CN109304141A - It is a kind of for adsorbing diatomite/molecular sieves compound material preparation method of volatile organic contaminant - Google Patents

It is a kind of for adsorbing diatomite/molecular sieves compound material preparation method of volatile organic contaminant Download PDF

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CN109304141A
CN109304141A CN201811522149.0A CN201811522149A CN109304141A CN 109304141 A CN109304141 A CN 109304141A CN 201811522149 A CN201811522149 A CN 201811522149A CN 109304141 A CN109304141 A CN 109304141A
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diatomite
hours
solution
molecular sieves
zeolite
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康春莉
刘芳
田涛
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Jilin University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/14—Diatomaceous earth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/10—Inorganic adsorbents
    • B01D2253/106—Silica or silicates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s

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Abstract

The invention discloses a kind of for adsorbing diatomite/molecular sieves compound material preparation method of volatile organic contaminant.The present invention modifies its surface and duct using strong acid and highly basic using Jilin Province's Dominant Mineral Resources diatomite as raw material, improves its purity and expands aperture by corrosion, to prevent macropore to be blocked and improve zeolite-loaded rate.Then diatomite area load nano zeolite crystal seed after modification, then so that the further growth of diatomite surface is gone out fine and close nano zeolite film by hydro-thermal process.Prepared diatomite/molecular sieves compound material specific surface area and the more original diatomite of pore volume have a distinct increment, and have ideal adsorption effect to volatile organic contaminant such as acetone, ethyl acetate and toluene.The experimental results showed that the advantages of diatomite/molecular sieves compound material selective absorption.In addition, the material can be applied even more extensively into industrial production by being mixed with granule adsorbent with clay.

Description

It is a kind of for adsorbing diatomite/molecular sieves compound material of volatile organic contaminant Preparation method
Technical field
The present invention relates to a kind of preparation methods of diatomite/molecular sieves compound material, and in particular to diatomite with The compound preparation method of Silialite-1 and Beta molecular sieve, for adsorbing volatile organic contaminant.
Background technique
In recent years, with the quickening of industrial development and urbanization process, air environmental pollution problem is increasingly sharpened, volatility A series of serious environment and human health that organic compound (Volatile Organic Compounds, VOCs) causes are asked Inscribe the extensive concern by the whole world.On the one hand, the VOCs being discharged into atmosphere can induce the environmental pollutions such as haze；On the other hand, The VOCs for contacting doses for a long time, may result in respiratory system or disease of hematopoietic system.
There are many kinds of the methods of current processing VOCs, mainly there is destruction technology and recovery technology, including absorption techniques, suction Attached technology, Purification biotechnology, catalytic combustion technology and plasma for purification technology etc..At present for many low concentration organic wastes The improvement of gas, absorption method is considered as low operating cost, good purification, low energy consumption, using ideal process route, in industry The application of aspect is also most wide.The key of absorption method is exactly the selection of adsorbent material and absorbing process, industrial at present most widely used Two kinds of adsorbents be active carbon and zeolite molecular sieve.Compared with active carbon, molecular sieve of Nano zeolite has well-regulated duct Structure has selection characterization of adsorption.In addition its thermal stability is high, has high-specific surface area and pore volume.But nanometer boiling at present There are still following problems for the industrial application of stone molecular screen material: (1) single pore-size distribution causes molecular sieve of Nano zeolite only right The small molecule VOCs of certain size has suction-operated, is unfavorable for the absorption of multicomponent VOCs；(2) reunite between Colloidal zeolites Problem can also reduce adsorption efficiency, improve pollutant process cost.Therefore, preparation has hierarchical porous structure, and dispersibility is preferable Nano zeolite composite material is the key that solve the above problems.
Diatomite is a kind of biogenic deposit rock formed after remains (diatom shell) deposited accumulation by diatom biology.Silicon Diatomaceous earth is the Dominant Mineral Resources that China's proved reserves occupy second place of the world, Jilin Province's diatomite prospective reserves at 300,000,000 tons or more, An important seat is accounted in China or even Asia diatomite reserves and exploitation pattern.Diatomite in China's reserves very abundant, and It is a kind of environment adsorbing materials with potential prospect and with the features such as Kong Rong great, chemical stability is good, but single silicon There is also the lower limitations of adsorption efficiency for diatomaceous earth.Diatomite is compound with molecular sieve, multistage pore canal novel absorption material is prepared, it will Its absorption for being applied to VOCs has great researching value and application value.
Summary of the invention
The object of the present invention is to provide a kind of diatomite/molecular sieves compound material, the material to volatile organic contaminant, As acetone, ethyl acetate, toluene have preferable adsorption capacity, and the selective absorption in multicomponent VOCs competitive Adsorption Property.
Cardinal principle of the invention is: (1) micro- mesoporous method: utilizing hydrochloric Acid Modification dissolution diatomite surface and intrapore viscous Native impurity is subsequently placed at heating water bath in sodium hydroxide solution.Soda boiling plays reaming, blocking when preventing load molecular sieve Macroporous structure, and it is capable of forming meso-hole structure, prepare multi-stage porous adsorbent material.(2) secondary growth method: by diatomite sun from Sub- polymerizer processing, keeps its positively charged；Molecular sieve is dispersed in ammonium hydroxide and prepares colloidal sol, adjusts pH to 9~10, keeps its band negative Electricity.Molecular sieve seed is loaded in diatomite, by the hydro-thermal reaction in zeolite Synthesis liquid, make molecular sieve in diatomite with Crystal seed is starting point, and growth is got up in an orderly manner, forms uniform zeolite membrane.
