CN109012620A - A kind of modified montmorillonoid-zeolite composite adsorbing material and its preparation method and application - Google Patents
A kind of modified montmorillonoid-zeolite composite adsorbing material and its preparation method and application Download PDFInfo
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Abstract
A kind of modified montmorillonoid-zeolite composite adsorbing material and its preparation method and application, which is made of zeolite, modified montmorillonoid, wood pulp cellulose, special fibre, water-insoluble fire retardant and adhesive.High-strength special type fiber, modified montmorillonoid and zeolite are added in composite adsorbing material prepared by the present invention, with hydrophobicity is good, anti-flammability is high, high mechanical strength, thermal stability are good, chemical stability is good, pore structure is unique, large specific surface area and the characteristics such as is not pulverized easily, the adsorption cleaning especially suitable for all kinds of VOCs exhaust gas is handled.Raw material sources of the present invention are extensive, and technical process is simple, can be processed into the product of the forms such as felt, band, cloth, have many advantages, such as that suction/desorption rate is fast, adsorption capacity is strong in ADSORPTION IN A FIXED BED and runner adsorption applications, can be recycled, regeneration level is high and pressure drop is small.
Description
Technical field
The invention belongs to technical field of function materials, and in particular to a kind of modified montmorillonoid-zeolite composite adsorbing material and
Preparation method and application.
Background technique
VOCs(volatile organic matter) refer generally under normal pressure state boiling point between 50-260 DEG C, saturated vapor pressure at room temperature
More than 134Pa, and there is very strong volatile organic compound.Improvement for low concentration, Wind Volume VOCs exhaust gas, mainly
Technology has absorption method and bioanalysis, when air quantity is greater than 10000 m3When/h, when according to Biochemical method VOCs, there is facilities
Bulky, the problems such as face is big for land occupation, system pressure drop is big and investment is high, so to the industrial VOCs exhaust gas of low concentration, Wind Volume,
It is handled using absorption method, there are the advantages such as efficient, energy-saving and environmental protection, a wide range of popularization has been obtained in engineering.
The key of absorption method is adsorbent, common adsorbent mainly active charcoal and zeolite.Active carbon hole is abundant, compares
Surface area is big, adsorption capacity is strong, has preferable wide spectrum applicability, but its poor fire (easily generation fire), regeneration difficulty, leads
Use scope is caused to be restricted.Compared with active carbon, zeolite is noncombustible matter, can tolerate high temperature to 1000 DEG C, can be used for height
Temperature absorption, has the advantages such as regeneration efficiency height, safety height, is also widely used for the processing of all kinds of VOCs gases in recent years,
But the disadvantages of that there are mechanical strengths is low for honeycomb zeolite, easy dusting and aperture are single.
Montmorillonite is bentonitic main component, is a kind of phyllosilicate, has the advantage that as VOCs adsorbent
(1) reserves are big, cheap；(2) modified montmorillonoid hydrophobicity is good, large specific surface area；(3) non-ignitable and pore structure is abundant,
There is wide use space in terms of VOCs exhaust-gas treatment.
Summary of the invention
Goal of the invention: being directed to the deficiencies in the prior art, and the present invention provides a kind of compound suction of modified montmorillonoid-zeolite
Enclosure material and preparation method thereof, has that anti-flammability is high, hydrophobicity at the advantages of having had both special fibre, zeolite and modified montmorillonoid
Well, thermal stability is good, chemical stability is good, pore structure is unique, large specific surface area, high mechanical strength, be not pulverized easily, gas leads to
The characteristics such as road is controllable, has a wide range of application, the adsorption cleaning especially suitable for all kinds of VOCs exhaust gas are handled.
In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention are as follows:
A kind of modified montmorillonoid-zeolite composite adsorbing material, prepare raw material contain modified montmorillonoid component, special fibre component and
Zeolite component.
The modified montmorillonoid-zeolite composite adsorbing material is by following weight percent at being grouped as: modified montmorillonoid
11.8-53.3%, wood pulp cellulose 14.2-47.4%, special fibre 3.5-17.8%, zeolite 15.8-53.3%, fire retardant 4.7-
9.5%, adhesive 4.7-17.8%, the sum of each component are 100%.
The adhesive be polyvinyl alcohol, starch, chitosan it is one or more.
The wood pulp cellulose is one of softwood pulp and hardwood pulp or a variety of.
The zeolite include ZSM-5 type zeolite, y-type zeolite, silica-rich zeolite β, M-13X type zeolite, in MCM-41 type zeolite
One or more, the specific surface area > 225m of hydrophobic type zeolite2/ g, sial mass ratio > 100.
The water-insoluble fire retardant is melamine phosphate, aluminum phosphate, magnesium phosphate, aluminium metaphosphate, magnesium hydroxide, hydrogen-oxygen
Change one of aluminium or a variety of.
