CN103395799A - Preparation method for titanium silicalite molecular sieve and applications - Google Patents
Preparation method for titanium silicalite molecular sieve and applications Download PDFInfo
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- CN103395799A CN103395799A CN2013103425009A CN201310342500A CN103395799A CN 103395799 A CN103395799 A CN 103395799A CN 2013103425009 A CN2013103425009 A CN 2013103425009A CN 201310342500 A CN201310342500 A CN 201310342500A CN 103395799 A CN103395799 A CN 103395799A
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Abstract
The invention discloses a titanium silicalite molecular sieve, a preparation method therefor and applications. The titanium silicalite molecular sieve is uncalcined titanium silicalite molecular sieve TS-1. The invention also discloses a new catalyst applied to systems of direct preparation of epoxypropane from propylene through gas-phase epoxidation. The catalyst employs the uncalcined titanium silicalite molecular sieve TS-1 as a carrier and loads the carrier with metal particles.
Description
Technical field
The present invention relates to catalyzer, relate in particular to blocked titanium-silicon molecular sieve TS-1 of a kind of micropore and preparation method thereof and prepare the purposes of propylene oxide system at the direct gas-phase epoxidation of propylene.
Background technology
Propylene oxide (PO) is a kind of important chemical intermediate, is the third-largest Organic chemical products that in acryloyl derivative, output is only second to polypropylene and vinyl cyanide.It is widely used in producing polyethers, propylene glycol, urethane etc., be also the 4th generation washing composition nonionogenic tenside, oil field demulsifier, farm chemical emulgent etc. main raw material, development prospect is wide.At present, in industry, the main method of production PO is chlorohydrination and conjugated oxidation.Yet chlorohydrination produces a large amount of waste water and chlorine byproducts in process of production, and large to equipment corrosion, does not meet the requirement of current environmental protection.And the economy of conjugated oxidation is subject to the restriction of a large amount of by products.Under the coexistence of hydrogen gas and oxygen condition, the method for working load gold catalyst catalyzing preparing epoxypropane by epoxidation of propene has environmental protection, simple to operate, selectivity high (〉 90%) etc. advantage, be subject to domestic and international extensive concern.In the middle of this system, although traditional HTS (TS-1) is compared and is had stronger hydrophobicity with other carriers, thereby the desorption that can promote the product propylene oxide improves the stability of catalyzer with active, but still there is significant inactivation problem (document 1:J.Catal.2012 in catalyzer, 287,178 – 189).Although report is arranged recently about using solid-state polishing to prepare the load gold catalyst of high stability, but catalyzer need to use expensive presoma, and this preparation method can't optionally be deposited on gold grain near the active sites titanium of HTS, wasted a part of gold, also invisible catalyzer cost (the document 2:Appl.Catal.B:Environ.2010 that increased, 95,430 – 438).Therefore, guaranteeing catalyzer simultaneously cheaply, the activity, the stability that improve catalyzer are problem demanding prompt solutions.
Summary of the invention
The present invention aims to provide the blocked titanium-silicon molecular sieve TS-1 preparation method of a kind of new micropore and the purposes for preparing the propylene oxide system at the direct gas-phase epoxidation of propylene.
In a first aspect of the present invention, a kind of preparation method of titanium-silicon molecular sieve TS-1 is provided, described method comprises step:
(1) the silicon source is mixed with the mixing solutions 1 that contains micropore template, tensio-active agent and water, obtain mixing solutions 2;
(2) mixing solutions 2 is mixed with the mixing solutions 3 that contains titanium source and Virahol, obtain solution A; With
(3) solution A is removed alcohol, centrifugal after crystallization, washing and dry, obtained the titanium-silicon molecular sieve TS-1 of not roasting.
In another preference, described tensio-active agent is tween 20; In mixing solutions 1, tween 20 is 1.5-10g, and water is 25-100g; More preferably tween 20 is 2.5-10g, water 40-100g; Most preferably tween 20 is 2g, water 25-40g.
In another preference, the molar concentration rate in described silicon source, micropore template, titanium source is 1:0.1-0.3:0.002-0.03.
In another preference, in step (2), mixing solutions 3 drops in solution 2 and obtains solution A, and drop rate is 0.1-0.5ml/ minute, and more preferably 0.2-0.5ml/ minute, most preferably be 0.1-0.2ml/ minute.
In another preference, in step (3), mixed solution A is removed pure 2-6 hour; More preferably except pure 2-4 hour; Most preferably except pure 4-6 hour.
