CN1088408C - Process for modifying Ti-Si molecular sieve - Google Patents
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Abstract
The present invention provides a method for modifying titanium-silicon molecular sieve (TS-1), which comprises the following steps: uniformly mixing TS-1 molecular sieves synthesized already and acid compounds with water in order to react at 5 to 95 DEG C for 5 minutes to 6 hours; obtaining the acidized TS-1 molecular sieves; uniformly mixing the acidized TS-1 molecular sieves and organic base with water in order to react at 120 to 200 DEG C in a sealed reaction kettle for 2 hours to 8 days under self-generated pressure, wherein the organic base is fatty amine, alcohol amine or quaternary ammonium base types of compounds; filtering, washing and drying the obtained product. Because titanium outside of a skeleton in pore canals of the TS-1 molecular sieves is eliminated by the method of the present invention, the ineffective decomposition of oxidants is reduced. Consequently, the catalyzed oxidation activity is obviously improved compared with the prior art, and the TS-1 molecular sieves simultaneously have preferable catalytic activity and stability.
Description
The present invention relates to a kind of method of modifying of HTS, more particularly relate to a kind of method of modifying of five-membered ring HTS (TS-1) of the MFI of having structure.
HTS is the novel hetero-atom molecular-sieve that early eighties begins to develop.The TS-1 that MFI type structure is arranged that has synthesized at present, the TS-2 of MEL type structure, and have than the TS-48 of macroporous structure etc.This molecular sieve analog is to many organic oxidizing reactions, for example the reactions such as oxidation of the epoxidation of alkene, aromatic hydrocarbons hydroxylating, cyclohexanone oximate, alcohol have excellent catalytic activity and selective paraffin oxidation performance, and they have a good application prospect as redox (redox) type molecular sieve catalyst.
The TS-1 molecular sieve is that the transition metal titanium is introduced formed a kind of new titanium-silicone molecular sieve with good selective paraffin oxidation catalytic performance in the framework of molecular sieve with ZSM-5 structure.TS-1 not only has the catalysed oxidn of titanium, but also has the shape effect selected and the advantages of excellent stability of ZSM-5 molecular sieve.Because the TS-1 molecular sieve is in organic oxidation reaction, can adopt free of contamination low concentration hydrogen peroxide as oxidant, oxidizing process complex process and problem of environment pollution caused have been avoided, have unrivaled energy-conservation, economy of conventional oxidation system and advantages of environment protection, and have good reaction selectivity, therefore favorable industrial application prospect is arranged.
The synthetic method of TS-1 disclosed (GB2071071A, USP4,410,501) first by people such as gondola Marco Taramasso in 1981.This method is to prepare a kind of silicon source, titanium source, organic base (RN of containing earlier
+) and/or basic anhydride (Men/
2O) reactant mixture, with this reactant mixture in autoclave in 130～200 ℃ of hydrothermal crystallizings 6～30 days, separate then, wash, dry, roasting and product.Silicon source wherein can be tetraalkyl esters of silicon acis, colloidal state SiO
2Or alkali silicate, the titanium source can be hydrolyzable titanium compound, preferred Ti (OC
2H
5)
4, the preferred TPAOH of organic base, wherein the mole compositing range of reactant mixture is:
The general range preferable range
SiO
2/TiO
2： 5～200 35～65
OH-/SiO
2： 0.1～1.0 0.3～0.6
H
2O/SiO
2： 20～200 60～100
Me/SiO
2： 0～0.5 0
RN
+/SiO
2： 0.1～2.0 0.4～1.0
People such as Thangaraj think enter skeleton in the TS-1 molecular sieve that said method synthesizes effective Ti content seldom, so they disclose a kind of method (Zeolites that can effectively increase the synthetic TS-1 molecular sieve of skeleton Ti content in 1992,1992, Vol.12, P943～950), it is said that the Si/Ti of the method gained molecular sieve that people such as Taramasso can be proposed is than dropping to 20 from 39.This method is that an amount of TPAOH (TPAOH) aqueous solution is joined stirring and dissolving certain hour in the ethyl silicate solution, slowly adds the liquid mixture that the aqueous isopropanol of butyl titanate obtains clarifying then and (must slowly drip to prevent that tetrabutyl titanate hydrolysis is too fast and form white TiO under vigorous stirring
2Precipitation), stirs after 15 minutes, slowly add an amount of TPAOH aqueous solution again, catch up with alcohol to be transferred to after 3～6 hours in the autoclave in 75～80 ℃ reactant mixture then, get the TS-1 molecular sieve after the drying in 170 ℃ of following hydrothermal crystallizings 3～6 days.Wherein the mole of reactant mixture consists of: SiO
2: (0.01～0.10) TiO
2: 0.36 TPAOH:35H
2O.
