CN104492373A - Diatomite-based composite porous ceramic material for adsorbing volatile organic pollutant and preparation method thereof - Google Patents
Diatomite-based composite porous ceramic material for adsorbing volatile organic pollutant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a diatomite-based composite porous ceramic material for adsorbing a volatile organic pollutant and a preparation method thereof. The preparation method comprises the following steps of: preparing a diatomite-based double-macropore ceramic carrier through a polyurethane template method by taking low-cost diatomite as a raw material; then uniformly loading pure silicon zeolite nano-particles on the surface of the carrier material through an in-situ reflux loading method to prepare the diatomite-based composite porous ceramic material. The diatomite-based composite porous ceramic material disclosed by the invention is a mass forming material, forms a double-macropore/micropore multi-level pore structure, has a pure silicon zeolite micropore and a macropore duplicated on a polyurethane template, and reserves the macroporous structure of the diatomite. In addition, the diatomite-based composite porous ceramic material disclosed by the invention is relatively high in heat stability and large in specific area and total pore volume, and has excellent adsorption property on gases of VOCs, namely benzene, dichloromethane, n-hexane and the like. In addition, the preparation method of the diatomite-based composite porous ceramic material, which is disclosed by the invention, has the characteristics of simple process, moderation in condition, low pollution, low energy consumption and wide industrial application prospect.
Description
Technical field:
The invention belongs to volatile organic contaminant and administer field, be specifically related to a kind of base composite porous ceramic material of diatomite adsorbed for volatile organic contaminant (VOCs) and preparation method thereof.
Background technology:
Volatile organic contaminant (VOCs) typically refers to boiling point 50-250 DEG C, under room temperature, saturated vapour pressure is more than the organic compound of 133.3Pa, comprise hydro carbons, halogenated hydrocarbons, aromatic hydrocarbon, polycyclic aromatic hydrocarbon etc., be in indoor-outdoor air ubiquity and the complicated class organic pollution of composition (Shen Xue is excellent, journal of Zhejiang university, 2001), emission source is mainly industrial waste gas, vehicle exhaust, construction material and indoor hardware fitting etc.Most of VOCs has toxicity and excitant, can teratogenesis, carcinogenic and mutagenesis, also can be used as presoma produce photochemical fog, serious harm is caused to health.
The processing method of VOCs mainly contains absorption method, bioanalysis, combustion method and photocatalytic degradation etc.Wherein absorption method is with its higher VOCs removal efficiency, low power consuming, low cost, and there is not the advantages such as secondary pollution becomes the most economical effective technology of VOCs control.High-efficiency adsorbent conventional at present mainly contains active carbon and zeolite molecular sieve etc.Active carbon has high specific surface area and pore volume, the gas absorption capacity higher because of it and be applied to gas absorption field.But because active carbon heat endurance 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), limits its application in industrial adsorption field.Compared with active carbon, the well-regulated pore passage structure of zeolitic molecular sieve, heat endurance is high, especially molecular sieve of Nano zeolite, has high-ratio surface sum pore volume, in gas absorption diffusion and desorption and regeneration, have advantage, is more suitable for commercial introduction application.But at present still there is following problem in the commercial Application of molecular sieve of Nano zeolite material: (1) single pore-size distribution causes molecular sieve of Nano zeolite only to have adsorptivity to the Small molecular VOCs of certain size, be unfavorable for the absorption (Xue etc. of multicomponent VOCs, Advanced Functional Materials, 2008); (2) between Colloidal zeolites, agglomeration traits also can reduce adsorption efficiency, improves pollutant processing cost.Therefore, preparation has hierarchical porous structure, and dispersed nano zeolite composite is preferably the key solved the problem.
