CN1071138C - Modifying method of beta zeolite - Google Patents
Modifying method of beta zeolite Download PDFInfo
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- CN1071138C CN1071138C CN97111954A CN97111954A CN1071138C CN 1071138 C CN1071138 C CN 1071138C CN 97111954 A CN97111954 A CN 97111954A CN 97111954 A CN97111954 A CN 97111954A CN 1071138 C CN1071138 C CN 1071138C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The present invention relates to a beta zeolite modification method which comprises that synthesized beta-zeolite raw power is uniformly mixed with a mixture of an Al2O3 source, a P2O5 source, an SiO2 source, H2O2 and water according to the weight ratio of beta-zeolite: Al2O3: P2O5: SiO2: H2O2: H2O is 1: (0.001 to 0.02): (0.01 to 0.30): (0 to 0.05): (0 to 0.10): (1.0 to 3.0). The mixture is dried to enhance temperature again to be baked for 1 to 5 hours at 400 to 650 DEG C., and then, the Na2O content is exchanged by ammonium ion to be less than 0.1 wt% by a conventional method. The method improves the activity stability of the beta-zeolite obviously, and the crystalline retaining degree of the beta-zeolite is improved simultaneously.
Description
The β zeolite is a kind of high silica alumina ratio mesoporous molecular sieve (USP 3308069) that U.S. Mobil company synthesized latter stage in the sixties, and its aperture is between macropore faujusite and mesopore Pentasil type zeolite, and the aperture is about 0.6 nanometer.β zeolite after the modification of process the whole bag of tricks can be used for hydrocracking, hydrofining, gently aliphatic hydrocarbon is converted into many petrochemical complex catalytic fields such as aromatic hydrocarbons, benzene alkylation, cracking, isomerization.In order to improve the catalytic performance of β zeolite, prior art has proposed many method of modifying at its application in differential responses, but at the β zeolite in cracking hydrocarbon reaction application and the method for modifying that carries out seldom sees report.
The aperture ratio ZSM-5 molecular sieve of beta-molecular sieve is big, and has excellent isomerization performance, might be good as gasoline selective, one of the active component in the catalytic cracking catalyst that gasoline octane rating is high.But beta-molecular sieve subject matter in use is that its structure is suffered damage on the one hand, is that easily dealuminzation thereby activity stability are relatively poor in reaction process on the other hand.
Having proposed a kind of method among the USP4605637, is to use microporous crystalline AlPO down in 80～370 ℃ in the liquid phase water system
4-5 aluminum phosphate materials such as grade are handled low tart zeolite for example the β zeolite, high silica ZSM-5 zeolite etc. of ZSM-5 zeolite, the boracic of boracic, the aluminium nuclear power is moved in the skeleton of zeolite, thereby improve the acidity of zeolite, increase lytic activity.
A kind of method of modifying of β zeolite has been proposed among the CN1043450A, this method is that Na β zeolite is taken out the part framework aluminum with acid after roasting, carrying out potassium exchange then, to make the zeolite potassium content be 0.5～2.5 heavy %, after drying and the roasting with comprising potassium hydrogen phosphate-potassium primary phosphate, Hypophosporous Acid, 50-potassium hypophosphite, phosphorous acid-potassium phosphite is interior, nearly neutral microcosmic salt buffered soln at room temperature soaked 4～10 hours, take the circumstances into consideration washing or do not wash to make that phosphorus content is 0.01～0.5 heavy % on the zeolite, dry then, roasting, be suitable for as the hydrocarbon processing catalyzer that relates to hydroisomerization reaction through the β zeolite after this method modification, but be not suitable as hydrocarbon cracking catalyzer, and the phosphorus on the dipping runs off easily at aqueous phase.
Present β zeolite all is synthetic by using organic formwork agent such as tetraethyl ammonium hydroxide, must will be blocked in organic formwork agent in the β zeolite cavity and remove and just can make it have catalytic activity before using as catalyzer.The organic formwork agent that employing standard roasting method removes in the β zeolite needs the long time, and the degree of crystallinity of zeolite descends more.Proposed a kind of method that removes organic amine template in the zeolite among the CN1117472A, promptly add the oxygenant that is selected from perchloric acid, hypochlorous acid or their salt of 1～40 heavy % in zeolite, roasting is 1～5 hour in 300～500 ℃ air.This method has improved takes off amine speed, improved the crystallization reservation degree that takes off the zeolite behind the amine, but this oxidizing roasting method can only make removing of organic formwork agent become easy, can not suppress its dealuminzation problem in use effectively, promptly can not solve the problem of beta-molecular sieve activity stability difference.
