CN1056473A - A kind of preparation method of low-Na and high-Si Y-type molecular sieve - Google Patents
A kind of preparation method of low-Na and high-Si Y-type molecular sieve Download PDFInfo
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- CN1056473A CN1056473A CN 90102645 CN90102645A CN1056473A CN 1056473 A CN1056473 A CN 1056473A CN 90102645 CN90102645 CN 90102645 CN 90102645 A CN90102645 A CN 90102645A CN 1056473 A CN1056473 A CN 1056473A
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Abstract
A kind of preparation method of low-Na and high-Si Y-type molecular sieve.Exactly be to handle the raw material Y zeolite, prepare the method for low-Na and high-Si Y-type molecular sieve with ammonium hexafluorosilicate.The difference of the present invention and prior art is, in the process with the ammonium hexafluorosilicate treatment of raw Y-type, does not add the material that pH is had regulating effect in the reaction system in addition.Compared with prior art, the present invention can save the Na of highly energy-consuming
2The O roasting process, and take off one step of sodium dealuminzation and finish, the present invention simultaneously also is a kind of method for preparing fluorine (silicon) ammonium aluminate sodium crystal.
Description
The present invention relates to a kind of Y zeolite and take off the method that the sodium dealuminzation prepares low-Na and high-Si Y-type molecular sieve, simultaneously, also relate to the preparation method of a kind of fluorine (silicon) ammonium aluminate sodium crystal.
Y zeolite is at industrial different acid catalyzed reaction catalyzer or the catalyst bases such as preparation catalytic cracking, hydrocracking, isomerization and alkylation of being widely used in.Direct hydro-thermal synthetic Y zeolite, the positively charged ion outside the skeleton is Na normally
+, and the NaY molecular sieve does not possess the acid catalysis activity, therefore when being used to prepare the acid catalyzed reaction catalyzer, must remove part Na
+Requiring to take off the sodium degree of depth when not really high, can adopt ion exchange technique, by once or ion-exchange several times realize.But requiring to take off the sodium degree of depth when higher, owing to only adopt ion exchange technique just can reach requirement through the exchange of tens times, tens times and even secondary ion up to a hundred, such process realized in industrial being difficult to, and therefore, all was to adopt energy-intensive Na usually
2O roasting and ion exchange phase bonded method, the patented technology of relevant this respect is a lot, is typically United States Patent (USP) 3293192,3402996,3781199 and 4036739.
More than summarized and from Y zeolite, removed Na
+Cationic prior art situation.In general, through taking off Na
+Replace Na in the Y zeolite of handling
+Be H
+Or NH
+ 4Positively charged ion, and H
+Or NH
+ 4Positively charged ion greatly can be from normal associating AlO with it
- 4Slough in the tetrahedron, produce electrovalent imbalance on molecular sieve structure, this just must cause its structural rearrangement, to recover the electricity price balance.Usually, in the total skeleton tetrahedron of molecular sieve, contain AlO greater than 40%
- 4During tetrahedron, required structural rearrangement just can not adapt to, and crystalline structure is damaged.Therefore in order to guarantee the stability of Y zeolite crystalline structure, particularly thermostability at high temperature must remove the aluminium atom in the part lattice.The y-type zeolite dealuminzation, existing method mainly contains: 1) complexing dealuminzation method (as United States Patent (USP) 3,442,795,3,640,681,4,093,560); 2) high-temperature water heat treating process (as United States Patent (USP) 3,493,519,3,506,400,3,513,108); 3) SlCl
4Gas-phase silicon method of substitution (as HU24,100); With 4) (NH related to the present invention
4)
2SlF
6Liquid-phase silicone method of substitution (as United States Patent (USP) 4,503,023).(NH wherein
4)
2SlF
6The liquid-phase silicone method of substitution is that the Y zeolite that part is taken off behind the sodium is made slurries, makes reaction system keep certain acidity with acid or buffer reagent, adding (NH
4)
2SlF
6Carry out the silicon substitution reaction, realize removing framework of molecular sieve aluminium.
From above-mentioned prior art as can be seen, prepare the low sodium Y zeolite of high silicon, must pass through above-mentioned sodium and two processes of dealuminzation of taking off, preparation process is very complicated, particularly take off the sodium process,, just must adopt the calcination steps of highly energy-consuming if require sodium content to reduce to very low degree.
