CN108101066A - A kind of preparation method and applications of the spherical ordered multi-stage porous silica adsorbent of hydrophobicity - Google Patents
A kind of preparation method and applications of the spherical ordered multi-stage porous silica adsorbent of hydrophobicity Download PDFInfo
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Abstract
The invention discloses spherical ordered multi-stage porous silica adsorbents of a kind of hydrophobicity and its preparation method and application, and preparation includes：(1) spherical ordered multi-stage porous silica is prepared；(2) the spherical ordered multi-stage porous silica is scattered in toluene, addition organo silane coupling agent, after hydro-thermal reaction, after reaction product is fully washed with toluene and absolute ethyl alcohol, be dried in vacuo to obtain the final product；The organo silane coupling agent is one or both of bromomethyl trimethyl silane, iodomethyl trimethyl silane, trifluoromethyl trimethylsilane and trim,ethylchlorosilane.Adsorbent hydrophobic performance prepared by the present invention is strong, adsorption capacity is big, aperture is adjustable, adsorption desorption is simple, has good adsorption and enrichment effect to the organic exhaust gas of Wind Volume, low concentration.
Description
Technical field
The invention belongs to environment functional material field, the particularly spherical ordered multi-stage porous silica suctions of a kind of hydrophobicity
The preparation of attached agent material and its concrete application.
Background technology
With China's economy and industrial high speed development, while the material requisite of people obtains meeting, to living environment matter
Amount is also paid attention to further, and environmental pollution becomes serious problems urgently to be resolved hurrily.Volatile organic contaminant (VOCs) refers under room temperature
Boiling point is less than 260 DEG C of a kind of compound, is the industries such as petrochemical industry, printing, coating, shoemaking, vehicle spray painting and motor vehicle
The major pollutants of exhaust emissions etc..Part VOCs is inflammable and explosive, has grave danger to production, transportation safety etc.；Part VOCs
Human nerve and mucosal tissue can be damaged, there is " three cause " effect；Also under illumination condition with nitrogen oxides light can occur for VOCs
Chemical reaction generates photochemical fog, and significant damage is generated to environment.
At present, foreign countries are that runner Adsorption Concentration is catalyzed with heat accumulating type to the processing method of volatile organic waste gas comparative maturity
Burning is combined.Common adsorbent is mainly activated carbon and micro porous molecular sieve, although activated carbon adsorption capacity is big, it is main
Shortcoming is inflammable with security risk and difficult desorption；And the aperture of micro porous molecular sieve is smaller, and macromolecular VOCs is spread and is inhaled
Attached ability is weaker and difficult desorption, easy generation clogged with soot duct decline its adsorption capacity, influence the processing of organic exhaust gas
Effect.There is micropore and mesoporous simultaneously in view of multistage porous molecular sieve, diffusional resistance can be effectively reduced but also be provided simultaneously with good
Good hydrothermal stability and high-specific surface area has huge application prospect.
At present, synthesizing the method for multistage porous molecular sieve includes post treatment method and template synthetic method.Post treatment method refers to
Using acid, alkali process, part silicon, the aluminium element removed in micro porous molecular sieve skeleton is mesoporous to introduce, the mesoporous pore size introduced
Size is uncontrollable, and the structure that can destroy moieties sieve reduces its performance.Using the multistage porous molecular sieve energy of Template synthesis
Ensure the order of structure, China publication CN106861614A proposes a kind of preparation of multi-stage porous 5A adsorbent of molecular sieve
Method is added to using polyquaternium as template in the sol system of silicon source and silicon source mixing, and hydrothermal synthesis has micropore-Jie
The multi-stage porous 4A molecular sieves of pore structure, then above-mentioned 4A molecular sieves progress calcium ion-exchanged, activation are obtained into micropore-mesopore structure
5A adsorbent of molecular sieve has higher equilibrium adsorption capacity to n-alkane, significantly improves diffusion of the n-alkane in molecular sieve
Coefficient, so as to improve the rate of adsorbing separation.China publication CN103949204A proposes that a kind of synthesis multistage pore canal is answered
The preparation method of adsorbent of molecular sieve is closed, it is necessary to first synthesize ten yuan of micro porous molecular sieves hydrothermal synthesis mesopore molecular sieve again, compound point
Sub- mesh size≤2.83nm, and specific surface area is smaller, preparation method is complicated, is not suitable for the absorption applied to industrial organic exhaust gas.