One of purpose of the present invention provides a kind of method of modifying of β zeolite, makes that the β zeolite after the modification has higher activity stability.
Two of purpose of the present invention provides a kind of method of modifying of β zeolite, makes that the β zeolite after the modification also has higher crystallization reservation degree when having higher activity stability.
The method of modifying of β zeolite provided by the present invention comprises: the β zeolite powder that will synthesize with contain Al
2O
3Source, P
2O
5Source, SiO
3Source, H
2O
2And the mixture of water is according to β zeolite: Al
2O
3: P
2O
5: SiO
2: H
2O
2: H
2O=1: (0.001～0.02): (0.01～0.30): (0～0.05): (0～0.10): the weight ratio of (1.0～3.0) mixes, after drying, be warming up to 400～650 ℃ of roastings 1～5 hour again, use then ordinary method through ammonium ion exchange to its Na
2O content is less than 0.1 heavy %.
Said Al in the method provided by the present invention
2O
3The source is meant aluminium hydroxide material or aluminum phosphates such as pseudo-boehmite, single diaspore, gibbsite; Pseudo-boehmite preferably wherein.
Said P in the method provided by the present invention
2O
5The source can be phosphoric acid or phosphoric acid salt, wherein phosphoric acid preferably.
Said SiO in the method provided by the present invention
2The source can be silicon gel, silicon sol or water glass, wherein preferably silicon sol or water glass.
Said β zeolite, Al in the method provided by the present invention
2O
3Source, P
2O
5Source, SiO
2Source, H
2O
2Deng mixing by arbitrary order.
The speed of said intensification is preferably 2～10 ℃/minute in the method provided by the present invention, and the roasting method of temperature programming is preferably adopted in wherein said roasting.
Said ammonium exchange also can be carried out before carrying out activation treatment with said mixture in the method provided by the present invention.
After with method provided by the present invention the β zeolite being carried out modification, since the oxide compound in the activator under the high-temperature roasting condition, can migrate in the framework of molecular sieve by the sedimentation state on molecular sieve surface with molecular sieve in skeletal atom form the certain structure form, thereby can suppress removing of skeleton Al in the molecular sieve effectively, improve the activity stability of molecular sieve.Improve a lot (bringing up to more than 95%) and olefins yield also has raising (seeing Table 1) with the pure hydrocarbon pyrolysis of the β zeolite after the inventive method modification after aging through 800 ℃/4 hours harsh water vapor conditions is active by 55.7% with the β zeolite of common roasting method modification.If in activator, also contain H in the method provided by the present invention
2O
2Oxygenant, owing to this oxygenant can be easier to the organic formwork agent oxidation in the β zeolite cavity to remove, make its structure loss in the process of removed template method of β zeolite less, crystallization reservation degree improves, and oxide compound activates and the oxidizing roasting removed template method can be finished in one step of while, and technology is simple.
The following examples will the present invention is further illustrated.
Comparative Examples 1
With the former powder of beta-molecular sieve (Fushun No.3 Petroleum Factory's product, with the tetraethyl ammonium hydroxide is template production, silica alumina ratio is 30) put into stoving oven and be heated to 350 ℃ of roastings 1 hour with 2～3 ℃/minute heat-up rate, be warming up to 450 ℃ of roastings 1 hour with this heat-up rate again, be warming up to 550 ℃ of roastings 2 hours to remove the template in the beta-molecular sieve with 5～7 ℃/minute heat-up rate again, use NH after the cooling
4Cl solution is according to β zeolite: NH
4Cl: H
2O=1: 1: 20 weight ratio exchanges the Na that makes in the molecular sieve according to a conventional method twice
2O content is less than 0.1 heavy %, and gained sample note is made C-1.This sample of X-ray diffraction (XRD) analysis revealed is compared its crystallization reservation degree and is 75% at (the 2 θ angles that will obtain with slow sweep be the peak area of 22.4 ° diffraction peak compare obtain) with the former powder of beta-molecular sieve before the roasting.
