CN104492373B - A kind of base composite porous ceramic material of kieselguhr for volatile organic contaminant absorption and preparation method thereof - Google Patents
A kind of base composite porous ceramic material of kieselguhr for volatile organic contaminant absorption and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of base composite porous ceramic material of kieselguhr for volatile organic contaminant absorption and preparation method thereof.The present invention, with cheap kieselguhr as raw material, prepares the double macropore ceramic monolith of diatom soil matrix by polyurethane template.Then by backflow load method in situ, by pure silica zeolites nano-particle uniform load in above-mentioned surfaces of carrier materials, the base composite porous ceramic material of kieselguhr is prepared.It is block moulding material, in double macropores/micropore hierarchical porous structure, has the micropore of pure silica zeolites, is replicated in the macropore of polyurethane template, remain diatomaceous macroporous structure simultaneously.It addition, this composite porous ceramic material heat stability is higher, specific surface area and total pore volume are big, have the absorption property of excellence to VOCs gases such as benzene, dichloromethane and normal hexane.The preparation method of the base composite porous ceramic material of kieselguhr that the present invention provides has technique simply simultaneously, and mild condition is polluted low, and the feature that energy consumption is low, prospects for commercial application is wide.
Description
Technical field:
The invention belongs to volatile organic contaminant and administer field, be specifically related to a kind of for volatile organic contaminant (VOCs)
Base composite porous ceramic material of kieselguhr of absorption and preparation method thereof.
Background technology:
Volatile organic contaminant (VOCs) typically refers to boiling point 50-250 DEG C, and under room temperature, saturated vapour pressure is more than 133.3Pa's
Organic compound, including hydro carbons, halogenated hydrocarbons, aromatic hydrocarbon, polycyclic aromatic hydrocarbon etc., is generally to exist in indoor-outdoor air and form again
A miscellaneous class organic pollution (Shen Xue is excellent, journal of Zhejiang university, 2001), emission source be mainly industrial waste gas, vehicle exhaust,
Construction material and indoor hardware fitting etc..Most of VOCs have toxicity and zest, can teratogenesis, carcinogenic and mutagenesis, also
Photochemical fog can be produced as presoma, health is caused serious harm.
The processing method of VOCs mainly has absorption method, bioanalysis, combustion method and photocatalytic degradation etc..Wherein absorption method is with it relatively
High VOCs removal efficiency, low power consuming, low cost, do not exist the advantages such as secondary pollution become VOCs control most economical effectively
Technology.The most conventional main active charcoal of high-efficiency adsorbent and zeolite molecular sieve etc..Activated carbon have high specific surface area and
Pore volume, the gas absorption capacity higher because of it and be applied to gas absorption field.But owing to activated carbon heat stability is poor,
Microcellular structure is complicated, and the gas of absorption is difficult to remove, regenerability poor (Zhou Chun how, Environmental Pollution and Control, 2009),
Limit its application in industrial adsorption field.Compared with activated carbon, the well-regulated pore passage structure of zeolitic molecular sieve, thermally-stabilised
Property high, especially molecular sieve of Nano zeolite, there is high-specific surface area and pore volume, have in terms of gas absorption diffusion and desorption and regeneration
Have superiority, be more suitable for commercial introduction application.But at present the commercial Application of molecular sieve of Nano zeolite material still suffers from problems with:
(1) single pore-size distribution causes molecular sieve of Nano zeolite only the little molecule VOCs of certain size to be had adsorptivity, is unfavorable for
The absorption (Xue etc., Advanced Functional Materials, 2008) of multicomponent VOCs;(2) between Colloidal zeolites
Agglomeration traits also can reduce adsorption efficiency, improves Pollutant Treatment cost.Therefore, preparation has hierarchical porous structure, and dispersibility is relatively
Good nano zeolite composite is the key solving the problems referred to above.
