CN1346795A - Process for preparing zeolite material with multi-class pore canal by zeolitizing diatomite - Google Patents
Process for preparing zeolite material with multi-class pore canal by zeolitizing diatomite Download PDFInfo
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- CN1346795A CN1346795A CN 01126842 CN01126842A CN1346795A CN 1346795 A CN1346795 A CN 1346795A CN 01126842 CN01126842 CN 01126842 CN 01126842 A CN01126842 A CN 01126842A CN 1346795 A CN1346795 A CN 1346795A
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Abstract
A process for preparing zeolite with multi-class pore canal structure by zeolitizing diatomite features use of laminating technique and gas-solid crystal conversion technique. For the laminating technique, an electrostatic attraction is used to assemble the nano zeolite onto diatomite. For the gas-solid crystal conversion technique, the amorphous SiO2 is converted to zeolite without damage to the form and structure of diatomite. Its advantages are simple operation, high speed, rich macropores, environmentally friendly process and wide application range.
Description
Technical field
The present invention is the method that the diatomaceous zeolitization of a kind of usefulness prepares the new zeolite material of multi-stage artery structure.
Background technology
Zeolite possesses abundant microporous, molecular screening performance and good heat and hydrothermal stability as a kind of porous inorganic material, is widely used in catalysis and the adsorptive separation technology.General direct synthetic zeolite is comparatively loose crystal powder, in actual applications, need to add various cakingagents (as clay or silicate etc.) moulding, but its result often makes the effective surface area of material obviously reduce, and has introduced diffusional limitation.The no cakingagent zeolite that occurs also is proved to be the bigger diffusion problem of existence equally, recently.A kind of better increase zeolite effective surface area, the method that reduces diffusion are the zeolitic materials that preparation has multi-stage artery structure.The preparation of this class material all needs to adopt removable template usually, just can obtain the multi-stage artery structure zeolitic material by remove template after forming needed zeolite wall on the template.
Mainly containing following several preparation method: Holland etc. at present is filled into the presoma of synthetic zeolite in the closely packed polystyrene sphere space, utilize the method for false solid phase crystallization zeolite on the throne to synthesize monoblock silicalite-1 zeolite (B.T.Holland with three-dimensional micropore/macroporous structure, L.Abrams and A.Stein, J.Am.Chem.Soc., 1999,121,4308); Valtchev etc. have then prepared silicalite-1 zeolite carbon fiber coated fibre with the method for crystal seed-film growth, and obtain silicalite-1 zeolite hollow fiber (V.Valtchev by roasting, B.J.Schoeman, J.Hedlund, S.Mintova and J.Sterte, Zeolites, 1996,17,408); Wang Xingdong etc. then utilize polystyrene sphere to be template, in its surface coverage one deck zeolite membrane, and obtain zeolite hollow ball (X.D.Wang, W.L.Yang by nano zeolite layer laminate assembling method by roasting, Y.Tang, Y.J.Wang, S.K.Fu and Z.Gao, Chem.Commun., 2000 (21), 2161) etc., but these methods all need to adopt a large amount of template to maintain required macroporous structure, and the removal of template also can not be underestimated the harm that environment causes.This class strength of materials is very poor after the more important thing is the removal template, is difficult to practical application.
Recently, Anderson etc. relate in the literature with diatomaceous zeolitization and prepare the hierarchical porous structure zeolitic material, mainly be after adopting diatomite as carrier loaded zeolite seed crystal, utilize external silicon source, aluminium source to promote seeded growth, form zeolite membrane on the diatomite surface and make zeolitic material (M.W.Anderson with high intensity and multi-stage artery structure, S.M.Holmes, N.Hanif and C.S.Cundy, Angew.Chem.Int.Ed., 2000,39,2707).Diatomite is the natural resource that a kind of distributed pole is wide, reserves are bigger, place's diatomite ore China has found 70 in 14 provinces (autonomous region) surplus, and 3.2 hundred million tons of proven reserve, prospective reserves is more than 1,000,000,000 tons.At present, diatomite mainly is used to flocculating aids, lagging material and support of the catalyst.How utilizing diatomite to prepare the zeolitic material of hierarchical porous structure, is the problem that this area research personnel pay close attention to.
