CN1321890C - Preparation method of L zeolite with high silicon aluminum ratio - Google Patents
Preparation method of L zeolite with high silicon aluminum ratio Download PDFInfo
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- CN1321890C CN1321890C CNB2004100086583A CN200410008658A CN1321890C CN 1321890 C CN1321890 C CN 1321890C CN B2004100086583 A CNB2004100086583 A CN B2004100086583A CN 200410008658 A CN200410008658 A CN 200410008658A CN 1321890 C CN1321890 C CN 1321890C
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Abstract
The present invention relates to a method for preparing L zeolite with a high silicon aluminum ratio. In the method, KL zeolite forms NH4L zeolite through ammonium ion exchange at the exchange degree more than 90%, multiple-silicon acid gelatin prepared from solid Na2SiO3.9H2O as a raw material is used as a silicon source and mixed with the NH4L zeolite and reacts for 2 to 5 hours at 500 to 800 DEG C under the steam condition for hydrothermal dealuminization and stabilization treatment of silicon complementation, and then L zeolite with high silicon aluminum ratio is prepared. The multiple-silicon acid gelatin has strong capability of transferring silicon to the aluminum vacancy of a zeolite framework in the process of hydrothermal dealuminization of the zeolite. The high-silicon L zeolite has the advantages of high crystallization reserving level, good hydrothermal stability, simple preparation process, easy acquirement of raw materials and no environmental pollution; the silica alumina ratio of the L zeolite framework is enhanced to 11 to 20 from 5.2 to 6.5 of KL initial powder, and the crystallization reserving level of the zeolite is from 75% to 85% after the zeolite is hydrothermally treated.
Description
Technical field
The present invention relates to a kind of preparation method of catalytic material, especially a kind of high silica alumina ratio L prepare zeolite method belongs to the chemical industry technical field.
Background technology
The L zeolite is a kind of artificial synthetic zeolite who does not find at occurring in nature as yet so far, and is synthetic with classical hydrothermal crystallization method first in nineteen sixty-five by Breck and Acara.The typical chemical constitution of L zeolite is K
9[(AlO
2)
9(SiO
2)
27] 21H
2O belongs to hexagonal system, and its basic structural unit is the cancrinite cage, framework si-al ratio (mol ratio) SiO of synthetic L zeolite
2/ Al
2O
3=5.2-7.0.The L zeolite has high thermostability and hydrothermal stability, uses increasingly important status in Hydrocarban coversion catalysts, as can be used as active ingredient or substrate material in catalyzer such as reformation, aromizing, isomerization, hydrofining, dehydrocyclization.
Because the restriction of L zeolite crystal structure, the silica alumina ratio lower (5.2-7.0) of synthetic L zeolite, but (as catalytic cracking of hydrocarbon, oil hydrogenation refining etc.) must use the L zeolite of high silica alumina ratio in some catalyzed reaction, with acidity, stability and the catalytic performance of modulation zeolite.
The prior art that improves L zeolite silica alumina ratio at present adopts hydrothermal dealumination and chemical dealuminization method, and the subject matter that the former exists is L crystallization of zeolites reservation degree low (only 30-40%).Reported in literature (NH
4)
2SiF
6And SiCl
4Behind the chemical dealuminization, the settling of the part duct of zeolite after by chemical reaction stops up, and zeolite adsorption ability and catalytic capability significantly descend.
Existing domestic and international technology about the L zeolite synthesis all adopts hydrothermal synthesis method, include direct synthesis technique, seed technology method and template agent method (USP 3216789, CN 85103013B, USP 2711565, EP 0220881 etc.), the silica alumina ratio of gained L zeolite powder is only at 5-7.Silica alumina ratio during USP 4701315 and CN85103013B patent report raising synthetic system feed intake, feed ratio (mol ratio) is respectively 8K
2O: Al
2O
3: 10SiO
2: 500H
2O and 6.6K
2O: Al
2O
3: 28SiO
2: 440H
2O, in autoclave pressure 100 ℃ crystallization 60-72 hour, gained L zeolite silica alumina ratio is 5.0-5.6, adopts this method poor effect.USP 4888105 has described and has used L zeolite itself as crystal seed, and cooperates tetraalkylammonium cation to make template, at reaction mixture SiO
2/ Al
2O
3=6-30, crystal seed dosage are SiO
210% of charging capacity (butt), the silica alumina ratio of synthetic L zeolite still is 5.0-5.6, other adopts directing agent method and the synthetic L zeolite (as CN 1023639C, EP 0220881) of pyroprocess can shorten crystallization time in addition, still can not improve the silica alumina ratio of L zeolite.