Of the invention is by the following method for adsorbing diatomite/molecular sieves compound material of volatile organic contaminant Preparation, the preparation method the following steps are included:
1) by ethyl orthosilicate, example 25:9:480 is mixed in molar ratio for tetrapropylammonium hydroxide and water, Silicalite-1 Zeolite Synthesis liquid, which stirs evenly, to be placed in water heating kettle, 100 DEG C crystallization 4 days, washing after separation of solid and liquid is dried at 60 DEG C, is done Product after dry is heated to 550 DEG C in air atmosphere, and roasting obtains nano Si licalite-1 in 6 hours；
2) sodium hydroxide, sodium metaaluminate, tetraethyl ammonium hydroxide and water 170:278:875:4600 in mass ratio are mixed, Solution A is stirred 2 hours to obtain at room temperature；Ethyl orthosilicate, tetraethyl ammonium hydroxide and water 214:65:195 in mass ratio are mixed, B solution is stirred 2 hours to obtain at room temperature；Solution A is added dropwise in B according to the ratio of solution A and B solution mass ratio 59:474, Beta zeolite Synthesis liquid continues stirring 2~4 hours to being uniformly placed in water heating kettle, 140 DEG C crystallization 24 hours.After separation of solid and liquid Washing is dried at 60 DEG C, and the product after drying is heated to 550 DEG C in air atmosphere, and roasting obtains a nanometer Beta in 6 hours；
3) diatomite is completely submerged in 6M hydrochloric acid solution, is sufficiently stirred at 60 DEG C 4 hours, dried after washing in 60 DEG C It is dry；
4) by step 3), treated that diatomite is completely submerged in the sodium hydroxide solution of pH=13.5, fills at 60 DEG C Divide stirring 4 hours, is dried after washing in 60 DEG C；
5) diatomite after will be dry in step 4), which is added in 0.5wt% polycation electrolyte solution, sufficiently to be impregnated, It is washed after separation of solid and liquid；
6) Silicalite-1 of step 1) preparation (or Beta of step 2) preparation) is added to the ammonium hydroxide of pH=9~10 It is uniformly dispersed in solution, prepares Silicalite-1 (Beta) zeolite ammonium hydroxide colloidal sol of 0.5wt%.By the diatomite in step 5) It is that 1g/20~60ml is added to by diatomite quality/Silicalite-1 (Beta) zeolite ammonium hydroxide sol volume ratio It sufficiently impregnates in Silicalite-1 (Beta) zeolite ammonium hydroxide colloidal sol, is sufficiently washed after separation of solid and liquid with the ammonium hydroxide of 0.1mol/L, Obtain the diatomaceous earth sample of area load zeolite seed crystal；
7) diatomaceous earth sample that step 6) has been loaded to zeolite seed crystal is by diatomite quality/zeolite Synthesis liquid volume ratio 1g/40ml is placed in the zeolite Synthesis liquid according to step 1) (or step 2)) preparation, 100 DEG C of crystallization 4 days (or 140 DEG C of crystallization 24 Hour), it is separated by solid-liquid separation, the product after washing after 60 DEG C of dryings, drying is heated to 550 DEG C in air atmosphere, and roasting 6 is small When, obtain diatomite/Silicalite-1 (or diatomite/Beta) composite material.
The diatomite is bought from Jilin Province Changbai Mountain mining area.
The polycation electrolyte solution is preferably the aqueous solution of polydimethyl diallyl ammonium chloride.
The solid-liquid isolation method can be centrifugal process or suction method.
Diatomite/the molecular sieves compound material can be mixed with granule adsorbent with clay, be generalized to actual industrial In production.
For the present invention compared to existing technology, advantage is as follows:
(1) using hydrochloric Acid Modification dissolution diatomite surface and intrapore clay impurity, can be improved diatomite purity, Specific surface area and pore volume.
(2) silica in diatomite can be reacted with highly basic, carried out part corrosion to diatomite, played the role of reaming, It prevents from blocking macroporous structure when load molecular sieve, and is capable of forming new mesoporous and micropore, be conducive to composite material specific surface Long-pending and pore volume raising.
(3) diatomite is impregnated by polycation electrolyte solution, and surface is positively charged, is easier to and the zeolite of negatively charged point Son sieve combines, to improve the load factor of molecular sieve, improves the specific surface area and pore volume of composite material.
(4) diatomite/molecular sieves compound material specific surface area for preparing by the method for the invention and pore volume relative to Diatomite has biggish promotion, has preferable adsorption effect to acetone, ethyl acetate, toluene.
(5) diatomite/molecular sieves compound material for preparing by the method for the invention is to acetone, ethyl acetate, toluene The selective absorption to ethyl acetate is shown in Multicomponent Competitive Adsorption Onto experiment.
(6) diatomite/molecular sieves compound material is mixed with business attapulgite 5:1 in mass ratio, and pressed disc method prepares partial size In the granule adsorbent of 1mm or so.It is used for Kinetic penetration adsorption experiment, is still had well to acetone, ethyl acetate, toluene Adsorption effect.
