CN1041543A - The preparation of ultrahydrophobic zeolite - Google Patents
The preparation of ultrahydrophobic zeolite Download PDFInfo
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- CN1041543A CN1041543A CN 88109090 CN88109090A CN1041543A CN 1041543 A CN1041543 A CN 1041543A CN 88109090 CN88109090 CN 88109090 CN 88109090 A CN88109090 A CN 88109090A CN 1041543 A CN1041543 A CN 1041543A
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- zeolite
- ultrahydrophobic
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Abstract
The present invention has narrated a kind of ultrahydrophobic zeolite, and this kind zeolite has passed through a kind of secondary synthesis step, carries out one time the steam-treated step subsequently again.Described preparation process can be prepared a kind of LZ-210 super-hydrophobicity molecular sieve and not need through a kind of stabilizing step or ammonium ion exchange step.
Description
The application relates to the field of ultrahydrophobic zeolite, particularly relates to passing through a kind of secondary synthesis step, carries out the field of the Y zeolite of a steam-treated step subsequently again.Preparation process of the present invention can be prepared a kind of LZ-210 super-hydrophobicity molecular sieve and not need through a kind of stabilizing step and a kind of ammonium ion exchange step.
Hydrophobic molecule sieve greatly advantageously as a kind of support applications in various catalyst systems, comprising fischer-tropsch (Fischer-Tropsch) type catalyzer and hydrocracking catalyst.
U. S. application series the 880th at the common transfer of on February 23rd, 1978 application, (be equivalent to Canadian Patent number 1 No. 561,131,195, issued June 9 nineteen eighty-two) in the disclosed research work of being undertaken by Earls point out, in order to produce UHP-Y(super-hydrophobicity Y-zeolite), need after the steam-treated step Y zeolite is carried out the ammonium ion exchange in the first time, otherwise, this kind zeolite can lose its X-ray degree of crystallinity greatly, the infrared band of the network broad that then becomes is though and to have carried out steam-treated step profile still unintelligible.
If can work out another kind of the needs this zeolite is produced ultrahydrophobic zeolite through a kind of method of ammonium ion exchange step of stability, this will be a very important contribution for the present technique field so.Now as listed below for the documents well known in the prior art that applicant of the present invention is known:
U.S. Patent number 3,293,172-are issued in 20 days-Z-14US zeolite and preparation method thereof-C.V.McDaniel and P.K.Maher December in 1966.
U.S. Patent number 3,447,070-are issued on June 10th, 1969-stable zeolite-C.V.McDaniel and P.K.Maher.
U.S. Patent Application Serial 880561-is filed in 23 days-ultrahydrophobic zeolite-D.Earls February in 1978.
U.S. Patent number 4,401,556-are issued in the hydrocracking of 30 days-middle distillate in August nineteen eighty-three-R.D.Bezman and J.A.Rabo.
U.S. Patent number 3506,400-issue in 1970-about the acid extraction-P.E.Eberly of the Y zeolite after the steam-treated, Jr.
Though above-mentioned document is not all narrated content of the present invention,, can think that all respects of these documents all are included in those skilled in the art's the ken, and become the basis of following content of the present invention.
The invention relates to the step of producing ultrahydrophobic zeolite, particularly about through a kind of secondary synthesis step with carry out the field of the Y zeolite of a steam-treated step subsequently again.Preparation process of the present invention can be prepared a kind of LZ-210 super-hydrophobicity molecular sieve and not need through a kind of stabilizing step and a kind of ammonium ion exchange step.
We have found that, use a kind of through LZ-210(at U.S. Patent number 4,503, open in 023, issued on March 5th, 1985; With U.S. Patent number 4,610,856, issued on September 9th, 1986) Y zeolite of secondary synthesis step, do not need through the desired ammonium ion exchange of this super-hydrophobicity Y zeolite (UHP-Y) method and for the second time the steam-treated step can prepare a kind of high-quality ultrahydrophobic zeolite.