Chinese invention patent " method of preparing zeolite material with multi-class pore canal by zeolitizing diatomite " (patent No.:
01126842.5), with natural minerals kieselguhr as matrix, the loose structure of kieselguhr itself is utilized, by its surface zeolitization, system
Must have the kieselguhr Zeolite composite materials of hierarchical porous structure.This material has certain absorbability to VOCs, as inhaled benzene
Attached amount is 46mg/g, but this material manufacturing cycle is longer, and hydrothermal reaction process energy consumption is high, and additionally gas-solid turns brilliant process mutually and need to make
With poisonous organic reagents such as ethylenediamines, there is latency environment hazardness.Chinese invention patent " compound of functionalization coal ash zeolite
The preparation method of grain " (patent No.: 201010588313.5), utilize the porous of industrial waste flyash, specific surface area big,
Surface high feature can carry out recycling, prepares the coal ash zeolite composite with hierarchical porous structure.Although preparation
Technique is relatively easy, but still needs to carry out hydro-thermal reaction, and energy consumption is high.It addition, above two material is powder body, inhale at VOCs
Easily by flow perturbation in additive process;And powder body material is not easily recycled process.
Compared with dusty material, block moulding material is susceptible to airflow influence, counter-bending strong with fold resistance, especially ceramic material,
Heat stability is good, it is possible to straight forming is applied.Industrial typically pottery is made loose structure carrier, adsorbent can be greatly increased
With the contact area of adsorbate, improve adsorption efficiency;Mass transfer can effectively extend to three dimensions simultaneously, and material property is able to
Improve.Chinese invention patent " Diatomite-based Porous Ceramics and the method for loading Ag doped with nano TiO 2 thereof " (patent No.:
201010216099.0), adopting kieselguhr is Ceramic Material, prepares Diatomite-based Porous Ceramics carrier through compacting, calcination process.
But the ceramic monolith that the method prepares comprises only diatomaceous macroporous structure, carrier aperture distribution is single, it is difficult to meets industry and inhales
Attached technique needs;It addition, pressing process needs to carry out under the conditions of elevated pressures, preparation cost is high, is unfavorable for actual application.
Summary of the invention:
It is an object of the invention to overcome the adsorbent pores structure preparing and using VOCs adsorbent to exist in prior art single, instead
Answer process energy consumption high, easily by shortcomings such as flow perturbations, it is provided that a kind of diatom adsorbed for volatile organic contaminant (VOCs)
Soil matrix composite porous ceramic material and preparation method thereof.The main advantage of the method is, utilizes the macroporous structure of polyurethane foam,
Use kieselguhr as Ceramic Material, prepare the double macropore ceramic monolith of diatom soil matrix with polyurethane template.Then former on its surface
Position one layer of nano zeolite granule of uniform load, prepares the kieselguhr based composite ceramic material with double macropore/micropore hierarchical porous structure,
This material has efficient absorption power to volatile organic contaminant.It is simple that this preparation method has technique, mild condition, and energy consumption is low,
The advantages such as latency environment harm is relatively low.
The base composite porous ceramic material of kieselguhr for volatile organic contaminant absorption of the present invention, it is by the following method
Preparation:
A, the preparation of Diatomite-based Porous Ceramics carrier: added by kieselguhr in compounding agent solution, stir 3~15 hours under room temperature,
Preparing ceramic size, described compounding agent solution, based on mass fraction 100%, including flux 1.7%-1.9%, binding agent
6.7%-16.2%, dispersant 5.0-6.0%, surplus is water, then immerses in ceramic size by polyurethane foam, vacuum impregnation 3-10
Minute, extrude additional size, such repeating vacuum dipping is extruded several times, after drying with≤5 DEG C/min ramp extremely
550-800 DEG C, it is incubated 2-5 hour, is then continuously heating to 850-1000 DEG C with≤10 DEG C/min speed, take after calcining 3-6 hour
Go out, obtain Diatomite-based Porous Ceramics carrier;
The preparation of the base composite porous ceramic material of b, kieselguhr: Diatomite-based Porous Ceramics carrier is joined polycation electrolyte
In solution, moving in pure silica zeolites synthesis liquid after being sufficiently impregnated with, 101-150 DEG C is heated at reflux 48-96 hour, is taken by solid product
Go out washing, calcine 5-10 hour in 500-600 DEG C after drying, prepare the diatom soil matrix for volatile organic contaminant absorption multiple
Close porous ceramic film material.
Being added by kieselguhr in compounding agent solution of described step a according to kieselguhr quality/compounding agent solution volume ratio is preferably
1g/2.5mL adds.