Detailed description of the invention
Fig. 1 be embodiment in for adsorb volatile organic contaminant diatomite/Silicalite-1 composite material, Silicalite-1 molecular sieve, diatomite X-ray diffractogram (using Broker D8ADVANCE type X-ray diffractometer survey It is fixed).
Fig. 2 is compound for adsorbing diatomite, the diatomite/Silicalite-1 of volatile organic contaminant in embodiment Material, diatomite/Beta composite material scanning electron microscope (SEM) photograph (are surveyed using TOPCON ABT-150S type scanning electron microscope It is fixed).
Fig. 3 is in embodiment for adsorbing diatomite/Silicalite-1 composite material, silicon of volatile organic contaminant Nitrogen adsorption-desorption isotherm (being measured using 2020 type physical adsorption appearance of Micromeritics ASAP) of diatomaceous earth.
Fig. 4 be diatomite/Silicalite-1 composite material to acetone, ethyl acetate, toluene one-component adsorbance with Multicomponent Competitive Adsorption Onto amount comparison diagram.
Fig. 5 is in embodiment for adsorbing diatomite/Beta composite material, the Beta molecule of volatile organic contaminant The X-ray diffractogram (being measured using Broker D8ADVANCE type X-ray diffractometer) of sieve, diatomite.
Fig. 6 is in embodiment for adsorbing diatomite/Beta composite material of volatile organic contaminant, the nitrogen of diatomite Gas adsorption-desorption isothermal (is measured) using 2020 type physical adsorption appearance of Micromeritics ASAP.
Fig. 7 diatomite/Beta composite material competes acetone, ethyl acetate, the one-component adsorbance of toluene and multicomponent Adsorbance comparison diagram.
Specific embodiment
Specific embodiments of the present invention are described further with reference to the accompanying drawing:
Embodiment 1
1) 56ml ethyl orthosilicate, 73ml tetrapropylammonium hydroxide solution (25%) and 31ml water are added in beaker, Stirring 12 hours is packed into hydrothermal reaction kettle, and 100 DEG C brilliant 4 days magnificent.Supernatant is removed in centrifugation after reaction, and remaining solid continues Addition distilled water, which is cleaned to supernatant, to be in neutrality, and dries solid at 60 DEG C after centrifugation.Later in Muffle in air atmosphere It is roasted 6 hours for 550 DEG C in furnace, obtaining solid is nano Si licalite-1.
2) 5g diatomite is added in 100ml6M hydrochloric acid solution, 60 DEG C stirring in water bath 4 hours.It filters later, by solid It is washed to supernatant liquor to be in neutrality, 60 DEG C of drying.
3) by step 2), treated that diatomite is added in the sodium hydroxide solution of 100ml pH=13.5,60 DEG C of water-baths Stirring 4 hours.It filters later, solid is washed to supernatant liquor and is in neutrality, 60 DEG C of drying.
4) by step 3) highly basic, treated that diatomite is added to 100ml 0.5wt% polydimethyl diallyl ammonium chloride It is stirred 1 hour in solution, stands 30 minutes and wash 3 times.
5) 2g step 4) treated diatomite is weighed, being added to 40ml concentration is 0.5wt%, pH=9~10 It in Silicalite-1 zeolite ammonium hydroxide colloidal sol, stirs 1 hour, stands 30 minutes.Using 0.1mol/L ammonia spirit as cleaning solution, Washing 3 times obtains the diatomaceous earth sample of one layer of zeolite seed crystal of load.
6) zeolite Synthesis liquid 40ml is prepared according to the method for step 1), weighs the diatom that 1g step 5) has loaded zeolite seed crystal Earth sample is placed in zeolite Synthesis liquid and stirs evenly, and is put into 100 DEG C of hydrothermal reaction kettle crystallization 4 days.It is centrifuged, washes after reaction It is in neutrality to supernatant, is dried in 60 DEG C, the product after drying is heated to 550 DEG C in air atmosphere, roasts 6 hours, obtains Diatomite/Silicalite-1 composite material.
It can be seen that diatomaceous earth sample by the X-ray diffractogram of Fig. 1 and amorphous silica occur at about 21.8 ° Diffraction maximum is attributed to the characteristic peak of diatom opal through data consultation.Silicalite-1 sieve sample at about 8.2 °, 9.1 °, 15.1 °, 18.0 °, 23.4 °, 24.3 ° and 24.8 ° there is the biggish diffraction maximum of intensity, by with standard diagram Comparison finds that this 7 diffraction maximums belong to the crystal face characteristic peak of Silicalite-1 molecular sieve.In diatomite/Silicalite-1 Also occur approximate diffraction maximum in composite material at the roughly the same angle of diffraction, this illustrate Silicalite-1 molecular sieve at Diatomite surface is loaded to function.
The diatomite prepared by the method for the invention /Silicalite-1 composite material specific surface area is up to 427.5m2/ G, pore volume is up to 0.40m3/ g, relative to diatomite (specific surface area 10.0m2/ g, pore volume 0.05m3/ g) there is biggish mention It rises, static state of the diatomite the prepared by the method for the invention /Silicalite-1 composite material to acetone, ethyl acetate, toluene Saturated extent of adsorption is respectively up to 0.99mmol/g, 1.31mmol/g and 0.69mmol/g.
