CN107583604B - A kind of hydrophobicity honeycomb-shaped zeolite material and its preparation method and application - Google Patents
A kind of hydrophobicity honeycomb-shaped zeolite material and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to inorganic non-metallic sorbing material environmental technology fields, and in particular to a kind of hydrophobicity honeycomb-shaped zeolite material and its preparation method and application.The material includes 5 type zeolites of ZSM and y-type zeolite, wherein 5 type zeolites of ZSM and y-type zeolite account for the 80 84% of hydrophobicity honeycomb-shaped zeolite material, turned crystalline substance and account for hydrophobicity honeycomb-shaped zeolite material 12 18%, the mass ratio between 5 type zeolites of ZSM and y-type zeolite is 2:3‑3:2, the hydrophobicity honeycomb-shaped zeolite material micropore diameter range is 0.5 2.0nm.Hydrophobicity honeycomb-shaped zeolite material provided by the invention, select the mixed processing to 5 type molecular sieve and Y type molecular sieve material of ZSM, so that honeycomb zeolitic material has widened the range (0.5 2.0nm) in aperture, the exhaust gas primary demand of different molecular size (i.e. 0.4nm 1.4nm) in absorption large-wind-volume low-concentration VOCs is met.By turn brilliant, hydrophobic, pickling, the hydrophobicity and specific surface area of honeycomb zeolitic material are improved, application of the hydrophobicity honeycomb-shaped zeolite material to large-wind-volume low-concentration VOCs in RH80% highly humid air environment is realized.
Description
Technical field
The invention belongs to inorganic non-metallic sorbing material environmental technology fields, and in particular to a kind of hydrophobicity honeycomb-shaped zeolite
(molecular sieve) material and its preparation method and application.
Background technology
Volatile organic compounds Volatile organic compounds are referred to as：VOCs is gas pollutant, boiling point
Below 260 DEG C, volatile contaminant of the vapour pressure less than 70Pa.Industrial VOCs mainly largely derives from a variety of industry and transport
The volatile organic compound pollutant that the industries such as industry generate, wherein specifically include packaging, printing, paint industry, e.g., make paint, electricity
Sub- printing, ink printing, container, automobile, train, steamer surface lacquer paint industry industrial processes in volatility
The use of organic diluent and produce large-wind-volume low-concentration (hydro carbons, ketone, alcohols, esters, alcohol ethers) volatile organic
Close object, wherein such as diluent banana oil, it by 15wt% acetic acid butyl esters, 15wt% ethyl acetates, 10-15wt% n-butanols,
10wt% ethyl alcohol, 5-10wt% acetone, 20wt% benzene, 20wt% dimethylbenzene form or by 20wt% acetic acid butyl esters,
20wt% ethyl acetates, 5wt% ethyl alcohol, 40wt% toluene, 5-10wt% ethylene glycol ethyl ethers, 10wt% methylisobutylketones are formed
Deng, and all molecular diameter sizes of the hydro carbons of the diluent, ketone, alcohols, esters, alcohol ethers solvent composition are all in 0.4-
Within the scope of 1.4nm (such as molecular diameter：The benzene of hydrocarbon solvent about 0.74nm, toluene about 0.69nm, dimethylbenzene about 0.7nm, alcohols
The methanol of solvent about 0.43nm, propyl alcohol about 0.7, ethyl alcohol about 0.51nm, the ethyl acetate about 0.67nm of lipid, the acetone of ketone is about
0.81nm etc.), and a large amount of ozone pollution object is produced again under photosynthesis, it is to remove solid-state dust, denitration, desulfurization pollution
The third-largest gaseous pollutant of beyond the region of objective existence.
Nearly two is domestic for the integrated system of large-wind-volume low-concentration VOCs Production by Catalytic Combustion Process or absorption method dress during the last ten years
In setting, the sorbing material therein for inhaling (de-) adsorption device is mainly honeycomb structure absorbent charcoal material, and RH60% hydrophobicitys are (quiet
State Xi Shui Shuai≤10%), specific surface area the performance (>=400m of the broad spectrum activity (0.7nm-2.0nm) of micropore, material micropore2/ g) all
The technology requirement for inhaling (de-) adsorption device and discharge standard can be met, but flame retardant property is very weak, inhales (de-) adsorption device and catches fire
Safety surely suffers from that phenomenon is more serious, and nearly two make adsorption desorption bed send out in operation because using Alveolate activated carbon material during the last ten years
Raw ignition safety accident happens occasionally.