Being joined by Diatomite-based Porous Ceramics carrier in polycation electrolyte solution of described step b is preferably kieselguhr
It is 0.5% that base cellular ceramic substrate joins mass fraction according to carrier quality/polycation electrolyte liquor capacity than 1g/40mL
Polycation electrolyte solution in.
Described polycation electrolyte solution is preferably the aqueous solution of PDDA, chitosan or chitosan;
Described pure silica zeolites synthesis liquid, preferably presses the amount portion rate of material, including TPAOH (TPAOH) 9-15
Part, tetraethyl orthosilicate (TEOS) 25 parts and 480 parts of water.
Described kieselguhr refers to the diatom shell mass percentage content kieselguhr more than 60% in raw ore.
Described flux is preferably the alkali metal chloride such as sodium chloride or potassium chloride;
Described binding agent is preferably non-hydrate sodium metasilicate or the alkali silicate such as sodium silicate or potassium silicate.
Described dispersant is preferably PDDA, chitosan or chitosan.
Advantages of the present invention and good effect embody a concentrated reflection of in following some:
1. instant invention overcomes powder body Zeolite composite materials easily by shortcomings such as flow perturbation, poor stabilities, prepare and inhale for VOCs
The base composite porous ceramic block material of attached kieselguhr.This kieselguhr base composite porous ceramic material heat stability is high, specific surface area
Big with total pore volume, the VOCs such as benzene, dichloromethane and normal hexane are had higher adsorbance (under room temperature, to benzene, dichloro
The static saturated adsorption capacity of methane and normal hexane respectively up to: 46mg/g for the base composite porous pottery of kieselguhr of VOCs absorption
Material, 219mg/g are used for, for the base composite porous ceramic material of kieselguhr, the 61mg/g of VOCs absorption, the silicon that VOCs adsorbs
The base composite porous ceramic material of diatomaceous earth).
2. the present invention overcomes the shortcoming that carrier hole structure is single, makes full use of the macroporous structure of polyurethane foam, uses polyurethane mould
The base composite porous ceramic material of kieselguhr with double macroporous structure is prepared in the calcining of plate method.This kieselguhr base composite porous pottery material
Expect the existing macropore (aperture integrated distribution is in 300-400 μm) being replicated in polyurethane template, remain diatomaceous macropore (hole simultaneously
Footpath integrated distribution is in 0.14 μm and 0.22 μm).
3. the present invention uses backflow load method in situ, at carrier surface one layer of pure silicon nano zeolite granule of load in situ.This was prepared
Journey need not high temperature and high pressure environment, and reaction condition temperature is closed, and technique is simple, and manufacturing cycle is short.Owing to pure silica zeolites is at carrier surface
" growing " in situ, zeolite granular uniform load, in Diatomite-based Porous Ceramics surface, improves the dispersive property of nano zeolite granule,
Be conducive to improving VOCs adsorption efficiency while reducing cost.
The present invention, with cheap kieselguhr as raw material, prepares the double macropore ceramic monolith of diatom soil matrix by polyurethane template.So
Afterwards by backflow load method in situ, by pure silica zeolites nano-particle uniform load in above-mentioned surfaces of carrier materials, prepare diatom soil matrix
Composite porous ceramic material.The base composite porous ceramic material of kieselguhr utilizing the present invention to prepare is block moulding material, in double greatly
Hole/micropore hierarchical porous structure, has the micropore of pure silica zeolites, is replicated in the macropore of polyurethane template, remain diatomaceous simultaneously
Macroporous structure.It addition, this composite porous ceramic material heat stability is higher, specific surface area and total pore volume are big, to benzene, dichloro
The VOCs gas such as methane and normal hexane has the absorption property of excellence.The base composite porous pottery of kieselguhr that the present invention provides simultaneously
It is simple that the preparation method of material has technique, and mild condition is polluted low, and the feature that energy consumption is low, prospects for commercial application is wide.