Chinese invention patent " method of the preparing zeolite material with multi-class pore canal by zeolitizing diatomite " (patent No.: 01126842.5), with natural minerals diatomite for matrix, utilize the loose structure of diatomite itself, by its surperficial zeolitization, the obtained diatomite Zeolite composite materials with hierarchical porous structure.This material has certain adsorption capacity to VOCs, and as being 46mg/g to benzene adsorbance, but this material manufacturing cycle is longer, and hydrothermal reaction process energy consumption is high, and gas-solid turns brilliant process mutually and need use the poisonous organic reagents such as ethylenediamine in addition, has latency environment harmfulness.Chinese invention patent " preparation method of functionalization coal ash zeolite the composite particles " (patent No.: 201010588313.5), utilize the feature that the porous of industrial waste flyash, specific area are large, surface energy is high to carry out recycling, prepare the coal ash zeolite composite with hierarchical porous structure.Although preparation technology is relatively simple, but still need carry out hydro-thermal reaction, energy consumption is high.In addition, above-mentioned bi-material is powder, in VOCs adsorption process, be subject to flow perturbation; And powder body material not easily recycles.
Compared with dusty material, block moulding material is not easily by airflow influence, counter-bending strong with fold resistance, especially ceramic material, and Heat stability is good can straight forming application.Industrially generally pottery is made loose structure carrier, greatly can increase the contact area of adsorbent and adsorbate, improve adsorption efficiency; Mass transfer can expand to three dimensions effectively simultaneously, and material property is improved.Chinese invention patent " method of Diatomite-based Porous Ceramics and loading Ag doped with nano TiO 2 thereof the " (patent No.: 201010216099.0), adopting diatomite is ceramic raw material, prepares Diatomite-based Porous Ceramics carrier through compacting, calcination process.But the ceramic monolith that the method obtains is only containing diatomaceous macroporous structure, carrier aperture distribution is single, is difficult to the technique needs meeting industrial adsorption; In addition, pressing process needs to carry out under elevated pressures condition, and preparation cost is high, is unfavorable for practical application.
Summary of the invention:
The object of the invention is to overcome the adsorbent pores structure that in prior art, preparation and use VOCs adsorbent exist single, course of reaction energy consumption is high, be subject to the shortcomings such as flow perturbation, base composite porous ceramic material of diatomite providing one to adsorb for volatile organic contaminant (VOCs) and preparation method thereof.The main advantage of the method is, utilizes the macroporous structure of polyurethane foam, adopts diatomite as ceramic raw material, obtains the two macropore ceramic monolith of diatom soil matrix with polyurethane template.Then at its surface in situ uniform load one deck nano zeolite particle, the obtained diatomite based composite ceramic material with two macropore/micropore hierarchical porous structure, this material has efficient adsorption power to volatile organic contaminant.The advantages such as it is simple that this preparation method has technique, mild condition, and energy consumption is low, and latency environment harm is lower.
The base composite porous ceramic material of diatomite for volatile organic contaminant absorption of the present invention, it is prepared by the following method:
A, the preparation of Diatomite-based Porous Ceramics carrier: diatomite is added in compounding agent solution, stirred at ambient temperature 3 ~ 15 hours, obtained ceramic size, described compounding agent solution, by mass fraction 100%, comprise flux 1.7%-1.9%, binding agent 6.7%-16.2%, dispersant 5.0-6.0%, surplus is water, then polyurethane foam is immersed in ceramic size, vacuum impregnation 3-10 minute, extrude additional size, repeating vacuum dipping like this extrudes several times, after drying with≤5 DEG C/min ramp to 550-800 DEG C, insulation 2-5 hour, then continue to be warming up to 850-1000 DEG C with≤10 DEG C/min speed, calcine after 3-6 hour and take out, obtain Diatomite-based Porous Ceramics carrier,
The preparation of the base composite porous ceramic material of b, diatomite: Diatomite-based Porous Ceramics carrier is joined in polycation electrolyte solution, move in pure silica zeolites synthesis liquid after abundant dipping, 101-150 DEG C of reflux heating 48-96 hour, calcine 5-10 hour in 500-600 DEG C after solid product being taken out washing, drying, obtain the base composite porous ceramic material of diatomite for volatile organic contaminant absorption.
Being added by diatomite in compounding agent solution of described step a is preferably that 1g/2.5mL adds according to diatomite quality/compounding agent solution volume ratio.