In a second aspect of the present invention, the titanium-silicon molecular sieve TS-1 of a kind of use not roasting that preparation method provided by the invention as above prepares is provided, described molecular sieve pore passage is stopped up by the micropore template, and molecular sieve is exposed outer surface only.
In a third aspect of the present invention, a kind of low charge capacity catalyzer is provided, described catalyzer is take not roasting HTS provided by the invention as above as the carrier to load metal particle; Described metallic particles is gold nano grain; Preferably charge capacity is 0.02-0.3%, and more preferably charge capacity is 0.02-0.1%, and charge capacity is 0.1-0.3% best.
In a fourth aspect of the present invention, a kind of preparation method of catalyzer provided by the invention as above is provided, described method comprises step: not roasting HTS provided by the invention as above and chlorauric acid solution are mixed, use mineral alkali or organic bases to reconcile pH, aging rear centrifugal, dry, obtain catalyzer provided by the invention as above.
In another preference, the digestion time of solution is 1-16 hour.
In another preference, the centrifugation rotating speed is 4000 rev/mins.
In another preference, at room temperature vacuum-drying 12 hours.
In a fifth aspect of the present invention, provide a kind of propylene gas-phase epoxidation that improves to prepare the method for propylene oxide activity and stability, use catalyzer provided by the invention as above.
Accordingly, provide a kind of solution to guarantee catalyzer simultaneously cheaply, the scheme of the activity of raising catalyzer, the problem of stability.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of the blocked titanium-silicon molecular sieve TS-1 of micropore in embodiment 1.
Fig. 2 is the UV-vis figure of the blocked titanium-silicon molecular sieve TS-1 of micropore in embodiment 1.
Fig. 3 is the transmission electron microscope TEM figure of the blocked titanium-silicon molecular sieve TS-1 of micropore in embodiment 1.
Fig. 4 is the scanning electron microscope sem figure of the blocked titanium-silicon molecular sieve TS-1 of micropore in embodiment 1.
Fig. 5 is N2 physical adsorption and the graph of pore diameter distribution of the blocked titanium-silicon molecular sieve TS-1 of micropore in embodiment 1.
Fig. 6 is the activity of propylene oxide in different embodiment (PO) and the difference of stability.
Embodiment
The contriver is through extensive and deep research, found that a kind of catalyst stability that improves namely prepares the blocked titanium-silicon molecular sieve TS-1 of micropore with active method, use simultaneously the deposition-precipitator method can selectivity with deposition of gold near the outside surface active sites titanium of TS-1, therefore under the prerequisite that guarantees low charge capacity, can improve catalyst activity and life-span.On this basis, completed the present invention.
As used herein, " room temperature " refers to 15-30 ℃, preferred 20-25 ℃.
The titanium-silicon molecular sieve TS-1 that micropore is blocked
The invention provides the blocked titanium-silicon molecular sieve TS-1 of a kind of micropore, compared to HTS of the prior art, its micropore is stopped up by template or other inert substances, mainly exposes its outside surface.
The blocked titanium-silicon molecular sieve TS-1 of micropore provided by the invention prepares by following step:
The first step, add the micropore template in the mixing solutions that contains tensio-active agent and water, obtains alkaline mixed solution 1;
Second step, be added to the silicon source in mixing solutions 1, obtains mixing solutions 2;
The 3rd step, the titanium source is mixed with Virahol, obtain mixing solutions 3;
In the 4th step, add to mixing solutions 3 in mixing solutions 2, obtains mixed solution A;
In the 5th step, mixed solution A is removed alcohol;
In the 6th step, will, except solution crystallization, centrifuge washing, the drying after alcohol, obtain the titanium-silicon molecular sieve TS-1 of not roasting.
The molar concentration rate in silicon source described in above-mentioned preparation method, titanium source is 1:0.002-0.03, is preferably 1:0.01; The molar concentration rate of described silicon source, micropore template is 1:0.1-0.3, and that better is 1:0.15.
Titanium source described in above-mentioned preparation method is selected from titanium-containing compound water-soluble or that dissolve in water, is preferably tetrabutyl titanate; Silicon source described in above-mentioned preparation method is selected from silicon-containing compound water-soluble or that dissolve in water, is preferably tetraethoxy; Micropore template described in above-mentioned preparation method is selected from Tetramethylammonium hydroxide (TMAOH), tetraethyl ammonium hydroxide (TEAOH), TPAOH (TPAOH) and TBAH (TBAOH), is preferably TPAOH.Tensio-active agent described in above-mentioned preparation method is tween 20.