Embodiment 2
1) 56ml ethyl orthosilicate, 73ml tetrapropylammonium hydroxide solution (25%) and 31ml water are added in beaker, Stirring 12 hours is packed into hydrothermal reaction kettle, and 100 DEG C brilliant 4 days magnificent.Supernatant is removed in centrifugation after reaction, and remaining solid continues Addition distilled water, which is cleaned to supernatant, to be in neutrality, and dries solid at 60 DEG C after centrifugation.Later in Muffle in air atmosphere It is roasted 6 hours for 550 DEG C in furnace, obtaining solid is nano Si licalite-1.
2) 5g diatomite is added in 100ml 6M hydrochloric acid solution, 60 DEG C stirring in water bath 4 hours.It filters, will consolidate later Body is washed to supernatant liquor and is in neutrality, 60 DEG C of drying.
3) by step 2), treated that diatomite is added in the sodium hydroxide solution of 100ml pH=13.5,60 DEG C of water-baths Stirring 4 hours.It filters later, solid is washed to supernatant liquor and is in neutrality, 60 DEG C of drying.
4) by step 3) highly basic, treated that diatomite is added to 100ml 0.5wt% polydimethyl diallyl ammonium chloride It is stirred 1 hour in solution, stands 30 minutes and wash 3 times.
5) 2g step 4) treated diatomite is weighed, being added to 120ml concentration is 0.5wt%, pH=9~10 It in Silicalite-1 zeolite ammonium hydroxide colloidal sol, stirs 1 hour, stands 30 minutes.Using 0.1mol/L ammonia spirit as cleaning solution, Washing 3 times obtains the diatomaceous earth sample of one layer of zeolite seed crystal of load.
6) zeolite Synthesis liquid 40ml is prepared according to the method for step 1), weighs the diatom that 1g step 5) has loaded zeolite seed crystal Earth sample is placed in zeolite Synthesis liquid and stirs evenly, and is put into 100 DEG C of hydrothermal reaction kettle crystallization 4 days.It is centrifuged, washes after reaction It is in neutrality to supernatant, is dried in 60 DEG C, the product after drying is heated to 550 DEG C in air atmosphere, roasts 6 hours, obtains Diatomite/Silicalite-1 composite material.
Fig. 2 (a, b), (c, d) are that diatomite and diatomite/Silicalite-1 composite material scanning electron microscope are shone respectively Piece.Observation Fig. 2 a can be seen that diatomaceous earth sample form is discoid for rule, and diameter of the housing is about 20 μm -25 μm, and shell table Gather macropore in face, the regularity of distribution, and cellular structure is more flourishing.It can be seen that the aperture of diatomaceous earth sample in 0.2-0.5 from Fig. 2 b μm or so.Fig. 2 c can substantially see that one layer of comparatively dense Silicalite-1 molecular sieve has been gone up in the covering of diatomaceous earth sample surface Film.Fig. 2 d shows that the granularity of Silicalite-1 molecular sieve is about 60nm-70nm.
The diatomite prepared by the method for the invention /Silicalite-1 composite material is to acetone, ethyl acetate, toluene Multicomponent Competitive Adsorption Onto experiment in show selective absorption to ethyl acetate.To acetone, acetic acid second in same system Ester, toluene adsorbance be respectively 0.21mmol/g, 0.81mmol/g and 0.05mmol/g.Fig. 4 be one-component adsorbance with it is competing Strive adsorbance comparison diagram, as we can see from the figure the competitive Adsorption amount of ethyl acetate account for the ratio of one-component adsorbance considerably beyond Acetone and toluene, therefore further illustrate that diatomite/Silicalite-1 composite material has Selective adsorption to ethyl acetate.
Embodiment 3
1) 56ml ethyl orthosilicate, 73ml tetrapropylammonium hydroxide solution (25%) and 31ml water are added in beaker, Stirring 12 hours is packed into hydrothermal reaction kettle, and 100 DEG C brilliant 4 days magnificent.Supernatant is removed in centrifugation after reaction, and remaining solid continues Addition distilled water, which is cleaned to supernatant, to be in neutrality, and dries solid at 60 DEG C after centrifugation.Later in Muffle in air atmosphere It is roasted 6 hours for 550 DEG C in furnace, obtaining solid is nano Si licalite-1.
2) 5g diatomite is added in 100ml 6M hydrochloric acid solution, 60 DEG C stirring in water bath 4 hours.It filters, will consolidate later Body is washed to supernatant liquor and is in neutrality, 60 DEG C of drying.
3) by step 2), treated that diatomite is added in the sodium hydroxide solution of 100ml pH=13.5,60 DEG C of water-baths Stirring 4 hours.It filters later, solid is washed to supernatant liquor and is in neutrality, 60 DEG C of drying.
4) by step 3) highly basic, treated that diatomite is added to 100ml 0.5wt% polydimethyl diallyl ammonium chloride It is stirred 1 hour in solution, stands 30 minutes and wash 3 times.
5) 2g step 4) treated diatomite is weighed, being added to 80ml concentration is 0.5wt%, pH=9~10 It in Silicalite-1 zeolite ammonium hydroxide colloidal sol, stirs 1 hour, stands 30 minutes.Using 0.1mol/L ammonia spirit as cleaning solution, Washing 3 times obtains the diatomaceous earth sample of one layer of zeolite seed crystal of load.