The existing technology that improves L zeolite silica alumina ratio is with the former powder of L zeolite after treatment, carries out dealumination process, can improve the silica alumina ratio of L zeolite, and dealumination process has chemical dealuminization and hydrothermal dealumination.Reatz etc. (USP 4909924) Hydrothermal Preparation dealuminzation L zeolite, the silica alumina ratio of L zeolite can be brought up to 7-8, but the crystallization reservation degree of L zeolite only is 30%.P.Bartl, W.F.Holderich (Microporousand Mesoporous Materials, 38 (2000) 279-286) adopts hydrothermal dealumination, (NH to the L zeolite powder
4)
2SiF
6And SiCl
4Dealumination process, hydrothermal dealumination dealuminzation L zeolite silica alumina ratio under optimal conditions is 8-10, but crystallization reservation degree only 37% adopts (NH
4)
2SiF
6Dealuminzation, L zeolite silica alumina ratio is 9.0 under the optimal conditions, crystallization reservation degree 76% changes (NH
4)
2SiF
6Consumption, L zeolite silica alumina ratio can reach 12.9, but crystallization reservation degree only 10%.Adopt SiCl
4The gas phase dealuminzation, silica alumina ratio can be brought up to 8-12, but zeolite to N2 adsorptive power drop by half about because the amorphous silicon aluminum oxide that generates in the reaction stops up zeolite cavity, if zeolite washs the settling of removing in the duct through sour water, can cause zeolite structured caving in.CN1121484A " a kind of preparation method of supersiliceous zeolite " (research institute of China Oil Chemical General Co.,Ltd. Oil Chemical) is to be raw material with NaY zeolite or ZSM-5 zeolite, after ammonium ion exchange and high-temperature roasting, but get HNaY HZSM-5 zeolite, mixing solutions at liquid phase and single silicic acid and mineral acid reacted 0.5-1.0 hour at 30-70 ℃, in the zeolite dealumination process, mend silicon, the type-Y high silicon zeolite lattice constant that makes is minimum to be 2.454nm, corresponding skeleton SiO
2/ Al
2O
3Be 9.86, degree of crystallinity reservation degree reaches more than 90%.After 4 hours, crystallization reservation degree is 57-68% to the high-silicon Y-Zeolite that this invention makes through 800 ℃, 100% steam aging.This patent is primarily aimed at y-type zeolite, does not relate to the L zeolite.
Summary of the invention
Technical problem to be solved by this invention is at the deficiencies in the prior art, a kind of new preparation process of high silica alumina ratio L zeolite is provided, in L zeolite system, add the poly silicic acid gel, carry out hydrothermal dealumination and mend the stabilization treatment of silicon, obtain the L zeolite of high silica alumina ratio, high-crystallinity and high hydrothermal stability.
Technical problem solved by the invention is achieved by the following technical solution:
A kind of high silica alumina ratio L prepare zeolite method, this method may further comprise the steps:
Step 1: get KOH, stirring and dissolving forms the aqueous solution in water, add Al (OH)
3Powder makes working fluid, after the cooling working fluid is added in the silicon sol, stirs into uniform silicoaluminate gelling system, adds the L zeolite powder again as crystal seed, and crystallization, washing, filtration, oven dry make potassium L zeolite, that is: the KL zeolite;
Step 2: with Na
2SiO
39H
2O is dissolved in the water, and successively passes through 10%H
2SO
4Solution and 15%NaOH solution regulator solution pH value, and it is carried out stabilization treatment, wash and suction filtration with deionized water, remove sodium ion, preparation poly silicic acid gel;
Step 3: with KL zeolite powder and NH
4 +Carry out once above exchange, through washing, filtration and oven dry preparation NH
4The L zeolite;
Step 4: carrying out dealuminzation or adopt the poly silicic acid gel of step 2 preparation to carry out the dealumination complement silicon reaction under water vapor condition, preparation generates the L zeolite of high silica alumina ratio.