Summary of the invention
The objective of the invention is to find a kind of novel method of synthetic multi-stage artery structure zeolitic material of simple and easy to control, economical rationality.
The method for preparing the multi-stage artery structure zeolitic material involved in the present invention is as follows:
1. the synthetic zeolite crystallite is dispersed in and forms boiling of desired concn and pH value in the salts solutions such as water or sodium-chlor
Stone colloidal solution;
2. pre-treatment is carried out on the diatomite surface, treatment process is at 0.1～5% polyelectrolyte solution with diatomite
Soaked 5 minutes～1 hour, and cleaned 1～6 time with distilled water then, make diatomite table after the modification
Wear electric charge;
3. diatomite in 2 is soaked the deposition regular hour in the zeolite glue of desired concn, take out with distillation
Water or weak acid or weak alkaline aqueous solution washing 1～10 time are alternately adsorbed polyelectrolyte then and nanometer is boiled
The stone colloid is to desired thickness;
With the product that obtains in 3 in the atmosphere of not corroding diatomite matrix through calcination process or without roasting
Burn to handle and get final product; Perhaps under the steam effect of the ammoniacal liquor of certain temperature and pressure or organic amine and water, locate
After the reason regular hour, take out with distilled water wash and dry;
5. the product that obtains in 3 or 4 is dried back roasting in the atmosphere of not corroding diatomite matrix, obtain many
The zeolitic material of level pore passage structure.
Wherein in 1 said zeolite glue micelle size between 1 nanometer to 2 micrometer range, concentration between 0.05～20%, the pH value between 1～14, salt concn 0～5M.
Polyelectrolyte can be polycation electrolyte or polyanion electrolyte in 2, can positively charged after the diatomite modification, and also can be electronegative.
3 mesolite colloids can be used surperficial positively charged, also can be with electronegative zeolites, and per deposition process time in step is 1 second to 20 hours.
Organic amine can be primary amine (C in 4
nH
2n+1NH
2, n=0～5), secondary amine (C
nH
2n+1C
mH
2m+1NH, n, m=0～5), tertiary amine (C
nH
2n+1C
mH
2m+1C
iH
2i+1N, n, m, i=0～5) and diamines in one or more mixture, and can be recycled.Maturing temperature is 200～1000 ℃, and treatment temp is 100～240 ℃, and pressure is the power of boosting certainly under the treatment temp.Time at 1 hour between January.
Maturing temperature is 200-1000 ℃ in 5.Calcination atmosphere is nitrogen, argon gas, helium, oxygen, air, carbonic acid gas, total roasting time 1～50 hour.
Aforesaid method can be used for various types of zeolites, and gelatin concentration and pH value can be adjusted in a big way as required.
If will deposit good multistage pore canal zeolitic material further processing certain hour under the vapor action of the ammonia of certain temperature and pressure or organic amine and water, part diatomite is converted into zeolite, improve the product zeolite content, thus can be than the multistage pore canal zeolitic material of high zeolite content.Organic amine can be an ammonia, primary amine, and secondary amine, the mixture of one or more in tertiary amine or the diamines, and can be recycled.Treatment temp is 100～240 ℃, and pressure is the power of boosting certainly under the treatment temp.Time at 1 hour between January.Last in the atmosphere of not corroding diatomite matrix 200～1000 ℃ following roasting 1-50 hour.
The present invention's implementation condition preferably is:
Zeolite colloidal particle size is 5～1000 nanometers.
The concentration of zeolite colloidal particle is 0.1～10%.
The pH value of zeolite colloidal solution is 2～12.
Salt concn is 0.01～1M.Routine can be NaCl with salt, and is good and cheap.
Polycation electrolyte such as Poly Dimethyl Diallyl Ammonium Chloride, polyanion electrolyte is as poly-p-sulfonic acid base vinylbenzene.
The inventive method is applicable to various types of zeolites, and after deposition, multistage pore canal zeolite effect is good.