6) zeolite Synthesis liquid 40ml is prepared according to the method for step 1), weighs the diatom that 1g step 5) has loaded zeolite seed crystal Earth sample is placed in zeolite Synthesis liquid and stirs evenly, and is put into 100 DEG C of hydrothermal reaction kettle crystallization 4 days.It is centrifuged, washes after reaction It is in neutrality to supernatant, is dried in 60 DEG C, the product after drying is heated to 550 DEG C in air atmosphere, roasts 6 hours, obtains Diatomite/Silicalite-1 composite material.
Diatomite/Silicalite-1 composite material is mixed with business attapulgite 5:1 in mass ratio, and pressed disc method prepares grain Granule adsorbent of the diameter in 1mm or so.It is used for Kinetic penetration adsorption experiment, it is full to the dynamic of acetone, ethyl acetate, toluene It is respectively 4.51mm/g, 6.05mmol/g and 1.80mmol/g with adsorbance.
Fig. 3 is diatomite/Silicalite-1 composite material N2Adsorption-desorption isothermal figure.The absorption-of diatomite is de- Attached IV type of thermoisopleth has a unconspicuous H3 type hysteresis loop, and it is a small amount of mesoporous that this shows that diatomite contains only.In P/P0≤ When 0.1, diatomite is to N2Adsorbance it is extremely low, this shows that diatomite is substantially free of micropore；In P/P0When close to 1, diatomaceous earth sample To N2Adsorbance have huge promotion, this shows diatomite macropore rich in.Diatomite/Silicalite-1 composite wood Material is in P/P0When≤0.1, to N2Adsorbance rapid development, illustrate that it contains a certain number of micropores, reason is molecule Sieve is a kind of poromerics, N in itself2It is packed into the rapid growth that adsorbance is caused in the micropore of molecular sieve rapidly.Experience is fast After speed increases, to N2Absorption tend towards stability, and finally in P/P0When close to 1, adsorbance rapidly rises again, this shows compound Still there are a considerable amount of macropores in material.And in the position of relative pressure about 0.8, the adsorption-desorption isothermal of composite material There is an apparent H3 type hysteresis loop in line, this shows occur meso-hole structure in composite material.This, which shows to have synthesized, has The material of multi-stage artery structure improves diatomite and the single situation of Molecular Sieve Pore.
Embodiment 4
1) 2g is added in 0.17g sodium hydroxide, 0.278g sodium metaaluminate and 3.5g tetraethyl ammonium hydroxide solution (25%) In distilled water, solution A is stirred 2 hours to obtain at room temperature；The positive silicon of 21.43g is added in 25.95g tetraethyl ammonium hydroxide solution (25%) B solution is stirred 2 hours to obtain in acetoacetic ester at room temperature；Solution A is added dropwise in B, continues stirring 2~4 hours to being uniformly placed on In water heating kettle, 140 DEG C crystallization 24 hours.It washs after separation of solid and liquid, dried at 60 DEG C, the product after drying is in air atmosphere 550 DEG C are heated to, roasting obtains a nanometer Beta in 6 hours.
2) 5g diatomite is added in 100ml6M hydrochloric acid solution, 60 DEG C stirring in water bath 4 hours.It filters later, by solid It is washed to supernatant liquor to be in neutrality, 60 DEG C of drying.
3) by step 2), treated that diatomite is added in the sodium hydroxide solution of 100ml pH=13.5,60 DEG C of water-baths Stirring 4 hours.It filters later, solid is washed to supernatant liquor and is in neutrality, 60 DEG C of drying.
4) by step 3) highly basic, treated that diatomite is added to 100ml 0.5wt% polydimethyl diallyl ammonium chloride It is stirred 1 hour in solution, stands 30 minutes and wash 3 times.
5) 2g step 4) treated diatomite is weighed, the Beta that 40ml concentration is 0.5wt%, pH=9~10 is added to It in zeolite ammonium hydroxide colloidal sol, stirs 1 hour, stands 30 minutes.Using 0.1mol/L ammonia spirit as cleaning solution, washs 3 times, obtain Load the diatomaceous earth sample of one layer of zeolite seed crystal.
6) zeolite Synthesis liquid 40ml is prepared according to the method for step 1), weighs the diatom that 1g step 5) has loaded zeolite seed crystal Earth sample is placed in zeolite Synthesis liquid and stirs evenly, and is put into 140 DEG C of hydrothermal reaction kettle crystallization 24 hours.Be centrifuged after reaction, It is washed to supernatant to be in neutrality, be dried in 60 DEG C.Then in air atmosphere in Muffle furnace 550 DEG C roast 6 hours, obtain silicon Diatomaceous earth/Beta composite material.
It can be seen that Beta sieve sample at about 7.5 °, 21.3 °, 22.4 ° by the X-ray diffractogram of Fig. 4, 25.2 °, 27.0 °, 29.5 ° there is the biggish diffraction maximum of intensity, find that this 6 diffraction maximums are equal by the comparison with standard diagram Belong to the crystal face characteristic peak of Beta molecular sieve.Also occur at the roughly the same angle of diffraction in diatomite/Beta composite material Approximate diffraction maximum, this illustrates that Beta molecular sieve has successfully loaded to diatomite surface.