Accompanying drawing illustrates:
Fig. 1 is the X-ray diffractogram of the base composite porous ceramic material of kieselguhr of embodiments of the invention 1 preparation.Can from figure
Arriving, through calcining, the base composite porous ceramic material of kieselguhr is cristobalite phase.The base composite porous ceramic material of kieselguhr both contained
The cristobalite phase of ceramic monolith, contains pure silica zeolites phase simultaneously, it was demonstrated that the base composite porous ceramic material of this kieselguhr is to be carried by pottery
Body is composited with pure silica zeolites.
Fig. 2 is the scanning electron microscope (SEM) photograph of the base composite porous ceramic material of kieselguhr of embodiments of the invention 1 preparation.It can be seen that
The base composite porous ceramic material of kieselguhr has macropore (pore-size distribution concentrates on 300-400 the μm) (figure being replicated in polyurethane template
2a), the skeleton of the base composite porous ceramic material of kieselguhr is formed (Fig. 2 b) by diatom shell bonding, the macroporous structure of diatom shell
Keep complete, one layer of pure silica zeolites nano-particle of surface of shell uniform load, in spherical, diameter about 80nm (Fig. 2 c).
Fig. 3 is the macropore diameter scattergram of the base composite porous ceramic material of kieselguhr of embodiments of the invention 1 preparation.From figure permissible
Finding out, diatomaceous macroporous structure remains in that completely (pore-size distribution concentrates on 0.14 μm and 0.22 μm), between diatomite particle
Accumulation hole be 6 μm.
Fig. 4 be the base composite porous ceramic material of the kieselguhr prepared by embodiments of the invention 1 (composite in figure) nitrogen inhale-
Desorption isotherm.It can be seen that low-pressure area nitrogen adsorption amount quickly increases, show the base composite porous pottery of this kieselguhr
Material contains micropore, and when relative pressure is close to 1.0, the increase of nitrogen adsorption amount then shows this kieselguhr base composite porous pottery material
Material is containing macropore.The base composite porous ceramic material of this kieselguhr belongs to IV type isothermal line, has H3 type and returns stagnant ring, according to BET
It is 122.9m that method records the specific surface area of this composite block material2/ g, total pore volume is 0.14cm3/g。
Detailed description of the invention:
Following example are to further illustrate the present invention rather than limitation of the present invention.
Embodiment 1:
1. the preparation of Diatomite-based Porous Ceramics carrier: take kieselguhr 40g and add in 100ml compounding agent solution, fully stir under room temperature
Mix 15 hours, prepare ceramic size.Described compounding agent solution, based on total mass fraction 100%, including sodium chloride 1.8%, nine
Water sodium metasilicate 9.9%, PDDA 5.6%, surplus is water.Then polyurethane foam is immersed above-mentioned
In ceramic size, vacuum impregnation 5 minutes, extrude additional size, so repeat polyurethane foam repeating vacuum is impregnated extrusion 3
Secondary, after drying with 1 DEG C/min ramp to 600 DEG C, it is incubated 3 hours, is then continuously heating to 850 DEG C with 10 DEG C/min,
Take out after calcining 6 hours, obtain Diatomite-based Porous Ceramics carrier.
2. the preparation of the base composite porous ceramic material of kieselguhr: by step 1) prepare Diatomite-based Porous Ceramics carrier take 1.5g
Add in the PDDA electrolyte solution that 60ml mass fraction is 0.5%, after being sufficiently impregnated with, move into pure silicon
(zeolite synthesis liquid is to be 9:25:480 mixing by your number ratio of TPAOH, tetraethyl orthosilicate and hydromassage to zeolite synthesis liquid
Obtain after uniformly) in, 101 DEG C are heated at reflux 72 hours, solid product takes out washing, calcines 5 in 600 DEG C after drying
Hour, prepare the base composite porous ceramic material of kieselguhr for volatile organic contaminant absorption.
Fig. 1 is the X-ray diffractogram of the base composite porous ceramic material of kieselguhr of embodiments of the invention 1 preparation.Can from figure
To see, through calcining, the base composite porous ceramic material of kieselguhr is cristobalite phase.The base composite porous ceramic material of kieselguhr was both
Cristobalite phase containing ceramic monolith, contains pure silica zeolites phase simultaneously, it was demonstrated that the base composite porous ceramic material of this kieselguhr is by making pottery
Ceramic carrier is composited with pure silica zeolites.