Wherein said step 1 specifically comprises:
Step 11: get KOH, soluble in water, stirring and dissolving, forming concentration is the solution of 5-15%;
Step 12: add Al (OH)
3Powder is that dissolved solids makes working fluid under 100 ℃ the condition in temperature, and its concentration is 4-32%;
Step 13: to be cooled to 40-50 ℃, working fluid is joined in the silicon sol, stir into uniform silicoaluminate gelling system, add the L zeolite powder again as crystal seed, crystal seed dosage and SiO
2Mass ratio be 1～3%, add the water silicon ratio of water management synthetic system, the composition that this synthetic system is respectively thrown material is calculated in molar ratio as: SiO
2/ Al
2O
3=8～20, K
2O/SiO
2=0.1～0.35, H
2O/SiO
2=10～40;
Step 14: the material that stirs is transferred in the autoclave, 100～170 ℃ of crystallization 20～72 hours.The crystallization product that obtains is washed, is filtered to filtrate pH=8,, promptly get the L zeolite powder, be the KL zeolite, SiO 110 ℃ of oven dry
2/ Al
2O
3=5.2～7.0, relative crystallinity is 75～100%, and relative crystallinity can reach 100% under optimal conditions.
Described step 2 specifically comprises:
Step 21: with solid Na
2SiO
39H
2O is dissolved in the water, SiO in the solution
2Be 2.5～8.7 grams/100 ml waters, in constantly stirring, drip 10%H
2SO
4Solution makes pH=1.0-3.0;
Step 22: regulate pH=9-10 with 15%NaOH solution again, generate the flocculence silicic acid gel;
Step 23: under 60-80 ℃ of condition gel was carried out stabilization treatment 0.5-1.0 hour, wash and suction filtration with deionized water, remove sodium ion, making water content is the poly silicic acid gel of 80-90%.
Described step 3 specifically comprises:
Step 31: the KL zeolite powder is carried out continuous quadratic NH
4 +Exchange, consumption is 1N NH
490-95 ℃ of exchange 1 hour, washing, filter and oven dry Cl/L zeolite=4～14 milliliter/gram, and roastings are 2～5 hours in the middle of 300～450 ℃;
Step 32: carry out secondary NH again
4 +Exchange, the exchange consumption is identical with step 31 with condition, through washing, filter and be dried into NH
4The L zeolite, KL zeolite K
2O content is 14～17 weight %, the K of product after secondary exchange and bakes to burn the article
2O content is 0.7～1.0%, and the K ion-exchange degree is more than 90%.
Dealuminzation in the described step 4 specifically comprises the steps:
Step 401: get SiO
2/ Al
2O
3=5.2～7.0 NH
4The L zeolite adds deionized water and is mixed into wetting attitude zeolite, in the dislocation crucible, compresses material;
Step 402: at the dealuminzation that under water vapor condition, carries out zeolite, be warming up to 650～800 ℃, reacted 2～6 hours, be prepared into the L zeolite of high silica alumina ratio, zeolite framework SiO with 5～10 ℃ of/minute intensification speed
2/ Al
2O
3=9～11, relative crystallinity 70～75%, crystallization reservation degree 70～75%.
The dealumination complement silicon of described step 4 specifically comprises the steps:
Step 411: get NH
4The L zeolite adds and contains SiO
2Silicic acid gel, water content is 90%, adds deionized water and is mixed into wetting attitude zeolite, in the dislocation crucible, compresses material;
Step 412: at hydrothermal dealumination that under water vapor condition, carries out zeolite and benefit pasc reaction, be warming up to 650～800 ℃, reacted 4 hours, be prepared into the L zeolite of high silica alumina ratio, zeolite framework SiO with 5～10 ℃ of/minute intensification speed
2/ Al
2O
3=11～12.5, relative crystallinity 70～78%, crystallization reservation degree 75～80%.
In sum, the present invention is different from prior art both domestic and external, and its principal character and advantage are:
1, adopts homemade activated silica source, a kind of poly silicic acid gel is introduced in the L zeolite system, carry out the stabilization treatment of hydrothermal dealumination, make in dealumination process, reduce dealuminzation speed, improve and mend silicon speed, make dealuminzation and mend silicon to reach certain balance, thereby can when improving the zeolite silica alumina ratio, keep higher zeolite crystallinity and stability.