The diatomite prepared by the method for the invention /Beta composite material specific surface area is up to 432.0m2/ g, pore volume Up to 0.28m3/ g, relative to diatomite (specific surface area 10.0m2/ g, pore volume 0.05m3/ g) have biggish promotion, to acetone, Ethyl acetate, toluene static saturated adsorption capacity respectively up to 1.36mmol/g, 1.42mmol/g and 1.03mmol/g.
Embodiment 5
1) 2g is added in 0.17g sodium hydroxide, 0.278g sodium metaaluminate and 3.5g tetraethyl ammonium hydroxide solution (25%) In distilled water, solution A is stirred 2 hours to obtain at room temperature；The positive silicon of 21.43g is added in 25.95g tetraethyl ammonium hydroxide solution (25%) B solution is stirred 2 hours to obtain in acetoacetic ester at room temperature；Solution A is added dropwise in B, continues stirring 2~4 hours to being uniformly placed on In water heating kettle, 140 DEG C crystallization 24 hours.It washs after separation of solid and liquid, dried at 60 DEG C, the product after drying is in air atmosphere 550 DEG C are heated to, roasting obtains a nanometer Beta in 6 hours.
2) 5g diatomite is added in 100ml 6M hydrochloric acid solution, 60 DEG C stirring in water bath 4 hours.It filters, will consolidate later Body is washed to supernatant liquor and is in neutrality, 60 DEG C of drying.
3) by step 2), treated that diatomite is added in the sodium hydroxide solution of 100ml pH=13.5,60 DEG C of water-baths Stirring 4 hours.It filters later, solid is washed to supernatant liquor and is in neutrality, 60 DEG C of drying.
4) by step 3) highly basic, treated that diatomite is added to 100ml 0.5wt% polydimethyl diallyl ammonium chloride It is stirred 1 hour in solution, stands 30 minutes and wash 3 times.
5) 2g step 4) treated diatomite is weighed, the Beta that 120ml concentration is 0.5wt%, pH=9~10 is added to It in zeolite ammonium hydroxide colloidal sol, stirs 1 hour, stands 30 minutes.Using 0.1mol/L ammonia spirit as cleaning solution, washs 3 times, obtain Load the diatomaceous earth sample of one layer of zeolite seed crystal.
6) zeolite Synthesis liquid 40ml is prepared according to the method for step 1), weighs the diatom that 1g step 5) has loaded zeolite seed crystal Earth sample is placed in zeolite Synthesis liquid and stirs evenly, and is put into 140 DEG C of hydrothermal reaction kettle crystallization 24 hours.Be centrifuged after reaction, It being washed to supernatant to be in neutrality, be dried in 60 DEG C, the product after drying is heated to 550 DEG C in air atmosphere, it roasts 6 hours, Obtain diatomite/Beta composite material.
Fig. 2 (e, f) is diatomite/Beta composite material stereoscan photograph.Fig. 2 e can substantially see diatom soil sample One layer of comparatively dense Beta molecular screen membrane has been gone up in the covering of product surface.Fig. 2 f shows that the granularity of Beta molecular sieve is about 80nm- 90nm。
The diatomite prepared by the method for the invention /Beta composite material to acetone, ethyl acetate, toluene multicomponent The selective absorption to ethyl acetate is shown in competitive Adsorption experiment.To acetone, ethyl acetate, toluene in same system Adsorbance is respectively 0.75mmol/g, 1.05mmol/g and 0.47mmol/g.Fig. 7 is one-component adsorbance and competitive Adsorption amount pair Than figure, the competitive Adsorption amount of ethyl acetate accounts for the ratio of one-component adsorbance considerably beyond acetone and first as we can see from the figure Benzene, therefore further illustrate that diatomite/Beta composite material has Selective adsorption to ethyl acetate.
Embodiment 6
1) 2g is added in 0.17g sodium hydroxide, 0.278g sodium metaaluminate and 3.5g tetraethyl ammonium hydroxide solution (25%) In distilled water, solution A is stirred 2 hours to obtain at room temperature；The positive silicon of 21.43g is added in 25.95g tetraethyl ammonium hydroxide solution (25%) B solution is stirred 2 hours to obtain in acetoacetic ester at room temperature；Solution A is added dropwise in B, continues stirring 2~4 hours to being uniformly placed on In water heating kettle, 140 DEG C crystallization 24 hours.It washs after separation of solid and liquid, dried at 60 DEG C, the product after drying is in air atmosphere 550 DEG C are heated to, roasting obtains a nanometer Beta in 6 hours.
2) 5g diatomite is added in 100ml 6M hydrochloric acid solution, 60 DEG C stirring in water bath 4 hours.It filters, will consolidate later Body is washed to supernatant liquor and is in neutrality, 60 DEG C of drying.
3) by step 2), treated that diatomite is added in the sodium hydroxide solution of 100ml pH=13.5,60 DEG C of water-baths Stirring 4 hours.It filters later, solid is washed to supernatant liquor and is in neutrality, 60 DEG C of drying.
4) by step 3) highly basic, treated that diatomite is added to 100ml 0.5wt% polydimethyl diallyl ammonium chloride It is stirred 1 hour in solution, stands 30 minutes and wash 3 times.
5) 2g step 4) treated diatomite is weighed, the Beta that 80ml concentration is 0.5wt%, pH=9~10 is added to It in zeolite ammonium hydroxide colloidal sol, stirs 1 hour, stands 30 minutes.Using 0.1mol/L ammonia spirit as cleaning solution, washs 3 times, obtain Load the diatomaceous earth sample of one layer of zeolite seed crystal.