The inventive method is if deposit on the diatomite with two or more nano zeolites, and the multistage pore canal zeolitic material effect of its gained has also obtained satisfactory result.Promptly form by two or more nano zeolite glue alternating deposit.
Among the present invention if with further handling under the vapor action of ammonia or organic amine and water, used organic amine primary amine, secondary amine, tertiary amine is as follows:
C
nH
2n+1NH
2, n=0～5, as: Tri N-Propyl Amine, n-Butyl Amine 99;
C
nH
2n+1C
mH
2m+1NH, n, m=0～5, as: diethylamine, tripropyl amine;
C
nH
2n+1C
mH
2m+1C
iH
2i+1N, n, m, i=0～5, as: triethylamine.
100～240 ℃ of temperature that gas-solid of the present invention is handled mutually are for well.
The time range that gas-solid of the present invention is handled mutually is very wide, is advisable in the scope with 1 hour to 20 days.
The organic amine that gas-solid is handled mutually is a n-Butyl Amine 99, Tri N-Propyl Amine, quadrol, a kind of or their mixture in the triethylamine.
120～200 ℃ of the temperature that gas-solid is handled mutually.
1 hour～10 days time that gas-solid is handled mutually.Reasonable time can improve preparation efficiency.
Organic amine can be recycled during gas-solid was handled mutually, and preparation cost is descended greatly.
The maturing temperature of roasting process is 400～800 ℃, keeps in nitrogen or the inert gas atmosphere 0～12 hour, keeps in oxygen or the air atmosphere 1～8 hour.
Present method can prepare the zeolitic material of the multi-stage artery structure that contains various structures (as MFI, BEA, A, structures such as FAU).
The zeolitic material of the multi-stage artery structure that the inventive method obtains has high zeolite content and evenly abundant macroporous structure, therefore is expected in catalysis fields such as fractionation by adsorption performance important application.
By preparing the product of the present invention that various types of zeolite molecular sieves obtain, have a clear superiority at the like product than single zeolite molecular sieve aspect catalyzer, sorbent material, separating agent and the water treatment.
Above-mentioned condition had both improved preparation efficiency, had guaranteed quality product and yield rate again.
The zeolite that method provided by the present invention obtains is compared with other existing method, has the specific surface height that produces finished product, and the macropore pore passage structure is regular, and zeolite content is adjustable, the characteristics that zeolite type can be controlled in advance.Layer laminate of the present invention and gas-solid phase crystallization method are implemented convenient and simple, and be less demanding to instrument, and deposition process is easy to outside regulation and control.And gas-solid phase rotating crystal method can be converted into zeolite with unbodied silicon-dioxide under the condition of not destroying the diatomite appearance structure, and this method is that an eco-friendly mode is hopeful to be used to prepare the composite zeolite material that has wide application prospects in catalysis, separation industries
Following example will be described further method of coming zeolitization diatomite to prepare the new zeolite material of multi-stage artery structure with the gentle solid phase commentaries on classics of layer laminate crystal technique provided by the invention.Part photo in the example is listed in the Figure of description.
Description of drawings
Fig. 1 is the SEM photo (insertion portion is the SEM photo of high multiple among the figure) of diatomite background.
Fig. 2 is a product A
6The SEM photo.
Fig. 3 is a product A
16The SEM photo.
Fig. 4 is a product A
14The SEM photo.
Fig. 5 is a products C
1The SEM photo.
Fig. 6 is a products C
8The SEM photo.
Fig. 7 is product D
2The SEM photo.
Fig. 8 is the XRD figure spectrum of diatomite substrate and portioned product; A is the XRD figure spectrum of diatomite substrate, and b is a product B
1XRD figure spectrum, c is a product B
3XRD figure spectrum, d is a products C
1XRD figure spectrum, e is a products C
8XRD figure spectrum.
Fig. 9 is the IR collection of illustrative plates of diatomite substrate and portioned product; A is the IR collection of illustrative plates of diatomite substrate, and b is a product B
1The IR collection of illustrative plates, c is a product B
2The IR collection of illustrative plates, d is a product B
3The IR collection of illustrative plates, e is a products C
1The IR collection of illustrative plates, f is a products C
8The IR collection of illustrative plates, g is the IR collection of illustrative plates of nano zeolite.