Fig. 2 is the scanning electron microscope (SEM) photograph of the base composite porous ceramic material of kieselguhr of embodiments of the invention 1 preparation.From figure permissible
Finding out, the base composite porous ceramic material of kieselguhr has and is replicated in the macropore of polyurethane template (pore-size distribution concentrates on
300-400 μm) (Fig. 2 a), the skeleton of the base composite porous ceramic material of kieselguhr is formed (Fig. 2 b) by diatom shell bonding, diatom
The macroporous structure of housing keeps complete, one layer of pure silica zeolites nano-particle of surface of shell uniform load, in spherical, and diameter about 80nm
(Fig. 2 c).
Fig. 3 is the macropore diameter scattergram of the base composite porous ceramic material of kieselguhr of embodiments of the invention 1 preparation.From figure
It can be seen that diatomaceous macroporous structure remains in that completely (pore-size distribution concentrates on 0.14 μm and 0.22 μm), kieselguhr
The accumulation hole of intergranular is 6 μm.
Fig. 4 is the nitrogen suction-desorption isotherm of the base composite porous ceramic material of the kieselguhr prepared by embodiments of the invention 1.From
It can be seen that low-pressure area nitrogen adsorption amount quickly increases in figure, show that the base composite porous ceramic material of this kieselguhr contains micropore,
When relative pressure is close to 1.0, the increase of nitrogen adsorption amount then shows that the base composite porous ceramic material of this kieselguhr contains macropore.Should
The base composite porous ceramic material of kieselguhr belongs to IV type isothermal line, has H3 type and returns stagnant ring, records this composite block according to BET method
The specific surface area of body material is 122.9m2/ g, total pore volume is 0.14cm3/g。
The base composite porous ceramic material of kieselguhr for volatile organic contaminant absorption of the preparation static saturated adsorption capacity to benzene
For 46mg/g (for the base composite porous ceramic material of kieselguhr of volatile organic contaminant absorption).
Embodiment 2:
A. the preparation of Diatomite-based Porous Ceramics carrier: take kieselguhr 40g and add in 100ml compounding agent solution, fully stir under room temperature
Mix 3 hours, prepare ceramic size.Described compounding agent solution, based on total mass fraction 100%, including sodium chloride 1.9%, nine
Water sodium metasilicate 6.7%, PDDA 6.0%, surplus is water.Then polyurethane foam is immersed above-mentioned
In ceramic size, vacuum impregnation 10 minutes, extrude additional size.Continue such repeating vacuum dipping extrusion 5 times, after drying with
1 DEG C/min ramp, to 800 DEG C, is incubated 2 hours, is then continuously heating to 1000 DEG C with 5 DEG C/min, calcines 6 hours
Rear taking-up, obtains Diatomite-based Porous Ceramics carrier.
2. the preparation of the base composite porous ceramic material of kieselguhr: by step 1) prepare Diatomite-based Porous Ceramics carrier take 1.5g
Add in the PDDA electrolyte solution that 60ml mass fraction is 0.5%, after being sufficiently impregnated with, move into pure silicon
(zeolite synthesis liquid is to be 9:25:480 mixing by your number ratio of TPAOH, tetraethyl orthosilicate and hydromassage to zeolite synthesis liquid
Obtain after uniformly) in, 150 DEG C are heated at reflux 48 hours, solid product take out washing, after drying in 500 DEG C of calcinings
10 hours, prepare the base composite porous ceramic material of kieselguhr for volatile organic contaminant absorption of the present embodiment.
The ratio table of the base composite porous ceramic material of kieselguhr for volatile organic contaminant absorption of preparation is recorded according to BET method
Area is 114.8m2/ g, total pore volume is 0.12m3/g。
The base composite porous ceramic material of kieselguhr for volatile organic contaminant absorption of preparation is saturated to the static state of dichloromethane
Adsorbance is 219mg/g (for the base composite porous ceramic material of kieselguhr of volatile organic contaminant absorption).