6) zeolite Synthesis liquid 40ml is prepared according to the method for step 1), weighs the diatom that 1g step 5) has loaded zeolite seed crystal Earth sample is placed in zeolite Synthesis liquid and stirs evenly, and is put into 140 DEG C of hydrothermal reaction kettle crystallization 24 hours.Be centrifuged after reaction, It being washed to supernatant to be in neutrality, be dried in 60 DEG C, the product after drying is heated to 550 DEG C in air atmosphere, it roasts 6 hours, Obtain diatomite/Beta composite material.
Diatomite/Beta composite material is mixed with business attapulgite 5:1 in mass ratio, and pressed disc method prepares partial size in 1mm The granule adsorbent of left and right.It is used for Kinetic penetration adsorption experiment, absorption is saturated to the dynamic of acetone, ethyl acetate, toluene Amount is respectively 5.49mm/g, 7.82mmol/g and 2.96mmol/g.
Fig. 5 is diatomite/Beta composite material N2Adsorption-desorption isothermal figure.Diatomite/Beta composite material is in P/ P0When≤0.1, to N2Adsorbance rapid development, illustrate that it contains a certain number of micropores, reason is molecular sieve itself It is a kind of poromerics, N2It is packed into the rapid growth that adsorbance is caused in the micropore of molecular sieve rapidly.Undergo rapid growth Afterwards, to N2Absorption tend towards stability, and finally in P/P0When close to 1, adsorbance rapidly rises again, this shows in composite material Still there are a considerable amount of macropores.And in the position of relative pressure about 0.9, the adsorption-desorption isothermal of composite material occurs One apparent H3 type hysteresis loop, this shows occur meso-hole structure in composite material.This, which shows to have synthesized, has multi-stage porous The material of road structure improves diatomite and the single situation of Molecular Sieve Pore.

Claims (5)

1. a kind of for adsorbing diatomite/molecular sieves compound material preparation method of volatile organic contaminant including following Step:
1) by ethyl orthosilicate, example 25:9:480 is mixed in molar ratio for tetrapropylammonium hydroxide and water, Silicalite-1 zeolite Synthesis liquid, which stirs evenly, to be placed in water heating kettle, 100 DEG C crystallization 4 days, washing after separation of solid and liquid is dried at 60 DEG C, after dry Product be heated to 550 DEG C in air atmosphere, roasting obtains nano Si licalite-1 in 6 hours；
2) sodium hydroxide, sodium metaaluminate, tetraethyl ammonium hydroxide and water 170:278:875:4600 in mass ratio are mixed, room temperature Lower stirring obtains solution A in 2 hours；Ethyl orthosilicate, tetraethyl ammonium hydroxide and water 214:65:195 in mass ratio are mixed, room temperature Lower stirring obtains B solution in 2 hours；Solution A is added dropwise in B according to the ratio of solution A and B solution mass ratio 59:474, Beta Zeolite Synthesis liquid continues stirring 2~4 hours to being uniformly placed in water heating kettle, 140 DEG C crystallization 24 hours.It is washed after separation of solid and liquid It washs, dried at 60 DEG C, the product after drying is heated to 550 DEG C in air atmosphere, and roasting obtains a nanometer Beta in 6 hours；
3) diatomite is completely submerged in 6M hydrochloric acid solution, is sufficiently stirred at 60 DEG C 4 hours, dried after washing in 60 DEG C；
4) by step 3), treated that diatomite is completely submerged in the sodium hydroxide solution of pH=13.5, sufficiently stirs at 60 DEG C It mixes 4 hours, is dried after washing in 60 DEG C；
5) diatomite after will be dry in step 4), which is added in 0.5wt% polycation electrolyte solution, sufficiently to be impregnated, solid-liquid It is washed after separation；
6) Silicalite-1 of step 1) preparation or step 2 Beta prepared are added in the ammonia spirit of pH=9~10 It is uniformly dispersed, prepares Silicalite-1 the or Beta zeolite ammonium hydroxide colloidal sol of 0.5wt%；Diatomite in step 5) is pressed into diatom Soil property amount/Silicalite-1 or Beta zeolite ammonium hydroxide sol volume ratio be 1g/20~60ml be added to Silicalite-1 or It is sufficiently impregnated in Beta zeolite ammonium hydroxide colloidal sol, is sufficiently washed after separation of solid and liquid with the ammonium hydroxide of 0.1mol/L, obtain area load The diatomaceous earth sample of zeolite seed crystal；
7) it is 1g/ that step 6) has been loaded to the diatomaceous earth sample of zeolite seed crystal by diatomite quality/zeolite Synthesis liquid volume ratio 40ml is placed according in step 1 or the zeolite Synthesis liquid of step 2 preparation, 100 DEG C of crystallization 4 days or 140 DEG C crystallization 24 hours, solid-liquid Separation, the product after washing after 60 DEG C of dryings, drying are heated to 550 DEG C in air atmosphere, roast 6 hours, obtain diatom Soil/Silicalite-1 or diatomite/Beta composite material.
2. according to claim 1 a kind of for adsorbing diatomite/molecular sieves compound material of volatile organic contaminant Preparation method, it is characterised in that: the diatomite be Jilin Province Changbai Mountain mining area.