The modified montmorillonoid-zeolite composite adsorbing material preparation method, comprising the following steps:
A) by the wood pulp cellulose of 30-70 ° of SR of beating degree, special fibre, modified montmorillonoid, zeolite powder, adhesive with it is non-
Water-soluble flame retardant adds water uniformly to be mixed according to the ratio, and mixed material concentration is 0.05-0.5%；
B) mixed material is put on the molding machine of filter screen drainage into planar material, then drying and shaping.
C) planar material is processed at high operating temperatures to corrugated, then pass through planar and corrugated material
Single-face corrugation material is made in adhesive stickup.
The diameter of the special fibre has permanent fire retardant at 5-100 μm, length 3-15mm.
The special fibre is selected from basalt fibre, Kafra fiber.
It is de- that the modified montmorillonoid is that organic quaternary ammonium salt modified montmorillonoid, amino acid modified montmorillonite, modified with organic acids cover
One of soil is a variety of.
The modified montmorillonoid-zeolite composite adsorbing material applies the adsorption cleaning processing in VOCs exhaust gas.
The utility model has the advantages that compared with prior art, modified montmorillonoid of the invention-zeolite composite adsorbing material has had both special type
The advantages of fiber, zeolite and modified montmorillonoid, with anti-flammability is high, hydrophobicity is good, thermal stability is good, chemical stability is good, hole
Gap structure uniqueness large specific surface area, high mechanical strength, is not pulverized easily, the characteristics such as gas passage is controllable, has a wide range of application, special
Not Shi Yongyu all kinds of VOCs exhaust gas adsorption cleaning processing.Since high-performance zeolite composite adsorbing material characteristic size is small, VOCs
Gas diffusion velocity is fast, thus suction/desorption rate is fast；It is superimposed single-face corrugation shape material to form honeycomb sorbent material
Material has lower air resistance, greatly reduces operating cost.And raw material sources are extensive, technical process is simple, can be freely
It is processed into the fibre (felt, band, cloth etc.) of different shape, there is adsorption capacity in ADSORPTION IN A FIXED BED and runner adsorption applications
It by force, can in-situ regeneration and recycling, the advantages that suction/desorption rate is fast, pressure drop is small.
Detailed description of the invention
Fig. 1 is the electron microscope of composite adsorbing material；
Fig. 2 is the structural schematic diagram of honeycomb composite adsorbing material；
Fig. 3 is adsorption/desorption Experimental equipment.
Specific embodiment
The present invention is described further combined with specific embodiments below.
In following embodiment, used special fibre is basalt fibre, from Jiangsu Condar husband new material science and technology
Co., Ltd, the product have high intensity, permanent fire retardant, short-term heatproof at 1000 DEG C or more, can be for a long time in 760 DEG C of temperature rings
It is used under border.
Embodiment 1
Weighing 2.2g beating degree is 62 ° of SR wood pulp celluloses, 0.8g special fibre (5 μm of diameter, length 6mm), 1.0 g polyethylene
Alcohol, 8.5g powdery zeolite, 1.5g modified montmorillonoid, 1g magnesium hydroxide, 20kg water are dispersed after each component mixing with blender
30 minutes.Mixed material after being uniformly dispersed is put into drainage on water-strainer to form and dry, it is carried out using scanning electron microscope
Characterization, as shown in Figure 1, as seen from Figure 1, wood pulp cellulose disorderly interweaves in a jumble in fine and close continuous structure, special fibre
Together and skeleton is formed, zeolite and modified montmorillonoid are fixed in the big gap of skeleton, and this structure facilitates zeolite and changes
Property montmorillonite dispersion, and then be conducive to the diffusion mass transfer of adsorbate.
Two contrast products, respectively contrast product 2 and contrast product 3 are prepared using above-mentioned same recipe and technique,
Wherein contrast product 2 substitutes special fibre using polyester fiber, and comparison 3 substitutes special fibre using glass fibre.To each product
Physical and chemical performance detected；
The combustibility of material is tested using horizontal vertical burning tester and (is executed U.S. UL94 standard), the ratio table of material
Area is tested using high fire-retardance specific surface and micropore through analyzer.
The comparison of 1 product physical and chemical performance of table
| Product 1 | Contrast product 2 | Contrast product 3 | |
| Tensile strength (N/m) | 1620 | 1103 | 1371 |
| Inter-layer bonding force (J/m2) | 136 | 92 | 106 |
| Flame retardant rating (vertical burn flammability) | 94V0 | Non-antiflaming property | 94V1 |
| Specific surface area (m2/ g) | 609 | 564 | 551 |
| Thermal decomposition temperature (DEG C) | 319 | 261 | 267 |
It can be seen that special fibre instead of previous polyester fiber or glass from the results of property of 1 embodiment 1 of table and comparative example product
Glass fiber can increase substantially mechanical strength (tensile strength and inter-layer bonding force), thermal stability and the flame retardant property of material,
And it is relatively small on the influence of the specific surface area of composite adsorbing material.