Carried out a series of experiments, its purpose is to produce the hydrophobic Y zeolite of HP-Y(from super beginning materials such as Y-72, Y-82 and LZ-210) use acid extraction HP-Y zeolite with preparation Hyper Y zeolite then.Use Earls steps outlined in his research work about UHP-Y (U. S. application series number 880561 is filed on February 23rd, 1978).Application Y-72 and Y-82 experimentize starting material are provided, so that compare with LZ-210.The research work of the UHP-Y of Earls has been supported in the experiment of Y-72 and Y-82, points out must after the steam-treated Y zeolite be carried out NH in the first time in order to produce the UHP-Y zeolite
4Exchange.
Example
Though the present invention usually describes as above, details of the present invention can be used for illustrating that example of the present invention understands better with following.
The example I
Begin with commercially available Y-72, Y-72 is carried out ammonium ion exchange prepare Y-82.Do like this is in order to eliminate the variation of the Y-82 that applied steam-treated condition is caused when preparing Y-72.These zeolites are as the contrast of following example.
The example II
Synthetic SiO
2/ Al
2O
3Than the LZ-210 zeolite (use U.S. Patent number 4503023, issue) that is 9: 1, by method (U.S. Patent number 4,597,956 that R.S.Hinchey narrated on March 5th, 1985, the preparation method who is narrated; Issued on July 1st, 1985), the method that adopts a kind of Tai-Ace S 150 crystallizing and washing to handle in pilot plant is to help to wash out applied fluorochemical in this secondary synthesis step.
The example III
Y-72, the Y-82 and the LZ-210 sample that prepare in example I-II were at room temperature stirred 3 hours in 6N hydrochloric acid, identify it then.Though acid extraction has destroyed the degree of crystallinity of all these three kinds of zeolites.Similar all aluminum oxide all extract from LZ-210.But Y-72 and Y-82 have still kept 4.5%(weight) aluminum oxide.(seeing Table 1).
Table 1
Zeolite character after the 6N HCl extraction
Zeolite Na
2O (NH
4)
2O SiO
2Al
2O
3
%(weight) %(weight) %(weight) %(weight)
Y-72 0.17 ＜0.05 95.9 4.3
Y-82 0.11 0.17 95.2 4.5
LZ-210 0.03 0.05 100.00 0.18
The example IV
Studied following two kinds of different steam-treated conditions:
1) under 400 ℃ in universe air with zeolite roasting three hours, in dryer, be cooled to room temperature then, in the tube furnace of preheating, carried out steam-treated 1 hour again at 750 ℃ of water vapors with 100%.2) before sample is put into process furnace, earlier tube furnace is preheating to 750 ℃, then zeolite was carried out steam-treated 16 hours at 750 ℃ in 100% water vapor.
After carrying out steam-treated with above-mentioned any step, product carries out acid extraction with following arbitrary method: at room temperature handle twice with concentrated hydrochloric acid, be earlier 1 hour be 16 hours then; Or reflux twice with the 6N hydrochloric acid soln, the time was respectively 4 hours and 3 hours.
As a class product, lose its at least very big one one X-ray degree of crystallinity through the Y-72 of steam-treated sample.Though its network infra red spectrum broadens and has carried out steam-treated and but acid extraction step profile is still unintelligible.
Kept its X-ray degree of crystallinity through the Y-82 of steam-treated, and its network infra red spectrum, as desired, be clearly to typical UHP-Y.In all cases, the SiO of the Y-82 product crossed of the steam-treated after acid extraction
2/ Al
2O
3Than than SiO through the Y-72 of steam-treated
2/ Al
2O
3Than higher (table 2).