It is in the polycation electrolyte solution of 0.5% that Diatomite-based Porous Ceramics carrier is preferably joined mass fraction according to carrier quality/polycation electrolyte liquor capacity than 1g/40mL in polycation electrolyte solution by being joined by Diatomite-based Porous Ceramics carrier of described step b.
Described polycation electrolyte solution is preferably the aqueous solution of PDDA, shitosan or chitosan;
Described pure silica zeolites synthesis liquid, preferably presses amount of substance portion rate, comprises TPAOH (TPAOH) 9-15 part, ethyl orthosilicate (TEOS) 25 parts and 480 parts, water.
Described diatomite refers to the diatomite that in raw ore, diatom shell mass percentage content is greater than 60%.
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 metasilicate or potassium silicate.
Described dispersant is preferably PDDA, shitosan or chitosan.
Advantage of the present invention and good effect embody a concentrated reflection of in following some:
1. instant invention overcomes powder Zeolite composite materials and be subject to flow perturbation, the shortcomings such as poor stability, obtain the base composite porous ceramic block material of diatomite for VOCs absorption.This diatomite base composite porous ceramic material heat endurance is high, specific area and total pore volume large, to VOCs such as benzene, carrene and n-hexanes, there is higher adsorbance (under room temperature, can reach respectively the static saturated adsorption capacity of benzene, carrene and n-hexane: the base composite porous ceramic material of diatomite that the base composite porous ceramic material of diatomite that 46mg/g adsorbs for VOCs, 219mg/g adsorb for VOCs, 61mg/g are used for the base composite porous ceramic material of diatomite that VOCs adsorbs).
2. the present invention overcomes the single shortcoming of carrier hole structure, makes full use of the macroporous structure of polyurethane foam, adopts the calcining of polyurethane template to prepare the base composite porous ceramic material of the diatomite with two macroporous structure.The existing macropore (aperture integrated distribution is in 300-400 μm) being replicated in polyurethane template of the base composite porous ceramic material of this diatomite, remains diatomaceous macropore (aperture integrated distribution is in 0.14 μm and 0.22 μm) simultaneously.
3. the present invention adopts original position backflow load method, at carrier surface original position load one deck pure silicon nano zeolite particle.This preparation process does not need high temperature and high pressure environment, and reaction condition temperature is closed, and technique is simple, and manufacturing cycle is short.Because pure silica zeolites is in carrier surface original position " growth ", zeolite granular uniform load, in Diatomite-based Porous Ceramics surface, improves the dispersive property of nano zeolite particle, is conducive to improving VOCs adsorption efficiency while reducing costs.
The present invention for raw material, goes out diatom soil matrix two macropore ceramic monolith by polyurethane template synthesis with the diatomite of cheapness.Then to be refluxed load method by original position, by pure silica zeolites nano particle uniform load in above-mentioned surfaces of carrier materials, the obtained base composite porous ceramic material of diatomite.The base composite porous ceramic material of the diatomite utilizing the present invention to obtain is block moulding material, in two macropore/micropore hierarchical porous structure, has the micropore of pure silica zeolites, is replicated in the macropore of polyurethane template, remain diatomaceous macroporous structure simultaneously.In addition, this composite porous ceramic material heat endurance is higher, and specific area and total pore volume greatly, have excellent absorption property to VOCs gases such as benzene, carrene and n-hexanes.The preparation method of the base composite porous ceramic material of diatomite provided by the invention has technique simply simultaneously, and mild condition, pollutes low, the feature that energy consumption is low, and prospects for commercial application is wide.
Accompanying drawing illustrates:
Fig. 1 is the X-ray diffractogram of the base composite porous ceramic material of diatomite prepared by embodiments of the invention 1.As we can see from the figure, through calcining, the base composite porous ceramic material of diatomite is cristobalite phase.The cristobalite phase of the base composite porous ceramic material of diatomite both containing ceramic monolith, simultaneously containing pure silica zeolites phase, proves that the base composite porous ceramic material of this diatomite is composited by ceramic monolith and pure silica zeolites.
