, and drying the adsorbent parent body after spraying is finished;
(6) and (5) repeating the step (5) for 3 times to obtain the VOCs adsorbent.
VOCs sorbent performance testing:
the adsorption capacity of the VOCs adsorbent to water and organic matters is tested by adopting a static adsorption method, 15g of the VOCs adsorbent is weighed, water or an organic solvent is contained in an open container, the water or the organic solvent is placed in a sealing device, the sealing device is vacuumized, the VOCs adsorbent is weighed again after 10 hours, the static adsorption capacity of the adsorbent to the water or the organic matters is calculated by adopting a differential method, and the calculation formula of the static adsorption capacity is as follows:
Figure BDA0002928759200000051
Figure BDA0002928759200000052
wherein m is After adsorption Denotes the mass of VOCs adsorbent after static adsorption, m Before adsorption Shows the quality of the VOCs adsorbent before adsorptionThe results of the bulk static adsorption are shown in Table 1.
Example 2
Preparation of VOCs adsorbent:
(1) prepared to contain 0.03M Mn 2+ 、0.03M Pr 3+ And 0.15M aqueous solution a of ammonium hypophosphite, wherein the source of Mn and the source of Pr are selected from soluble salts thereof;
(2) according to the mass fraction percentage, 20 percent of activated carbon, 30 percent of molecular sieve and 20 percent of SiO 2 And 30% of ceramic is used as an adsorbent parent body, the adsorbent parent body is mixed with the aqueous solution a, the volume of the solution a is 3 times of that of the adsorbent parent body, the mixed solution is stirred for 15 hours, and the mixed solution is taken out, drained and irradiated under an ultraviolet lamp for 1 hour to obtain an adsorbent precursor;
(3) carrying out heat treatment on the adsorbent precursor for 3.5h at 350 ℃ in a nitrogen atmosphere to obtain a roughened adsorbent parent; in this process, Pr is adsorbed in the adsorbent precursor 3+ 、Mn 2+ Respectively react with P to generate corresponding phosphide PrP and Mn 3 P 2 。
(4) Preparing a toluene solution b of octadecyl trichlorosilane with the volume concentration of 1.5 percent;
(5) uniformly spraying the solution b on the roughened adsorbent parent, wherein the volume of the solution b is 2 times that of the roughened adsorbent parent, and drying the adsorbent parent after spraying is finished;
(6) and (5) repeating the step (5) for 3 times to obtain the VOCs adsorbent.
VOCs sorbent performance testing: the same as in example 1.
Example 3
Preparation of VOCs adsorbent:
(1) prepared to contain 0.02M Fe 3+ 、0.04M Mo 6+ And a 0.15M aqueous solution a of phytic acid, wherein the Fe source and Mo source are selected from soluble salts thereof;
(2) according to the mass fraction percentage, 20 percent of activated carbon, 30 percent of molecular sieve and 20 percent of SiO 2 And 30% of ceramic as adsorbent matrix, mixing the adsorbent matrix with the above aqueous solution a, wherein the volume of the solution a is 3 times of that of the adsorbent matrix, and stirring the mixed solutionTaking out, draining, and irradiating under an ultraviolet lamp for 1h to obtain an adsorbent precursor;
(3) carrying out heat treatment on the adsorbent precursor for 3.5h at 350 ℃ in a nitrogen atmosphere to obtain a roughened adsorbent parent; in this process, Fe adsorbed in the adsorbent matrix 3+ 、Mo 6+ Respectively react with P to generate corresponding phosphide Fe 3 P and MoP.
(4) Preparing an isopropanol solution b of 1.5% volume concentration polydimethylsiloxane;
(5) spreading the roughened adsorbent parent body, uniformly spraying the solution b on the roughened adsorbent parent body by adopting a spraying method, wherein the volume of the solution b is 2 times that of the roughened adsorbent parent body, and drying the adsorbent parent body after spraying is finished;
(6) and (5) repeating the step (5) for 3 times to obtain the VOCs adsorbent.
VOCs sorbent performance testing: the same as in example 1.