Du Hongwei etc. have proposed a kind of preparation method of TS-1 molecular sieve in CN1167082A, this method is that the titanium source is dissolved in TPAOH (TPAOH) aqueous solution, and mix with the solid silicone bead and to obtain reactant mixture, with this reactant mixture in autoclave in 130～200 ℃ of hydrothermal crystallizings 1～6 day, filter according to a conventional method then, wash, drying and roasting.
The subject matter that exists in the prior art of above-mentioned synthetic TS-1 molecular sieve is: owing to there is the titanium of major part to be trapped in the duct of molecular sieve as the outer titanium of skeleton, the outer titanium of this part skeleton does not only play effective catalysed oxidn, but also caused the invalid decomposition of oxidant (hydrogen peroxide), therefore, cause prepared TS-1 molecular sieve catalytic oxidation activity low on the one hand, also acquisition has the TS-1 molecular sieve of good catalytic oxidation activity owing to the instability of the outer titanium amount of skeleton is difficult for stably on the other hand, the activity stability of gained TS-1 molecular sieve is relatively poor, has so restricted the commercial Application of TS-1 molecular sieve.
The objective of the invention is to overcome the shortcoming of prior art, the method for the HTS (TS-1) of the MFI structure that a kind of preparation has the outer titanium of less skeleton is provided, make gained TS-1 molecular sieve have better catalytic oxidation activity and activity stability preferably.
The method of modifying of HTS provided by the present invention (TS-1) comprising:
(1). TS-1 molecular sieve, acid compound and the water that will synthesize mix, and react 5 minutes to 6 hours down at 5～95 ℃, preferably react 10 minutes to 3 hours down at 15～60 ℃, obtain acid-treated TS-1 molecular sieve;
(2). (1) gained is mixed through acid-treated TS-1 molecular sieve, organic base and water, the gained mixture is put into sealed reactor, 2 hours to the 8 day time of reaction under 120～200 ℃ temperature and self-generated pressure, preferably reaction 2 hours to 3 days under 150～180 ℃ and self-generated pressure, with products therefrom filter, washing and dry.
Can also comprise repetition one or many step (1) and the described process of step (2) in the method provided by the present invention,, thereby improve the molecular sieve catalytic oxidation activity with the outer titanium amount of further minimizing framework of molecular sieve.
The said TS-1 molecular sieve of step in the method provided by the present invention (1) can be the TS-1 molecular sieve that synthesizes according to the whole bag of tricks of the prior art, and it can pass through or without calcination process, promptly can contain or not conform to organic formwork agent.
The said acid compound of step in the method provided by the present invention (1) can be organic acid compound such as aliphatic acid R (COOH)
n, wherein R is the alkyl with 1～4 carbon atom, n=1～2; Also can be inorganic mineral acid example hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, hydrofluoric acid etc.; Or bisalt compound such as ammonium chloride, ammonium phosphate, ammonium nitrate, ammonium sulfate and ammonium fluoride etc.; Wherein preferred acid compound is an inorganic acid.
The ratio of the said molecular sieve of step in the method provided by the present invention (1), acid compound and water is molecular sieve (gram): acid compound (mole): water (mole)=100: (0.010～2.0): (5～250) are preferably 100: (0.080～0.80): (10～100).
The said organic base of step in the method provided by the present invention (2) is fatty amine, alcamines or quaternary ammonium base compounds, wherein preferably alcamine compound or quaternary ammonium base compounds.
Its general formula of said fat amine compound is R (NH
2)
n, wherein R is the alkyl with 1～4 carbon atom, n=1～2, and wherein preferred fat amine compound is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
Its general formula of said alcamine compound is (HOR ')
mN, wherein R ' is the alkyl with 1～4 carbon atom, m=1～3, wherein preferred alcamine compound is MEA, diethanol amine or triethanolamine.