The preparation method who the purpose of this invention is to provide a kind of low-Na and high-Si Y-type molecular sieve simplifies preparation process, saves the Na of highly energy-consuming
2The O roasting.Simultaneously, another object of the present invention provides the technology of preparing of a kind of novel substance-fluorine (silicon) ammonium aluminate sodium crystal.
The preparation method of the low sodium Y zeolite of high silicon of the present invention is to be raw material with the Y zeolite, handles with ammonium hexafluorosilicate under suitable medium and condition, makes Na
+Remove simultaneously with framework aluminum, and in reaction system, generate a kind of new material-fluorine (silicon) ammonium aluminate sodium crystal.This just crystalline is separated out and is made Na
+Be able to constantly from molecular sieve, deviate from.Since in this reaction process, Na
+Can from molecular sieve, deviate from simultaneously with framework aluminum, and can make silicon in the ammonium hexafluorosilicate enter framework of molecular sieve to fill up, thereby can make the very low high-Si Y-type molecular sieve of sodium content because of the lattice vacancy (cave) that dealuminzation produces.In general, in this reaction process, Na
+Carry out simultaneously with deviating from of framework aluminum by certain ratio.Therefore, when preparing low-Na and high-Si Y-type molecular sieve with method of the present invention, must be according to the sodium content and the SlO of product Y zeolite requirement
2/ Al
2O
3Molecule is recently selected suitable Na
+Content and SiO
2/ Al
2O
3The Y zeolite raw material of molecular ratio.If directly make raw material with the NaY molecular sieve, require simultaneously products molecule sieve Na
2O content very low (as＜0.2 heavy %), the SlO of products molecule sieve so
2/ Al
2O
3It is very high that molecular ratio will reach, even framework aluminum almost all must be removed.If require the Na of products molecule sieve
2O content is very low, simultaneously SlO
2/ Al
2O
3During molecular ratio not really high again (as＜15), just NaY molecular sieve raw material must be carried out in advance the ammonium exchange, make Na
2O content drops to suitable degree (as≤5 heavy %).
Method of the present invention is that the raw material Y zeolite is made certain density slurries with distilled water or deionized water, and slurries heat up to stir down and add hexafluorosilicic acid aqueous ammonium or crystal, and Y zeolite raw material and ammonium hexafluorosilicate are reacted, and remove the Na in the molecular sieve
+With the part framework aluminum.Importantly not having a mind to add other salts, acid in this reaction process regulates PH and does not also add the PH buffer reagent.The product of the inventive method is low-Na and high-Si Y-type molecular sieve and fluorine (silicon) ammonium aluminate sodium crystal, and the proportion of two kinds of products differs bigger, can separate with the physical method of routine.
Method of the present invention requires: 1, molecular sieve is made certain density slurries, and per 100 milliliters of slurries contain 5～30 gram raw material Y zeolites, and preferably per 100 milliliters of slurries contain 10～25 gram raw material Y zeolites; 2, reaction mixture temperature maintains 50～120 ℃ in the reaction process, preferably 70～100 ℃; 3, add enough ammonium hexafluorosilicate, generally add at least 10 grams, preferably 20～50 grams by per 100 gram Y zeolite raw materials; 4, guarantee that enough slow ammonium hexafluorosilicate adds speed, general per hour pressing, per 100 gram Y zeolite raw materials add maximum 30 grams, preferably 5～25 grams; 5, keep the sufficiently long reaction times, promptly add ammonium hexafluorosilicate after, at 50～120 ℃, preferably kept 0.1～24 hour under 70～100 ℃ of stirrings, preferably kept 0.5～5 hour; 6, used molecular sieve raw material NH preferably
4NaY molecular sieve, wherein Na
2O content is best≤and 5%(is heavy), SiO
2/ Al
2O
3Molecular ratio between 3.5～7.0, preferably 4.5～7.0.
According to method of the present invention, Y zeolite takes off the sodium dealuminzation, and to prepare the step of low-Na and high-Si Y-type molecular sieve and fluorine (silicon) ammonium aluminate sodium crystal as follows:
1, with raw material Y type molecule (NH
4NaY or NaY) be mixed and made into certain density slurries with water as requested, be heated to temperature of reaction;
2, speed as requested adds the hexafluorosilicic acid ammonium solution or the crystal of q.s, reacts;
3, continue to stir and keep temperature of reaction in the certain hour after ammonium hexafluorosilicate adds;
4, carry out settlement separate to post reaction mixture;
5,, obtain the finished product to isolated low-Na and high-Si Y-type molecular sieve with fluorine (silicon) ammonium aluminate sodium crystal is washed respectively, filtered and dry.