In one embodiment of the invention, thus above-mentioned preparation method's the 4th step is the mixing solutions 3 that will contain titanium source and Virahol slowly to add in mixing solutions 2 and obtains mixed solution A; Be the form that drips described adding, and speed is 0.1-0.5ml/ minute, is preferably 0.2-0.5ml/ minute, more preferably 0.1-0.2ml/ minute.
In one embodiment of the invention, the mixed solution A that above-mentioned preparation method's the 4th step is obtained is removed pure 2-6 hour in 80 degree; Preferably except pure 2-4 hour; More preferably, except pure 4-6 hour.
In one embodiment of the invention, above-mentioned preparation method's the 6th step be with mixed solution A be placed in include 10mL water autoclave at 160-180 ℃ of crystallization 18-48 hour, preferably 170 ℃ of crystallization 18 hours.
In one embodiment of the invention, the solid particulate that obtains after the 6th of above-mentioned preparation method the step crystallization carries out centrifuge washing, drying can be carried out according to the usual manner of this area.Solid directly uses without roasting.
Catalyzer
The blocked titanium-silicon molecular sieve TS-1 of micropore provided by the invention can be used for Kaolinite Preparation of Catalyst, such as but not limited to the titanium-silicon molecular sieve TS-1 catalyst for preparing loaded metal.
In one embodiment of the invention,, utilize the deposition-precipitator method that gold is loaded to the titanium-silicon molecular sieve TS-1 outside surface that micropore is stopped up by template, and then prepare catalyzer as precipitation agent by mineral alkali.
In one embodiment of the invention,, utilize the deposition-precipitator method that gold is loaded to the titanium-silicon molecular sieve TS-1 outside surface that micropore is stopped up by template, and then prepare catalyzer as precipitation agent by organic bases (urea).
Mineral alkali described in above-mentioned preparation method is NaOH or Na
2CO
3, be preferably NaOH; Organic bases described in above-mentioned preparation method is urea.
In one embodiment of the invention, the titanium-silicon molecular sieve TS-1 that micropore provided by the invention is stopped up by template and chlorauric acid solution mix, and making pH is 7.0-8.0, aging rear centrifugal, dry and the titanium-silicon molecular sieve catalyst of gold-supported.In a preference of the present invention, the digestion time of solution is 1-16 hour; The centrifugation rotating speed is 4000 rev/mins; At room temperature vacuum-drying 12 hours; The concentration of hydrochloro-auric acid is 0.001-0.05mol/L.
In one embodiment of the invention, the titanium-silicon molecular sieve TS-1 that micropore provided by the invention is stopped up by template and chlorauric acid solution mix, and add urea, are warming up to 90 degree, aging rear centrifugal, dry and the titanium-silicon molecular sieve catalyst of gold-supported.In a preference of the present invention, the digestion time of solution is 3-6 hour; The centrifugation rotating speed is 4000 rev/mins; At room temperature vacuum-drying 12 hours; The concentration of hydrochloro-auric acid is 0.001-0.05mol/L.
By the deposition-precipitator method, gold is loaded on the meso-porous nano titanium-silicon molecular sieve TS-1, the test of the catalyzer of preparation process, when low charge capacity 0.1wt%, air speed 14000mLh
-1g
Cat -1Under, Propylene Selectivity is greater than 90%, and the propylene oxide generating rate can reach 130g
POh
-1g
Cat -1, activity can be kept 50 hours; Improve charge capacity to 0.2wt%, the propylene oxide generating rate can reach 160g
POh
-1g
Cat -1, charge capacity is higher than 0.3% active decline.
The catalyzer provided by the invention that obtains by aforesaid method can be used for various catalyzed reactions, is to prepare propylene oxide for propylene gas-phase epoxidation in one embodiment of the invention.In one embodiment of the invention, the charge capacity of the gold of described oxidation catalyst of cyclopropene is 0.02-0.3%.
Propylene gas-phase epoxidation prepares propylene oxide
Propylene ring oxidation reaction can be carried out in atmospheric fixed bed reactor, use in the present invention above-mentioned catalyzer provided by the invention to react, in one embodiment of the invention, reactant gases consists of propylene/hydrogen/oxygen/nitrogen=1:1:1:7(volume ratio), air speed is 4000-14000mLh
-1g
Cat -1, temperature of reaction is 200 degree, reaction product is by gas chromatographic analysis.