2, the prepared activated silica source of the present invention is a kind of poly silicic acid gel through purifying of nascent state, and in the hydrothermal dealumination process, the silicon transfer ability is strong, and the preparation method is simple.
3, the present invention is raw material with the potassium type L zeolite, passes through NH
4 +After the exchange, directly add the activated silica source, carrying out stabilization treatment under water vapor condition, obtain the high silicon L zeolite of excellent property, all technology is simple, and good reproducibility is free from environmental pollution.
Description of drawings
Fig. 1 is preparation method's technology main-process stream synoptic diagram of the present invention;
Fig. 2 is the process flow diagram of step 1 of the present invention;
Fig. 3 is the process flow diagram of step 2 of the present invention;
Fig. 4 is the process flow diagram of step 3 of the present invention;
Fig. 5 is the process flow diagram of step 4 of the present invention;
Fig. 6 is X-ray diffraction (XRD) spectrogram (SiO of L zeolite standard specimen
2/ Al
2O
3=6.98, relative crystallinity 100%);
Fig. 7 is X-ray diffraction (XRD) spectrogram (SiO of the high silicon L of the present invention zeolite
2/ Al
2O
3=11.6, relative crystallinity 76.1%).
Embodiment
Below in conjunction with the drawings and specific embodiments technical scheme of the present invention is described in detail.
As shown in Figure 1, be preparation method's technology main-process stream synoptic diagram of the present invention, as can be known from Fig. 1, the present invention is a kind of high silica alumina ratio L prepare zeolite method, and this method may further comprise the steps:
Step 1: use SiO
2Content is 20～40 weight %, Na
2O content is that the silicon sol of 0.1～0.3 weight % is the silicon source, Al (OH)
3Be the aluminium source, KOH is an alkali source, preparation KL zeolite;
Step 2: with Na
2SiO
39H
2O is dissolved in the water, and successively passes through 10%H
2SO
4Solution and 15%NaOH solution regulator solution pH value, and it is carried out stabilization treatment, wash and suction filtration with deionized water, remove sodium ion, preparation poly silicic acid gel;
Step 3: with KL zeolite powder and NH
4 +Carry out once above exchange, through washing, filtration and oven dry preparation NH
4The L zeolite;
Step 4: in dealuminzation that carries out zeolite under water vapor condition or dealumination complement silicon reaction, preparation generates the L zeolite of high silica alumina ratio.
Embodiment one:
As shown in Figure 2, be the process flow diagram of step 1 of the present invention.As can be seen from Figure 2, this preparation method's technological process is such:
Step 1: KL prepare zeolite: use SiO
2Content is 28.4 weight %, Na
2O content is that the silicon sol (Beijing Research Inst. of Aeronautic Material provides) of 0.2 weight % is silicon source, Al (OH)
3(Beijing Chemical Plant, chemical pure) is the aluminium source, and KOH (Beijing Chemical Plant, chemical pure, effective content ≮ 82%) is an alkali source.Take by weighing 47.89 gram KOH, be dissolved in the 250 gram water, after the stirring and dissolving, add 27.3 gram Al (OH)
3Powder, dissolved solids makes working fluid under little condition of boiling, and is to be cooled to 40-50 ℃, and working fluid is joined in the 370.2 gram silicon sol, stirs into uniform silicoaluminate gelling system, adds the L zeolite powder again as crystal seed (crystal seed dosage/SiO
2(mass ratio)=1～3%), add the water silicon ratio of water management synthetic system, the composition (meter in molar ratio) that this synthetic system is respectively thrown material is: SiO
2/ Al
2O
3=10, K
2O/SiO
2=0.20, H
2O/SiO
2=16.2.Then the material that stirs is transferred in the autoclave of 1 liter, 150 ℃ of crystallization 24 hours.The crystallization product that obtains is washed, is filtered to filtrate pH=8,, promptly get the L zeolite powder, SiO 110 ℃ of oven dry
2/ Al
2O
3=6.5, relative crystallinity is 94%.