Therefore, especially national each universities and colleges, scientific research institutions, enviromental protection enterprise have all put into greatly over nearly 3 years in last decade
The manpower and materials and fund of amount, related governmental departments at different levels, which set up the project to inject capital into one after another, has carried out honeycomb structure zeolite (molecule
Sieve) material research.Wherein：Flame-retardant materials research is essentially all using inorganic non-metallic fire proofing-porosity zeolite
(molecular sieve) material, but the porous inorganic material as desiccant applications is in the prevalence of the hydrophilic of inherent moisture minor structure
Property and absorption large-wind-volume low-concentration VOCs cannot be met inhale (de-) adsorption device in highly humid air environment to material hydrophobic
The technology requirement of competitive Adsorption could expire therefore, it is necessary to hydrophobic modified to the progress of the inorganic zeolite of the honeycomb (molecular sieve) material
Sufficient ambient humidity is at RH60%-90%, the requirement that uses VOCs competitive Adsorptions.For this purpose, Chinese patent literature
CN102389773A discloses a kind of manufacturing method of the molecular sieve honeycomb body of absorption volatile organic matter comprising following step
Suddenly：By the way that powder zeolite molecular sieve, inorganic bond, ceramic fibre and paper pulp are configured to suspension, it is added and helps after discongesting
Agent is stayed, is ferreted out molecular sieve plane cardboard using copy paper machine, reheating is pressed into corrugated molecular sieve cardboard, molecular sieve is further made
Honeycomb ceramics.The molecular sieve honeycomb body have droop loss is small, large specific surface area, to organic matter large amount of adsorption, good hydrothermal stability,
Manufacturing process is simple, the advantages that can working in the environment of different temperatures/humidity, and fixed absorbing unit or runner can be used as to inhale
Wheel core can be widely used in industrial organic exhaust gas processing or indoor air clean field.But gained molecular sieve honeycomb body
Only there is preferable adsorption effect to the one-component in volatile organic matter, can not meet in absorption VOCs exhaust gas extensively
The demand of the component of different molecular size diameter (0.4nm-1.7nm), formula in 5-20% ceramic clay (attapulgite and
Kaolin) as binder inorganic material clay the intrinsic hydrophily of crystal structure, nothing in postorder high-temperature process
Method changes its hydrophilic nmature, therefore not proper as the binder in formula, can only increase the hydrophilic amount of the hydrophobic honeycomb molecular sieve,
Cannot meet the needs of competitive Adsorption VOCs under more than RH60% environmental conditions.Although utilizing hydrophobicity point in addition, disclosing
Hydrophobic performance of son sieve itself allows molecular sieve honeycomb body in different humidity as the adsorbent of molecular sieve honeycomb body
Under the conditions of carry out absorption organic matter, but there is no open hydrophobicity honeycomb molecular sieves to carry out hydrophobic preparation method, and existing
The process treatment process of hydrophobicity honeycomb molecular sieve is complicated in technology, and cost is high, can also cause shadow to the specific surface area of molecular sieve
Ring etc..
Invention content
Therefore, the technical problem to be solved in the present invention is to overcome honeycomb-shaped zeolite in the prior art (molecular sieve) material
Aperture is single, hydrophobic treatment step is complicated, big defect is influenced on zeolite specific surface area, cellular to provide a kind of hydrophobicity
Zeolite (molecular sieve) material and its preparation method and application.
In order to solve the above technical problems, the present invention is using following specific technical solution：
A kind of hydrophobicity honeycomb-shaped zeolite (molecular sieve) material, including ZSM-5 types zeolite (molecular sieve), y-type zeolite (molecule
Sieve) and turn brilliant material, wherein the mass ratio of ZSM-5 types zeolite (molecular sieve) and y-type zeolite (molecular sieve) is 2:3-3:2 etc.,
And the ZSM-5 types zeolite (molecular sieve) and y-type zeolite (molecular sieve) account for hydrophobicity honeycomb-shaped zeolite material gross mass and (do not include
Carrier quality) 80-84%, described turn of brilliant material is by ZSM-5 types zeolite (molecular sieve) and y-type zeolite (molecular sieve) through turning brilliant
Reason is made, and its quality accounts for hydrophobicity honeycomb-shaped zeolite material gross mass 12-18%, and the hydrophobicity honeycomb-shaped zeolite material is micro-
Bore dia is 0.5-2.0nm, silica alumina ratio 40-400, specific surface area 400-570m2/g。
Further, the crystallinity of the type ZSM 5 molecular sieve is 70% or more, and silica alumina ratio is more than 100, and material is micro-
Bore dia 0.5-0.6nm, specific surface area are more than 300 ㎡/g, and grain fineness is less than 325 mesh.
Further, the crystallinity of the Y type molecular sieve is 70% or more, and silica alumina ratio is more than 7, material micro-pore diameter
0.8-2.0nm, specific surface area are more than 300 ㎡/g, and grain fineness is less than 325 mesh.
A kind of preparation method of above-mentioned hydrophobicity honeycomb-shaped zeolite (molecular sieve) material, includes the following steps：
(1) ZSM-5 types zeolite and y-type zeolite are mixed, obtains mixed powder；
(2) by the mixed powder and auxiliary material mixed-forming, cellular blank is obtained；
(3) required hydrophobicity honeycomb-shaped zeolite material is made through a turn brilliant, hydrophobic and pickling processes in the cellular blank,
Wherein, the cellular blank is carried out using ethylenediamine method, silicon tetrachloride method or ammonium hexafluorosilicate method turning crystalline substance, is turned
- 500 DEG C of brilliant temperature 70 C, soaking time 2h-12h；
Hydro-thermal method hydrophobic treatment is carried out to the material after turning brilliant, hydrophobic treatment temperature is 400-650 DEG C, water flowing flow 100-
140ml/min, hydrophobic treatment time 4h-12h, then Temperature fall.
Further, pickling processes are carried out to the material after hydrophobic treatment, the material Jing Guo hydrophobic treatment is dipped into dilute
In hydrochloric acid or dilute nitric acid solution, solution temperature is 60 DEG C -80 DEG C, soaking time 2-6h, then with after water wash to neutrality, from
It is so dry, most dried afterwards through 100 DEG C of -160 DEG C of temperature.