3. according to claim 1 a kind of for adsorbing diatomite/molecular sieves compound material of volatile organic contaminant Preparation method, it is characterised in that: polycation electrolyte solution described in step 5) is preferably poly dimethyl allyl chlorine Change the aqueous solution of ammonium.
4. according to claim 1 a kind of for adsorbing diatomite/molecular sieves compound material of volatile organic contaminant Preparation method, it is characterised in that: solid-liquid isolation method described in step 5) can be centrifugal process or suction method.
5. according to claim 1 a kind of for adsorbing diatomite/molecular sieves compound material of volatile organic contaminant Preparation method, it is characterised in that: the diatomite/molecular sieves compound material can be mixed with granule adsorbent with clay.
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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112316912A (en) * 2020-11-06 2021-02-05 广州太玮生物科技有限公司 Material for adsorbing carbon dioxide and VOCs (volatile organic compounds) gas
CN112547027A (en) * 2020-11-17 2021-03-26 吉林大学 Preparation method of kaolin-doped conjugated microporous polymer composite material
CN114146681A (en) * 2021-11-30 2022-03-08 广州东联环保科技有限公司 Composite material for treating nitrogen-containing sewage and preparation method and application thereof
CN114984906A (en) * 2021-07-30 2022-09-02 上海秀湖化工有限公司 VOC (volatile organic compound) removing master batch with high adsorption and gas retention capacity and preparation method thereof
CN115044351A (en) * 2022-06-29 2022-09-13 哈尔滨工业大学 Molecular sieve/diatomite-based low-heat-conductivity composite shape-stabilized phase change material and preparation method thereof
CN115448324A (en) * 2022-09-27 2022-12-09 吉林大学 MFI structure molecular sieve hierarchical pore material and preparation method thereof
CN116726879A (en) * 2023-07-18 2023-09-12 中国矿业大学(北京) Zeolite activated carbon composite material and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101003377A (en) * 2006-01-19 2007-07-25 中国石油化工股份有限公司 Method for preparing zeolite material in perforation type of multilevel pore canals
CN103084144A (en) * 2013-02-06 2013-05-08 中国科学院广州地球化学研究所 Diatomite-based porous composite material for adsorbing volatile organic pollutants and preparation method thereof
CN106268936A (en) * 2016-08-08 2017-01-04 中国科学院广州地球化学研究所 A kind of kieselguhr/nanometer TS 1 Ti-Si zeolite composite with multi-stage artery structure and preparation method thereof
CN107640777A (en) * 2017-09-05 2018-01-30 华南理工大学 A kind of method for preparing big/mesoporous zeolite molecular sieve of crystal seed induction

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101003377A (en) * 2006-01-19 2007-07-25 中国石油化工股份有限公司 Method for preparing zeolite material in perforation type of multilevel pore canals
CN103084144A (en) * 2013-02-06 2013-05-08 中国科学院广州地球化学研究所 Diatomite-based porous composite material for adsorbing volatile organic pollutants and preparation method thereof
CN106268936A (en) * 2016-08-08 2017-01-04 中国科学院广州地球化学研究所 A kind of kieselguhr/nanometer TS 1 Ti-Si zeolite composite with multi-stage artery structure and preparation method thereof
CN107640777A (en) * 2017-09-05 2018-01-30 华南理工大学 A kind of method for preparing big/mesoporous zeolite molecular sieve of crystal seed induction

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YAJUN WANG ET AL: "Zeolitization of diatomite to prepare hierarchical porous zeolite materials through a vapor-phase transport process", 《J. MATER. CHEM.》 *
何适 等: "硅藻土-分子筛复合吸附材料的制备及其对苯酚吸附性能的研究", 《科学技术与工程》 *

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112316912A (en) * 2020-11-06 2021-02-05 广州太玮生物科技有限公司 Material for adsorbing carbon dioxide and VOCs (volatile organic compounds) gas
CN112316912B (en) * 2020-11-06 2023-02-28 广州太玮生物科技有限公司 Material for adsorbing carbon dioxide and VOCs (volatile organic compounds) gas
CN112547027A (en) * 2020-11-17 2021-03-26 吉林大学 Preparation method of kaolin-doped conjugated microporous polymer composite material
CN114984906A (en) * 2021-07-30 2022-09-02 上海秀湖化工有限公司 VOC (volatile organic compound) removing master batch with high adsorption and gas retention capacity and preparation method thereof
CN114146681A (en) * 2021-11-30 2022-03-08 广州东联环保科技有限公司 Composite material for treating nitrogen-containing sewage and preparation method and application thereof
CN115044351A (en) * 2022-06-29 2022-09-13 哈尔滨工业大学 Molecular sieve/diatomite-based low-heat-conductivity composite shape-stabilized phase change material and preparation method thereof
CN115044351B (en) * 2022-06-29 2024-09-24 哈尔滨工业大学 Molecular sieve/diatomite-based low-heat-conductivity composite shaping phase-change material and preparation method thereof
CN115448324A (en) * 2022-09-27 2022-12-09 吉林大学 MFI structure molecular sieve hierarchical pore material and preparation method thereof
CN116726879A (en) * 2023-07-18 2023-09-12 中国矿业大学(北京) Zeolite activated carbon composite material and preparation method and application thereof

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