Said its general formula of quaternary ammonium base compounds is R "
3NOH, wherein R are " for having the alkyl of 1～4 carbon atom, preferably propyl group.
The ratio of the said molecular sieve of step in the method provided by the present invention (2), organic base and water is molecular sieve (gram): organic base (mole): water (mole)=100: (0.0050～0.50): (5～200) are preferably 100: (0.010～0.15): (20～80).
Fig. 1 is X-ray diffraction (XRD) the crystalline phase figure of embodiment 1 gained sample.
The present invention is owing to adopt the method for soda acid mixed processing, the outer titanium amount of skeleton of gained TS-1 molecular sieve is reduced, thereby make its catalytic oxidation activity compared with prior art obviously improve (seeing embodiment 9), have stability of catalytic activity (seeing embodiment 10) preferably simultaneously.
Following embodiment will the present invention is further illustrated.In each of the embodiments described below, used TPAOH is that the Tokyo changes into product, and all the other reagent are commercially available chemically pure reagent.
Comparative Examples 1
The effect of TS-1 molecular sieve is not synthesized in the explanation of this Comparative Examples according to the method for of the present invention, prior art (Zeolites, 1992, Vol.12, the 943rd～950 page).
The positive tetraethyl orthosilicate of 22.5 grams is mixed with 7.0 gram TPAOHs, and add 59.8 the gram distilled water, mix the back in normal pressure and 60 ℃ of following hydrolysis 1.0 hours, obtain the hydrating solution of positive tetraethyl orthosilicate, under vigorous stirring, add the solution of forming by 1.1 gram butyl titanates and 5.0 gram anhydrous isopropyl alcohols lentamente, the gained mixture was stirred 3 hours down at 75 ℃, obtain the clear colloid.This colloid is put into the stainless steel sealed reactor, and constant temperature was placed 6 days under 170 ℃ temperature and self-generated pressure, obtained the mixture of crystallization product; This mixture is filtered, is washed with water to pH is 6～8, and in 110 ℃ of dryings 60 minutes, obtains the former powder of TS-1.The former powder of this TS-1 in 550 ℃ of following air atmosphere roastings 4 hours, is got the TS-1 molecular sieve.Its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 1
The TS-1 molecular sieve of getting Comparative Examples 1 gained is according to molecular sieve (gram): sulfuric acid (mole): the ratio of water (mole)=100: 0.15: 150 mixes, reacted 5.0 hours down in 90 ℃, filter according to a conventional method then, wash and drying, obtain acid-treated TS-1 molecular sieve.
With above-mentioned acid-treated TS-1 molecular sieve according to molecular sieve (gram): triethanolamine (mole): the ratio of water (mole)=100: 0.35: 180 mixes, put into the stainless steel sealed reactor, constant temperature is placed 0.5 day time under 190 ℃ temperature and self-generated pressure, after the cooling release, filter according to a conventional method, wash, drying, and, obtaining the TS-1 molecular sieve of modification of the present invention 550 ℃ of following air atmosphere roastings 3 hours, its XRD crystalline phase figure is as shown in Figure 1.
Embodiment 2
The TS-1 molecular sieve of getting Comparative Examples 1 gained is according to molecular sieve (gram): hydrofluoric acid (mole): the ratio of water (mole)=100: 0.25: 60 mixes, reacted 3.0 hours down in 50 ℃, filter according to a conventional method then, wash and drying, obtain acid-treated TS-1 molecular sieve.
With above-mentioned through acid-treated TS-1 molecular sieve according to molecular sieve (gram): TPAOH (mole): the ratio of water (mole)=100: 0.010: 80 mixes, put into the stainless steel sealed reactor, constant temperature is placed 1 day time under 170 ℃ temperature and self-generated pressure, after the cooling release, filter according to a conventional method, wash, drying, and, obtaining the TS-1 molecular sieve of modification of the present invention 550 ℃ of following air atmosphere roastings 3 hours, its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 3
The TS-1 molecular sieve of getting Comparative Examples 1 gained is according to molecular sieve (gram): phosphoric acid (mole): the ratio of water (mole)=100: 1.55: 250 mixes, reacted 0.3 hour down in 68 ℃, filter according to a conventional method then, wash and drying, obtain acid-treated TS-1 molecular sieve.