Figure 10 is the nitrogen adsorption curve collection of illustrative plates of diatomite substrate and portioned product; A is the nitrogen adsorption curve collection of illustrative plates of diatomite substrate, and b is a product B
1Nitrogen adsorption curve collection of illustrative plates, c is a products C
1Nitrogen adsorption curve collection of illustrative plates, d is a products C
8Nitrogen adsorption curve collection of illustrative plates.
Embodiment
Example 1
Tetraethoxy-silicane, TPAOH and distilled water are mixed according to 25: 9: 480 mole proportioning, vigorous stirring is 1 day under the room temperature, in the 373K oil bath backflow 18-72 hour, obtain nanometer silicalite-1 (MFI skeleton structure) zeolite glue, again with the colloid centrifugation repeatedly that obtains, again be dispersed in the distilled water after the washing, obtain pH and be about 9.5, mass percent is 1% silicalite-1 zeolite glue.Earlier pre-treatment is carried out on the diatomite surface before the deposition zeolite, method is that diatomite was soaked 20 minutes in concentration is the solution of 0.5% polycation electrolyte Poly Dimethyl Diallyl Ammonium Chloride, clean 4 times with distilled water then, make the diatomite surface lotus that becomes positively charged, the diatomite of surperficial lotus positive electricity was soaked 20 minutes in the zeolite glue, taking-up is washed 4 times with the ammonia soln of pH value about 9.5, and room temperature is dried and promptly obtained the layer laminate multi-stage artery structure nano zeolite sample A that diatomite is substrate
1
Example 2-4
Carry out the layer laminate experiment with the method identical, but the mass percent concentration of zeolite colloidal solution is carried out modulation, use 0.1%, 0.5%, 6% silicalite-1 zeolite glue respectively with example 1; Having obtained diatomite is the layer laminate multi-stage artery structure nano zeolite sample of substrate, is designated as A respectively
2, A
3, A
4
Example 5-7
Carry out the layer laminate experiment with the method identical with example 3, but the salt concn of zeolite colloidal solution is carried out modulation, the salt concn of zeolite glue is respectively 0.01M, when 0.1M and 0.5M; Having obtained diatomite is the layer laminate multi-stage artery structure nano zeolite sample of substrate, is designated as A respectively
5, A
6, A
7
Example 8-11
Carrying out the layer laminate experiment with the method identical with example 6, but the pH value of zeolite colloidal solution is carried out modulation, is respectively 1,4,7 and 12 silicalite-1 zeolite glue with the pH value; Having obtained diatomite is the layer laminate multi-stage artery structure nano zeolite sample of substrate, is designated as A respectively
8, A
9, A
10, A
11
Example 12-14
Carrying out the layer laminate experiment with the method identical with example 6, but use the zeolite of different-grain diameter to be building block, is 60nm with particle diameter respectively, the silicalite-1 zeolite glue of 150nm and 300nm; Having obtained diatomite is the layer laminate multi-stage artery structure nano zeolite sample of substrate, is designated as A respectively
12, A
13, A
14
Example 15-18
Carry out the layer laminate experiment with the method identical with example 6, but the thickness to the deposition zeolite membrane is regulated and control, alternately adsorb the zeolite membrane that polycation electrolyte and nano zeolite colloidal cycle index obtain different thickness by changing, through 2,3, it is the layer laminate multi-stage artery structure nano zeolite sample of substrate that 5,10 sorption cycle have obtained diatomite, is designated as A respectively
15, A
16, A
17, A
18
Example 19
Carry out the layer laminate experiment with the method identical, but select for use polyanion electrolyte to gather p-sulfonic acid base vinylbenzene in the experimentation with example 6; Having obtained diatomite is the layer laminate multi-stage artery structure nano zeolite sample of substrate, is designated as A
19
Example 20-21
Carrying out the layer laminate experiment with the method identical with example 19, but the pH value of zeolite colloidal solution is carried out modulation, is respectively 1 and 4 silicalite-1 zeolite glue with the pH value; Having obtained diatomite is the layer laminate multi-stage artery structure nano zeolite sample of substrate, is designated as A respectively
20, A
21
Example 22-27
Carry out the layer laminate experiment with the method identical, but change the type of employed nano zeolite, by ZSM-5 with example 6, TS-1, Beta, A, type such as X and Y nano zeolite is a building block, and having obtained diatomite is the layer laminate multi-stage artery structure nano zeolite sample of substrate, is designated as A respectively