As shown in Figure 3, be the process flow diagram of step 2 of the present invention, as can be known from Fig. 3:
Step 2: the preparation of poly silicic acid gel: with solid Na
2SiO
39H
2O 23.6 grams are dissolved in 50～175 ml waters SiO in the solution
2Be 5 grams/100 ml waters, in constantly stirring, drip 10%H
2SO
4Solution, make pH=1.0-3.0, regulate pH=9-10 with 15%NaOH solution again, generate the flocculence silicic acid gel, under 60-80 ℃ of condition, gel was carried out stabilization treatment 0.5-1.0 hour, wash and suction filtration with deionized water, remove sodium ion, making water content is the poly silicic acid gel of 80-90%.
As shown in Figure 4, be the process flow diagram of step 3 of the present invention, as can be known from Fig. 4:
Step 3: NH
4The L prepare zeolite: the KL zeolite powder connects the secondary NH that continues
4 +Exchange, consumption is 1N NH
490-95 ℃ of exchange 1 hour, washing, filter and oven dry Cl/L zeolite=8 milliliter/gram, and roastings are carried out secondary NH after 3 hours again in the middle of 450 ℃
4 +Exchange, exchange consumption and condition are the same, through washing, filter and be dried into NH
4The L zeolite.KL zeolite K
2O content is 16.4 weight %, hands over a roasting two to hand over the K of after product through two
2O content is 1%, and the K ion-exchange degree reaches 94%.NH
4The relative crystallinity of L zeolite is consistent with the KL zeolite powder to be 94%, NH
4The L zeolite carries out hydrothermal dealumination can improve silica alumina ratio.
As shown in Figure 5, be the process flow diagram of step 2 of the present invention, as can be known from Fig. 5:
Step 4: get 10 gram SiO
2/ Al
2O
3=6.4 NH
4L zeolite (butt) adds 5 gram deionized waters and is mixed into wetting attitude zeolite, in the dislocation 25ml crucible, compress material,, be warming up to 700 ℃ with 10 ℃ of/minute intensification speed at the dealuminzation that under water vapor condition, carries out zeolite, reacted 4 hours, and be prepared into the L zeolite of high silica alumina ratio.Lattice constant a=1.8285nm, c=0.7451nm, zeolite framework SiO
2/ Al
2O=10.8, relative crystallinity 70.1%, crystallization reservation degree 74.5%.
Embodiment two:
Because step 1, two, three identical with embodiment one described corresponding steps does not repeat them here.
Step 4: under the prerequisite of dealuminzation, further mend silicon.Specifically comprise: get 10 gram NH
4L zeolite (butt) adds and contains SiO
2Be silicic acid gel 2 grams (water content is 90%) of 0.2 gram, add 5 gram deionized waters and be mixed into wetting attitude zeolite, in the dislocation 25ml crucible, compress material, at hydrothermal dealumination that under water vapor condition, carries out zeolite and benefit pasc reaction, be warming up to 700 ℃ with 10 ℃ of/minute intensification speed, reacted 4 hours, be prepared into the L zeolite of high silica alumina ratio.Lattice constant a=1.8272nm, c=0.7441nm, zeolite framework SiO
2/ Al
2O
3=11.6, relative crystallinity 76.1%, crystallization reservation degree 81.0%.
Embodiment three:
Because step 1, two, three identical with embodiment one described corresponding steps does not repeat them here.
Step 4: under the prerequisite of dealuminzation, further mend silicon.Specifically comprise: get 10 gram NH
4L zeolite (butt) adds and contains SiO
2Be silicic acid gel 8 grams of 0.8 gram, add 5 gram deionized waters and be mixed into wetting attitude zeolite, in the dislocation 25ml crucible, compress material at hydrothermal dealumination that under water vapor condition, carries out zeolite and benefit pasc reaction, be warming up to 700 ℃ with 10 ℃ of/minute intensification speed, reacted 4 hours, and be prepared into the L zeolite of high silica alumina ratio.Lattice constant a=1.8248nm, c=0.7435nm, zeolite framework SiO
2/ Al
2O
3=12.0, relative crystallinity 71.9%, crystallization reservation degree 76.4%.
Comprehensive the foregoing description as can be known, the consumption difference of silicic acid gel can make NH
4The silica alumina ratio difference of the L zeolite that the L zeolite prepares after the hydrothermal dealumination process, lattice constant difference.