With above-mentioned acid-treated TS-1 molecular sieve according to molecular sieve (gram): hexamethylene diamine (mole): the ratio of water (mole)=100: 0.50: 200 mixes, put into the stainless steel sealed reactor, constant temperature is placed 6 day time under 140 ℃ temperature and self-generated pressure, after the cooling release, filter according to a conventional method, wash, drying, and, obtaining the TS-1 molecular sieve of modification of the present invention 550 ℃ of following air atmosphere roastings 3 hours, its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 4
The TS-1 molecular sieve of getting Comparative Examples 1 gained is according to molecular sieve (gram): ammonium nitrate (mole): the ratio of water (mole)=100: 3.25: 200 mixes, reacted 1.5 hours down in room temperature (25 ℃), filter according to a conventional method then, wash and drying, obtain acid-treated TS-1 molecular sieve.
With above-mentioned acid-treated TS-1 molecular sieve according to molecular sieve (gram): n-butylamine (mole): the ratio of water (mole)=100: 0.18: 30 mixes, put into the stainless steel sealed reactor, constant temperature is placed 4.0 day time under 160 ℃ temperature and self-generated pressure, after the cooling release, filter according to a conventional method, wash, drying, and, obtaining the TS-1 molecular sieve of modification of the present invention 500 ℃ of following air atmosphere roastings 4 hours, its XRD crystalline phase figure and Fig. 2 are similar.
Embodiment 5
The unfired TS-1 molecular screen primary powder of getting Comparative Examples 1 gained is according to molecular sieve (gram): hydrochloric acid (mole): the ratio of water (mole)=100: 0.75: 260 mixes, reacted 6.0 hours down in 15 ℃, filter according to a conventional method then, wash and drying, obtain acid-treated TS-1 molecular sieve.
With above-mentioned acid-treated TS-1 molecular sieve according to molecular sieve (gram): butanediamine (mole): the ratio of water (mole)=100: 0.30: 10 mixes, put into the stainless steel sealed reactor, constant temperature is placed 3 day time under 155 ℃ temperature and self-generated pressure, after the cooling release, filter according to a conventional method, wash, drying, and, obtaining the TS-1 molecular sieve of modification of the present invention 600 ℃ of following air atmosphere roastings 2 hours, its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 6
The TS-1 molecular sieve of getting Comparative Examples 1 gained is according to molecular sieve (gram): ethanedioic acid (mole): the ratio of water (mole)=100: 4.5: 30 mixes, reacted 2.5 hours down in 80 ℃, filter according to a conventional method then, wash and drying, obtain acid-treated TS-1 molecular sieve.
With above-mentioned acid-treated TS-1 molecular sieve according to molecular sieve (gram): diethanol amine (mole): the ratio of water (mole)=100: 0.30: 50 mixes, put into the stainless steel sealed reactor, constant temperature is placed 2 day time under 165 ℃ temperature and self-generated pressure, after the cooling release, filter according to a conventional method, wash, drying, and, obtaining the TS-1 molecular sieve of modification of the present invention 550 ℃ of following air atmosphere roastings 3 hours, its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 7
The TS-1 molecular sieve of getting Comparative Examples 1 gained is according to molecular sieve (gram): ammonium fluoride (mole): the ratio of water (mole)=100: 0.05: 80 mixes, reacted 4.5 hours down in 35 ℃, filter according to a conventional method then, wash and drying, obtain acid-treated TS-1 molecular sieve.
With above-mentioned acid-treated TS-1 molecular sieve according to molecular sieve (gram): tetraethyl ammonium hydroxide (mole): the ratio of water (mole)=100: 0.25: 60 mixes, put into the stainless steel sealed reactor, constant temperature is placed 3 day time under 175 ℃ temperature and self-generated pressure, after the cooling release, filter according to a conventional method, wash, drying, and, obtaining the TS-1 molecular sieve of modification of the present invention 550 ℃ of following air atmosphere roastings 3 hours, its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 8
Repeat embodiment 7 described steps one time, the TS-1 molecular sieve that different is uses the method by embodiment 7 to obtain replaces the TS-1 molecular sieve of wherein said Comparative Examples 1 gained, promptly obtains according to of the present invention with the soda acid TS-1 molecular sieve of modification repeatedly.Its XRD crystalline phase figure and Fig. 1 are similar.