22, A
23, A
24, A
25, A
26, A
27
Example 28
Carry out the layer laminate experiment with the method identical with example 6, but alternately change the type of employed nano zeolite, by silicalite-1 and the alternately absorption of beta nano zeolite, the diatomite that has obtained is the layer laminate multi-stage artery structure composite Nano zeolite Silicalite-1/Beta sample of substrate, is designated as A
28
Example 29
With example 6 resulting sample A
6Roasting is warming up to 550 ℃ with 5 ℃/minute temperature programming speed, logical nitrogen 8 hours, and organic molecule is removed in roasting 6 hours in oxygen atmosphere under the uniform temp then, and having obtained diatomite is the layer laminate multi-stage artery structure nano zeolite sample of substrate, is designated as B
1
Example 30-31
By the method roasting identical with example 29, but the sample of institute's roasting changes A into
15, A
16, obtain the zeolitic material that diatomite is the multi-stage artery structure of substrate, be designated as respectively and be designated as B respectively
2And B
3
Example 32-33
By the method roasting identical with example 29, but changing ventilating mode is direct aerating oxygen, and maturing temperature becomes 350 ℃ and 750 ℃, and roasting time was respectively 40 hours and 1 hour, having obtained diatomite is the layer laminate multi-stage artery structure nano zeolite sample of substrate, is designated as B respectively
4And B
5
Example 34
With 0.2 gram sample B
1Place reactor porous plate top.Inject 2 gram quadrols with syringe to the reactor bottom, the mixture of triethylamine and distilled water (mol ratio is 2: 9: 6) was 180 ℃ of following crystallization 5 days, taking-up with distilled water wash after room temperature dry, be warming up to 550 ℃ with 5 ℃/minute temperature programming speed, logical nitrogen 8 hours, roasting 6 hours in oxygen atmosphere under the uniform temp then, the zeolitic material C of brilliant multi-stage artery structure is changeed in the gas-solid that promptly obtains diatomite and be substrate mutually
1
Example 35-38
Experimentize with the method identical, but change crystallization temperature with example 34, at 140 ℃, 160 ℃, 180 ℃ and 200 ℃ of crystallization, the zeolitic material of brilliant multi-stage artery structure is changeed in the gas-solid that obtains diatomite and be substrate mutually, is designated as C respectively
2, C
3, C
4, C
5
Example 39-42
Experimentize with the method identical, but change crystallization time with example 34, through 1 day, 3 days, 10 days and 20 days crystallization, the zeolitic material of brilliant multi-stage artery structure is changeed in the gas-solid that obtains diatomite and be substrate mutually, is designated as C respectively
6, C
7, C
8, C
9
Example 43-45
Experimentize with the method identical, but change the amount of used organic amine mixture, add 0.5 gram with example 34,1 gram, 4 gram organic amine mixture, the zeolitic material of brilliant multi-stage artery structure is changeed in the gas-solid that obtains diatomite and be substrate mutually, is designated as C respectively
10, C
11, C
12
Example 46-50
Experimentize with the method identical with example 34, but change the mole proportioning of used organic amine, change the mixture quadrol, the mol ratio of triethylamine and distilled water is 1: 0: 3,1: 0: 6, and 6: 0: 1,1: 9: 6,0: 9: 6, the zeolitic material of brilliant multi-stage artery structure was changeed in the gas-solid that obtains diatomite and be substrate mutually, is designated as C respectively
13, C
14, C
15, C
16, C
17
Example 51-53
Experimentize with the method identical, but change the kind of used organic amine, the triethylamine in the mixture is replaced with ammonia with example 34, butylamine or Tri N-Propyl Amine, the zeolitic material of brilliant multi-stage artery structure is changeed in the gas-solid that obtains diatomite and be substrate mutually, is designated as C respectively
18, C
19, C
20
Example 54-56
Experimentize with the method identical, but change the kind of used organic amine, the quadrol in the mixture is replaced with ammonia with example 34, butylamine or Tri N-Propyl Amine, the zeolitic material of brilliant multi-stage artery structure is changeed in the gas-solid that obtains diatomite and be substrate mutually, is designated as C respectively
21, C
22, C
23
Example 57
With example 34 resulting sample C
1, (120W, 50kHz) ultrasonic 10 minutes, 30 minutes, 60 minutes, the zeolitic material of brilliant multi-stage artery structure was changeed in the gas-solid that obtains diatomite and be substrate mutually, is designated as D respectively under the ultrasonic wave effect
1, D
2, D
3.