Therefore, study a kind of large specific surface area, aperture is adjustable and the multistage porous molecular sieve of the simple and convenient commercial Application of synthesis condition very
It is necessary.
There is researcher's discovery, when using Template synthesis silica, after template agent removing is removed in calcination or solvent extraction
Substantial amounts of silicone hydroxyl (Si-OH) can be formed on surface, there is very strong affinity to water, when adsorbing VOCs, hydrone can be with
VOCs molecules form competitive Adsorption in adsorbent surface, influence VOCs absorption purifying effects.Dou et al. [Dou B, Hu Q, Li
J,et al.Adsorption performance of VOCs in ordered mesoporous silicas with
different pore structures and surface chemistry[J].Journal of Hazardous
Materials,2011,186(2–3):1615-1624.] mesopore molecular sieve is carried out using trimethoxy-benzene base silane (PTES)
It is modified, it turns out that the surface grafting sample of silane coupling agent, under the conditions of having existing for steam adsorbs the selection of VOCs
Property is higher, and for the smaller MCM-41 molecular sieves in aperture (aperture≤3nm), is not obvious using PTES modified effects.Li Cheng
[Li Chenglong, Liu Cailin, Yang Haijun wait research [J] chemistry that .ZSM-5 high-silica zeolites Silanized hydrophobic is modified to grind to dragon et al.
Study carefully and apply, 2013,25 (2):236-239.] high silica alumina ratio ZSM-5 molecular sieve is carried out using n-octytriethoxysilane
Silane surface is modified, the experimental results showed that, modified molecular sieve has dropped the adsorbance of water 1.46%, but its specific surface area
It is decreased obviously with pore volume.It can be seen that the pore volume that can cause adsorbent using the modifying agent of Long carbon chain declines, even can when serious
Duct is blocked, declines its absorption property.
The content of the invention
It is an object of the invention to improve existing adsorbent shortcoming, provide that a kind of hydrophobic performance is strong, adsorption capacity is big, aperture
Adjustable, the simple multi-stage porous silica adsorbent of adsorption desorption preparation method and and its application, the hydrophobicity multi-stage porous absorption
Agent has good adsorption and enrichment effect to the organic exhaust gas of Wind Volume, low concentration.
A kind of preparation method of the spherical ordered multi-stage porous silica adsorbent of hydrophobicity, includes the following steps：
(1) P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer) is dissolved in hydrochloric acid, CTAB
(cetyl trimethylammonium bromide) and TMB (1,3,5- trimethylbenzene) are completely dissolved in deionized water, and two kinds of solution are mixed
Uniformly, tetraethyl orthosilicate is then added dropwise, is vigorously stirred, template is made to be fully hydrolyzed with tetraethyl orthosilicate, after stirring,
Mixture is transferred to two step hydro-thermal process in tetrafluoroethene water heating kettle, is then washed solid particle to neutrality with deionized water,
It is roasted after drying up to spherical ordered multi-stage porous silica for 500~600 DEG C；
(2) the spherical ordered multi-stage porous silica is scattered in toluene, adds in organo silane coupling agent, hydro-thermal is anti-
Ying Hou after reaction product is fully washed with toluene and absolute ethyl alcohol, is dried in vacuo to obtain the final product；The organo silane coupling agent is bromine
Methyltrimethylsilane (TMBS), iodomethyl trimethyl silane (TMIS), trifluoromethyl trimethylsilane (TFMTMS) and front three
One or both of base chlorosilane (TMCS).