The LZ-210 sample has kept its X-ray degree of crystallinity and its network infra red spectrum as to desired with the typical UHP-Y of known step preparation with Y-82, is clearly.Its difference only be the LZ-210 through a steam-treated have with through after steam-treated and the ammonium ion exchange, pass through the similar character of Y-82 of steam-treated again.The important dissimilarity of another of LZ-210 and Y-82 is Na in the product
2The content of O.Used LZ-210 contains 1.2%(weight) Na
2O, this Na
2O content obviously is higher than the 0.25%(weight of Y-82) Na
2O content.With prior art narrate opposite, it is thought, Na
2The content of O must be lower than 1.0%(weight).The previous research work of known to the applicant all is all thought: for producing the UHP-Y zeolite, the SiO that needs
2/ Al
2O
3Be limited to 6 on the ratio.Therefore, use a kind of SiO that has
2/ Al
2O
3Than being 8 or being higher than 8 and high Na
2The LZ-210 of O content is that known systems is dissenting fully.
Table 2
The characteristic of steam-treated sample
Crystallization keeps, the water vapor place
Area weight Si
2O/Al
2O
3H
2The O capacity, the reason time,
a
0(%) (%) is than 4.6 torrs hour acid concentration
Y-72
Sample 1 24.21 65.2 57.2 27 9.0 1 dense HCl
2 24.13 33.2 19.8 45 6.6 1 6N HCl
3 24.26 9.1 5.5 9 3.8 16 dense HCl
4 24.27 7.7 5.5 12 5.6 16 6N HCl
Y-82
Sample 1 24.26 94.9 86.6 33 5.8 1 dense HCl
2 24.26 93.7 85.1 79 7.6 1 6N HCl
3 24.27 91.7 80.9 21 4.1 16 dense HCl
4 24.27 84.7 72.6 113 2.5 16 6N HCl
LZ-210
（9.1）
Sample 1 24.28 92.7 79.7 50 4.1 1 dense HCl
2 24.24 105.2 99.4 68 1.7 1 6N HCl
3 24.26 76.3 66.1 18＜0.1 16 dense HCl
4 24.26 69.9 59.9 23 1.4 16 6N HCl
The example V
With SiO
2/ Al
2O
3Than the LZ-210 sample that is 6.2 and 9.0, use the step (600 ℃, 100% steam-treated 1 hour) of Y-72 and carry out steam-treated, and then carry out ammonium ion exchange and make it be similar to Y-82.With this kind sample 750 ℃ of 100% steam-treated 1 hour to produce UHP-Y type product.X-ray diffracting spectrum shows that this kind sample is the zeolite of highly crystalline and the infrared spectra network with typical super-hydrophobicity Y zeolite.For SiO
2/ Al
2O
3Than the LZ-210 that is 6.2 and 9.0, its surface-area is about 100 and 150 meters squared per gram respectively, all greater than the surface-area of typical UHP-Y.So even LZ-210 is being carried out steam-treated when producing a kind of UHP-Y, it also can generate a kind of more stable crystallinity zeolite.
Have been found that super-hydrophobicity LZ-210 zeolite among the present invention is preferably and has SiO
2/ Al
2O
3Than greater than 8, it is about 9 to 15 to be more preferably their ratio, and best be that their ratio is about 9 to 11.
The super-hydrophobicity LZ-210 of steam treatment of the present invention is a kind of new zeolitic material, has excursion bigger medium acidity and hydrophobicity than common UHP-Y.
Although invention has been described according to various embodiments, should be realized that the present invention is not subjected to the restriction of these embodiments, and can in the scope of each claim, implement.
Claims (22)
1, a kind of method for preparing super-hydrophobicity stone zeolite wherein with a kind of secondary synthesis step of Y zeolite process, is carried out one time the steam-treated step subsequently again.
2, a kind of according to the secondary synthesis step that the process of claim 1 wherein that this secondary synthesis step is a kind of LZ-210.
3, the method for claim 2, the SiO of wherein prepared LZ-210
2/ Al
2O
3Than being equal to or greater than 8.
4, the method for claim 2, the SiO of wherein prepared LZ-210
2/ Al
2O
3Than being 9.0 to 15.0.