Further, in step (2) carrier-free directly extrude method it is molding the specific steps are：In terms of being weighed by weight quota,
40-50 parts of mixed powder, 2-6 parts of binder, 30-70 parts of semisolid lubricant, 5-20 parts of water, be sufficiently mixed into mud, mud refining at section,
By the rectangular of different specification size size, hexagon or round honeycomb structure punching block, is shaped, obtained using extrusion moulding
Honeycomb structure blank.
Further, the binder is CMC (carboxymethyl cellulose), MC (methylcellulose), polyvinyl alcohol, biology
Glue, animal glue etc..
Further, the semisolid lubricant is Ludox, Aluminum sol, zirconium colloidal sol etc..
Further, have in step (2) carrier slurrying infusion process it is molding the specific steps are：In terms of being weighed by weight quota,
27-40 parts of mixed powder, 27-47 parts of adhesive, 15-40 parts of water fully mix into suspension slurry, then big with different specification size
Small rectangular, hexagon, circular corrugated honeycomb glass pottery cellucotton be carrier or be load with metallic honeycomb
Body, being impregnated repeatedly using positive and negative pressure infusion process, which makes suspension slurry uniformly apply, hangs on carrier, spontaneously dries and dries through room temperature, obtains
To cellular blank.
Further, the adhesive is Ludox, Aluminum sol, zirconium colloidal sol etc..
Further, which is characterized in that step (3) turn brilliant and hydrophobic treatment process in high temperature metal activation stove into
Row, the volume of high-temperature metal activation furnace is about 3-4m3Differ.
Further, in the ethylenediamine method ethylenediamine dosage be cellular blank 0.1-0.4wt%；The tetrachloro
The dosage of silicon tetrachloride is the 0.1-0.4wt% of cellular blank in SiClx method；Ammonium hexafluorosilicate in the ammonium hexafluorosilicate method
Dosage be cellular blank 0.4-0.7wt%.
Further, the mass concentration of dilute hydrochloric acid or dilute nitric acid solution is 4-10% in acid pickling step；The cellular hair
The drying temperature of base is 50-70 DEG C.
A. powder raw material hole matches：Exhaust gas is a variety of in the large-wind-volume low-concentration VOCs generated according to industries such as packet, applications
The different molecular structures size diameter range of composition should select type ZSM 5 molecular sieve powder in 0.4nm-1.4nm requirements, one,
Its silica alumina ratio is more than 100, crystallinity and is more than 70%, material specific surface area more than 300m2/ g, and material micro-pore diameter limit model on the lower side
Enclose the powder of 0.5nm-0.6nm.Secondly Y type molecular sieve powder should be selected, silica alumina ratio is more than 7 and crystallinity is more than 70%, ratio
Surface area is more than 300m2/ g, and the powder of the inclined upper range 0.8nm-2.0nm of material micro-pore diameter.Both the above powder mixes
Material micropore diameter range is 0.5nm-2.0nm, powder granule degree 325-800 mesh.
B. molecular screen material mixing match：It can at random be allocated according to emission molecule diameter, between two kinds of materials
Proportioning is 2:3-3:2 etc..The proportioning of two kinds of material powders can be allocated suitably according to the market demand.
Turn brilliant, hydrophobic, acid cleaning process technology：Purpose be by turn brilliant, hydrophobic, pickling technical finesse reduction aluminium polarity from
Son improves silica alumina ratio, is modified to the nonpolarity ion of silica, hydrophobic to achieve the purpose that.
A kind of above-mentioned hydrophobicity honeycomb-shaped zeolite (molecular sieve) material inhales (de-) attaching in large-wind-volume low-concentration VOCs exhaust gas
Set the application in processing.
Further, the concentration in large-wind-volume low-concentration VOCs exhaust gas is less than 700mg/m3, the wind of exhaust gas in processing procedure
Amount is 4000-400000m3/h。
Technical solution of the present invention has the following advantages that：
1. hydrophobicity honeycomb-shaped zeolite (molecular sieve) material provided by the invention, including ZSM-5 types zeolite, y-type zeolite and
Turn brilliant zeolite, described turn of brilliant zeolite is made by ZSM-5 types zeolite and y-type zeolite through turning brilliant processing, and the zeolite of different crystal forms is mutual
The application range in aperture has been widened in cooperation, and with the distribution of rational bore diameter gradient；Simultaneously by ZSM-5 types zeolite and y-type zeolite
Through turn it is brilliant treated turns a brilliant zeolite, improve the hydrophobic performance of zeolitic material.According to absorption large-wind-volume low-concentration VOCs exhaust gas
Different molecular diameter range is (i.e.：Stressing property demand ratio 0.4nm-1.4nm) is selected to type ZSM 5 molecular sieve material
The aperture (0.5-0.6nm) and Y type molecular sieve material (0.8-2.0nm) carries out stressing property combined hybrid, and stressing property group composition and division in a proportion is 2：3
Or 3：2 etc..
