CN1029202C - Preparation method of super-steady Y-zeolite contianing amorphous aluminium oxide - Google Patents
Preparation method of super-steady Y-zeolite contianing amorphous aluminium oxide Download PDFInfo
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- CN1029202C CN1029202C CN 90108740 CN90108740A CN1029202C CN 1029202 C CN1029202 C CN 1029202C CN 90108740 CN90108740 CN 90108740 CN 90108740 A CN90108740 A CN 90108740A CN 1029202 C CN1029202 C CN 1029202C
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Abstract
The present invention relates to a preparing method of ultrastable Y type zeolite containing amorphous aluminium oxide. In the method, alumina gel is added in NaY or HNaY zeolite, and then USY zeolite containing 35 to 30 wt% of amorphous Al2O3 can be obtained by the processes of ammonium ion exchange in conventional hydrothermal methods, filtration and hydrothermal calcination. Since the added alumina gel can react with ammonium sulfate remained in zeolite filtered cakes to reduce the damage effect of the ammonium sulfate to zeolite structure and lower the undulated amplitude of the crystal reservation of the zeolite caused by the fluctuation of the content of the ammonium sulfate, the zeolite prepared by the present invention has higher crystal reservation than that of zeolite prepared by conventional hydrothermal methods.
Description
The present invention relates to contain the preparation method of the ultrastable of unformed aluminium oxide.
In the catalytic cracking of hydrocarbon process, an important channel of reducing coke yield and raising octane number is to replace conventional rare earth Y type zeolite (REY) as the activity of such catalysts constituent element with ultrastable (USY).
USY prepare zeolite method is a lot, for example report Sicl among the USP4273753
4Steam and NaY zeolite at high temperature carry out prepared in reaction USY zeolite, and the method for preparing Silicon-rich USY zeolite among the USP4503023 is that the NaY zeolite is first through ammonium ion exchange, uses (NH again
4)
2SiF
6Solution-treated.Yet, based on production equipment be easy to process, production scale is big, the consideration of aspects such as free from environmental pollution, at present industrial main still employing prepares the USY zeolite based on the hydro-thermal method of USP3292192, the key step of hydro-thermal method has: the NaY zeolite carries out ion-exchange reactions with the solution that contains ammonium ion, filter and the hydrothermal calcine process.
Consider from production cost, usually use ammonium sulfate as the ion-exchange ammonium ion source, because the difference of filter plant type selecting in the difference of ammonium concentration and the filtration step in the ion-exchange step, more or less have partly free ammonium sulfate in the filter also that obtains after feasible the filtration, this part ammonium sulfate can react with the aluminium in the zeolitic frameworks in the hydrothermal calcine process, accelerate dealuminzation speed, cause zeolite structured transition avalanche, reduce the crystallization reservation degree of USY zeolite.Though can adopt reduce ammonium concentration in the exchange liquid or repeatedly the washing filter and method reduce filter and in the content of free sulfuric acid ammonium, ammonium concentration can reduce the production capacity for preparing the USY zeolite in the exchange liquid but reduce, and the method for repeatedly washing, since flush away the filter and in salt, the rate of filtration is descended significantly, so that be difficult to keep ordinary production.
In order to solve the problem that prior art exists, the object of the present invention is to provide the simple and high method for preparing the USY zeolite of product crystallization reservation degree of a kind of production technology.
USY zeolite preparation method provided by the invention is:
1. getting concentration is that 3～6 heavy %(are with Al
2O
3Meter) aluminum sulfate solution, transferring its pH value with ammoniacal liquor is 3.5～7.5, preferably 3.5～5.5, adding NaY or HNaY zeolite make the slurries mesolite: gluey Al
2O
3=95～70: 5～30, preferably 95～85: 5～15(weight ratio butt), mix.
2. the 1st step gains mix by the conventional method of ammonium ion exchange in the Hydrothermal Preparation USY zeolite process and ammonium sulfate and water, carry out ammonium ion exchange and react its mesolite: ammonium sulfate: preferably 1: 0.8～1.5: 10～40(of water weight ratio).
3. transferring the pH value of the 2nd step gains with ammoniacal liquor is 6.5～8.5, preferably 6.5～7.5, and filtration.