Embodiment 9
The method gained TS-1 molecular sieve of present embodiment explanation the inventive method and Comparative Examples is used for the effect of the catalytic oxidation of phenol hydroxylation.
The TS-1 molecular sieve that the foregoing description and Comparative Examples 1 is prepared is according to TS-1: phenol: the weight ratio of acetone=1: 20.0: 16.0 mixes in a there-necked flask that has a condenser pipe, be warming up to 80 ℃, then under stirring according to phenol: the weight ratio of hydrogen peroxide=1: 0.39 adds the hydrogen peroxide that concentration is 30 heavy %, reaction is 6 hours under this temperature, products therefrom uses the OV-101 capillary column on the Varian3400 chromatograph (30m * 0.25mm) measure each product to distribute the results are shown in Table 1.In table 1:
Table 1
| Title | Phenol conversion % | Benzenediol selectivity % | Product distribution % | ||
| Catechol | Hydroquinones | Benzoquinones | |||
| Embodiment 1 | 16.43 | 98.72 | 51.80 | 46.93 | 1.28 |
| Embodiment 2 | 21.82 | 99.18 | 52.29 | 46.88 | 0.82 |
| Embodiment 3 | 13.75 | 97.53 | 52.65 | 44.87 | 2.47 |
| Embodiment 4 | 15.64 | 98.34 | 49.17 | 49.17 | 1.66 |
| Embodiment 5 | 16.01 | 98.88 | 50.47 | 48.41 | 1.12 |
| Embodiment 6 | 12.10 | 96.86 | 50.74 | 46.12 | 3.14 |
| Embodiment 7 | 22.15 | 99.50 | 49.57 | 49.93 | 0.50 |
| Embodiment 8 | 22.72 | 99.34 | 50.26 | 49.08 | 0.66 |
| Comparative Examples 1 | 12.54 | 90.35 | 45.37 | 44.98 | 9.65 |
Embodiment 10
Activity stability when the method gained TS-1 molecular sieve of present embodiment explanation the inventive method and Comparative Examples is used for the catalytic oxidation of phenol hydroxylation.
The TS-1 molecular sieve that embodiment 1 and Comparative Examples 1 is prepared is respectively according to TS-1: phenol: the weight ratio of acetone=1: 20.0: 16.0 mixes in a there-necked flask that has a condenser pipe, be warming up to 80 ℃, then under stirring according to phenol: the weight ratio of hydrogen peroxide=1: 0.39 adds the hydrogen peroxide that concentration is 30 heavy %, reaction different time sampling under this temperature, institute's sample thief uses OV-101 capillary column (30m * 0.25mm) measure each product to distribute on the Varian3400 chromatograph, result of the test sees Table 2, and the definition of phenol conversion is identical with embodiment 9 in the table 2.As can be seen from Table 2 after the inventive method modification gained HTS and Comparative Examples 1 gained molecular sieve mutually specific activity improve, and activity stability is better, reaction time prolongs the back phenol conversion and does not descend, promptly further be not converted into tar and coke, illustrate that the outer Ti content of HTS skeleton after the inventive method modification is less.
Table 2 differential responses time phenol conversion (mole %)
| Reaction time h | 2 | 4 | 6 | 8 | 10 | 12 | 24 | 36 | 48 |
| Embodiment 1 | 16.57 | 20.64 | 22.72 | 22.68 | 22.59 | 22.14 | 22.05 | 21.27 | 21.08 |
| Comparative Examples 1 | 5.26 | 13.15 | 12.54 | 14.29 | 12.45 | 11.87 | 10.24 | 9.85 | 8.64 |
Claims (17)
1. method of modifying with HTS (TS-1) of MFI structure is characterized in that this method comprises:
(1). TS-1 molecular sieve, acid compound and the water that will synthesize mix, and under 5～95 ℃, reacted 5 minutes to 6 hours, obtain acid-treated TS-1 molecular sieve, wherein the ratio of molecular sieve, acid compound and water is molecular sieve (gram): acid compound (mole): water (mole)=100: (0.010～2.0): (5～250);
(2). (1) gained is mixed through acid-treated TS-1 molecular sieve, organic base and water, the gained mixture is put into sealed reactor, 2 hours to the 8 day time of reaction under 120～200 ℃ temperature and self-generated pressure, products therefrom is filtered, washs and drying, and wherein the ratio of molecular sieve, organic base and water is molecular sieve (gram): organic base (mole): water (mole)=100: (0.0050～0.50): (5～200).