2. the preparation method of hydrophobicity honeycomb-shaped zeolite (molecular sieve) material provided by the invention, by Z-type and Y types point
Son sieve material carries out turning brilliant, hydrophobic, pickling processes, and gained hydrophobic molecule sieves material can be in the above highly humid air rings of high humidity RH80%
It is excellent to the competitive Adsorption ability of VOCs in border.First, ethylenediamine method or silicon tetrachloride method or ammonium hexafluorosilicate method are used, is carried out
What aluminium changed silicon materials turns brilliant processing, then hydro-thermal method is used to carry out hydrophobic treatment, by generating high-temperature vapour to zeolitic material
The silica alumina ratio that progress dealumination treatment further improves material is further improved using the residual aluminium in a pickling lattice
The specific surface area of material is finally obtained good hydrophobicity, wide spectrum aperture and high-specific surface area honeycomb zeolite (molecular sieve) material
Expect product, meets the application demand for inhaling (de-) adsorption device in current environment protection treating large-wind-volume low-concentration VOCs complexes.
3. inhaling the technical property requirements of (de-) adsorption device according to large-wind-volume low-concentration VOCs, the present invention provides hydrophobicity honeycomb
The preparation method of shape zeolite (molecular sieve) material increases selecting the raw material of ZSM-5 types and Y type mixed powders on forming technique
Many difficulty, especially honeycomb carrier-free direct forming technology of preparing has been added to propose higher to binder, semisolid lubricant
Hydrophobicity and plasticity particular/special requirement, the present invention by selecting a small amount of organic binder and inorganic semisolid lubricant,
Play the role of bonding and semisolid lubricant in forming process, and has a small amount of in later stage high temperature hydrophobic treatment process
Machine binder removes, and not only solves the problems, such as not influence material hydrophobic, but also solves the technology hardly possible of mixed powder difficult forming
Topic increases the silica alumina ratio and specific surface area of material by turning brilliant processing again simultaneously because semisolid lubricant selects inorganic material
And Kong Rong.
Description of the drawings
Fig. 1 present invention gained hydrophobicity honeycomb-shaped zeolite (molecular sieve) material sample figures；
Wherein, in figure photo upper left sample be using metallic aluminium honeycomb ceramics as carrier, using infusion process, through process dredge
Water honeycomb hexagon zeolitic material product, specification：100x100x100mm；
In figure photo upper right sample be using glass make pottery cellucotton honeycomb ceramics as carrier, using infusion process, through process dredge
Water corrugated honeycomb zeolitic material product, specification：100x100x100mm；
Lower two samples of photo are to use to directly extrude method in figure, the hydrophobic honeycomb zeolitic material product through process,
Specification：50x50x50mm.
The different humidity adsorption isothermal curve of Fig. 2 activated carbons honeycomb and present invention gained hydrophobicity cellular material.
Specific implementation mode
Embodiment 1
A kind of preparation method of hydrophobicity honeycomb-shaped zeolite (molecular sieve) material, includes the following steps (no-load is body formed)：
Raw material select and proportioning：Two parts of type ZSM 5 molecular sieve powders are weighed, crystallinity is 70% or more, and sial rubs
, than being more than 100, specific surface area is more than 300 ㎡/g for you；Three parts of Y type molecular sieve powders are weighed, crystallinity is 70% or more, sial
Molar ratio is more than 7, and specific surface area is more than 300 ㎡/g；Two kinds of material powders are uniformly mixed, mixed powder is obtained.
Honeycomb moulding step：With share poidometer, 41 parts of mixed powder, 5 parts of CMC, 40 parts of Ludox, about 14 parts of water fill
Point be mixed into mud, mud refining at section, by the honeycomb structure punching block of certain size, cellular hair is configured to using extrusion moulding
Base, after blank spontaneously dries, then through 70 DEG C of dryings.
Turn brilliant, hydrophobic, acid pickling step：Specific implementation is that 70 DEG C of dried cellular blanks are fitted into about four cubic metres
High-temperature metal activation furnace, furnace bottom addition are the ethylenediamine of the 0.1wt% of blank, carry out turning crystalline substance using ethylenediamine method, turn brilliant temperature
80 DEG C or so, soaking time 10h of degree, in addition, hydro-thermal method is taken to further increase the hydrophobic ability of material silica alumina ratio, by furnace temperature after
Continue and be warming up to 640 DEG C or so progress hydrophobic treatments, and water flowing flow about 140ml/min, it, will after about 6h of hydrophobic time Temperature fall
Product, which takes out, carries out the residual aluminium increasing specific surface area technique of next step pickling：Product is fitted into acid corrosion-resistant sink, it is molten in sink
A concentration of 10wt% dilute hydrochloric acid of liquid, about 70 DEG C -80 DEG C of solution temperature take out to be put into originally sink after soaking time 4h and carried out
Water is after leaching is neutral clearly, then takes out room temperature natural drying, then into 140 DEG C of drying of trip temperature, packaging.After tested, gained
The micropore diameter range of hydrophobicity honeycomb-shaped zeolite material is 0.5-2.0nm, specific surface area 440m2/ g, Static Adsorption water
Shuai≤2%.
Embodiment 2
A kind of preparation method of hydrophobicity honeycomb-shaped zeolite (molecular sieve) material, includes the following steps (no-load is body formed)：
Raw material select and proportioning：Three parts of type ZSM 5 molecular sieve materials are weighed, crystallinity is 70% or more, and sial rubs
, than being more than 100, specific surface area is more than 300 ㎡/g for you；Two parts of Y type molecular sieve materials are weighed, crystallinity is 70% or more, sial
Molar ratio is more than 7, and specific surface area is more than 300 ㎡/g；Two kinds of materials are uniformly mixed, mixed powder is obtained.