Embodiment 3:
1. the preparation of Diatomite-based Porous Ceramics carrier: take kieselguhr 40g and add in 100ml compounding agent solution, fully stir under room temperature
Mix 15 hours, prepare ceramic size.Described compounding agent solution, based on total mass fraction 100%, including sodium chloride 1.7%, nine
Water sodium metasilicate 16.2%, PDDA 5.0%, surplus is water.Then polyurethane foam is immersed above-mentioned
In ceramic size, vacuum impregnation 3 minutes, extrude additional size.So repeat to impregnate polyurethane foam repeating vacuum, extrusion
5 times, after drying with 1 DEG C/min ramp to 550 DEG C, it is incubated 5 hours, is then continuously heating to 850 DEG C with 5 DEG C/min,
Take out after calcining 3 hours, obtain Diatomite-based Porous Ceramics carrier.
2. the preparation of the base composite porous ceramic material of kieselguhr: by step 1) prepare Diatomite-based Porous Ceramics carrier take 1.5g
Add in the PDDA electrolyte solution that 60ml mass fraction is 0.5%, after being sufficiently impregnated with, move into pure silicon
(zeolite synthesis liquid is to be 15:25:480 mixing by your number ratio of TPAOH, tetraethyl orthosilicate and hydromassage to zeolite synthesis liquid
Obtain after uniformly) in, 101 DEG C are heated at reflux 96 hours, solid product takes out washing, calcines 5 in 600 DEG C after drying
Hour, prepare the base composite porous ceramic material of kieselguhr for volatile organic contaminant absorption.
The ratio table of the base composite porous ceramic material of kieselguhr for volatile organic contaminant absorption of preparation is recorded according to BET method
Area is 109.4m2/ g, total pore volume is 0.14m3/g。
The saturated suction of static state to normal hexane of the base composite porous ceramic material of kieselguhr for volatile organic contaminant absorption of preparation
Attached amount is 61mg/g (for the base composite porous ceramic material of kieselguhr of volatile organic contaminant absorption).
Claims (2)
1. the preparation method for the base composite porous ceramic material of kieselguhr of volatile organic contaminant absorption, it is characterised in that
Comprise the following steps:
A, the preparation of Diatomite-based Porous Ceramics carrier: added by kieselguhr in compounding agent solution, stir 3~15 hours under room temperature,
Preparing ceramic size, described compounding agent solution, based on mass fraction 100%, including flux 1.7%-1.9%, binding agent
6.7%-16.2%, dispersant 5.0-6.0%, surplus is water, then immerses in ceramic size by polyurethane foam, vacuum impregnation 3-10
Minute, extrude additional size, such repeating vacuum dipping is extruded several times, after drying with≤5 DEG C/min ramp extremely
550-800 DEG C, it is incubated 2-5 hour, is then continuously heating to 850-1000 DEG C with≤10 DEG C/min speed, take after calcining 3-6 hour
Go out, obtain Diatomite-based Porous Ceramics carrier;
The preparation of the base composite porous ceramic material of b, kieselguhr: Diatomite-based Porous Ceramics carrier is joined polycation electrolyte
In solution, moving in pure silica zeolites synthesis liquid after being sufficiently impregnated with, 101-150 DEG C is heated at reflux 48-96 hour, is taken by solid product
Go out washing, calcine 5-10 hour in 500-600 DEG C after drying, prepare the diatom soil matrix for volatile organic contaminant absorption multiple
Close porous ceramic film material;
Being added in compounding agent solution by kieselguhr of described step a is to be 1g/2.5mL according to kieselguhr quality/compounding agent solution volume ratio
Add;
Being joined in polycation electrolyte solution by Diatomite-based Porous Ceramics carrier of described step b is for by diatom soil matrix
It is 0.5% that cellular ceramic substrate joins mass fraction according to carrier quality/polycation electrolyte liquor capacity than 1g/40mL
In polycation electrolyte solution;
The described aqueous solution that polycation electrolyte solution is PDDA, chitosan or chitosan;
Described pure silica zeolites synthesis liquid, by the amount portion rate of material, including TPAOH 9-15 part, tetraethyl orthosilicate
25 parts and 480 parts of water;
Described flux is sodium chloride or potassium chloride;
Described binding agent is non-hydrate sodium metasilicate, sodium silicate or potassium silicate;
Described dispersant is PDDA, chitosan or chitosan.
2. the diatom soil matrix for volatile organic contaminant absorption prepared according to the preparation method described in claim 1
Composite porous ceramic material.
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