4. the 3rd step gained is filtered and is carried out hydrothermal calcine by the conventional method of hydrothermal calcine in the Hydrothermal Preparation USY zeolite process, promptly gets to contain unformed Al
2O
3The USY zeolite of 5～30 heavy %.
Above-mentioned HNaY zeolite can be the NaY zeolite by the HNaY zeolite of the conventional hydro-thermal method of USY zeolite preparation gained behind ammonium ion exchange and hydrothermal calcine.
In method provided by the invention, gluey aluminium oxide is introduced in the zeolite filter also, when hydrothermal calcine, aluminium glue can with filter and in remaining free sulfuric acid ammonium interact, reduce the destruction of ammonium sulfate to skeleton structure of zeolite, alleviated owing to filter and in the fluctuation of the indefinite USY zeolite product degree of crystallinity that causes that rises and falls of free ammonium sulfate content, thereby help the production of under the prerequisite that obtains high-quality USY zeolite, stablizing the USY zeolite.The USY zeolite facies ratio that the USY zeolite that the present invention prepares and conventional hydro-thermal method are made, has higher crystallization reservation degree, improved the catalytic activity of the catalyst that contains this zeolite, method provided by the invention in addition is simple, is applicable to that more commercial scale prepares the USY zeolite.
Below will the present invention will be further described by embodiment.
Example 1～4
One. prepare zeolite by method of the present invention
(1) gets 200 grams respectively and contain Al
2O
35.0 aluminum sulfate (chemical pure, the Beijing Chemical Plant) solution of heavy % is that the ammoniacal liquor adjust pH of 10 heavy % is 5.2 with concentration, adds 90 and restrains NaY zeolites (silica alumina ratio 4.9, degree of crystallinity 92%, Chang Ling catalyst plant), mixes.
An amount of ammonium sulfate of adding and water make the content of slurries mesolite, ammonium sulfate and water reach following ratio in (2) (1) the step gains: (Table A is seen the literary composition back)
Stir, be warming up to 90 ℃, carried out ion-exchange reactions 1.0 hours under stirring,
(3) transferring the pH value of (2) step gains with ammoniacal liquor is 6.5, filters.
Stainless steel tubulose reactor is put in (4) (3) steps gained filter also (solid content 41.7 heavy %), is heated to 570 ℃, and roasting is 2.0 hours in 100% water vapour, promptly gets zeolite A, the B, C and the D that contain the unformed aluminium oxide of 10 heavy %.
Two. Hydrothermal Preparation contrasts zeolite sample routinely
(1) gets 100 gram NaY respectively and carry out the ammonium ion exchange reaction, filter by first part (2) one step process.
(2) (1) step gains by first partly the method in (4) step carries out hydrothermal calcine, promptly get and contrast zeolite sample A-contrast, B-contrast, C-contrast and D-and contrast.
Three. measure the structural parameters of zeolite
Measured the crystallization reservation degree of the lattice constant of zeolite A～D and contrast zeolite sample A-contrast～D-contrast with x-ray diffraction method, and with the sodium content in the chemical gauging zeolite of routine, aluminium content and SO
2-Content the results are shown in Table 1.
From table 1, can see, along with the minimizing of the ion-exchange step water yield, the SO in the filter also
2- 4
Content increases, the contrast zeolite that conventional hydro-thermal method is made its crystallization reservation degree when its structure cell shrinkage amplitude increases also sharply descends, and the zeolite that the present invention makes can be when keeping and contrasting the close structure cell shrinkage amplitude of zeolite, and its crystallization reservation degree decline degree is also less.(table 1 is seen the literary composition back)
Example 5～8
1. prepare zeolite by the inventive method
Get the second partly prepared comparative sample A-contrast in the example 1, first part method by example 1～4 prepares zeolite E, F, G and H respectively.
Two. Hydrothermal Preparation contrasts zeolite sample routinely
Get the second partly comparative sample A-contrast of gained in the example 1, press method preparation contrast zeolite sample E-contrast, F-contrast, G-contrast and the H-contrast of second portion in the example 1～4 respectively.