Sphericity mesoporous silicon dioxide has hydrothermal stability height, large specific surface area, pore volume is big and pore passage structure uniformly has
The advantages of sequence, is widely used in the fields such as chromatography substrate, catalyst carrier, drug diffusion, electrode material and absorption.It compares
Conventional microporous adsorbent of molecular sieve, spherical ordered multi-stage porous silica adsorbent have that adsorption capacity is big, diffusional resistance is low and
It is desorbed the advantages such as simple.Therefore, the present invention uses bromomethyl trimethyl silane, iodomethyl trimethyl silane, the trifluoro of short carbon chain
Methyltrimethylsilane, trim,ethylchlorosilane are modified the orderly multi-stage porous silica of synthesis, while improve titanium dioxide
The pore passage structure and hydrophobic properties of the surface of silicon adsorbent, it is good to develop a kind of hydrophobic performance, stable structure, and adsorption capacity is big and expands
The small high-efficiency adsorbent of resistance is dissipated, for handling the organic exhaust gas of industrial low concentration, Wind Volume.
The present invention is reused solvent-thermal method and silica is carried out using the synthesizing ordered multi-stage porous silica of hydrothermal method
Hydrophobically modified is prepared for the adsorbent of adsorption and enrichment industry Wind Volume, low-concentration organic exhaust gas, i.e., a kind of hydrophobicity ball
The orderly multi-stage porous silica adsorbent of shape.
Son of the invention is in the spherical ordered multi-stage porous silica adsorbent surface grafting bromomethyl trimethyl silane of hydrophobicity
(TMBS), iodomethyl trimethyl silane (TMIS), trifluoromethyl trimethylsilane (TFMTMS), trim,ethylchlorosilane (TMCS),
Hydrophobicity can be with comparing favourably using Long carbon chain is silane coupler modified, but the variation of pore volume, specific surface area relatively introduces Long carbon chain and changes
The influence of property agent is small.The specific surface area for the spherical ordered multi-stage porous silica adsorbent of finished product that the method for the present invention is prepared is
500~1000m2/ g, channel diameter are 0.1~100nm, and pore volume is 0.4~1.5cm3/g。
Preferably, the molar ratio of tetraethyl orthosilicate and P123 are 20~200 in step (1)；Mole of P123 and CTAB
Ratio is 0.001~1；The mass ratio of P123 and TMB is 0.01~50.
It is further preferred that the molar ratio of tetraethyl orthosilicate and P123 are 50~150 in step (1)；P123 and CTAB
Molar ratio be 0.2~0.7；The mass ratio of P123 and TMB is 0.5~10, the mass ratio of further preferred P123 and TMB
Example is 0.5~2.
Most preferably, the molar ratio of tetraethyl orthosilicate and P123 are 90 in step (1)；The molar ratio of P123 and CTAB
For 0.36；The mass ratio of P123 and TMB is 0.5.
Preferably, for the concentration of hydrochloric acid for 1~12mol/L, the molar ratio of hydrochloric acid and tetraethyl orthosilicate is 1 in step (1)
~10.It is further preferred that the concentration of hydrochloric acid is 2mol/L, the molar ratio of hydrochloric acid and tetraethyl orthosilicate is 2~5；Most preferably
For 3.
Preferably, hydrolysis whipping temp is at 35~60 DEG C in step (1), and mixing time is in 0.5~48h；At two step hydro-thermals
The temperature of reason is 35~200 DEG C, and the reaction time is in 0~48h.
It is further preferred that hydrolysis whipping temp is at 35~40 DEG C in step (1), mixing time is in 10~25h；First rank
The temperature of section hydro-thermal process is 60~100 DEG C, and the reaction time, second stage hydro-thermal process temperature was 80~150 in 20~25h
DEG C, the reaction time 6~for 24 hours.
It is further preferred that hydrolysis whipping temp is at 35~36 DEG C in step (1), mixing time is in 15~25h；First
The temperature of stage hydro-thermal process is 60~80 DEG C, and the reaction time, second stage hydro-thermal process temperature was 100~130 in 24~25h
DEG C, the reaction time is in 6~15h.
Most preferably, hydrolysis whipping temp is at 35 DEG C in step (1), and mixing time is in 20h；First stage hydro-thermal process
Temperature is 70 DEG C, and the reaction time, second stage hydro-thermal process temperature was 120 DEG C, reaction time 12h for 24 hours.