The above-mentioned feature that the present invention mentions, or the feature that embodiment mentions can arbitrary combination.All features that this case specification sheets discloses can with any composition forms and use, each feature that discloses in specification sheets, can anyly provide the alternative characteristics of identical, impartial or similar purpose to replace.Therefore except special instruction is arranged, the feature that discloses is only the general example of equalization or similar features.
Major advantage of the present invention is:
1, the present invention adopts the template original position to stop up the duct of titanium-silicon molecular sieve TS-1, the titanium-silicon molecular sieve TS-1 that the synthetic micropore that only contains tetrahedron skeleton titanium is stopped up by template.
2, the main exposed outer surface of titanium-silicon molecular sieve TS-1 stopped up by template of micropore provided by the invention, therefore when using deposition-precipitation method to carry out the load of gold grain, make gold grain be carried on the carrier outside surface, the diffusion of efficient hardening reaction product, reduce coking rate, and then the extending catalyst life-span;
3, Au catalyst preparation method provided by the invention, use hydrochloro-auric acid cheap and easy to get as presoma, prepares low charge capacity catalyzer, improves catalyst activity and stability when reducing the catalyzer cost.
, below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only are not used in and limit the scope of the invention for explanation the present invention.The experimental technique of unreceipted actual conditions in the following example, usually according to normal condition or the condition of according to manufacturer, advising.Unless otherwise indicated, otherwise all percentage ratio, ratio, ratio or umber by weight.
Unit in percent weight in volume in the present invention is well-known to those skilled in the art, for example refers to the weight of solute in the solution of 100 milliliters.
Unless otherwise defined, the same meaning that all specialties and scientific words and the one skilled in the art who uses in literary composition is familiar with.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The use that better implementation method described in literary composition and material only present a demonstration.
Embodiment 1
The preparation of the titanium-silicon molecular sieve TS-1 that micropore is stopped up by template
Get the 1.5g tween 20, the 25g deionized water is placed in the beaker mix and blend, obtains mixing solutions 1.Getting 66g tetraethoxy, 26g TPAOH adds in solution 1 to stir and obtained mixing solutions 2 in 30 minutes.Get 20mL Virahol and 0.22g tetrabutyl titanate mix and blend 1 hour, and obtained mixing solutions 3.Solution 3 is added in solution 2 and stirred 1 hour with the speed of 0.5ml/ minute, obtain solution A.Mixed solution A was removed alcohol 2 hours in 80 degree.To be placed in autoclave except the solution after alcohol, crystallization is 18 hours under 160 degree conditions, takes out the washing drying.
Embodiment 2
The preparation of the titanium-silicon molecular sieve TS-1 that micropore is stopped up by template
Get the 10g tween 20, the 100g deionized water is placed in the beaker mix and blend, obtains mixing solutions 1.Getting 66g tetraethoxy, 52g TPAOH adds in solution 1 to stir and obtained mixing solutions 2 in 30 minutes.Get 20mL Virahol and 3.08g tetrabutyl titanate mix and blend 1 hour, and obtained mixing solutions 3.Solution 3 is added in solution 2 and stirred 1 hour with the speed of 0.1ml/ minute, obtain solution A.Mixed solution A was removed alcohol 6 hours in 80 degree.To be placed in autoclave except the solution after alcohol, crystallization is 48 hours under 180 degree conditions, takes out the washing drying.
Embodiment 3
The carrier 0.5g that gets in embodiment 1 is placed in the 250mL beaker, and adding wherein 10mL concentration is the chlorauric acid solution of 0.001mol/L, and stir after 30 minutes and regulate pH to 7 with 1mol/L sodium hydroxide, and aging 6 hours; After centrifugation and washing, catalyzer vacuum-drying under 30 degree is spent the night, obtain low charge capacity 0.1% catalyzer.
Embodiment 4
The carrier 0.5g that gets in embodiment 1 is placed in the 250mL beaker, adds wherein 0.001g hydrochloro-auric acid and 0.3g urea, and solution is warming up to 90 degree, and aging 6 hours; After centrifugation and washing, catalyzer vacuum-drying under 30 degree is spent the night, obtain low charge capacity 0.1% catalyzer.
Embodiment 5(contrast)
The carrier 0.5g that gets in embodiment 1 is placed in the 250mL beaker, and adding wherein 10mL concentration is the chlorauric acid solution of 0.005mol/L, and stir after 30 minutes and regulate pH to 7 with 1mol/L sodium hydroxide, and aging 16 hours; After centrifugation and washing, catalyzer vacuum-drying under 30 degree is spent the night, obtain high capacity amount 1% catalyzer.