The L zeolite that the present invention generates preparation adopts following analysis test method to differentiate:
(1) relative crystallinity: x-ray diffraction method;
(2) lattice constant calculation formula:
A, b, c are the lattice constant (a=b) of hexagonal cells;
H, k, l are the crystal indices, d is the crystal face distance;
(3) skeleton SiO
2/ Al
2O
3Than calculating:
29SiMASNMR obtains;
(4) K
2O, Na
2O assay: flare photometer.
The L zeolite of Different Silicon aluminum ratio, different lattice constant and different crystallinity, data are listed in table 1.The suitable dosage of control silicic acid gel, it is very important optimizing reaction conditions.
The different dosages of table 1 silicic acid gel are to the influence of hydrothermal dealumination L zeolite silica alumina ratio
| | Raw material | 0 # | 1 # | 2 # | 3 # | 4 # | 5 # | |
| The silicic acid gel dosage is (with SiO 2Meter) weight % | The KL zeolite powder | 0.0 | 2.0 | 5.0 | 8.0 | 10.0 | 15.0 | |
| Lattice constant a, nm | 1.8398 | 1.8285 | 1.8272 | 1.8268 | 1.8248 | 1.8247 | 1.8240 | |
| Lattice constant c, nm | 0.7509 | 0.7451 | 0.7441 | 0.7438 | 0.7435 | 0.7435 | 0.7433 | |
| Relative crystallinity % | 94 | 70.1 | 76.1 | 74.1 | 71.9 | 67.1 | 65.8 | |
| Framework si-al ratio SiO 2/Al 2O 3 | 6.52 | 10.8 | 11.6 | 11.9 | 12.0 | 12.1 | 12.3 |
Annotate: 0
#, 1
#, 2
#, 3
#, 4
#, 5
#Each sample is all with NH
4The L zeolite is starting material (seeing step 3), carries out hydro-thermal and takes off and mend pasc reaction, and particular content is corresponding in the step 4 in three embodiment has respectively done detailed explanation.
In sum, the present invention adopts the L zeolite to add the L zeolite that active poly silicic acid gel prepares high silica alumina ratio, high-crystallinity and high hydrothermal stability in the hydrothermal dealumination process, the effect of invention:
(1) silicic acid gel of the present invention's employing is by SiO
2Concentration is the sodium silicate solution of 5-10%, and the counter again alkaline condition (pH=9-10) of being transferred to generates floccular poly silicic acid gel after acidifying, makes the purification silicic acid gel that water content is 80-90% through purifying treatment, has reactive behavior.
(2) the high silicon L zeolite crystal formation rule that make of the present invention just, correct, the no stray crystal of pattern, the hexagon length of side minimum of its hexagonal cells constant is 1.824nm, the hexagonal prism height is minimum to be 0.743nm, accordingly skeleton SiO
2/ Al
2O
3Be 12.3, with KL zeolite raw material (SiO
2/ Al
2O
3=5.2-6.5) to compare, silica alumina ratio improves 5.8-7.1, the high silicon L crystallization of zeolites reservation degree 70-85% (the crystallization reservation degree that the hydrothermal dealumination legal system of prior art is equipped with high silicon L zeolite is 30-40%) that the present invention makes.
(3) the high silicon L zeolite that makes of the present invention is through 780 ℃, and 100% steam-treated is after 4 hours, and crystallization reservation degree is 70-85% (the hydrothermal dealumination legal system of prior art is equipped with high silicon L zeolite behind hydrothermal aging, and crystallization reservation degree is 50-70%).
According to above-mentioned preparation method, the structure cell of zeolite is shunk, framework si-al ratio has high-crystallinity (relative crystallinity＞80%) and high hydrothermal stability greater than more than 10, and its preparation technology is simple, raw material is easy to get, free from environmental pollution.
As Fig. 6, shown in Figure 7, be respectively X-ray diffraction (XRD) spectrogram of L zeolite standard specimen and X-ray diffraction (XRD) spectrogram of the high silicon L of the present invention zeolite.
From Fig. 6, Fig. 7 as can be known, the X-coordinate among the figure is diffraction angle 2 θ (unit is degree), and ordinate zou is the relative intensity (unit is cps, i.e. the X-ray of per second count number) of diffraction peak.Its result shows, the SiO of Fig. 2
2/ Al
2O
3=6.98, relative crystallinity 100%; The SiO of Fig. 3
2/ Al
2O
3=11.6, relative crystallinity 76.1%.