Honeycomb moulding step：With share poidometer, 47 parts of mixed powder, 6 parts of MC, 42 parts of Aluminum sol, about 5 parts of water, fully
Be mixed into mud, mud refining at section, by the honeycomb structure punching block of certain size, cellular hair is configured to using extrusion moulding
Base, after blank spontaneously dries, then through 70 DEG C of dryings.
Turn brilliant, hydrophobic, acid pickling step：Specific implementation is that 70 DEG C of dried cellular blanks are fitted into about four cubic metres
High-temperature metal activation furnace, addition is the silicon tetrachloride of the 0.4wt% of blank in stove, carries out turning crystalline substance using silicon tetrachloride method, turn
450 DEG C or so, soaking time 2h of brilliant temperature, in addition, taking hydro-thermal method to further increase the hydrophobic ability of material silica alumina ratio, by stove
Temperature is warming up to 640 DEG C or so progress hydrophobic treatments, and water flowing flow about 100ml/min, after hydrophobic time 6h Temperature falls, will produce
Product, which take out, carries out the residual aluminium increasing specific surface area technique of next step pickling：Product is fitted into acid corrosion-resistant sink, solution in sink
A concentration of 7wt% dilute nitric acid solutions, about 70 DEG C -80 DEG C of solution temperature take out to be put into originally sink after soaking time 6h and carry out
It after crossing water leaching being neutral clearly, takes out room temperature and spontaneously dries, then into 140 DEG C of drying of trip temperature, packaging.After tested, gained is dredged
The micropore diameter range of aqueous honeycomb-shaped zeolite material is 0.5-2.0nm, specific surface area 540m2/ g, Static Adsorption water rate
≤ 1.4%.
Embodiment 3
A kind of preparation method of hydrophobicity honeycomb-shaped zeolite (molecular sieve) material, includes the following steps (no-load is body formed)：
Raw material select and proportioning：A type ZSM 5 molecular sieve powder is weighed, crystallinity is 70% or more, and sial rubs
, than being more than 100, specific surface area is more than 300 ㎡/g for you；A Y type molecular sieve powder is weighed, crystallinity is 70% or more, sial
Molar ratio is more than 7, and specific surface area is more than 300 ㎡/g；Two kinds of materials are uniformly mixed, mixed powder is obtained.
Honeycomb moulding step：With share poidometer, 50 parts of mixed powder, 4 parts of animal glue, 44 parts of zirconium colloidal sol, about 2 parts of water,
Be sufficiently mixed into mud, mud refining at section, by the honeycomb structure punching block of certain size, be configured to using extrusion moulding cellular
Blank, after blank spontaneously dries, then through 70 DEG C of dryings.
Turn brilliant, hydrophobic, acid pickling step：Specific implementation is to load to the ammonium fluosilicate solution of the 0.6wt% of blank through about
It on 70 DEG C of dried cellular blanks, is then charged into about four cubic metres of high-temperature metal activation furnaces and carries out turning crystalline substance, turn brilliant temperature
70 DEG C or so, soaking time 12h, in addition, hydro-thermal method is taken to further increase the hydrophobic ability of material silica alumina ratio, furnace temperature is continued
It is warming up to 640 DEG C or so progress hydrophobic treatments, and water flowing flow about 140ml/min, after hydrophobic time 4h Temperature falls, by product
It takes out and carries out the residual aluminium increasing specific surface area technique of next step pickling：Product is fitted into acid corrosion-resistant sink, solution is dense in sink
Degree is the hydrochloric acid of 7wt%, about 70 DEG C -80 DEG C of solution temperature, takes out after soaking time 6h and is put into originally sink that carry out water clear
It after leaching is neutral, takes out room temperature and spontaneously dries, then into 140 DEG C of drying of trip temperature, packaging.After tested, gained hydrophobicity bee
The micropore diameter range of nest shape zeolite (molecular sieve) material is 0.5-2.0nm, specific surface area 570m2/ g, Static Adsorption water
Shuai≤1.2%.
Embodiment 4
A kind of preparation method of hydrophobicity honeycomb-shaped zeolite (molecular sieve) material, includes the following steps and (has carrier molding)：
Raw material select and proportioning：Two parts of type ZSM 5 molecular sieve powders are weighed, crystallinity is 70% or more, and sial rubs
, than being more than 100, specific surface area is more than 300 ㎡/g for you；Three parts of Y type molecular sieve powders are weighed, crystallinity is 70% or more, sial
Molar ratio is more than 7, and specific surface area is more than 300 ㎡/g；Two kinds of zeolites are uniformly mixed, mixed powder is obtained.
Honeycomb moulding step：With share poidometer, 30 parts of mixed powder, 42 parts of zirconium colloidal sol, about 28 parts of water are fully mixed into
Suspend slurry, then as carrier or uses 90x90x100mm using 100x100x100mm square corrugated honeycomb glass pottery cellucotton
Metallic honeycomb is carrier, and being impregnated repeatedly using the progress of positive and negative pressure infusion process, which makes slurries uniformly hang, is coated on carrier, often
Temperature is spontaneously dried dries with 140 DEG C, cellular blank is obtained, after blank spontaneously dries, then through 70 DEG C of dryings.