Three. measure the structural parameters of zeolite
The method of pressing example 1 is measured the structural parameters and the zeolite composition of zeolite E～H and contrast zeolite E-contrast～H-contrast, the results are shown in Table 2.By table 2 as seen, filter and middle SO
2- 4The increase of content the crystallization reservation degree of the zeolite that conventional hydro-thermal method makes is sharply descended, and the zeolite that the present invention makes can keep higher crystallization reservation degree.(table 2 is seen the literary composition back)
Example 9～12
One. prepare zeolite by the inventive method
(1) gets respectively and contain Al
2O
35.0 aluminum sulfate solution 200 grams of heavy % are that 10 ammoniacal liquor that weigh % transfer its pH value to be with concentration:
Example 9 10 11 12
pH 3.5 4.5 5.5 7.2
Add 90 gram NaY zeolites (with example 1), mix.
(2) add an amount of ammonium sulfate respectively in the gains and water makes the slurries mesolite: ammonium sulfate in (1) step: water is 1: 1: the 10(weight ratio), be warming up to 90 ℃, stir the ion-exchange reactions of carrying out down 10 hours.
(3) transferring the pH value of (2) step gained slurries with ammoniacal liquor is 6.8, filters.
The filter of (4) (3) step gained also (solid content 40.8 heavy %) is put respectively in the stainless steel tubulose reactor and is heated to 570 ℃, and roasting is 2.0 hours in 100% steam, promptly gets zeolite I, the J, K and the L that contain the unformed aluminium oxide of 10 heavy %.
Two. measure the structural parameters of zeolite
Measure structural parameters and the composition of zeolite I～L and C with the method for example 1, and compare, the results are shown in Table 3 with contrast zeolite C-contrast.(table 3 is seen the literary composition back)
The zeolite of the present invention's preparation is when keeping and contrasting the close structure cell shrinkage amplitude of zeolite as seen from the table, and crystallization reservation degree is all higher.
Example 13～14
Method by example 3 prepares zeolite M and N, and just (3) step slurry pH value is:
Zeolite M N
PH value 7.5 8.5
The structural parameters of zeolite M, N and C see Table 4.(table 4 is seen the literary composition back)
By the table in as can be known, the crystallization of zeolites reservation degree that the present invention makes is higher.
Example 15～19
(1) getting an amount of aluminum sulfate solution respectively, is 5.2 with the ammoniacal liquor adjust pH, adds an amount of NaY zeolite (with example 1), mixes; The concrete operations condition is:
Aluminum sulfate solution
Example NaY zeolite consumption, gram
Concentration, heavy % consumption, gram
15 5.0 100 95
16 4.0 375 85
17 5.0 400 80
18 5.0 500 75
19 6.0 500 70
(2) identical with (2) step of example 3.
(3) identical with (3) step of example 3.
(4) identical with (4) step of example 3, promptly must contain unformed aluminium oxide 5 heavy %, 15 heavy %, 20 heavy %, 25 heavy % and 30 heavily zeolite O, P, Q, R and the S of % respectively.
The structural parameters of zeolite O～S see Table 5, and by table as seen, the increase of amorphous alumina content in the zeolite helps improving crystallization reservation degree.(table 5 is seen the literary composition back)
Example 20～21
The zeolite of the present invention's preparation is as the activity of such catalysts component.
Get zeolite C and G respectively and carry out ammonium ion exchange: zeolite: ammonium sulfate: water=1: 1: 40,90 ℃ of temperature, 1 hour time by following condition.Refilter, with 20 times of deionized water washings, gained filter and by zeolite: the weight ratio and the carrier of semi-synthetic carrier=30: 70 mix, promptly get catalyst CAT-C and CAT-G after the oven dry, wherein semi-synthetic carrier contains 25 heavy %(in aluminium oxide) boehmite (Shandong Aluminum Plant's production) and 75 heavy % kaolin (the Suzhou machine selects 2#), be by boehmite with after appropriate hydrochloric acid is mixed, add kaolin again and make, its pH value is 2.9.
Get C-contrast of contrast zeolite and G-contrast and make comparative catalyst CAT-contrast C and CAT-contrast G as stated above.
Catalyst CAT-C, CAT-G, CAT-contrast C and CAT-contrast G are under 800 ℃, 100% water vapour condition after aging 4 hours, the structural parameters of catalyst mesolite see Table 6, the zeolite that is made by the present invention has the high total crystallization reservation degree of making than conventional hydro-thermal method of zeolite as shown in Table 6, illustrates that the zeolite that the present invention makes has higher structural stability.