Example 58
With 0.2 gram sample A
6Place reactor porous plate top.Inject 2 gram quadrols with syringe to the reactor bottom, the mixture of triethylamine and distilled water (mol ratio is 2: 9: 6) was 180 ℃ of following crystallization 5 days, taking-up with distilled water wash after room temperature dry, be warming up to 550 ℃ with 5 ℃/minute temperature programming speed, logical nitrogen 8 hours, roasting 6 hours in oxygen atmosphere under the uniform temp then, the zeolitic material C of brilliant multi-stage artery structure is changeed in the gas-solid that obtains diatomite and be substrate mutually
24
Example 59-61
Organic amine after crystallization in the example 34 handled is recycled, and other condition is used respectively through 1 time with example 34, and it is that the zeolitic material that brilliant multi-stage artery structure is changeed in the gas-solid of substrate mutually is designated as C respectively that the organic amine after recycling for 2 times and 3 times obtains diatomite
25, C
26, C
27
Example 62-64
Experimentize with the method identical, but the sample of institute's crystallization changes A into example 32
15, A
16, the zeolitic material of brilliant multi-stage artery structure is changeed in the gas-solid that obtains diatomite and be substrate mutually, is designated as C respectively
28, C
29, C
30
Example 65
The SEM photo of the said products absorbs on Philips XL30 D6716 instrument, Fig. 2-the 7th, and the electromicroscopic photograph of sample segment, the electromicroscopic photograph of all the other samples is similarly; The XRD spectrum of sample records (see figure 8) on Rigaku D/max-IIA type X-ray diffractometer; The infrared spectra of sample records on Magna 550 infrared spectrometers; With Micromeritics ASAP-2000 physical adsorption appearance measurement the specific area.From electromicroscopic photograph as can be seen, layer laminate method of the present invention can prepared zeolite membrane fast in the diatomite substrate under the more convenient condition, it evenly reaches the concentration of compactness extent and zeolite deposit fluid, the pH value, the factors such as size of salt concn and zeolite particles are relevant, wherein the concentration at deposit fluid is 0.5%, 1%, pH is 9.5,11, salt concn is 0.1M, and the size of zeolite particles is in that can to obtain the zeolite coating in the diatomite substrate under the condition of 20～150nm even, complete, fine and close zeolite membrane (seeing Fig. 2-7).In Fig. 8, along with the increase of zeolite adsorption cycle index, the characteristic peak of the XRD diffraction pattern mesolite of product constantly strengthens.550cm in infrared spectra
-1The characteristic peak that the place belongs to the MFI structural zeolite also constantly strengthens (see figure 9) along with the increase of zeolite adsorption cycle index.This appendix amount that has proved zeolite particles can be controlled by the zeolite adsorption cycle index.This method also has the advantage of universality, can be applied to the metal and the oxide colloid of various types of zeolite colloids and other kind, and can also obtain the zeolite membrane of heterozygosis by alternately adsorbing different types of colloid.Gas-solid phase rotating crystal method can be under the condition of not destroying the diatomite appearance structure with diatomite in unbodied silicon-dioxide be converted into zeolite, compare with other existing method, have the specific surface height that produces finished product, the macropore pore passage structure is regular, the characteristics that zeolite content is adjustable.As can be seen from Figure 8, along with the increase of gas-solid phase crystallization time, the characteristic peak of the XRD diffraction pattern mesolite of product significantly strengthens.550cm in infrared spectra
-1The characteristic peak that the place belongs to the MFI structural zeolite also significantly strengthens (see figure 9) along with the prolongation of crystallization time.As can be seen from Figure 10, along with the increase of gas-solid phase crystallization time, the nitrogen adsorption amount of sample obviously improves.The sample specific surface of handling through 10 days and 5 days crystallization can reach 210m respectively
2g
-1And 119m
2g
-2, and undressed diatomite specific surface only is 8m
2g
-1About.The product mechanical stability that this method makes is fine, through after the ultrasonication, does not find coming off of zeolite.In addition, this method still is an eco-friendly mode, is hopeful to be used to prepare the composite zeolite material that has wide application prospects in catalysis, separation industries.