Two one-step hydrothermals hydro-thermal at low temperature first, can guarantee the shape of the larger micropore specific area of sample and Micropore volume
Into second stage can guarantee the effect of expanding agent TMB in higher temperature hydro-thermal, further expand while microcellular structure is kept
The aperture of multistage porous molecular sieve, and the structure more steady ordered of synthesized multistage porous molecular sieve can be promoted.
200~the 500rpm of speed of agitator being vigorously stirred.
Preferably, roasting time is 1~20h in step (1), and heating rate is in 1~20 DEG C/min.
It is further preferred that calcination temperature is 550 DEG C in step (1), roasting time is 3~6h, and heating rate is 1~3
℃/min。
Most preferably, calcination temperature is 550 DEG C in step (1), and roasting time 5h, heating rate is in 3 DEG C/min.
Preferably, concentration of the spherical ordered multi-stage porous silica in toluene is 5~20g/L in step (2).
Preferably, hydrothermal temperature is 70~200 DEG C in step (2), and the reaction time is 2~36h.Further preferably
Ground, hydrothermal temperature is 80~120 DEG C in step (2), and the reaction time is 20~25h.Most preferably, hydro-thermal in step (2)
Reaction temperature is 100 DEG C, and the reaction time is for 24 hours.
Preferably, toluene and absolute ethyl alcohol wash time are 1~5h in step (2)；Vacuum drying temperature is 70~150
DEG C, the time for 6~for 24 hours.
It is further preferred that vacuum drying temperature is 100 DEG C, drying time 12h.
The present invention also provides a kind of spherical ordered multi-stage porous titanium dioxides of hydrophobicity being prepared such as preparation method of the present invention
Silicon adsorbent.The adsorbent is applied to industrial Wind Volume, the Adsorption Concentration of low-concentration organic exhaust gas.
Application process is as follows：
By appropriate sorbent-loaded on honeycomb ceramic carrier, making industrial organic exhaust gas, organic matter is inhaled by adsorbent
Attached, gas is purified, and then, the adsorbent of adsorption saturation turns to renewing zone under the drive of motor, and elevated temperature desorption makes suction
Attached dose is regenerated, and the adsorbent after regeneration turns to adsorption zone and re-start absorption immediately after cooling, with turn
The rotation of wheel, adsorbent periodically carry out adsorption and desorption and cooling, realize the purification to organic exhaust gas.
Compared with prior art, the present invention has the following advantages：
(1) the multi-stage porous silica aperture that the present invention synthesizes can add in the ratio of silane coupling agent and be added by changing
Enter TMB to be regulated and controled, aperture can change in 2~50nm.Synthetic method is simple, reaction condition is mild, is suitable for industrialized production.
(2) the multi-stage porous silica that synthesizes of the present invention is compared to general micro-porous adsorption agent, has that adsorption capacity is big, diffusion
The advantages that resistance is small, desorption is simple, multiple adsorption desorption remains to keep higher adsorption capacity after cycling, be not easy carbon distribution.
(3) the hydrophobicity multi-stage porous silica prepared by the present invention is using bromomethyl trimethyl silane (TMBS), iodine first
Base trimethyl silane (TMIS), trifluoromethyl trimethylsilane (TFMTMS), trim,ethylchlorosilane (TMCS) connect as modifying agent
The carbochain of branch to adsorbent surface is shorter, smaller on the pore passage structure influence of adsorbent, is keeping multi-stage porous silica
Remain to keep higher hydrophobicity on the basis of absorption property.
Description of the drawings
Fig. 1 is the small angle XRD spectrum of the sintetics of embodiment 3.
Fig. 2 is the low temperature nitrogen adsorption-desorption isothermal figure of the sintetics of embodiment 3.
Fig. 3 is that the sintetics of embodiment 3 is desorbed to obtain pore volume and aperture relational graph by BJH.
Fig. 4 is the adsorption breakthrough curve figure of sintetics TMCS-sphericalSBA-15.
Fig. 5 is the adsorption desorption cycle performance data of sintetics TMCS-sphericalSBA-15.
Fig. 6 is the stereoscan photograph of sintetics.
Fig. 7 is the transmission electron microscope photo of sintetics.