Example 4
Preparation of VOCs adsorbent:
(1) prepared to contain 0.01M Co 2+ 、0.03M Pr 3+ And a 0.2M aqueous solution a of phytic acid, wherein the Co source and the Pr source are selected from soluble salts thereof;
(2) according to the mass fraction percentage, 20 percent of activated carbon, 35 percent of molecular sieve and 20 percent of SiO 2 And 25% of ceramic is used as an adsorbent parent body, the adsorbent parent body is mixed with the aqueous solution a, the volume of the solution a is 3.5 times of that of the adsorbent parent body, the mixed solution is stirred for 20 hours, and the mixed solution is taken out, drained and irradiated under an ultraviolet lamp for 1.5 hours to obtain an adsorbent precursor;
(3) carrying out heat treatment on the adsorbent precursor for 4h at 300 ℃ in a nitrogen atmosphere to obtain a roughened adsorbent parent; in this process, Co adsorbed in the adsorbent matrix 2+ 、Pr 3+ Respectively react with P to generate corresponding phosphide CoP and PrP.
(4) Preparing a toluene solution b of dodecyl trichlorosilane with the volume concentration of 0.5 percent;
(5) spreading the roughened adsorbent parent body flatly, uniformly spraying the solution b on the roughened adsorbent parent body by adopting a spraying method, wherein the volume of the solution b is 1.5 times that of the roughened adsorbent parent body, and drying the adsorbent parent body after spraying is finished;
(6) and (5) repeating the step (5) for 4 times to obtain the VOCs adsorbent.
VOCs sorbent performance testing: the same as in example 1.
Example 5
Preparation of VOCs adsorbent:
(1) preparation of a composition containing 0.03M Ni 2+ 、0.05M La 3+ And an aqueous solution a of 0.1M potassium hypophosphite, wherein the Ni source and La source are selected from soluble salts thereof;
(2) according to mass fraction percentage, 15 percent of activated carbon, 35 percent of molecular sieve and 25 percent of SiO 2 And 25% of ceramic is used as an adsorbent parent body, the adsorbent parent body is mixed with the aqueous solution a, the volume of the solution a is 2 times of that of the adsorbent parent body, the mixed solution is stirred for 10 hours, and the mixed solution is taken out, drained and irradiated under an ultraviolet lamp for 0.5 hour to obtain an adsorbent precursor;
(3) carrying out heat treatment on the adsorbent precursor for 3h at 350 ℃ in a nitrogen atmosphere to obtain a roughened adsorbent parent; in this process, Ni is adsorbed in the adsorbent matrix 2+ 、La 3+ React with P to form the corresponding phosphides NiP and LaP, respectively.
(4) Preparing an ethanol solution b of 1% by volume of trifluoropropyltriethoxysilane;
(5) spreading the roughened adsorbent parent body flatly, uniformly spraying the solution b on the roughened adsorbent parent body by adopting a spraying method, wherein the volume of the solution b is 2.5 times that of the roughened adsorbent parent body, and drying the adsorbent parent body after spraying is finished;
(6) and (6) repeating the step (5) for 2 times to obtain the VOCs adsorbent.
VOCs sorbent performance testing: the same as in example 1.
Example 6
Preparation of VOCs adsorbent:
(1) the preparation contains 0.075M Mn 2+ 、0.075M La 3+ And 0.25M phosphorousAn aqueous solution a of sodium acid, wherein the source of Mn and the source of La are selected from soluble salts thereof;
(2) according to mass fraction percentage, 25 percent of activated carbon, 15 percent of molecular sieve and 20 percent of SiO 2 And 40% of ceramic is used as an adsorbent parent body, the adsorbent parent body is mixed with the aqueous solution a, the volume of the solution a is 1 time of that of the adsorbent parent body, the mixed solution is stirred for 5 hours, and the mixed solution is taken out, drained and irradiated under an ultraviolet lamp for 0.5 hour to obtain an adsorbent precursor;
(3) carrying out heat treatment on the adsorbent precursor for 3h at 300 ℃ in a nitrogen atmosphere to obtain a roughened adsorbent parent; in this process, Mn is adsorbed in the adsorbent matrix 2+ 、La 3+ Respectively react with P to generate corresponding phosphide Mn 3 P 2 And LaP.
(4) Preparing an ethanol solution b of perfluorooctyltrimethoxysilane with the volume concentration of 1%;
(5) spreading the roughened adsorbent parent body, uniformly spraying the solution b on the roughened adsorbent parent body by adopting a spraying method, wherein the volume of the solution b is 2 times that of the roughened adsorbent parent body, and drying the adsorbent parent body after spraying is finished;
(6) and (5) repeating the step (5) for 5 times to obtain the VOCs adsorbent.