Claims (19)
1. the method for a preparing zeolite material with multi-class pore canal by zeolitizing diatomite, it is characterized in that the nano zeolite glue as the absorption deposit fluid, diatomite is as matrix, and carry out pre-treatment, utilize the electrostatic attraction between nano zeolite and the polyelectrolyte, nano zeolite is deposited on the diatomite matrix in the layer laminate mode, the gelatin concentration that nano zeolite is dispersed in the water is 0.05～20% (wt%), pH is 1～14, salt concn is 0～5M, and 200～1000 ℃ of roastings can prepare the multi-stage artery structure zeolitic material in the atmosphere of not corroding diatomite matrix.
2. the method for preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 1, it is characterized in that depositing the back handles under the steam effect of the ammonia of certain temperature and pressure or organic amine and water, organic amine is a primary amine, secondary amine, the mixture of one or more in tertiary amine or the diamines, treatment temp is 100～240 ℃, pressure is the power of boosting certainly under the treatment temp, time 1 hour between January, last in the atmosphere of not corroding diatomite matrix 200～1000 ℃ of roastings can prepare the multi-stage artery structure zeolitic material.
3. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 1 is characterized in that the zeolite grain size is 5～1000 nanometers.
4. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 1 is characterized in that zeolite grain dispersive gelatin concentration is 0.1～10%.
5. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 1 is characterized in that the pH value of nano zeolite glue is 2～12.
6. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 1 is characterized in that nano zeolite glue salt concn is 0.01～1M.
7. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 1 is characterized in that polyelectrolyte can be polycation dielectric medium or polyanion dielectric medium.
8. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 7 is characterized in that polycation electrolyte is a Poly Dimethyl Diallyl Ammonium Chloride, and polyanion electrolyte is poly-p-sulfonic acid base vinylbenzene.
9. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 1 is characterized in that this method is applicable to various types of zeolites.
10. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 1 is characterized in that nano zeolite can be two or more.
11. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 2 is characterized in that organic amine is a primary amine, secondary amine, and tertiary amine is:
C
nH
2n+1NH
2，n＝0～5；
C
nH
2n+1C
mH
2m+1NH，n，m＝0～5；
C
nH
2n+1C
mH
2m+1C
iH
2i+1N，n，m，i＝0～5。
12. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 2 is characterized in that the temperature that the gas-solid of ammonia or organic amine and water is handled mutually is 100～240 ℃.
13. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 2 is characterized in that time that gas-solid handles mutually is between 1 hour to 20 days.
14. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 2, it is characterized in that gas-solid handle mutually in organic amine can be ammonia, n-Butyl Amine 99, Tri N-Propyl Amine, quadrol, the mixture of one or more in the triethylamine.
15. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 2 is characterized in that the temperature that gas-solid is handled mutually is 120-200 ℃.
16. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 2 is characterized in that 1 hour-10 days time that gas-solid is handled mutually.
17. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 2, it is characterized in that gas-solid handle mutually in organic amine be to recycle.
18. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 1 and 2, it is characterized in that maturing temperature is 400～800 ℃, in not corroding the fibre substrate gas atmosphere, kept 0～12 hour, and perhaps kept in oxygen or the air 1～8 hour.
19. the method for a kind of preparing zeolite material with multi-class pore canal by zeolitizing diatomite according to claim 1 and 2 is characterized in that the multi-stage artery structure zeolitic material that this method makes is used for catalyzer or sorbent material or separating agent.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325375C (en) * | 2004-10-29 | 2007-07-11 | 中国石油化工股份有限公司 | Beta zeolite granule possessing multiple grade pore passage and its preparation method |
| CN102553631A (en) * | 2010-12-23 | 2012-07-11 | 中国石油天然气股份有限公司 | Preparation method of in-situ crystallization type catalytic cracking catalyst |
| CN102989500A (en) * | 2011-09-14 | 2013-03-27 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking cocatalyst |
| CN103084144A (en) * | 2013-02-06 | 2013-05-08 | 中国科学院广州地球化学研究所 | Diatomite-based porous composite material for adsorbing volatile organic pollutants and preparation method thereof |
| CN103252258A (en) * | 2012-02-16 | 2013-08-21 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN103771439A (en) * | 2014-01-04 | 2014-05-07 | 吉林化工学院 | Method for preparing Beta zeolite molecular sieve from diatomite |
| CN107511140A (en) * | 2017-10-09 | 2017-12-26 | 常州建轩纺织品有限公司 | A kind of preparation method of high dephosphorization amount diatomite adsorbing material |
| CN109503137A (en) * | 2018-10-29 | 2019-03-22 | 裴文韬 | A kind of preparation method of the ecological ceramic brick with humidity conditioning function |
| CN109942274A (en) * | 2019-03-11 | 2019-06-28 | 昆明理工大学 | A method of using red mud and coal ash for manufacturing for multi-stage porous haydite |
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2001
- 2001-09-24 CN CN 01126842 patent/CN1226096C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1325375C (en) * | 2004-10-29 | 2007-07-11 | 中国石油化工股份有限公司 | Beta zeolite granule possessing multiple grade pore passage and its preparation method |
| CN102553631A (en) * | 2010-12-23 | 2012-07-11 | 中国石油天然气股份有限公司 | Preparation method of in-situ crystallization type catalytic cracking catalyst |
| CN102553631B (en) * | 2010-12-23 | 2014-06-04 | 中国石油天然气股份有限公司 | Preparation method of in-situ crystallization type catalytic cracking catalyst |
| CN102989500A (en) * | 2011-09-14 | 2013-03-27 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking cocatalyst |
| CN103252258A (en) * | 2012-02-16 | 2013-08-21 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN103252258B (en) * | 2012-02-16 | 2015-05-27 | 中国石油天然气股份有限公司 | Preparation method of catalytic cracking catalyst |
| CN103084144A (en) * | 2013-02-06 | 2013-05-08 | 中国科学院广州地球化学研究所 | Diatomite-based porous composite material for adsorbing volatile organic pollutants and preparation method thereof |
| CN103084144B (en) * | 2013-02-06 | 2014-11-05 | 中国科学院广州地球化学研究所 | Diatomite-based porous composite material for adsorbing volatile organic pollutants and preparation method thereof |
| CN103771439A (en) * | 2014-01-04 | 2014-05-07 | 吉林化工学院 | Method for preparing Beta zeolite molecular sieve from diatomite |
| CN107511140A (en) * | 2017-10-09 | 2017-12-26 | 常州建轩纺织品有限公司 | A kind of preparation method of high dephosphorization amount diatomite adsorbing material |
| CN109503137A (en) * | 2018-10-29 | 2019-03-22 | 裴文韬 | A kind of preparation method of the ecological ceramic brick with humidity conditioning function |
| CN109942274A (en) * | 2019-03-11 | 2019-06-28 | 昆明理工大学 | A method of using red mud and coal ash for manufacturing for multi-stage porous haydite |
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