Sample C-1 behind 800 ℃/4 hours, 100 ℃ water vapor hydrothermal agings, is carried out normal heptane (nC with pulse micro-inverse-chromatogram arrangement
7) pure hydrocarbon pyrolysis activity rating (100 milligrams of sample loading amounts, nC
7Sample size 0.5 microlitre, 480 ℃ of temperature of reaction), record its n C
7Cracking conversion rate is 55.8%.
Embodiment 1
20.4 gram phosphoric acid (concentration is 85 heavy %, down together) are joined mixing in the 350 gram water, to wherein adding 1.17 gram pseudo-boehmite (Al
2O
3Content is 73.8 heavy %, together following) and stir, add the former powder of 300 gram beta-molecular sieves again (with Comparative Examples 1, solid content is 72.2 heavy %, down together), continue to stir after 1 hour, (concentration is 30 heavy % to wherein adding 44.0 gram aqueous hydrogen peroxide solutions, together following) and stir, with the gained mixture in 60 ℃ down air-dry after, put into muffle furnace and be heated to 350 ℃ of roastings 1 hour with 2～3 ℃/minute heat-up rate earlier, be heated to 450 ℃ of roastings 1 hour with this heat-up rate again, be warming up to 550 ℃ of roastings 2 hours, cooled sample NH with 5～7 ℃/minute heat-up rate then
4Cl solution exchanges the Na that makes in the molecular sieve according to a conventional method twice
2O content is less than 0.1 heavy %, and gained sample note is made E-1.XRD analysis shows that it is 85% that this sample is compared its crystallization reservation degree with the former powder of beta-molecular sieve before the roasting.
Behind 800 ℃/4 hours, 100 ℃ water vapor hydrothermal agings, recording its normal heptane cracking conversion rate with pulse micro-inverse-chromatogram arrangement is 92.1% with sample E-1.
Embodiment 2
16.4 gram phosphoric acid are joined mixing in the 280 gram water, restrain pseudo-boehmites to wherein adding 1.90, and stir, add the former powder of 138 gram beta-molecular sieves again, fully behind the mixing, add 20.0 gram aqueous hydrogen peroxide solutions again, continue to stir 30 minutes, at room temperature air-dry then.The gained mixture is placed muffle furnace, elder generation is heated to 350 ℃ of roastings 1 hour with 2～3 ℃/minute heat-up rate, be heated to 450 ℃ of roastings 1 hour with this heat-up rate again, be warming up to 550 ℃ of roastings 2 hours, cooled sample NH with 5～7 ℃/minute heat-up rate then
4Cl solution exchanges the Na that once makes in the molecular sieve according to a conventional method
2O content is less than 0.1 heavy %, and gained sample note is made E-2.XRD analysis shows that it is 86% that this sample is compared its crystallization reservation degree with the former powder of beta-molecular sieve before the roasting.
Behind 800 ℃/4 hours, 100 ℃ water vapor hydrothermal agings, recording its normal heptane cracking conversion rate with pulse micro-inverse-chromatogram arrangement is 95.0% with sample E-2.
Embodiment 3
With 9.40 gram phosphoric acid and 15.4 gram silicon sol (Changhong chemical plant, the 90 middle school, Beijing product, SiO
2Content is 26.0 heavy %, down with) join in the 300 gram water and stir, to wherein adding 1.10 gram pseudo-boehmites, and stir, add the former powder of 138 gram beta-molecular sieves again, continue to stir 40 minutes, add 27.0 gram aqueous hydrogen peroxide solutions and stirring then, with the gained mixture after 110 ℃ of dryings, put into the first heat-up rate of muffle furnace and be heated to 350 ℃ of roastings 1 hour with 2～3 ℃/minute, be warming up to 600 ℃ of roastings 2 hours, cooled sample NH with 5～7 ℃/minute heat-up rate again
4Cl solution exchanges the Na that once makes in the molecular sieve according to a conventional method
2O content is less than 0.1 heavy %, and gained sample note is made E-3.XRD analysis shows that it is 87% that this sample is compared its crystallization reservation degree with the former powder of beta-molecular sieve before the roasting.
Behind 800 ℃/4 hours, 100 ℃ water vapor hydrothermal agings, recording its normal heptane cracking conversion rate with pulse micro-inverse-chromatogram arrangement is 98.0% with sample E-3.