This method is different from domestic and international existing technology at present fully, adopt homemade activated silica source to introduce in the L zeolite system, carry out the stabilization treatment of hydrothermal dealumination, make in dealumination process, reduce dealuminzation speed, improve and mend silicon speed, make dealuminzation and mend silicon to reach certain balance, thereby can when improving the zeolite silica alumina ratio, keep higher zeolite crystallinity and stability.
Because improving the silica alumina ratio of L zeolite is the important channel of improving multiple Hydrocarban coversion catalysts performance, so the present invention has important practical value.
Need to prove at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (6)
1, a kind of high silica alumina ratio L prepare zeolite method, this method may further comprise the steps:
Step 1: get KOH, stirring and dissolving forms the aqueous solution in water, add Al (OH)
3Powder makes working fluid, after the cooling working fluid is added in the silicon sol, stirs into uniform silicoaluminate gelling system, adds the L zeolite powder again as crystal seed, and crystallization, washing, filtration, oven dry make potassium L zeolite, that is: the KL zeolite;
Step 2: with Na
2SiO
39H
2O is dissolved in the water, and successively passes through 10%H
2SO
4Solution and 15%NaOH solution regulator solution pH value, and it is carried out stabilization treatment, all deionized waters wash and suction filtration, remove sodium ion, preparation poly silicic acid gel;
Step 3: with KL zeolite powder and NH
4 +Carry out once above exchange, through washing, filtration and oven dry preparation NH
4The L zeolite;
Step 4: carrying out dealuminzation or adopt the poly silicic acid gel of step 2 preparation to carry out the dealumination complement silicon reaction under water vapor condition, preparation generates the L zeolite of high silica alumina ratio.
2, high silica alumina ratio L prepare zeolite method according to claim 1, it is characterized in that: described step 1 specifically comprises:
Step 11: get KOH, soluble in water, stirring and dissolving, forming concentration is the solution of 5-15%;
Step 12: add Al (OH)
3Powder is that dissolved solids makes working fluid under 100 ℃ the condition in temperature, and its concentration is 4-32%;
Step 13: to be cooled to 40-50 ℃, working fluid is joined in the silicon sol, stir into uniform silicoaluminate gelling system, add the L zeolite powder again as crystal seed, crystal seed dosage and SiO
2Mass ratio be 1～3%, add the water silicon ratio of water management synthetic system, the composition that this synthetic system is respectively thrown material is calculated in molar ratio as: SiO
3/ Al
2O
3=8～20, K
2O/SiO
2=0.1～0.35, H
2O/SiO
2=10～40;
Step 14: the material that stirs is transferred in the autoclave,, with the crystallization product washing that obtains, be filtered to filtrate pH=8,, promptly got the L zeolite powder, be the KL zeolite, SiO 110 ℃ of oven dry 100～170 ℃ of crystallization 20～72 hours
2/ Al
2O
3=5.2～7.0, relative crystallinity is 75～100%.
3, high silica alumina ratio L prepare zeolite method according to claim 1, it is characterized in that: described step 2 specifically comprises:
Step 21: with solid Na
2SiO
39H
2O is dissolved in the water, SiO in the solution
2Be 2.5～8.7 grams/100 ml waters, in constantly stirring, drip 10%H
2SO
4Solution makes pH=1.0-3.0;
Step 22: regulate pH=9-10 with 15%NaOH solution again, generate the flocculence silicic acid gel;
Step 23: under 60-80 ℃ of condition gel was carried out stabilization treatment 0.5-1.0 hour, wash and suction filtration with deionized water, remove sodium ion, making water content is the poly silicic acid gel of 80-90%.
4, high silica alumina ratio L prepare zeolite method according to claim 1, it is characterized in that: described step 3 specifically comprises:
Step 31: the KL zeolite powder is carried out continuous quadratic NH
4 +Exchange, consumption is 1N NH
490-95 ℃ of exchange 1 hour, washing, filter and oven dry Cl/L zeolite=4～14 milliliter/gram, and roastings are 2～5 hours in the middle of 300～450 ℃;
Step 32: carry out secondary NH again
4 +Exchange, the exchange consumption is identical with step 31 with condition, through washing, filter and be dried into NH
4The L zeolite, KL zeolite K
2O content is 14～17 weight %, the K of product after secondary exchange and bakes to burn the article
2O content is 0.7～1.0%, and the K ion-exchange degree is more than 90%.