VOCs sorbent performance testing: the same as in example 1.
Example 7
Preparation of the VOCs adsorbent:
(1) preparation of a composition containing 0.05M Ni 2+ 、0.1M Ce 3+ And a 0.1M aqueous solution a of phytic acid, wherein the Ni source and the Ce source are selected from soluble salts thereof;
(2) according to mass fraction percentage, 25 percent of activated carbon, 35 percent of molecular sieve and 10 percent of SiO 2 And 30% of ceramic is used as an adsorbent parent body, the adsorbent parent body is mixed with the aqueous solution a, the volume of the solution a is 2.5 times of that of the adsorbent parent body, the mixed solution is stirred for 25 hours, and the mixed solution is taken out, drained and irradiated under an ultraviolet lamp for 2 hours to obtain an adsorbent precursor;
(3) heat treating the adsorbent precursor at 400 deg.C for 4h in nitrogen atmosphere to obtain crude productA roughened adsorbent precursor; in this process, Ni is adsorbed in the adsorbent matrix 2+ 、Ce 3+ Respectively react with P to generate corresponding phosphide NiP and Ce P.
(4) Preparing an ethanol solution b of heptadecafluorodecyltrimethoxysilane with the volume concentration of 2 percent;
(5) spreading the roughened adsorbent parent body flatly, uniformly spraying the solution b on the roughened adsorbent parent body by adopting a spraying method, wherein the volume of the solution b is 1.5 times that of the roughened adsorbent parent body, and drying the adsorbent parent body after spraying is finished;
(6) and (5) repeating the step (5) for 3 times to obtain the VOCs adsorbent.
VOCs sorbent performance testing: the same as in example 1.
Example 8
Preparation of VOCs adsorbent:
(1) prepared to contain 0.005M Mn 2+ 、0.005M Pr 3+ And 0.05M aqueous solution a of ammonium hypophosphite, wherein the Mn source and the Pr source are selected from soluble salts thereof;
(2) according to the mass fraction percentage, 20 percent of activated carbon, 30 percent of molecular sieve and 20 percent of SiO 2 And 30% of ceramic is used as an adsorbent parent body, the adsorbent parent body is mixed with the aqueous solution a, the volume of the solution a is 4 times of that of the adsorbent parent body, the mixed solution is stirred for 30 hours, and the mixed solution is taken out, drained and irradiated under an ultraviolet lamp for 1.5 hours to obtain an adsorbent precursor;
(3) carrying out heat treatment on the adsorbent precursor for 3.5h at 350 ℃ in a nitrogen atmosphere to obtain a roughened adsorbent parent; in this process, Mn is adsorbed in the adsorbent matrix 2+ 、Pr 3+ Respectively react with P to generate corresponding phosphide Mn 3 P 2 And PrP.
(4) Preparing an isopropanol solution b of 1.5% volume concentration polydimethylsiloxane;
(5) spreading the roughened adsorbent parent body, uniformly spraying the solution b on the roughened adsorbent parent body by adopting a spraying method, wherein the volume of the solution b is 2 times that of the roughened adsorbent parent body, and drying the adsorbent parent body after spraying is finished;
(6) and (5) repeating the step (5) for 4 times to obtain the VOCs adsorbent.
VOCs sorbent performance testing: the same as in example 1.
Comparative example 1
Preparation of VOCs adsorbent (bimetallic to monometallic, remainder of example 1):
(1) prepared to contain 0.06M La 3+ And an aqueous solution a of 0.15M sodium hypophosphite, wherein the La source is selected from its soluble salts;
(2) according to the mass fraction percentage, 20 percent of activated carbon, 30 percent of molecular sieve and 20 percent of SiO 2 And 30% of ceramic is used as an adsorbent parent body, the adsorbent parent body is mixed with the aqueous solution a, the volume of the solution a is 3 times of that of the adsorbent parent body, the mixed solution is stirred for 15 hours, and the mixed solution is taken out, drained and irradiated under an ultraviolet lamp for 1 hour to obtain an adsorbent precursor;
(3) carrying out heat treatment on the adsorbent precursor for 3.5h at 350 ℃ in a nitrogen atmosphere to obtain a roughened adsorbent parent; in this process, La adsorbed in the adsorbent matrix 3+ Reaction with P produces the corresponding phosphide LaP.