Turn brilliant, hydrophobic, acid pickling step：Specific implementation is that 70 DEG C of dried cellular blanks are fitted into about four cubic metres
High-temperature metal activation furnace, addition is the ethylenediamine of the 0.2wt% of blank in stove, carries out turning crystalline substance using ethylenediamine method, turns brilliant temperature
80 DEG C, soaking time 10h of degree, in addition, taking hydro-thermal method to further increase the hydrophobic ability of material silica alumina ratio, by furnace temperature after of continuing rising
Temperature is to 400 DEG C or so progress hydrophobic treatments, and water flowing flow 100ml/min will be produced after hydrophobic time 4h is naturally cooling to room temperature
Product, which take out, carries out the residual aluminium increasing specific surface area technique of next step pickling：Product is fitted into acid corrosion-resistant sink, solution in sink
For concentration 4wt% hydrochloric acid, about 60 DEG C of solution temperature takes out to be put into originally sink after soaking time 2h and carried out during water leaching clearly is
Property after, taking out room temperature spontaneously dries, then into the drying of about 140 DEG C of trip temperature, packaging.After tested, gained hydrophobicity is cellular
The micropore diameter range of zeolite (molecular sieve) material is 0.5-2.0nm, specific surface area 428m2/ g, Static Adsorption water Shuai≤
2%.
Embodiment 5
A kind of preparation method of hydrophobicity honeycomb-shaped zeolite (molecular sieve) material, includes the following steps and (has carrier molding)：
Raw material select and proportioning：Three parts of type ZSM 5 molecular sieve powders are weighed, crystallinity is 70% or more, and sial rubs
, than being more than 100, specific surface area is more than 300 ㎡/g for you；Two parts of Y type molecular sieve powders are weighed, crystallinity is 70% or more, sial
Molar ratio is more than 7, and specific surface area is more than 300 ㎡/g；Two kinds of materials are uniformly mixed, mixed powder is obtained.
Honeycomb moulding step：With share poidometer, 37 parts of mixed powder, 42 parts of Ludox, about 21 parts of water are fully mixed into
Suspend slurry, then as carrier or uses 90x90x100mm using 100x100x100mm square corrugated honeycomb glass pottery cellucotton
Metallic honeycomb is carrier, and being impregnated repeatedly using the progress of positive and negative pressure infusion process, which makes slurries uniformly hang, is coated on carrier, often
Temperature is spontaneously dried dries with 140 DEG C, cellular blank is obtained, after blank spontaneously dries, then through 70 DEG C of dryings.
Turn brilliant, hydrophobic, acid pickling step：Specific implementation is that 70 DEG C of dried cellular blanks are fitted into about four cubic metres
High-temperature metal activation furnace, addition is the silicon tetrachloride of the 0.3wt% of blank in stove, carries out turning crystalline substance using silicon tetrachloride method, turn
400 DEG C, soaking time 1h of brilliant temperature, in addition, hydro-thermal method is taken to further increase the hydrophobic ability of material silica alumina ratio, by furnace temperature after
It is continuous to be warming up to 400 DEG C or so progress hydrophobic treatments, and water flowing flow 100ml/min, after hydrophobic time 4h is naturally cooling to room temperature,
Product is taken out and carries out the residual aluminium increasing specific surface area technique of next step pickling：Product is fitted into acid corrosion-resistant sink, in sink
Solution concentration is 4wt% salpeter solutions, about 60 DEG C of solution temperature, takes out to be put into originally sink after soaking time about 2h and carried out
Water takes out room temperature and spontaneously dries after leaching is neutral clearly, then into about 140 DEG C of drying of trip temperature, packaging.After tested, gained is dredged
The micropore diameter range of aqueous honeycomb-shaped zeolite (molecular sieve) material is 0.5-2.0nm, specific surface area 479m2/ g, static state are inhaled
Water Shuai≤2%.
Embodiment 6
A kind of preparation method of hydrophobicity honeycomb-shaped zeolite (molecular sieve) material, includes the following steps and (has carrier molding)：
Raw material select and proportioning：A type ZSM 5 molecular sieve powder is weighed, crystallinity is 70% or more, and sial rubs
, than being more than 100, specific surface area is more than 300 ㎡/g for you；A Y type molecular sieve powder is weighed, crystallinity is 70% or more, sial
Molar ratio is more than 7, and specific surface area is more than 300 ㎡/g；Two kinds of materials are uniformly mixed, mixed powder is obtained.
Honeycomb moulding step：With share poidometer, 40 parts of mixed powder, 42 parts of Aluminum sol, about 18 parts of water are fully mixed into
Suspend slurry, then makes pottery cellucotton as carrier or use using the glass of 100x100x100mm square corrugated honeycombs
90x90x100mm metallic honeycombs are carrier, and being impregnated repeatedly using the progress of positive and negative pressure infusion process, which makes slurries uniformly hang, is coated in
It on carrier, spontaneously dries through room temperature and is dried with 140 DEG C, cellular blank is obtained, after blank spontaneously dries, then through 70 DEG C of dryings.