Adopt method of the present invention that Y zeolite is taken off the sodium dealuminzation, can make the Na of Y zeolite
2O content is reduced to 0.2%(and is weighed) below, and correspondingly improve SlO
2/ Al
2O
3Ratio, its degree of crystallinity can keep 60% at least, generally can keep more than 80% even 90%.The ammonium exchange degree that method of the present invention in addition can be by adjusting the raw material Y zeolite and the add-on of ammonium hexafluorosilicate are controlled the Na of product Y zeolite
2O content and SlO
2/ Al
2O
3Molecular ratio, thus obtain meeting the product of different needs.Compared with prior art, it is simple that method of the present invention also has process, do not need the Na of highly energy-consuming
2The characteristics of O roasting.
Another kind of product-fluorine (silicon) ammonium aluminate sodium crystal of the inventive method has the d spacing of the listed X-ray powder diffraction of table 1 or X-ray powder diffraction figure shown in Figure 1 at least, and has infrared spectrum shown in Figure 2.
Further describe feature of the present invention below by example.
Example 1
Take by weighing that the ammonium exchange degree is about 80%, the raw material NH of calcination loss of weight 27.1%
4NaY molecular sieve 2057.6 grams, put into white steel drum, with 9 liters of distilled water making beating, and under agitation condition heat temperature raising to 95 ℃, drip the solution of preparing by 495.0 gram ammonium hexafluorosilicate and 3500 ml distilled waters with even velocity then, dropwised with 2 hour time, this rear slurry was kept 2 hours under 95 ℃ of agitation conditions, stop to stir leave standstill about 10 minutes after, isolate fluorine (silicon) the ammonium aluminate sodium crystal that is deposited in white steel drum bottom with decantation, and through washing, reclaim dry back, and this sample is carried out the X-ray powder diffraction material phase analysis, and the result shows that fluorine (silicon) ammonium aluminate sodium crystal has the listed d spacing of table 1.Topple over the molecular sieve pulp that and carry out suction filtration, and, take out filter cake then and carry out drying, promptly get the product low-Na and high-Si Y-type molecular sieve with the flushing of suction filtration limit, about 30 liters of thermal distillation watersides.Raw material NH
4The main physico-chemical property of NaY molecular sieve and low-Na and high-Si Y-type molecular sieve sees Table 2.As can be seen from Table 2, the low-Na and high-Si Y-type molecular sieve with the inventive method preparation has characteristics such as low sodium, high silicon, high-crystallinity and high thermal stability.
Example 2
Take by weighing raw molecule sieve NaY(calcination loss of weight～48%, Na
2O content 9.67% weight, silica alumina ratio 5.33, lattice constant 24.63A) 300 grams, put into there-necked flask, use, under refluxad heat to 95 ℃ by 300 gram ammonium nitrate and the formulated solution making beating of 1500 ml distilled waters, suction filtration is then carried out in constant temperature ion-exchange 1 hour.And under the suction filtration condition with 2 liters of distilled water flushing molecular sieve filter cakes.Then filter cake is moved in the there-necked flask, 1000 milliliters of making beating of adding distil water, and under the backflow agitation condition heat temperature raising to 75 ℃, constant temperature evenly drips the solution that is made into by 59.4 gram ammonium hexafluorosilicate and 450 ml distilled waters, added with 2 hour time, this rear slurry was kept 2 hours under 75 ℃ of backflow agitation conditions again, then stop to stir and leaving standstill about 5 minutes, pour out the molecular sieve pulp on upper strata with decantation, take advantage of heat to carry out suction filtration, and under the suction filtration condition, wash, take out filter cake with 6 liters of hot distilled waters, carry out drying, promptly get the product low-Na and high-Si Y-type molecular sieve.The crystalline substance of staying in the flask promptly gets fluorine (silicon) ammonium aluminate sodium crystal after washing, drying.