5, the method for claim 2, the SiO of wherein prepared LZ-210
2/ Al
2O
3Than being 9.0 to 11.0.
6, a kind of method that right is wanted 1 ultrahydrophobic zeolite, SiO of the UHP zeolite that is wherein produced of preparing
2/ Al
2O
3Than greater than 8 and have an X-ray diffracting spectrum that is similar to Y zeolite.
7, a kind of ultrahydrophobic zeolite wherein contains a kind of Y zeolite, and this kind Y zeolite carries out one time the steam-treated step subsequently again through a kind of secondary synthesis step.
8, a kind of ultrahydrophobic zeolite, wherein this secondary synthesis step synthesis step that is a kind of LZ-210 according to claim 7.
9, a kind of ultrahydrophobic zeolite according to claim 7, the SiO of this kind zeolite
2/ Al
2O
3Ratio is greater than 8.
10, a kind of ultrahydrophobic zeolite according to claim 7, the SiO of this kind zeolite
2/ Al
2O
3Than being 9 to 15.
11, a kind of ultrahydrophobic zeolite according to claim 7, the SiO of this kind zeolite
2/ Al
2O
3Than being 9 to 11.
12, a kind of ultrahydrophobic zeolite according to claim 7, the SiO of this kind zeolite
2/ Al
2O
3Than greater than 8 and have an X-ray diffracting spectrum that is similar to the Y-zeolite.
13, a kind of catalyzer wherein contains a kind of ultrahydrophobic zeolite according to the prepared a kind of carrier of conduct of the method for claim 1.
14, a kind of catalyzer wherein contains a kind of ultrahydrophobic zeolite according to the prepared a kind of carrier of conduct of the method for claim 1, the SiO of described ultrahydrophobic zeolite
2/ Al
2O
3Ratio is greater than 8.
15, a kind of catalyzer wherein contains a kind of ultrahydrophobic zeolite according to the prepared a kind of carrier of conduct of the method for claim 1, the SiO of described ultrahydrophobic zeolite
2/ Al
2O
3Than being 9 to 15.
16, a kind of catalyzer wherein contains a kind of ultrahydrophobic zeolite according to the prepared a kind of carrier of conduct of the method for claim 1, the SiO of described ultrahydrophobic zeolite
2/ Al
2O
3Than being 9 to 11.
17, a kind of method according to claim 3 is wherein carried out cationic exchange subsequently with this product.
18, a kind of method according to claim 17, this wherein used positively charged ion is an ammonium ion.
19, a kind of method according to claim 3 is wherein carried out acid extraction subsequently with this product.
20, a kind of method according to claim 19 is wherein with this product hcl as extraction agent.
21, a kind of catalyzer wherein contains a kind of ultrahydrophobic zeolite by the prepared a kind of carrier of conduct of claim 17.
22, a kind of catalyzer wherein contains a kind of ultrahydrophobic zeolite by the prepared a kind of carrier of conduct of claim 19.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88109090 CN1041543A (en) | 1988-09-01 | 1988-10-01 | The preparation of ultrahydrophobic zeolite |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP88114256A EP0356560A1 (en) | 1988-09-01 | 1988-09-01 | Preparation of ultrahydrophobic zeolite |
| CN 88109090 CN1041543A (en) | 1988-09-01 | 1988-10-01 | The preparation of ultrahydrophobic zeolite |
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| Publication Number | Publication Date |
|---|---|
| CN1041543A true CN1041543A (en) | 1990-04-25 |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053429C (en) * | 1996-10-15 | 2000-06-14 | 中国石油化工总公司 | Super-hydrophobic Y zeolite and its preparing process |
-
1988
- 1988-10-01 CN CN 88109090 patent/CN1041543A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053429C (en) * | 1996-10-15 | 2000-06-14 | 中国石油化工总公司 | Super-hydrophobic Y zeolite and its preparing process |
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