5, high silica alumina ratio L prepare zeolite method according to claim 1, it is characterized in that: the dealuminzation in the described step 4 specifically comprises the steps:
Step 401: get SiO
2/ Al
2O
3=5.2～7.0 NH
4The L zeolite adds deionized water and is mixed into wetting attitude zeolite, in the dislocation crucible, compresses material;
Step 402: at the dealuminzation that under water vapor condition, carries out zeolite, be warming up to 650～800 ℃, reacted 2～6 hours, be prepared into the L zeolite of high silica alumina ratio, zeolite framework SiO with 5～10 ℃ of/minute intensification speed
2/ Al
2O
3=9～11, relative crystallinity 70～75%, crystallization reservation degree 70～75%.
6, high silica alumina ratio L prepare zeolite method according to claim 1, it is characterized in that: the dealumination complement silicon of described step 4 specifically comprises the steps:
Step 411: get NH
4The L zeolite adds and contains SiO
2Silicic acid gel, water content is 90%, adds deionized water and is mixed into wetting attitude zeolite, in the dislocation crucible, compresses material;
Step 412: at hydrothermal dealumination that under water vapor condition, carries out zeolite and benefit pasc reaction, be warming up to 650～800 ℃, reacted 4 hours, be prepared into the L zeolite of high silica alumina ratio, zeolite framework SiO with 5～10 ℃ of/minute intensification speed
2/ Al
2O
3=11～12.5, relative crystallinity 70～78%, crystallization reservation degree 75～80%.
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| CN101746774B (en) * | 2008-11-28 | 2012-05-23 | 中国石油化工股份有限公司 | Tin-containing L zeolite and preparation method thereof |
| CN102476809B (en) * | 2010-11-29 | 2013-08-21 | 中国科学院大连化学物理研究所 | Method for preparing Ba-containing L zeolite from kaolin performer |
| CN102794196B (en) * | 2012-09-03 | 2014-07-02 | 浙江师范大学 | Catalyst for methylbenzene directional chlorination reaction and preparation method thereof |
| CN107473238B (en) * | 2016-06-08 | 2019-11-01 | 中国石油化工股份有限公司 | A kind of KL molecular sieve and its preparation method and application |
| CN108144637B (en) * | 2016-12-05 | 2021-10-15 | 中国科学院大连化学物理研究所 | Catalyst for reverse water gas shift reaction and preparation and application thereof |
| CN108033462B (en) * | 2018-01-10 | 2020-04-28 | 中科合成油技术有限公司 | Hierarchical porous LTL molecular sieve and synthesis method and application thereof |
| CN108929207B (en) * | 2018-06-01 | 2022-01-18 | 齐鲁师范学院 | Synthetic method of penconazole intermediate |
| CN109759043B (en) * | 2019-02-13 | 2021-08-13 | 郑州大学 | Solid acid catalyst, preparation method thereof and preparation method of p-hydroxyphenylglycine |
| CN113830789B (en) * | 2021-09-03 | 2022-11-22 | 化学与精细化工广东省实验室 | KL molecular sieve dynamically synthesized by using seed crystal as structure directing agent and preparation method thereof |
| CN116328826A (en) * | 2021-12-24 | 2023-06-27 | 中国石油化工股份有限公司 | Barium-containing L molecular sieve and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4909924A (en) * | 1986-08-13 | 1990-03-20 | Institut Francais Du Petrole | Decationized, dealuminated and stabilized L zeolite and use thereof |
| CN1121484A (en) * | 1994-10-25 | 1996-05-01 | 中国石油化工总公司石油化工科学研究院 | High-silicon zeolite preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4909924A (en) * | 1986-08-13 | 1990-03-20 | Institut Francais Du Petrole | Decationized, dealuminated and stabilized L zeolite and use thereof |
| CN1121484A (en) * | 1994-10-25 | 1996-05-01 | 中国石油化工总公司石油化工科学研究院 | High-silicon zeolite preparation |
Non-Patent Citations (1)
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| L沸石合成晶化区研究 李靖如等，郑州大学学报（工学版），第24卷第3期 2003 * |
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