Product fluorine (silicon) ammonium aluminate sodium crystal X-ray powder diffraction material phase analysis shows that this crystalline substance has the listed d spacing of table 1 equally.Product low-Na and high-Si Y-type molecular sieve analytical results shows, its Na
2O content is heavy less than 0.1%(), SlO
2/ Al
2O
3Molecular ratio 11.85, lattice constant 24.48A, relative crystallinity 96%, 1116 ℃ of DTA structure deteriorate peak temperatures, 858 meters of specific surface areas
2/ gram, 0.367 milliliter/gram of pore volume, skeletal vibration frequency antisymmetric stretching vibration 1042cm
-1With symmetrical stretching vibration 814cm
-1, infrared acidity B acid 1.577mmol/g, L acid 0.084mmol/g, total acid 1.661mmol/g.
Example 3～7
Example 3 belongs to method of the present invention.Example 4～7 belongs to the reference example, promptly adds the ammonium salt that PH is had regulating effect in reacting slurry.
In example 3～7, take by weighing 269.8 gram raw material NH respectively
4NaY molecular sieve (calcination loss of weight 26%, Na
2O content 4.7%(is heavy), SlO
2/ Al
2O
3Molecular ratio 5.07) puts into 2000 milliliters there-necked flask, and use 1200 ml distilled waters respectively, 3.5M ammonium nitrate solution, 3.5M ammonium chloride solution, 3.5N ammoniumsulphate soln and the making beating of 3.5M Spirit of Mindererus, and under 95 ℃ of constant temperature backflow agitation conditions, drip respectively by 90.0 gram ammonium hexafluorosilicate and the formulated solution of 450 ml distilled waters with even velocity, added with 3 hours, and then under 95 ℃ of constant temperature reflux conditionss, continue to stir 2 hours, then left standstill 5～10 minutes, the molecular sieve pulp of pouring out the upper strata with decantation carries out heat filtering, and under the suction filtration condition, wash the molecular sieve filter cake with 6 liters of hot distilled waters, then take out the filter cake drying and promptly get the products molecule sieve.Crystal at the bottom of staying bottle is through washing, the recovery of dry back.The crystal that the differential responses dielectric method is obtained carries out X-ray powder diffraction, the result shows, the crystal that makes with the distilled water making beating presents the listed d spacing of table 1, and the crystal that makes with ammonium nitrate, ammonium chloride, ammonium sulfate and Spirit of Mindererus making beating also has the peculiar d spacing of hexafluoro-ammonium aluminate and/or tetrafluoro ammonium aluminate crystal except that presenting the listed d spacing of table 1.This explanation is fluorine (silicon) the ammonium aluminate sodium crystal with the crystal that the making beating of solution such as ammonium nitrate makes except that part is arranged, and also having part is hexafluoro-ammonium aluminate and/or tetrafluoro ammonium aluminate crystal.
Products molecule sieve and the raw material NH of example 3-7
4The main physico-chemical property of NaY molecular sieve sees Table 3.As can be seen from Table 3, the Na of the products molecule sieve that makes with distilled water making beating according to method of the present invention
2It is heavy that O content is lower than 0.2%(), and the products molecule of example 4-7 sieve Na
2O content is higher.
Example 8
Take by weighing 269.8 gram NH
4NaY molecular sieve raw material (identical with used molecular sieve among the example 3-7) is put into 2000 milliliters of there-necked flasks, pull an oar with 1200 ml distilled waters, and under the backflow agitation condition heat temperature raising to 95 ℃, then under 95 ℃ of constant temperature backflow agitation conditions, added once with per 5 minutes, the speed of each 2.5 grams is added to 90.0 gram ammonium hexafluorosilicate crystal in the above-mentioned slurries, and rear slurry continues to stir 2 hours under 95 ℃ of constant temperature reflux conditionss, left standstill about 10 minutes after stopping to stir, the molecular sieve pulp of pouring out the upper strata with decantation carries out hot suction filtration, and with the flushing of 6 liters of hot distilled waters, take out filter cake then, drying gets the products molecule sieve.Fluorine (silicon) the ammonium aluminate sodium crystal of staying in the flask reclaims after washing, drying.The fluorine that makes (silicon) ammonium aluminate sodium crystal carries out the X-ray powder diffraction material phase analysis, and the result shows that its X-ray powder diffraction figure has the listed d spacing of table 1.The product low-Na and high-Si Y-type molecular sieve that makes shows by analysis, its Na