Embodiment 4
1.50 gram phosphoric acid are joined 200 grams to stir in the water, to wherein adding 1.10 gram pseudo-boehmites, and mix, the former powder of 138 gram beta-molecular sieves is joined in the said mixture, stir after one hour, add 23.0 gram aqueous hydrogen peroxide solutions and stirring again, with the gained mixture after 60 ℃ of following dryings, put into the first heat-up rate of muffle furnace and be heated to 350 ℃ of roastings 1 hour with 2～3 ℃/minute, be heated to 500 ℃ of roastings 3 hours, cooled sample NH with 5～7 ℃/minute heat-up rate again
4Cl solution exchanges the Na that makes in the molecular sieve according to a conventional method twice
2O content is less than 0.1 heavy %, and gained sample note is made E-4.XRD analysis shows that it is 82% that this sample is compared its crystallization reservation degree with the former powder of beta-molecular sieve before the roasting.
Behind 800 ℃/4 hours, 100 ℃ water vapor hydrothermal agings, recording its normal heptane cracking conversion rate with pulse micro-inverse-chromatogram arrangement is 93.0% with sample E-4.
Embodiment 5
16.4 gram phosphoric acid are joined 200 grams to stir in the water, to wherein adding 1.90 gram pseudo-boehmites and mixing, the 138 gram former powder of beta-molecular sieve and 17.0 gram superoxols are joined in the said mixture and continue stirred 30 minutes, with the gained mixture after 60 ℃ of following dryings, put into muffle furnace and be heated to 500 ℃ of roastings 2 hours, cooled sample NH with 4 ℃/minute heat-up rate
4Cl solution exchanges the Na that makes in the molecular sieve according to a conventional method twice
2O content is less than 0.1 heavy %, and gained sample note is made E-5.XRD analysis shows that it is 80% that this sample is compared its crystallization reservation degree with the former powder of beta-molecular sieve before the roasting.
Behind 800 ℃/4 hours, 100 ℃ steam agings, recording its normal heptane cracking conversion rate with pulse micro-inverse-chromatogram arrangement is 90.2% with sample E-5.
Embodiment 6
28.2 gram phosphoric acid are joined 600 grams stir in the water, to wherein adding 5.0 gram solid silicone (Qingdao silica gel factory product, SiO
2Content is 96 heavy %) and 1.6 restrain pseudo-boehmites and stir, the 415 gram former powder of beta-molecular sieve and 20.0 gram aqueous hydrogen peroxide solutions are joined in the said mixture and continue stirred 20 minutes, with the gained mixture after 60 ℃ of following dryings, put into the first heat-up rate of muffle furnace and be heated to 350 ℃ of roastings 1 hour with 2～3 ℃/minute, be heated to 550 ℃ of roastings 2 hours with 5～7 ℃/minute heat-up rate again, cooled sample is with (NH
4)
2SO
4Solution exchanges the Na that makes in the molecular sieve according to a conventional method twice
2O content is less than 0.1 heavy %, and gained sample note is made E-6.XRD analysis shows that it is 86% that this sample is compared its crystallization reservation degree with the former powder of beta-molecular sieve before the roasting.
Behind 800 ℃/4 hours, 100 ℃ steam agings, recording its normal heptane cracking conversion rate with pulse micro-inverse-chromatogram arrangement is 93.6% with sample E-6.
Embodiment 7
With 7.00 gram water glass (Qilu Petrochemical company Zhou village catalyst plant product, SiO
2Content is 20.0 heavy %) join in the 200 gram water and mix, stirring adds 9.4 gram phosphoric acid down and stirs, to wherein adding 0.60 gram pseudo-boehmite and stirring evenly, the 138 gram former powder of beta-molecular sieve and 30.0 gram aqueous hydrogen peroxide solutions are joined in the said mixture and continue stirred 30 minutes, with the gained mixture after 60 ℃ of following dryings, put into the first heat-up rate of muffle furnace and be heated to 450 ℃ of roastings 4 hours, cooled sample NH with 4 ℃/minute
4Cl solution exchanges the Na that makes in the molecular sieve according to a conventional method twice
2O content is less than 0.1 heavy %, and gained sample note is made E-7.XRD analysis shows that it is 85% that this sample is compared its crystallization reservation degree with the former powder of beta-molecular sieve before the roasting.
Behind 800 ℃/4 hours, 100 ℃ steam agings, recording its normal heptane cracking conversion rate with pulse micro-inverse-chromatogram arrangement is 96.7% with sample E-7.