Specific embodiment
With reference to embodiments, further the present invention is described in detail：
Embodiment 1：The preparation of TMBS-sphericalSBA-15 adsorbents：
It is 90 to control the molar ratio of tetraethyl orthosilicate and P123, and P123 is dissolved in 90ml 2mol/L hydrochloric acid solutions, is controlled
The mass ratio of P123 and TMB processed are 0.5, the molar ratio of P123 and CTAB are 0.25, by TMB and CTAB be dissolved in 30ml go from
In sub- water, two kinds of mixed liquors at 35 DEG C are mixed, tetraethyl orthosilicate is added dropwise.Mixture will be turned after stirring 20h
Enter in polytetrafluoroethyllining lining stainless steel water heating kettle, 70 DEG C of hydro-thermals for 24 hours after 120 DEG C of hydro-thermal 12h again, then will precipitation cleaning into
Property, it dries, 550 DEG C of roasting 5h are spare.The sphericalSBA-15 after 1g roastings is taken, adds in 100ml toluene and 0.2mmol
TMBS, hydro-thermal reaction is for 24 hours at 100 DEG C.After reaction, suspension is through filtering, obtained solid particle toluene and anhydrous second
Alcohol washs 3h, and the molecular sieve of bromomethyl trimethyl silane modification is obtained after 100 DEG C of dry 12h, is denoted as TMBS-
sphericalSBA-15。
After tested, the specific surface area of TMBS-sphericalSBA-15 adsorbents is 761.2m2/ g, pore volume are
0.65cm3/ g, BJH absorption aperture are 8.9nm, and 30 DEG C of Toluene dynamic saturated extent of adsorption reach 99.3mg/g.
Embodiment 2：The preparation of TFMTMS-sphericalSBA-15 adsorbents：
It is 90 to control the molar ratio of tetraethyl orthosilicate and P123, and P123 is dissolved in 90ml 2mol/L hydrochloric acid solutions, is controlled
The mass ratio of P123 and TMB processed are 0.5, the molar ratio of P123 and CTAB are 0.5, by TMB and CTAB be dissolved in 30ml go from
In sub- water, two kinds of mixed liquors at 35 DEG C are mixed, tetraethyl orthosilicate is added dropwise.Mixture will be turned after stirring 20h
Enter in polytetrafluoroethyllining lining stainless steel water heating kettle, 70 DEG C of hydro-thermals for 24 hours after 120 DEG C of hydro-thermal 12h again, then will precipitation cleaning into
Property, it dries, 550 DEG C of roasting 5h are spare.The sphericalSBA-15 after 1g roastings is taken, adds in 100ml toluene and 0.2mmol
TFMTMS, hydro-thermal reaction is for 24 hours at 100 DEG C.After reaction, suspension is through filtering, obtained solid particle toluene and anhydrous
Ethyl alcohol washs 3h, obtains the molecular sieve of trifluoromethyl trimethylsilane modification, is denoted as TFMTMS-sphericalSBA-15.
After tested, the specific surface area of TFMTMS-sphericalSBA-15 adsorbents is 825.6m2/ g, pore volume are
0.87cm3/ g, BJH absorption aperture are 11.8nm, and 30 DEG C of Toluene dynamic saturated extent of adsorption reach 103.9mg/g.
Embodiment 3：The preparation of TMCS-sphericalSBA-15 adsorbents：
It is 90 to control the molar ratio of tetraethyl orthosilicate and P123, and P123 is dissolved in 90ml 2mol/L hydrochloric acid solutions, is controlled
The mass ratio of P123 and TMB processed are 0.5, the molar ratio of P123 and CTAB are 0.36, by TMB and CTAB be dissolved in 30ml go from
In sub- water, two kinds of mixed liquors at 35 DEG C are mixed, tetraethyl orthosilicate is added dropwise.Mixture will be turned after stirring 20h
Enter in polytetrafluoroethyllining lining stainless steel water heating kettle, 70 DEG C of hydro-thermals for 24 hours after 120 DEG C of hydro-thermal 12h again, then will precipitation cleaning into
Property, it dries, 550 DEG C of roasting 5h are spare.The sphericalSBA-15 after 1g roastings is taken, adds in 100ml toluene and 0.2mmol
TMCS, hydro-thermal reaction is for 24 hours at 100 DEG C.After reaction, suspension is through filtering, obtained solid particle toluene and anhydrous second
Alcohol washs 3h, obtains the molecular sieve of trim,ethylchlorosilane modification, is denoted as TMCS-sphericalSBA-15.