On standard light oil micro-reactor, estimate the catalytic cracking reaction performance of above-mentioned catalyst, reaction condition: feedstock oil is huge port straight-run diesel oil (200～300 ℃ of fractions), catalyst loading amount 5.0 grams (20-40 order), 460 ℃ of reaction temperatures, oil ratio 3, weight space velocity 16 hours
-1, reaction result sees Table 6, and by finding out in the table, the catalyst that contains the zeolite that the present invention prepares has advantages of high catalytic activity.(table 6 is seen the literary composition back)
Table A
Example 1234
Zeolite: ammonium sulfate: water 1: 1: 40 1: 1: 20 1: 1: 10 1: 1: 5
Table 1
Ion-exchange slurries zeolite is formed, heavy % structural parameters
Ammonium sulfate concentrations lattice constant a in the zeolite
0
Na
2O Al
2O
3SO
2- 4Crystallization reservation degree %
Heavy % (nanometer)
A 2.5 3.2 30.04 1.11 2.462 98.0
B 5.0 3.3 - 2.32 2.458 93.5
C 10.0 3.4 - 4.26 2.455 89.2
D 20.0 3.3 - 8.52 2.454 85.0
A-contrasts 2.5 3.6 22.20 1.01 2.461 92.0
B-contrasts 5.0 3.6-2.12 2.456 82.0
C-contrasts 10.0 3.8-4.02 2.454 76.0
D-contrasts 20.0 3.7-8.03 2.453 70.0
Annotate: wherein crystallization reservation degree is:
Crystallization reservation degree=
(533 crystal face peak heights of zeolite behind the hydrothermal calcine)/(533 crystal face peak heights of zeolite before the hydrothermal calcine) * 100%
Table 2
Ion-exchange slurries zeolite is formed, heavy % structural parameters
Ammonium sulfate concentrations lattice constant a in the zeolite
0
Na
2O Al
2O
3SO
2- 4Crystallization reservation degree %
Heavy % (nanometer)
E 2.5 1.3 29.84 1.20 2.445 94.2
F 5.0 1.2 - 2.30 2.443 91.2
G 10.0 1.1 - 4.32 2.442 85.6
H 20.0 1.2 - 8.65 2.440 79.9
E-contrasts 2.5 1.4 22.30 0.98 2.446 85.0
F-contrasts 5.0 1.5-2.02 2.442 76.8
G-contrasts 10.0 1.6-3.98 2.438 72.0
H-contrasts 20.0 1.4-7.95 2.436 66.0
Table 3
Sodium and sulfate radical content in (1) the step zeolite, heavy % structural parameters
The lattice constant a of zeolite slurry
0
Na
2O SO
2- 4Crystallization reservation degree %
PH value (nanometer)
I 3.5 2.9 4.20 2.454 90.5
J 4.5 3.1 3.98 2.455 91.4
C 5.2 3.4 4.26 2.455 89.2
K 5.5 3.1 4.12 2.455 91.5
L 7.2 3.3 4.42 2.456 87.5
C-contrasts 3.8 4.02 2.454 76.0
Table 4
The content of sodium and sulfate radical in (3) the step zeolite, heavy % structural parameters
The lattice constant a of zeolite slurry
0
Na
2O SO
2- 4Crystallization reservation degree %
PH value (nanometer)
C 6.5 3.4 4.26 2.455 89.2
M 7.5 3.2 4.10 2.456 91.5
N 8.5 3.3 4.05 2.455 90.8
C-contrasts 3.8 4.02 2.454 76.0
Table 5
The sodium of no zeolite and SO in the zeolite
2- 4Content, heavy % structural parameters
Example zeolite setting Al
2O
3Lattice constant a
0
Na
2O SO
2- 4Crystallization reservation degree %
: zeolite (nanometer)
15 O 5∶95 3.4 4.02 2.454 86.9
3 C 10∶90 3.4 4.26 2.455 89.2
16 P 15∶85 3.2 4.38 2.456 90.5
17 Q 20∶80 3.1 4.53 2.455 91.4
18 R 25∶75 2.9 4.61 2.454 88.5
19 S 30∶70 2.8 4.74 2.454 87.8
3 C-contrast 0: 100 3.8 4.02 2.454 76.0
Table 6
CAT-C CAT-G CAT-contrast C CAT-contrast G
Lattice constant, 2.428 2.427 2.426 2.427
a
0(nanometer)
Total crystallization protects 62.4 66.4 44.5 41.1
Office Copy *, %
Micro-activity, % 52 64 53 51
* total crystallization reservation degree=(zeolite 533 crystal face diffracted intensities after the catalyst ageing)/(zeolite 533 crystal face diffracted intensities before the hydrothermal calcine) * 100%