Embodiment 2
Weigh 1.8g beating degree be 40 ° of SR wood pulp celluloses, 0.6g special fibre (5 μm of diameter, length 6mm), 2.25g chitosan,
6.75g powdery zeolite, 3g modified montmorillonoid, 0.6g aluminium hydroxide, 33.3kg water are divided after each component mixing with blender
It dissipates 30 minutes.Mixed material after being uniformly dispersed is put into drainage on water-strainer to form and dry.
Embodiment 3
Weigh 2.25g beating degree be 50 ° of SR wood pulp celluloses, 0.75g special fibre (10 μm of diameter, length 10mm), 0.9g starch,
4.95g powdery zeolite, 4.95g modified montmorillonoid, 0.6g aluminum phosphate, 0.6g magnesium phosphate, 3.34kg water, with stirring after each component mixing
It mixes device and carries out dispersion 16 minutes.Mixed material after being uniformly dispersed is put into drainage on water-strainer to form and dry.
Embodiment 4
Weighing 2.85g beating degree is 60 ° of SR wood pulp celluloses, 0.9g special fibre (15 μm of diameter, length 15mm), the poly- second of 0.75g
Enol, 3g powdery zeolite, 6.75g modified montmorillonoid, 0.75g aluminum phosphate, 16.7kg water, each component mixing after with blender into
Row dispersion 45 minutes.Mixed material after being uniformly dispersed is put into drainage on water-strainer to form and dry.
Embodiment 5
4.5g beating degree is weighed as 30 ° of SR wood pulp celluloses, 2.25g special fibre (100 μm of diameter, length 10mm), 0.6g shell gathers
Sugar, 3.75g powdery zeolite, 3.15g modified montmorillonoid, 0.75g aluminium hydroxide, 20kg water, each component mixing after with blender into
Row dispersion 65 minutes.Mixed material after being uniformly dispersed is put into drainage on water-strainer to form and dry.
Embodiment 6
Weigh 6g beating degree be 75 ° of SR wood pulp celluloses, 0.45g special fibre (10 μm of diameter, length 8mm), 1.5g starch,
3.15g powdery zeolite, 3g modified montmorillonoid, 0.9g aluminium metaphosphate, 20kg water carry out dispersion 55 with blender after each component mixing
Minute.Mixed material after being uniformly dispersed is put into drainage on water-strainer to form and dry.
Using the method for embodiment 1, physical and chemical performance measurement is carried out to each product, concrete outcome is as shown in table 2.
2 product physical and chemical performance Comparative result of table
| Product 2 | Product 3 | Product 4 | Product 5 | Product 6 | |
| Tensile strength (N/m) | 1795 | 2025 | 1685 | 2162 | 2956 |
| Inter-layer bonding force (J/m2) | 164 | 172 | 151 | 182 | 198 |
| Anti-flammability (vertical burn flammability) | 94V0 | 94V0 | 94V0 | 94V0 | 94V0 |
| Specific surface area (m2/g) | 592 | 427 | 452 | 541 | 519 |
From the results shown in Table 2, the amount of being used in compounding of special fibre and water-insoluble fire retardant is bigger, the anti-flammability of material
It can be better；The additive amount of special fibre is bigger, and the tensile strength and inter-layer bonding force to material are promoted more significant.As it can be seen that formula
Middle special fibre and water-insoluble fire retardant compounding play good synergistic effect, can promote the flame retardant property and intensity of material
Index, the safety coefficient of material is high when thermal current regenerates, and has further expanded the application range of material.Meanwhile modified montmorillonoid,
The amount of being used in compounding of zeolite and special fibre is bigger, and the tensile strength and inter-layer bonding force of material are promoted also bigger.
Absorption property test
Product 2 prepared by embodiment 2 is subjected to adsorptivity with the honeycomb zeolite provided by Beijing Zhong Tianhenghai Chung Inc.
It can test, specific experiment method and experiment condition are as follows:
Adsorption/desorption experimental rig is as shown in figure 3, package unit mainly includes electric control box, air filter, blower, dosing
Pump, exhaust gas generator, electric heating tube, flowmeter and fixed-bed adsorber composition, the Bubbling method mainly used generate toluene gas,
Then it is mixed with dry air, toluene waste gas required for generating, probe is protruded into bottom by thermocouple by the temperature in reactor
Portion measures, and the concentration of toluene is analyzed using gas chromatograph after reactor disengaging.