2. according to the method for claim 1, it is characterized in that this method also comprises the described process of repetition one or many step (2).
3. according to the process of claim 1 wherein that the said TS-1 molecular sieve of step (1) is the TS-1 molecular sieve that synthesizes according to the whole bag of tricks of the prior art.
4. according to the process of claim 1 wherein that the said acid compound of step (1) is that general formula is R (COOH)
nThe organic fatty acid compounds, wherein R is selected from the alkyl with 1～4 carbon atom; N=1 or 2.
5. according to the process of claim 1 wherein that the said acid compound of step (1) is the inorganic acids compound that is selected from hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid and hydrofluoric acid.
6. according to the process of claim 1 wherein that the said acid compound of step (1) is the bisalt compound that is selected from ammonium chloride, ammonium fluoride, ammonium phosphate, ammonium nitrate and ammonium sulfate.
7. according to the process of claim 1 wherein that the ratio of the said molecular sieve of step (1), acid compound and water is molecular sieve (gram): acid compound (mole): water (mole)=100: (0.080～0.80): (10～100).
8. according to the process of claim 1 wherein in the step (1) that said reaction is 15～60 ℃ of reactions 10 minutes to 3 hours down.
9. according to the process of claim 1 wherein that the said organic base of step (2) is fat amine compound, alcamine compound or quaternary amine alkali compounds.
10. according to the method for claim 9, wherein said its general formula of fat amine compound is R (NH
2)
n, wherein R is selected from the alkyl with 1～4 carbon atom, n=1 or 2.
11. according to the method for claim 10, wherein said fat amine compound is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
12. according to the method for claim 9, wherein said its general formula of alcamine compound is (HOR ')
mN, wherein R ' is selected from the alkyl with 1～4 carbon atom, m=1,2 or 3.
13. according to the method for claim 12, wherein said alcamine compound is MEA, diethanol amine or triethanolamine.
14. according to the method for claim 9, wherein said its general formula of quaternary amine alkali compounds is R "
3NOH, wherein R " are selected from the alkyl with 1～4 carbon atom.
15. according to the method for claim 14, wherein said quaternary amine alkali compounds is a TPAOH.
16. according to the process of claim 1 wherein that the ratio of the said molecular sieve of step (2), organic base and water is molecular sieve (gram): organic base (mole): water (mole)=100: (0.010～0.15): (20～80).
17. according to the process of claim 1 wherein in the step (2) that said reaction is reaction 2 hours to 3 days under 150～180 ℃ and self-generated pressure.
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| CN106964400B (en) * | 2016-01-14 | 2019-09-24 | 中国石油化工股份有限公司 | The method of the forming method and preformed catalyst and its application and oxidizing cyclohexanone of Titanium Sieve Molecular Sieve |
| CN111484031B (en) * | 2019-01-28 | 2023-03-10 | 中国石油化工股份有限公司 | Modified titanium-silicon molecular sieve, preparation method and application thereof, and thioether oxidation method |
| CN113880101A (en) * | 2020-07-01 | 2022-01-04 | 中国石油化工股份有限公司 | TS-1 molecular sieve and preparation method and application thereof |
| CN114522719A (en) * | 2022-02-18 | 2022-05-24 | 广西科学院 | Preparation method and application of titanium silicalite molecular sieve catalyst |
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|---|---|---|---|---|
| US3828812A (en) * | 1971-06-14 | 1974-08-13 | B Read | Pressure-monitoring relief valve |
| US4853202A (en) * | 1987-09-08 | 1989-08-01 | Engelhard Corporation | Large-pored crystalline titanium molecular sieve zeolites |
| US5082641A (en) * | 1987-05-22 | 1992-01-21 | Rhone-Poulenc Chimie | Silicon/titanium oxide mfi zeolites |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3828812A (en) * | 1971-06-14 | 1974-08-13 | B Read | Pressure-monitoring relief valve |
| US5082641A (en) * | 1987-05-22 | 1992-01-21 | Rhone-Poulenc Chimie | Silicon/titanium oxide mfi zeolites |
| US4853202A (en) * | 1987-09-08 | 1989-08-01 | Engelhard Corporation | Large-pored crystalline titanium molecular sieve zeolites |
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