Fig. 2 is the scanning electron microscope (SEM) photograph of the base composite porous ceramic material of diatomite prepared by embodiments of the invention 1.As can be seen from the figure, the base composite porous ceramic material of diatomite have be replicated in polyurethane template macropore (pore-size distribution concentrates on 300-400 μm) (Fig. 2 a), the skeleton of the base composite porous ceramic material of diatomite is bondd by diatom shell and forms (Fig. 2 b), the macroporous structure of diatom shell keeps complete, surface of shell uniform load one deck pure silica zeolites nano particle, in spherical, diameter is about 80nm (Fig. 2 c).
Fig. 3 is the macropore diameter distribution map of the base composite porous ceramic material of diatomite prepared by embodiments of the invention 1.As can be seen from the figure, diatomaceous macroporous structure still keeps complete (pore-size distribution concentrates on 0.14 μm and 0.22 μm), and the accumulation hole between diatomite particle is 6 μm.
Fig. 4 is the nitrogen suction-desorption isotherm of the base composite porous ceramic material of diatomite (composite in figure) prepared by embodiments of the invention 1.As can be seen from the figure, low-pressure area nitrogen adsorption amount increases fast, shows that the base composite porous ceramic material of this diatomite contains micropore, when relative pressure close to 1.0 time nitrogen adsorption amount increase then show that the base composite porous ceramic material of this diatomite contains macropore.The base composite porous ceramic material of this diatomite belongs to IV type thermoisopleth, has H3 type and returns stagnant ring, and the specific area recording this composite block material according to BET method is 122.9m
2/ g, total pore volume is 0.14cm
3/ g.
Detailed description of the invention:
Following examples further illustrate of the present invention, instead of limitation of the present invention.
Embodiment 1:
1. the preparation of Diatomite-based Porous Ceramics carrier: get diatomite 40g and add in 100ml compounding agent solution, fully stirs 15 hours under room temperature, obtained ceramic size.Described compounding agent solution, by gross mass mark 100%, comprises sodium chloride 1.8%, non-hydrate sodium metasilicate 9.9%, PDDA 5.6%, and surplus is water.Then polyurethane foam is immersed in above-mentioned ceramic size, vacuum impregnation 5 minutes, extrude additional size, polyurethane foam repeating vacuum dipping is so repeated to extrude 3 times, with 1 DEG C/min ramp to 600 DEG C after drying, be incubated 3 hours, then continue to be warming up to 850 DEG C with 10 DEG C/min, calcine after 6 hours and take out, obtain Diatomite-based Porous Ceramics carrier.
2. the preparation of the base composite porous ceramic material of diatomite: by step 1) obtained Diatomite-based Porous Ceramics carrier gets 1.5g to add 60ml mass fraction is in the PDDA electrolyte solution of 0.5%, (zeolite synthesis liquid is by TPAOH to move into pure silica zeolites synthesis liquid after abundant dipping, ethyl orthosilicate and your number of hydromassage obtain than mixing for 9:25:480 afterwards) in, 101 DEG C of reflux heatings 72 hours, solid product is taken out washing, in 600 DEG C of calcinings 5 hours after drying, obtain the base composite porous ceramic material of diatomite for volatile organic contaminant absorption.
Fig. 1 is the X-ray diffractogram of the base composite porous ceramic material of diatomite prepared by embodiments of the invention 1.As we can see from the figure, through calcining, the base composite porous ceramic material of diatomite is cristobalite phase.The cristobalite phase of the base composite porous ceramic material of diatomite both containing ceramic monolith, simultaneously containing pure silica zeolites phase, proves that the base composite porous ceramic material of this diatomite is composited by ceramic monolith and pure silica zeolites.
Fig. 2 is the scanning electron microscope (SEM) photograph of the base composite porous ceramic material of diatomite prepared by embodiments of the invention 1.As can be seen from the figure, the base composite porous ceramic material of diatomite have be replicated in polyurethane template macropore (pore-size distribution concentrates on 300-400 μm) (Fig. 2 a), the skeleton of the base composite porous ceramic material of diatomite is bondd by diatom shell and forms (Fig. 2 b), the macroporous structure of diatom shell keeps complete, surface of shell uniform load one deck pure silica zeolites nano particle, in spherical, diameter is about 80nm (Fig. 2 c).