(4) Preparing a toluene solution b of vinyl triethoxysilane with a volume concentration of 1.5%;
(5) spreading the roughened adsorbent parent body, uniformly spraying the solution b on the roughened adsorbent parent body by adopting a spraying method, wherein the volume of the solution b is 2 times that of the roughened adsorbent parent body, and drying the adsorbent parent body after spraying is finished;
(6) and (5) repeating the step (5) for 3 times to obtain the VOCs adsorbent.
VOCs sorbent performance testing: the same as in example 1.
Comparative example 2
Preparation of VOCs adsorbent (bimetallic to monometallic, remainder of example 2):
(1) prepared to contain 0.06M Mn 2+ And 0.15M aqueous solution a of ammonium hypophosphite, wherein the source of Mn is selected from soluble salts thereof;
(2) according to mass fraction percentage, 20 percent of activated carbon and 30 percent of moleculesSieve, 20% SiO 2 And 30% of ceramic is used as an adsorbent parent body, the adsorbent parent body is mixed with the aqueous solution a, the volume of the solution a is 3 times of that of the adsorbent parent body, the mixed solution is stirred for 15 hours, and the mixed solution is taken out, drained and irradiated under an ultraviolet lamp for 1 hour to obtain an adsorbent precursor;
(3) carrying out heat treatment on the adsorbent precursor for 3.5h at 350 ℃ in a nitrogen atmosphere to obtain a roughened adsorbent parent; in this process, Mn is adsorbed in the adsorbent matrix 2+ Reaction with P to form the corresponding phosphide Mn 3 P 2 。
(4) Preparing a toluene solution b of octadecyl trichlorosilane with the volume concentration of 1.5 percent;
(5) uniformly spraying the solution b on the roughened adsorbent parent, wherein the volume of the solution b is 2 times that of the roughened adsorbent parent, and drying the adsorbent parent after spraying is finished;
(6) and (5) repeating the step (5) for 3 times to obtain the VOCs adsorbent.
VOCs sorbent performance testing: the same as in example 1.
Comparative example 3
Preparation of VOCs adsorbent (hydrophobic layer not constructed, the rest of the same as in example 1):
(1) prepared to contain 0.03M La 3+ 、0.03M Ce 3+ And an aqueous solution a of 0.15M sodium hypophosphite, wherein the La source and the Ce source are selected from soluble salts thereof;
(2) according to the mass fraction percentage, 20 percent of activated carbon, 30 percent of molecular sieve and 20 percent of SiO 2 And 30% of ceramic is used as an adsorbent parent body, the adsorbent parent body is mixed with the aqueous solution a, the volume of the solution a is 3 times of that of the adsorbent parent body, the mixed solution is stirred for 15 hours, and the mixed solution is taken out, drained and irradiated under an ultraviolet lamp for 1 hour to obtain an adsorbent precursor;
(3) carrying out heat treatment on the adsorbent precursor for 3.5h at 350 ℃ in a nitrogen atmosphere to obtain a VOCs adsorbent; in this process, La adsorbed in the adsorbent matrix 3+ 、Ce 3+ React with P to form the corresponding phosphide LaP and CeP, respectively.
VOCs sorbent performance testing: the same as in example 1.
Comparative example 4
Preparation of VOCs adsorbent (rough layer not constructed, otherwise same as in example 1):
(1) according to the mass fraction percentage, 20 percent of activated carbon, 30 percent of molecular sieve and 20 percent of SiO 2 And 30% of ceramic is used as a matrix of the adsorbent;
(2) preparing a toluene solution b of vinyl triethoxysilane with a volume concentration of 1.5%;
(3) spreading the roughened adsorbent parent body, uniformly spraying the solution b on the roughened adsorbent parent body by adopting a spraying method, wherein the volume of the solution b is 2 times that of the adsorbent parent body, and drying the adsorbent parent body after spraying is finished;
(4) and (4) repeating the step (3) for 3 times to obtain the VOCs adsorbent.
VOCs sorbent performance testing: the same as in example 1.
Comparative example 5
Preparation of VOCs adsorbent (for the construction of rough and hydrophobic layers, the remainder of example 1):
according to the mass fraction percentage, 20 percent of activated carbon, 30 percent of molecular sieve and 20 percent of SiO 2 And 30% of the ceramic is a VOCs adsorbent.