After tested, the specific surface area of TMCS-sphericalSBA-15 adsorbents is 738.8m2/ g, pore volume are
0.88cm3/ g, BJH absorption aperture are 10.2nm, and 30 DEG C of Toluene dynamic saturated extent of adsorption reach 105.0mg/g.
Embodiment 4：The preparation of TMIS-sphericalSBA-15 adsorbents
It is 150 to control the molar ratio of tetraethyl orthosilicate and P123, and P123 is dissolved in 90ml 2mol/L hydrochloric acid solutions,
The mass ratio for controlling P123 and TMIS is 1, TMB and CTAB is dissolved in 30ml deionized waters, by two kinds of mixed liquors at 35 DEG C
Lower mixing, is added dropwise tetraethyl orthosilicate.Mixture will be transferred to polytetrafluoroethyllining lining stainless steel hydro-thermal after stirring 20h
In kettle, 70 DEG C of hydro-thermals are for 24 hours and after 120 DEG C of hydro-thermal 12h, and by precipitation cleaning to neutrality, drying, 550 DEG C of roasting 5h are spare.Take 1g
SphericalSBA-15 after roasting, adds in 100ml toluene and 0.2mmol TMIS, and hydro-thermal reaction is for 24 hours at 100 DEG C.Reaction knot
Shu Hou, through filtering, obtained solid particle washs 3h with toluene and absolute ethyl alcohol, obtains iodomethyl trimethyl silane and change suspension
The molecular sieve of property, is denoted as TMIS-sphericalSBA-15.
After tested, the specific surface area of TMIS-sphericalSBA-15 adsorbents is 752.6m2/ g, pore volume are
0.65cm3/ g, BJH absorption aperture are 9.1nm, and 30 DEG C of Toluene dynamic saturated extent of adsorption reach 103.9mg/g.
Embodiment 5：The structural characterization of sintetics of the present invention
The present embodiment is the structural characterization of the TMCS-sphericalSBA-15 adsorbents obtained to embodiment 3, is mainly had
The following aspects；
X-ray powder diffraction is used to analyze the hole of unmodified sphericalSBA-15 and TMCS-sphericalSBA-15
Structure, the result is shown in Figure 1.It can be seen from the figure that TMCS-sphericalSBA-15 remains unmodified sphericalSBA-15
Meso-hole structure and long-range order.
Adsorbent specific surface area and pore-size distribution are tested using precise and tiny Gao Bo specific surface area measuring instrument, the result is shown in Fig. 2 and figure
3.It is unmodified from adsorption isothermal curve as can be seen that modified sample micropore specific area does not change substantially
The specific surface area of sphericalSBA-15 and TMCS-sphericalSBA-15 is respectively 871.4m2/ g and 738.8m2/ g, pore volume
Respectively 0.94cm3/ g and 0.88cm3/ g, aperture are respectively 10.8nm and 10.2nm, it is seen that specific surface area and pore volume are protected
It stays.
Embodiment 6：The absorption property test of sintetics of the present invention
Toluene (500ppm, 50ml/min) is selected to be adsorbed as target contaminant using micro fixed-bed reactor
Experiment.0.1g TMCS-sphericalSBA-15 adsorbents are taken, in the case where 30 DEG C, relative humidity is 0% and 50% respectively into action
State adsorption experiment, with the concentration of toluene in gas chromatographic detection import and exit gas.
As control, adsorption experiment is carried out under the same conditions with unmodified sphericalSBA-15.
Figure 4, it is seen that modified TMCS-sphericalSBA-15 adsorbents are in the case where relative humidity is 50%
It remains to keep preferable adsorption capacity, saturated adsorption capacity 80.1mg/g, unmodified sphericalSBA-15 is relatively wet
It spends under conditions of 50%, saturated adsorption capacity is decreased obviously, is only 32.9mg/g.