Absorption phase, using 150 mg/m of toluene3Air respectively enter as unstripped gas equipped with honeycomb zeolite and product 2
The fixed bed reactors of (such as Fig. 3), experiment air quantity are 50m3/ h, adsorption operations temperature are 25 DEG C；When desorption stage, using hot empty
Qi exhaustion is attached, and air quantity is adjusted to 10 m3/ h, desorption temperature adjust the aperture of electric heater by electric control box to control, averagely take off
Enclosure temperature is 135 DEG C.
Specific experiment condition and experimental result are shown in Table 3.
2 adsorption applications experimental result of 3 honeycomb zeolite of table and product
| Index | Honeycomb zeolite | Product 2 |
| Time of break-through (min) | 24 | 36 |
| Penetrate adsorbance (mg/g) | 60 | 95 |
| It is desorbed used time (min) | 20 | 18 |
| Pressure drop (Pa/m) | 4800 | 3900 |
Note: using exit concentration as inlet concentration 5% when as breakthrough point.
As shown in Table 3, compared with honeycomb zeolite, product 2 has faster adsorption/desorption rate, bigger penetrates adsorbance
With smaller pressure drop.
The above examples only illustrate the technical idea of the present invention, and this does not limit the scope of protection of the present invention, all
According to the technical idea provided by the invention, any changes made on the basis of the technical scheme each falls within the scope of the present invention
Within.
Claims (11)
1. a kind of modified montmorillonoid-zeolite composite adsorbing material, which is characterized in that prepare raw material contain modified montmorillonoid component,
Special fibre component and zeolite component.
2. modified montmorillonoid according to claim 1-zeolite composite adsorbing material, which is characterized in that by following weight hundred
Point ratio at being grouped as: modified montmorillonoid 11.8-53.3%, wood pulp cellulose 14.2-47.4%, special fibre 3.5-17.8%, zeolite
15.8-53.3%, fire retardant 4.7-9.5%, adhesive 4.7-17.8%, the sum of each component are 100%.
3. modified montmorillonoid according to claim 2-zeolite composite adsorbing material, which is characterized in that the adhesive is
Polyvinyl alcohol, starch, chitosan it is one or more.
4. modified montmorillonoid according to claim 2-zeolite composite adsorbing material, which is characterized in that the wood pulp cellulose
For one of softwood pulp and hardwood pulp or a variety of.
5. modified montmorillonoid according to claim 2-zeolite composite adsorbing material, which is characterized in that the zeolite includes
One of ZSM-5 type zeolite, y-type zeolite, silica-rich zeolite β, M-13X type zeolite, MCM-41 type zeolite are a variety of, hydrophobic type boiling
The specific surface area > 225m of stone2/ g, sial mass ratio > 100.
6. modified montmorillonoid according to claim 2-zeolite composite adsorbing material, which is characterized in that described water-insoluble
Fire retardant is one of melamine phosphate, aluminum phosphate, magnesium phosphate, aluminium metaphosphate, magnesium hydroxide, aluminium hydroxide or a variety of.
7. modified montmorillonoid described in claim 1-zeolite composite adsorbing material preparation method, which is characterized in that including with
Lower step:
By the wood pulp cellulose of 30-70 ° of SR of beating degree, special fibre, modified montmorillonoid, zeolite powder, adhesive with it is non-aqueous
Dissolubility fire retardant adds water uniformly to be mixed according to the ratio, and mixed material concentration is 0.05-0.5%；
Mixed material is put on the molding machine of filter screen drainage into planar material, then drying and shaping；
Planar material is processed into corrugated at high operating temperatures, planar and corrugated material is then passed through into adhesive
Single-face corrugation material is made in stickup.
8. modified montmorillonoid according to claim 7-zeolite composite adsorbing material preparation method, which is characterized in that institute
The diameter of special fibre is stated at 5-100 μm, length 3-15mm, and there is permanent fire retardant.
9. the modified montmorillonoid according to claim 8 or 7-zeolite composite adsorbing material preparation method, which is characterized in that
The special fibre is selected from basalt fibre, Kafra fiber.
10. the modified montmorillonoid according to claim 8 or 7-zeolite composite adsorbing material preparation method, feature exist
In, the modified montmorillonoid be organic quaternary ammonium salt modified montmorillonoid, amino acid modified montmorillonite, in modified with organic acids montmorillonite
It is one or more.
11. modified montmorillonoid of any of claims 1 or 2-zeolite composite adsorbing material applies the adsorption cleaning in VOCs exhaust gas
Processing.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811097043.0A CN109012620B (en) | 2018-09-20 | 2018-09-20 | Modified montmorillonite-zeolite composite adsorption material and preparation method and application thereof |
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| CN201811097043.0A CN109012620B (en) | 2018-09-20 | 2018-09-20 | Modified montmorillonite-zeolite composite adsorption material and preparation method and application thereof |
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| CN109012620B (en) | 2021-06-11 |
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