Embodiment 8
13.3 gram silicon sol are joined in the 380 gram water, under agitation add 20.4 gram phosphoric acid again, add 1.17 gram pseudo-boehmites then, stir after 30 minutes,, continue to stir 30 minutes to wherein adding the former powder of 300 gram beta-molecular sieves, with the gained mixture after 60 ℃ of following dryings, put into muffle furnace and be heated to 350 ℃ of roastings 1 hour, be heated to 550 ℃ of roastings 2 hours with identical heat-up rate then, cooled sample NH with 4 ℃/minute heat-up rate
4Cl solution exchanges the Na that makes in the molecular sieve according to a conventional method twice
2O content is less than 0.1 heavy %, and gained sample note is made E-8.XRD analysis shows that it is 75% that this sample is compared its crystallization reservation degree with the former powder of beta-molecular sieve before the roasting.
Behind 800 ℃/4 hours, 100 ℃ steam agings, recording its normal heptane cracking conversion rate with pulse micro-inverse-chromatogram arrangement is 92.3% with sample E-8.
Embodiment 9
2.70 gram pseudo-boehmites are joined in the 530 gram water, stir the 17.6 gram phosphoric acid of adding down, the former powder NH of 348 gram beta-molecular sieves
4Cl solution exchanges the Na that makes in the molecular sieve according to a conventional method twice
2O content joins in the said mixture after weighing % less than 0.1, and continue to stir 30 minutes, with the gained mixture after 120 ℃ of following dryings, put into muffle furnace and be heated to 350 ℃ of roastings 1 hour with 4 ℃/minute heat-up rate, be heated to 550 ℃ of roastings 3 hours with identical heat-up rate again, cooling back gained sample note is made E-9.XRD analysis shows that it is 74% that this sample is compared its crystallization reservation degree with the former powder of beta-molecular sieve before the roasting.
Behind 800 ℃/4 hours, 100 ℃ steam agings, recording its normal heptane cracking conversion rate with pulse micro-inverse-chromatogram arrangement is 93.6% with sample E-9.
Embodiment 10
Comparative Examples 1, embodiment 1 and embodiment 8 prepared sample C-1, E-1 and E-8 mixed with semi-synthetic carrier (the heavy % pseudo-boehmites in 75 heavy % kaolin+25) respectively be spray dried to three kinds of catalyzer according to a conventional method, note is made CC-1, CE-1 and CE-8 respectively, and the content of sieve sample C-1, E-1 and E-8 all is 15 heavy % in the catalyzer.(evaluation method is seen " petrochemical complex analytical procedure (RIPP test method) " through carrying out the light oil micro anti-evaluation behind 800 ℃/12 hours, 100% water vapor hydrothermal aging with these three kinds of catalyzer, Yang Cui waits volume surely, Science Press, and nineteen ninety publishes, the 263rd page), evaluation result is as shown in table 1.Table 1 data show that the β zeolite with the inventive method modification has the active and gas olefins yield of higher hydrocarbon cracking than conventional β zeolite.
Table 1
| The catalyzer numbering | CC-1 | CE-1 | CE-8 |
| Temperature of reaction (℃) | 520 | 520 | 520 |
| Micro anti-active index | 63 | 67 | 70 |
| Product distribution (heavy %) H 2-C 2 C 3-C 4 C 5-216 ℃ of fraction＞216 ℃ fraction coke+losses | 1.46 20.44 32.86 37.02 8.22 | 1.34 21.55 36.66 33.02 7.42 | 1.37 22.38 41.04 30.33 4.88 |
| Gas olefins yield (heavy %) | 14.12 | 15.20 | 15.95 |
Claims (9)
1. the method for modifying of a β zeolite is characterized in that this method comprises the β zeolite powder that will synthesize and contains Al
2O
3Source, P
2O
5Source, SiO
2Source, H
2O
2And the mixture of water is according to β zeolite: Al
2O
3: P
2O
5: SiO
2: H
2O
2: H
2O=1: (0.001～0.02): (0.01～0.30): (0～0.05): (0～0.10): the weight ratio of (1.0～3.0) mixes, after drying, be warming up to 400～650 ℃ of roastings 1～5 hour again, use then ordinary method through ammonium ion exchange to its Na
2O content weighs % less than 0.1,
2. according to the process of claim 1 wherein said Al
2O
3The source is meant aqua oxidation aluminum or the aluminum phosphate that comprises pseudo-boehmite, single diaspore, gibbsite.
3. according to the method for claim 2, wherein said Al
2O
3The source is a pseudo-boehmite.