Turn brilliant, hydrophobic, acid pickling step：Specific implementation is to load to the ammonium fluosilicate solution of the 0.5wt% of blank through 70
On DEG C dried cellular blank, it is then charged into about four cubic metres of high temperature metal activation stoves and is carried out using ammonium fluosilicate method
Turn crystalline substance, turns brilliant 80 DEG C, soaking time 11h of temperature, in addition, hydro-thermal method is taken to further increase the hydrophobic ability of material silica alumina ratio,
Furnace temperature is continuously heating to 400 DEG C or so progress hydrophobic treatments, and water flowing flow 100ml/min, hydrophobic time 2h Temperature falls
To room temperature, product is taken out and carries out the residual aluminium increasing specific surface area technique of next step pickling：Product is packed into acid corrosion-resistant sink
In, solution is the hydrochloric acid of concentration 7wt% in sink, and about 60 DEG C of solution temperature takes out after soaking time 2h and is put into originally sink
It after carrying out water leaching being neutral clearly, takes out room temperature and spontaneously dries, then into about 140 DEG C of drying of trip temperature, packaging.Gained is hydrophobic
Property honeycomb-shaped zeolite (molecular sieve) material micropore diameter range be 0.5-2.0nm, specific surface area 504m2/ g, static water absorption
Liang Shuai≤2%.
Comparative example
A kind of preparation method of honeycomb-shaped zeolite (molecular sieve) material, includes the following steps (no-load is body formed)：
Raw material select and proportioning：A type ZSM 5 molecular sieve powder is weighed, crystallinity is 70% or more, and sial rubs
, than being more than 100, specific surface area is more than 300 ㎡/g for you；A Y type molecular sieve powder is weighed, crystallinity is 70% or more, sial
Molar ratio is more than 7, and specific surface area is more than 300 ㎡/g；Two kinds of materials are uniformly mixed, mixed powder is obtained.
Honeycomb moulding step：With share poidometer, 50 parts of mixed powder, 4 parts of animal glue, 44 parts of semisolid lubricant, water 2
Part, be sufficiently mixed into mud, mud refining at section, by the honeycomb structure punching block of certain size, bee is configured to using extrusion moulding
Nest shape blank, blank natural drying are fitted into about four cubic metres of stoves after 70 DEG C dry and carry out 640 DEG C of sintering, after heat preservation 2h certainly
So it is cooled to room temperature.
The embodiment of the present invention and comparative example are tested for the property, wherein specific surface area, Kong Rong, pore diameter range number
According to being shown in Table 1；Gained sample is shown in Table 2 to certain company VOCs absorption property test datas.
1 each sample performance parameter test data of table
| Sample | BET specific surface area , ㎡/g | MP pore volumes, ML/g | Micropore diameter range, nm |
| Comparative example | 340 | 0.316 | 0.5-2.0 |
| Embodiment 1 | 440 | 0.354 | 0.5-2.0 |
| Embodiment 2 | 540 | 0.388 | 0.5-2.0 |
| Embodiment 3 | 570 | 0.394 | 0.5-2.0 |
| Embodiment 4 | 428 | 0.327 | 0.5-2.0 |
| Embodiment 5 | 479 | 0.369 | 0.5-2.0 |
| Embodiment 6 | 504 | 0.374 | 0.5-2.0 |
From the data in table 1 it is found that carrying out turning brilliant and further hydrophobic, pickling processes by different chemical-agent techniques,
Specific surface area and Kong Rong have obtained obvious raising.Z-type and Y type molecular sieve material select excellent matching to make mixed powder material hole
The range of diameter size has fully met the demand that large-wind-volume low-concentration VOCs inhales (de-) adsorption device.
Table 2 tests % using certain domestic southern company's painting line with the absorption dose rate that diluent (banana oil) carries out
From the data in table 2 it is found that VOCs VOCs under different partial pressure states adsorb dose rate, different (static RH is
0%), under RH80% ambient air humidities, first, by turning brilliant and further hydrophobic, pickling processes example 1-6, adsorbance
Rate is significantly higher than comparative example.Secondly, carrier-free, which directly extrudes forming method and is generally higher than, carrier impregnation method.Thirdly, no matter have,
Carrier-free, but turn crystalline substance through ammonium hexafluorosilicate method and be better than silicon tetrachloride method turn crystalline substance, silicon tetrachloride method is better than ethylenediamine method and turns crystalline substance again.
Explanation：Occupied using the said firm's production line (banana oil) main composition：25% benzene (molecular diameter about 0.75nm), 20%
Dimethylbenzene (molecular diameter about 0.70nm), 15% ethyl acetate (molecular diameter about 0.67nm), (molecular diameter is about for 10% methanol
0.43nm), 15% acetic acid butyl ester (molecular diameter about 0.55nm), 10% n-butanol (molecular diameter about 0.57nm), 5% acetone
(molecular diameter about 0.81nm) mixed molecules diameter range is in 0.43-0.81nm).
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (16)
1. a kind of hydrophobicity honeycomb-shaped zeolite material, which is characterized in that including ZSM-5 types zeolite, y-type zeolite and turn brilliant material,
Wherein, the mass ratio of ZSM-5 types zeolite and y-type zeolite is 2:3-3:2, and the ZSM-5 types zeolite and y-type zeolite account for hydrophobicity
The 80-84% of honeycomb-shaped zeolite material gross mass, does not include carrier quality, and described turn of brilliant material is boiled by ZSM-5 types zeolite and Y types
Shi Jing turns brilliant processing and is made, and its quality accounts for hydrophobicity honeycomb-shaped zeolite material gross mass 12-18%, and the hydrophobicity is cellular
Zeolitic material micro-pore diameter is 0.5-2.0nm.