Fig. 3 is the macropore diameter distribution map of the base composite porous ceramic material of diatomite prepared by embodiments of the invention 1.As can be seen from the figure, diatomaceous macroporous structure still keeps complete (pore-size distribution concentrates on 0.14 μm and 0.22 μm), and the accumulation hole between diatomite particle is 6 μm.
Fig. 4 is the nitrogen suction-desorption isotherm of the base composite porous ceramic material of diatomite prepared by embodiments of the invention 1.As can be seen from the figure, low-pressure area nitrogen adsorption amount increases fast, shows that the base composite porous ceramic material of this diatomite contains micropore, when relative pressure close to 1.0 time nitrogen adsorption amount increase then show that the base composite porous ceramic material of this diatomite contains macropore.The base composite porous ceramic material of this diatomite belongs to IV type thermoisopleth, has H3 type and returns stagnant ring, and the specific area recording this composite block material according to BET method is 122.9m
2/ g, total pore volume is 0.14cm
3/ g.
The base composite porous ceramic material of diatomite for volatile organic contaminant absorption of preparation is 46mg/g (the base composite porous ceramic material of diatomite for volatile organic contaminant absorption) to the static saturated adsorption capacity of benzene.
Embodiment 2:
A. the preparation of Diatomite-based Porous Ceramics carrier: get diatomite 40g and add in 100ml compounding agent solution, fully stirs 3 hours under room temperature, obtained ceramic size.Described compounding agent solution, by gross mass mark 100%, comprises sodium chloride 1.9%, non-hydrate sodium metasilicate 6.7%, PDDA 6.0%, and surplus is water.Then polyurethane foam immersed in above-mentioned ceramic size, vacuum impregnation 10 minutes, extrudes additional size.Continue repeating vacuum like this dipping and extrude 5 times, with 1 DEG C/min ramp to 800 DEG C after drying, be incubated 2 hours, then continue to be warming up to 1000 DEG C with 5 DEG C/min, calcine after 6 hours and take out, obtain Diatomite-based Porous Ceramics carrier.
2. the preparation of the base composite porous ceramic material of diatomite: by step 1) obtained Diatomite-based Porous Ceramics carrier gets 1.5g to add 60ml mass fraction is in the PDDA electrolyte solution of 0.5%, (zeolite synthesis liquid is by TPAOH to move into pure silica zeolites synthesis liquid after abundant dipping, ethyl orthosilicate and your number of hydromassage obtain than mixing for 9:25:480 afterwards) in, 150 DEG C of reflux heatings 48 hours, solid product is taken out washing, in 500 DEG C of calcinings 10 hours after drying, the base composite porous ceramic material of diatomite for volatile organic contaminant absorption of obtained the present embodiment.
The specific area recording the base composite porous ceramic material of diatomite for volatile organic contaminant absorption of preparation according to BET method is 114.8m
2/ g, total pore volume is 0.12m
3/ g.
The base composite porous ceramic material of diatomite for volatile organic contaminant absorption of preparation is 219mg/g (the base composite porous ceramic material of diatomite for volatile organic contaminant absorption) to the static saturated adsorption capacity of carrene.
Embodiment 3:
1. the preparation of Diatomite-based Porous Ceramics carrier: get diatomite 40g and add in 100ml compounding agent solution, fully stirs 15 hours under room temperature, obtained ceramic size.Described compounding agent solution, by gross mass mark 100%, comprises sodium chloride 1.7%, non-hydrate sodium metasilicate 16.2%, PDDA 5.0%, and surplus is water.Then polyurethane foam immersed in above-mentioned ceramic size, vacuum impregnation 3 minutes, extrudes additional size.So repeat polyurethane foam repeating vacuum to flood, extrude 5 times, with 1 DEG C/min ramp to 550 DEG C after drying, be incubated 5 hours, then continue to be warming up to 850 DEG C with 5 DEG C/min, calcine after 3 hours and take out, obtain Diatomite-based Porous Ceramics carrier.