4. according to the process of claim 1 wherein said P
2O
5The source is phosphoric acid or phosphoric acid salt.
5. according to the method for claim 4, wherein said P
2O
5The source is a phosphoric acid.
6. according to the process of claim 1 wherein said SiO
2The source is silicon sol, silicon gel or water glass.
7. according to the process of claim 1 wherein that the speed of said intensification is 2～10 ℃/minute.
8. according to the process of claim 1 wherein that said roasting is the roasting method that adopts temperature programming.
9. carried out before carrying out activation treatment according to the process of claim 1 wherein that said ammonium exchanges with said mixture.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97111954A CN1071138C (en) | 1997-07-10 | 1997-07-10 | Modifying method of beta zeolite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97111954A CN1071138C (en) | 1997-07-10 | 1997-07-10 | Modifying method of beta zeolite |
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|---|---|
| CN1205249A CN1205249A (en) | 1999-01-20 |
| CN1071138C true CN1071138C (en) | 2001-09-19 |
Family
ID=5171976
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|---|---|---|---|
| CN97111954A Expired - Lifetime CN1071138C (en) | 1997-07-10 | 1997-07-10 | Modifying method of beta zeolite |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100425534C (en) | 2005-05-31 | 2008-10-15 | 中国石油化工股份有限公司 | Modified beta zeolite |
| CN101205072B (en) * | 2006-12-18 | 2011-04-20 | 中国石油化工股份有限公司 | Method for synthesizing low silica-alumina ratio beta zeolite |
| WO2010099650A1 (en) * | 2009-03-03 | 2010-09-10 | Basf Se | Isomorphously substituted silicate |
| CN104549457B (en) * | 2013-10-22 | 2017-05-24 | 中国石油化工股份有限公司 | Preparation method of iron-containing beta zeolite |
| CN104841477B (en) * | 2015-05-04 | 2018-09-14 | 北京旭阳科技有限公司 | Preparation method for 2- methyl naphthalenes and the catalyst of n butanoic anhydride acylation reaction |
| CN105249563A (en) * | 2015-11-13 | 2016-01-20 | 无锡桥阳机械制造有限公司 | Mask for preventing and treating haze |
| CN106994364B (en) * | 2016-01-25 | 2019-07-23 | 中国石油化工股份有限公司 | A kind of method of phosphorous modified ZSM-5 molecular sieve |
| CN112691650B (en) * | 2019-10-23 | 2022-09-06 | 中国石油化工股份有限公司 | Adsorbent and preparation method and application thereof |
| CN113880666B (en) * | 2021-09-29 | 2022-12-16 | 浙江省农业科学院 | Mineral-based soil conditioner for improving coastal saline soil and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4605637A (en) * | 1983-02-14 | 1986-08-12 | Mobil Oil Corporation | Hydrothermal activation of acid zeolites with aluminum phosphates |
| CN1043450A (en) * | 1988-12-17 | 1990-07-04 | 中国石油化工总公司石油化工科学研究院 | The method of modifying of β zeolite |
| US5030786A (en) * | 1989-06-23 | 1991-07-09 | Fina Technology, Inc. | Liquid phase aromatic conversion process |
| US5457078A (en) * | 1993-11-29 | 1995-10-10 | Mobil Oil Corporation | Manufacture of improved zeolite Beta catalyst |
| EP2174280A1 (en) * | 2007-06-20 | 2010-04-14 | QUALCOMM Incorporated | Dynamic electronic coupon for a mobile environment |
-
1997
- 1997-07-10 CN CN97111954A patent/CN1071138C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4605637A (en) * | 1983-02-14 | 1986-08-12 | Mobil Oil Corporation | Hydrothermal activation of acid zeolites with aluminum phosphates |
| CN1043450A (en) * | 1988-12-17 | 1990-07-04 | 中国石油化工总公司石油化工科学研究院 | The method of modifying of β zeolite |
| US5030786A (en) * | 1989-06-23 | 1991-07-09 | Fina Technology, Inc. | Liquid phase aromatic conversion process |
| US5457078A (en) * | 1993-11-29 | 1995-10-10 | Mobil Oil Corporation | Manufacture of improved zeolite Beta catalyst |
| EP2174280A1 (en) * | 2007-06-20 | 2010-04-14 | QUALCOMM Incorporated | Dynamic electronic coupon for a mobile environment |
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|---|---|
| CN1205249A (en) | 1999-01-20 |
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