2. hydrophobicity honeycomb-shaped zeolite material according to claim 1, which is characterized in that the knot of the ZSM-5 types zeolite
Brilliant degree is 70% or more, and silica alumina ratio is more than 100, and micro-pore diameter 0.5-0.6nm, specific surface area is more than 300 ㎡/g, and particle is thin
Degree is less than 325 mesh.
3. hydrophobicity honeycomb-shaped zeolite material according to claim 1, which is characterized in that the crystallinity of the y-type zeolite
It is 70% or more, silica alumina ratio is more than 7, and micro-pore diameter 0.8-2.0nm, specific surface area is more than 300 ㎡/g, and grain fineness is less than
325 mesh.
4. a kind of preparation method of claim 1-3 any one of them hydrophobicity honeycomb-shaped zeolite material, which is characterized in that packet
Include following steps：
（1）ZSM-5 types zeolite and y-type zeolite are mixed, mixed powder is obtained；
（2）By the mixed powder and auxiliary material mixed-forming, cellular blank is obtained；
（3）Required hydrophobicity honeycomb-shaped zeolite material is made through a turn brilliant, hydrophobic and pickling processes in the cellular blank,
Wherein, the cellular blank is carried out using ethylenediamine method, silicon tetrachloride method or ammonium hexafluorosilicate method turning crystalline substance, turns brilliant temperature
70 DEG C -500 DEG C of degree, soaking time 2h-12h；
Hydro-thermal method hydrophobic treatment is carried out to the material after turning brilliant, hydrophobic treatment temperature is 400-650 DEG C, water flowing flow 100-
140ml/min, hydrophobic treatment time 4h-12h, then Temperature fall.
5. the preparation method of hydrophobicity honeycomb-shaped zeolite material according to claim 4, which is characterized in that hydrophobic treatment
Material afterwards carries out pickling processes, the material Jing Guo hydrophobic treatment is dipped into dilute hydrochloric acid or dilute nitric acid solution, solution temperature
It is 60 DEG C -80 DEG C, soaking time 2-6h, then with after water wash to neutrality, spontaneously dries, most afterwards through 100 DEG C of -160 DEG C of temperature
Degree drying.
6. the preparation method of hydrophobicity honeycomb-shaped zeolite material according to claim 4, which is characterized in that use carrier-free
It directly extrudes method and is molded the cellular blank, step includes in parts by weight, weighing 40-50 parts of mixed powder, binder
2-6 parts, 30-70 parts of semisolid lubricant, 5-20 parts of water, be sufficiently mixed into mud, mud refining is used at section by honeycomb structure punching block
Extrusion moulding is configured to cellular blank.
7. the preparation method of hydrophobicity honeycomb-shaped zeolite material according to claim 6, which is characterized in that the binder
For CMC, MC, polyvinyl alcohol or biogum.
8. the preparation method of hydrophobicity honeycomb-shaped zeolite material according to claim 6, which is characterized in that the plasticity profit
Lubrication prescription is Ludox, Aluminum sol, zirconium colloidal sol.
9. the preparation method of hydrophobicity honeycomb-shaped zeolite material according to claim 4, which is characterized in that using has carrier
Slurrying infusion process is molded the cellular blank, and step includes in parts by weight, taking 27-40 parts of mixed powder, adhesive
27-47 parts, 15-40 parts of water, fully mix into suspension slurry, then using the glass of corrugated honeycomb make pottery cellucotton as carrier or with
Metallic honeycomb is carrier, and being impregnated repeatedly using positive and negative pressure infusion process, which makes suspension slurry uniformly apply, hangs on carrier, through room temperature
It spontaneously dries and dries, obtain cellular blank.
10. the preparation method of hydrophobicity honeycomb-shaped zeolite material according to claim 9, which is characterized in that the gluing
Agent is Ludox, Aluminum sol, zirconium colloidal sol.
11. according to the preparation method of claim 4-10 any one of them hydrophobicity honeycomb-shaped zeolite materials, which is characterized in that
Step（3）Turn brilliant and a hydrophobic treatment process carries out in high temperature metal activation stove.
12. the preparation method of hydrophobicity honeycomb-shaped zeolite material according to claim 11, which is characterized in that the second two
The dosage of ethylenediamine is the 0.1-0.4wt% of cellular blank in amine method；The dosage of silicon tetrachloride is bee in the silicon tetrachloride method
The 0.1-0.4wt% of nest shape blank；The dosage of ammonium hexafluorosilicate is the 0.4- of cellular blank in the ammonium hexafluorosilicate method
0.7wt%。
13. the preparation method of hydrophobicity honeycomb-shaped zeolite material according to claim 11, which is characterized in that acid pickling step
The mass concentration of middle dilute hydrochloric acid or dilute nitric acid solution is 4-10%.
14. the preparation method of hydrophobicity honeycomb-shaped zeolite material according to claim 11, which is characterized in that step（3）
Described in cellular blank drying temperature be 50 DEG C -70 DEG C.
15. described in a kind of any one of claim 1-3 hydrophobicity honeycomb-shaped zeolite materials or claim any one of 4-14
Application of the hydrophobicity honeycomb-shaped zeolite material that is prepared of preparation method in VOCs exhaust gas adsorption desorption devices.
16. application according to claim 15, which is characterized in that the concentration of VOCs is less than 700mg/m3, processing in exhaust gas
The air quantity of exhaust gas is 4000-400000m3/h in the process.
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