2O content 0.16%(is heavy), SlO
2/ Al
2O
3Molecular ratio 11.75, lattice constant are 24.50A, and relative crystallinity is 90%, and DTA structure deteriorate peak temperature is 1095 ℃, and infrared skeletal vibration frequency is antisymmetric stretching vibration 1034cm
-1With symmetrical stretching vibration 809cm
-1
The d spacing of table 1 fluorine (silicon) ammonium aluminate sodium crystal
The d spacing, A 4.78 4.15 2.94 2.40 2.08 1.91 1.86 1.70 1.60 1.47
Strongest in the power among the strong strongest of intensity
1.41?1.39
Weak
Table 2 raw material NH
4The main physico-chemical property of NaY molecular sieve and product low-Na and high-Si Y-type molecular sieve
Molecular sieve raw material NH
4NaY product Y zeolite
Na
2O content, %～2 0.04
SiO
2/ Al
2O
3Molecular ratio 5.27 9.67
Lattice constant, A 24.67 24.52
Relative crystallinity, % 100 105
DTA structure deteriorate peak temperature, ℃ 920 1066
Infrared skeletal vibration frequency, cm
-1
Antisymmetric stretching vibration 1,014 1034
Symmetrical stretching vibration 789 807
Infrared acidity, m mol/g
B acid 1.734
L acid 0.056
Total acid 1.790
Table 3 example 3-7 products molecule sieve and raw material NH
4The physico-chemical property of NaY molecular sieve
Example number raw material 34567
Na
2O content, %(is heavy) 4.7 0.11 0.83 1.6 1.4 1.5
SiO
2/ Al
2O
3Molecular ratio 5.07 11.88 10.50 11.03 10.43 8.05
Lattice constant, A 24.67 24.50 24.49 24.48 24.49 24.54
Relative crystallinity, % 100 87 83 85 79 62
DTA structure deteriorate peak temperature, ℃ 920 1,105 1,078 1,070 1,113 1016
Infrared skeletal vibration frequency, cm
-1
Antisymmetric stretching vibration 1,016 1,057 1,053 1,055 1,053 1079
Symmetrical stretching vibration 791 810 812 812 811 803
Annotate:
Reaction medium-distilled water 3.5M 3.5M 3.5N 3.5M
NH
4NO
3NH
4Cl （NH
4）
2SO
4NH
4OAC
Claims (8)
1, a kind of low-Na and high-Si Y-type molecular sieve preparation method, the raw material Y zeolite is carried out contact reacts with ammonium hexafluorosilicate in intensification and certain reaction medium, then isolate product, through washing, filter and drying, it is characterized in that taking off sodium and dealumination reaction is once finished, its reaction medium is a water, be about to raw material Y zeolite water and make slurries, slurries are warming up to 50～120 ℃ (best 70～100 ℃), under the agitation condition, directly add hexafluorosilicic acid aqueous ammonium or crystal, needn't add other salts in the reaction system, acid is regulated PH or is made buffered soln.
2, according to the method for claim 1, it is characterized in that adding at least 10 grams by per 100 gram Y zeolite raw materials in the reaction process, preferably the ratio of 20～50 gram ammonium hexafluorosilicate feeds intake.
3, according to the method for claim 2, the adding that it is characterized in that ammonium hexafluorosilicate is by per hour, and per 100 gram Y zeolites add maximum 30 grams, and preferably 5～25 gram speed are carried out.
4,, it is characterized in that the raw material Y zeolite is NH according to the method for claim 1
4The NaY molecular sieve, Na
2O content is best≤and 5%(is heavy).
5,, it is characterized in that the SiO of raw material Y zeolite according to the method for claim 1 or 4
2/ Al
2O
3Molecular ratio is between 3.5～7.0, preferably between 4.5～7.0.
6, according to the method for claim 1, the slurries before it is characterized in that reacting contain preferably 10～25 gram raw material Y zeolites of 5～30 grams for per 100 milliliters.
7, according to the method for claim 1, it is characterized in that adding reaction mixture after the ammonium hexafluorosilicate maintain 50～120 ℃ preferably 70～100 ℃ continue to stir preferably 0.5～5 hour 0.1～24 hour.
8,, it is characterized in that reacting and finish the new crystalline substance that the back is isolated the product low-Na and high-Si Y-type molecular sieve and had the listed d spacing of table 1 at least with sedimentation-separation technology such as decantation, and wash respectively and drying according to the method for claim 1 to 7.
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|---|---|---|---|
| CN 90102645 CN1026313C (en) | 1990-05-16 | 1990-05-16 | Process for preparing low-Na and high-Si Y-type molecular sieve |
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| CN1026313C CN1026313C (en) | 1994-10-26 |
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