Claims (6)
1, a kind of method for preparing ultrastable is characterized in that being made up of following several steps:
(1) getting concentration is that 3～6 heavy % are (with Al
2O
3Meter) aluminum sulfate solution, transferring its pH value with ammoniacal liquor is 3.5～7.5, adds NaY zeolite or HNaY zeolite and makes the slurries mesolite: gluey Al
2O
3=95～70: 5～30 (weight ratio, butts) mix;
(2) (1) step gains mix by the conventional method of ammonium ion exchange in the Hydrothermal Preparation USY zeolite process and ammonium sulfate and water, carry out ammonium ion exchange and react;
(3) transferring the pH value of (2) step gains with ammoniacal liquor is 6.5～8.5, filters;
(4) (3) step gained are filtered and are carried out hydrothermal calcine by the conventional method of hydrothermal calcine in the Hydrothermal Preparation USY zeolite process, promptly get to contain unformed Al
2O
3The ultrastable of 5～30 heavy %.
2,, it is characterized in that said pH value is 3.5～5.5 in (1) step by the described method of claim 1.
3,, it is characterized in that said zeolite and gluey Al in (1) step by the described method of claim 1
2O
3Ratio be 95～85: 5～15(weight ratio).
4,, it is characterized in that (2) step mesolite: ammonium sulfate: water=1: 0.8～1.5: 10～40(weight ratio) by the described method of claim 1.
5,, it is characterized in that the pH value in (3) step is 6.5～7.5 by the described method of claim 1.
6, by the described method of claim 1, it is characterized in that said HNaY zeolite in (1) step be the NaY zeolite by the conventional hydro-thermal method of preparation USY zeolite behind ammonium ion exchange and hydrothermal calcine the HNaY zeolite.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90108740 CN1029202C (en) | 1990-11-02 | 1990-11-02 | Preparation method of super-steady Y-zeolite contianing amorphous aluminium oxide |
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|---|---|---|---|
| CN 90108740 CN1029202C (en) | 1990-11-02 | 1990-11-02 | Preparation method of super-steady Y-zeolite contianing amorphous aluminium oxide |
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| CN1029202C true CN1029202C (en) | 1995-07-05 |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1047105C (en) * | 1992-11-17 | 1999-12-08 | 中国科学院大连化学物理研究所 | Metallic zeolite catalyst for reaction of converting synthetic gas into dimethyl ether |
| CN1055063C (en) * | 1996-09-27 | 2000-08-02 | 中国石油化工总公司 | Modified zeolite and manufacture thereof |
| CN1078819C (en) * | 1997-08-27 | 2002-02-06 | 中国石油化工集团公司 | Process for preparing overstable gamma zeolite |
| CN1069552C (en) * | 1997-08-29 | 2001-08-15 | 中国石油化工总公司 | Preparation of super-stable Y molecular sieves |
| CN101633507B (en) * | 2008-07-24 | 2011-03-30 | 中国石油化工股份有限公司石油化工科学研究院 | Ammonium ion exchange method for Y-type molecular sieve |
| CN106673031B (en) * | 2015-11-09 | 2018-06-19 | 中国石油化工股份有限公司 | A kind of NaY molecular sieve and alumina compound and preparation method thereof |
| CN110871103B (en) * | 2018-08-29 | 2022-09-27 | 中国石油化工股份有限公司 | Composite material containing gamma-alumina structure and preparation method thereof |
| CN116139913B (en) * | 2023-02-09 | 2023-10-13 | 无锡双翼汽车环保科技有限公司 | Catalyst for purifying tail gas of explosion-proof diesel engine and preparation method thereof |
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1990
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