2. the preparation of the base composite porous ceramic material of diatomite: by step 1) obtained Diatomite-based Porous Ceramics carrier gets 1.5g to add 60ml mass fraction is in the PDDA electrolyte solution of 0.5%, (zeolite synthesis liquid is by TPAOH to move into pure silica zeolites synthesis liquid after abundant dipping, ethyl orthosilicate and your number of hydromassage obtain than mixing for 15:25:480 afterwards) in, 101 DEG C of reflux heatings 96 hours, solid product is taken out washing, in 600 DEG C of calcinings 5 hours after drying, obtain the base composite porous ceramic material of diatomite for volatile organic contaminant absorption.
The specific area recording the base composite porous ceramic material of diatomite for volatile organic contaminant absorption of preparation according to BET method is 109.4m
2/ g, total pore volume is 0.14m
3/ g.
The base composite porous ceramic material of diatomite for volatile organic contaminant absorption of preparation is 61mg/g (the base composite porous ceramic material of diatomite for volatile organic contaminant absorption) to the static saturated adsorption capacity of n-hexane.
Claims (9)
1., for a preparation method for the base composite porous ceramic material of diatomite of volatile organic contaminant absorption, it is characterized in that,
Comprise the following steps:
A, the preparation of Diatomite-based Porous Ceramics carrier: diatomite is added in compounding agent solution, stirred at ambient temperature 3 ~ 15 hours, obtained ceramic size, described compounding agent solution, by mass fraction 100%, comprise flux 1.7%-1.9%, binding agent 6.7%-16.2%, dispersant 5.0-6.0%, surplus is water, then polyurethane foam is immersed in ceramic size, vacuum impregnation 3-10 minute, extrude additional size, repeating vacuum dipping like this extrudes several times, after drying with≤5 DEG C/min ramp to 550-800 DEG C, insulation 2-5 hour, then continue to be warming up to 850-1000 DEG C with≤10 DEG C/min speed, calcine after 3-6 hour and take out, obtain Diatomite-based Porous Ceramics carrier,
The preparation of the base composite porous ceramic material of b, diatomite: Diatomite-based Porous Ceramics carrier is joined in polycation electrolyte solution, move in pure silica zeolites synthesis liquid after abundant dipping, 101-150 DEG C of reflux heating 48-96 hour, calcine 5-10 hour in 500-600 DEG C after solid product being taken out washing, drying, obtain the base composite porous ceramic material of diatomite for volatile organic contaminant absorption.
2. preparation method according to claim 1, is characterized in that, being added in compounding agent solution by diatomite of described step a is that 1g/2.5mL adds according to diatomite quality/compounding agent solution volume ratio.
3. preparation method according to claim 1, it is characterized in that, being joined in polycation electrolyte solution by Diatomite-based Porous Ceramics carrier of described step b is in the polycation electrolyte solution of 0.5% for Diatomite-based Porous Ceramics carrier is joined mass fraction according to carrier quality/polycation electrolyte liquor capacity than 1g/40mL.
4. the preparation method according to claim 1,2 or 3, is characterized in that, described polycation electrolyte solution is the aqueous solution of PDDA, shitosan or chitosan.
5. the preparation method according to claim 1,2 or 3, is characterized in that, described pure silica zeolites synthesis liquid, by amount of substance portion rate, comprises TPAOH 9-15 part, ethyl orthosilicate 25 parts and 480 parts, water.
6. the preparation method according to claim 1,2 or 3, is characterized in that, described flux is sodium chloride or potassium chloride.
7. the preparation method according to claim 1,2 or 3, is characterized in that, described binding agent is non-hydrate sodium metasilicate, sodium metasilicate or potassium silicate.
8. the preparation method according to claim 1,2 or 3, is characterized in that, described dispersant is PDDA, shitosan or chitosan.
9. the base composite porous ceramic material of diatomite for volatile organic contaminant absorption prepared according to preparation method according to claim 1.
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