VOCs sorbent performance testing: the same as in example 1.
TABLE 1 static adsorption Capacity of VOCs adsorbents
Figure BDA0002928759200000111
The results in the table show that the hydrophobic performance of the VOCs adsorbent with the rough layer and the hydrophobic layer prepared by the method is obviously superior to that of the adsorbent without the hydrophobic layer, and the static adsorption capacity for water can be less than 6%. The adsorption capacity of the VOCs adsorbent with the rough layer to cyclohexane, toluene, trichloroethylene and dimethyl sulfide is obviously larger than that of the VOCs adsorbent without the rough layer, under the preferable experimental condition, the adsorption effect of the adsorbent with the rough layer made of multi-metal phosphide is obviously better than that of the adsorbent with the rough layer made of single-metal phosphide, and the static adsorption capacity to dimethyl sulfide can be larger than 44%.

Claims (8)

1. The VOCs adsorbent is characterized by comprising an adsorbent parent body, wherein a rough layer is constructed on the surface of the adsorbent parent body, and a hydrophobic layer is constructed on the surface of the rough layer;
the adsorbent matrix comprises activated carbon, molecular sieve and SiO 2 Or a ceramic;
the composition of the rough layer comprises Fe 3 P, CoP, NiP, MoP, LaP, CeP, PrP or Mn 3 P 2 At least two of;
the hydrophobic layer is composed of a hydrophobic polymer, and the hydrophobic polymer comprises at least one of polydimethylsiloxane, dodecyl trichlorosilane, octadecyl trichlorosilane, vinyl triethoxysilane or fluorosilane;
the preparation method of the VOCs adsorbent comprises the following steps:
(1) constructing a rough layer on the adsorbent parent body to obtain a rough adsorbent parent body;
(2) constructing a hydrophobic layer on the rough layer;
the step (1) is specifically as follows:
A) mixing the adsorbent parent body with a solution a containing a phosphating agent and an auxiliary agent metal element M, stirring for 5-30 h, taking out and then carrying out
Placing under an ultraviolet lamp for irradiation for 0.5-2 h to obtain an adsorbent precursor;
B) heat treating the precursor in an inert atmosphere to obtain the roughened adsorbent precursor;
the phosphating agent comprises hypophosphite or phytic acid, and the auxiliary metal element M comprises at least two of Fe, Co, Ni, Mo, La, Ce, Pr or Mn; the concentration of P in the phosphating agent is 0.05-0.25M, the concentration of M is 0.01-0.15M, and the volume ratio of the adsorbent parent body to the solution a is 1: 2-4;
the temperature of the heat treatment in the step B) is 300-400 ℃, and the heat treatment time is 3-4 h.
2. The VOCs adsorbent of claim 1, wherein the adsorbent matrix comprises, by mass, 15-25% of activated carbon, 15-35% of molecular sieve, and 10-25% of SiO 2 And 25-40% of ceramic.
3. The adsorbents of claim 2, wherein the adsorbent matrix comprises, by mass, 20% activated carbon, 30% molecular sieve, 20% SiO 2 And 30% ceramic.
4. The adsorbents of claim 3, wherein the molecular sieve has a silica to alumina ratio greater than 300.
5. The VOCs adsorbent of claim 1, wherein in step A), the adsorbent precursor is obtained by mixing the adsorbent precursor with a solution a containing a phosphating agent and an auxiliary metal element M, stirring for 10-20 h, taking out, and then irradiating under an ultraviolet lamp for 1-1.5 h.
6. The adsorbents of VOCs according to claim 1, wherein step (2) is specifically: and spraying a solution b containing a hydrophobic polymer on the flat-laid roughened adsorbent matrix, drying, and repeating for 2-5 times to obtain the VOCs adsorbent.
7. A VOCs adsorbent according to claim 6 wherein the hydrophobic polymer concentration in step (2) is 0.5-2% by volume, and the ratio of the roughened adsorbent precursor to the solution b is 1: 1.5 to 2.5.
8. The VOCs adsorbent of claim 7, wherein the hydrophobic polymer is present in a concentration of 1-2% by volume, and the ratio of the roughened adsorbent precursor to the solution b is 1: 2.
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