Embodiment 7：The adsorption desorption cycle performance test of sintetics of the present invention
Adsorption desorption loop test carries out in miniature fixed bed, by embodiment 6 relative humidity be 0% time adsorption saturation
TMCS-sphericalSBA-15 purged at 150 DEG C with nitrogen and there is no toluene into tail gas, be cooled to after 30 DEG C again into
Mobile state adsorption experiment, the de-adsorption cycle performance of synthesized product are as shown in Figure 5, it is seen that when adsorption desorption is recycled to the 10th time,
Toluene dynamic saturated adsorption capacity of the sample at 30 DEG C remains to be maintained at 103.0mg/g, and loss capacity is only 1.9%, it was demonstrated that
Synthesized sample has superior adsorption desorption performance, and (150 DEG C) power of regeneration is good at a lower temperature, and commercial application potentiality is huge
Greatly.
The foregoing is merely the specific implementation case of patent of the present invention, but the technical characteristic of patent of the present invention is not limited to
This, any those skilled in the relevant art in the field of the invention, all cover in the special of the present invention by the variation or modification made
Among sharp scope.
Claims (10)
1. a kind of preparation method of the spherical ordered multi-stage porous silica adsorbent of hydrophobicity, which is characterized in that including walking as follows
Suddenly：
(1) polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer is dissolved in hydrochloric acid, cetyl trimethyl
Ammonium bromide and 1,3,5- trimethylbenzenes are completely dissolved in deionized water, and two kinds of solution are uniformly mixed, silicic acid is then added dropwise
Tetra-ethyl ester is vigorously stirred, and template is made to be fully hydrolyzed with tetraethyl orthosilicate, and after stirring, mixture is transferred to tetrafluoroethene
Then two step hydro-thermal process in water heating kettle is washed solid particle to neutrality with deionized water, 500~600 DEG C of roastings after drying
Up to spherical ordered multi-stage porous silica；
(2) the spherical ordered multi-stage porous silica is scattered in toluene, adds in organo silane coupling agent, hydro-thermal reaction
Afterwards, reaction product with toluene and absolute ethyl alcohol is fully washed, be dried in vacuo to obtain the final product；The organo silane coupling agent is bromomethyl
One or both of trimethyl silane, iodomethyl trimethyl silane, trifluoromethyl trimethylsilane and trim,ethylchlorosilane.
2. preparation method according to claim 1, which is characterized in that the molar ratio of tetraethyl orthosilicate and P123 in step (1)
Example is 20~200；The molar ratio of P123 and CTAB is 0.001~1；The mass ratio of P123 and TMB is 0.01~50.
3. preparation method according to claim 1, which is characterized in that in step (1) concentration of hydrochloric acid be 1~12mol/L, salt
The molar ratio of acid and tetraethyl orthosilicate is 1~10.
4. preparation method according to claim 1, which is characterized in that hydrolysis whipping temp is stirred at 35~60 DEG C in step (1)
The time is mixed in 10~48h；In two step hydrothermal treatment process：The temperature of first stage hydro-thermal process is 60~100 DEG C, the reaction time
In 20~25h, second stage hydro-thermal process temperature is 80~150 DEG C, the reaction time 6~for 24 hours.
5. preparation method according to claim 1, which is characterized in that in step (1) roasting time be 1~20h, heating rate
In 1~20 DEG C/min.
6. preparation method according to claim 1, which is characterized in that spherical ordered multi-stage porous silica exists in step (2)
Concentration in toluene is 5~20g/L.
7. preparation method according to claim 1, which is characterized in that hydrothermal temperature is 70~200 DEG C in step (2),
Reaction time is 2~36h.
8. preparation method according to claim 1, which is characterized in that toluene and absolute ethyl alcohol wash time are 1 in step (2)
~5h；Vacuum drying temperature is 70~150 DEG C, the time for 6~for 24 hours.
9. a kind of spherical ordered multistage of hydrophobicity that preparation method as described in claim 1~8 any claim is prepared
Hole silica adsorbent.
10. a kind of spherical ordered multi-stage porous silica adsorbent of hydrophobicity as claimed in claim 9 is in industrial Wind Volume, low dense
Spend the application in the Adsorption Concentration of organic exhaust gas.
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