Embodiment 6(contrast)
Get common HTS carrier 0.5g and be placed in the 250mL beaker, adding wherein 10mL concentration is the chlorauric acid solution of 0.003mol/L, stir after 30 minutes and regulate pH to 7 with 1mol/L sodium hydroxide, and aging 3 hours; After centrifugation and washing, at room temperature vacuum-drying of catalyzer is spent the night.Catalyzed reaction the results are shown in Figure 5.
The result of contrast shows, uses the Au catalyst of the titanium-silicon molecular sieve TS-1 load that micropore stopped up by template to carry out propylene gas-phase epoxidation and prepares propylene oxide and have higher stability with active; When charge capacity is too high, catalyst activity and stability decreases.
The foregoing is only preferred embodiment of the present invention, not in order to limit essence technology contents scope of the present invention, essence technology contents of the present invention is broadly to be defined in the claim scope of application, any technology entity or method that other people complete, if defined identical with the claim scope of application, also or a kind of change of equivalence, all will be regarded as being covered by among this claim scope.
Claims (10)
1. the preparation method of a titanium-silicon molecular sieve TS-1, described method comprises step:
(1) the silicon source is mixed with the mixing solutions 1 that contains micropore template, tensio-active agent and water, obtain mixing solutions 2;
(2) mixing solutions 2 is mixed with the mixing solutions 3 that contains titanium source and Virahol, obtain solution A;
(3) solution A is removed alcohol, centrifugal after crystallization, washing and dry, obtained the titanium-silicon molecular sieve TS-1 of not roasting.
2. preparation method as claimed in claim 1, is characterized in that, described tensio-active agent is tween 20; In mixing solutions 1, tween 20 is 1.5-10g, and water is 25-100g; Preferred tween 20 is 2.5-10g, water 40-100g; More preferably tween 20 is 2g, water 25-40g.
3. preparation method as claimed in claim 1, is characterized in that, the molar concentration rate in described silicon source, micropore template, titanium source is 1:0.1-0.3:0.002-0.03.
4. preparation method as claimed in claim 1, is characterized in that, in step (2), mixing solutions 3 drops in solution 2 and obtains solution A, and drop rate is 0.1-0.5ml/ minute, is preferably 0.2-0.5ml/ minute, more preferably 0.1-0.2ml/ minute.
5. preparation method as claimed in claim 1, is characterized in that, in step (3), mixed solution A removed pure 2-6 hour; Preferably except pure 2-4 hour; More preferably except pure 4-6 hour.
6. the titanium-silicon molecular sieve TS-1 with the not roasting for preparing as the described preparation method of claim 1-5 any one, is characterized in that, described molecular sieve pore passage is stopped up by the micropore template, and molecular sieve is exposed outer surface only.
7. one kind low charge capacity catalyzer, is characterized in that, described catalyzer is take not roasting HTS as claimed in claim 6 as the carrier to load metal particle; Described metallic particles is gold nano grain.
8. catalyzer as claimed in claim 7, is characterized in that, charge capacity is 0.02-0.3%, and the preferred negative carrying capacity is 0.02-0.1%, more preferably 0.1-0.3%.
9. preparation method of catalyzer as claimed in claim 7 or 8, it is characterized in that, described method comprises step: not roasting HTS as claimed in claim 6 and chlorauric acid solution are mixed, use mineral alkali or organic bases to reconcile pH, aging rear centrifugal, dry, obtain catalyzer as claimed in claim 7 or 8.
10. one kind is improved propylene gas-phase epoxidation and prepares the active method with stability of propylene oxide, it is characterized in that, uses catalyzer as claimed in claim 7 or 8.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107265474A (en) * | 2017-05-26 | 2017-10-20 | 中国石油大学(华东) | A kind of honeycomb hexagon HTS and its production and use |
| CN111924852A (en) * | 2019-04-26 | 2020-11-13 | 中国石油大学(华东) | Preparation method of titanium-silicon molecular sieve |
| CN112279267A (en) * | 2019-07-23 | 2021-01-29 | 南京理工大学 | Preparation method of TS-1 molecular sieve with high titanium content |
| CN114471700A (en) * | 2022-02-28 | 2022-05-13 | 华东理工大学 | Physical mixed catalyst for propylene hydrogen oxygen epoxidation and preparation method and application thereof |
| CN115155653A (en) * | 2022-08-12 | 2022-10-11 | 华东理工大学 | Sulfur-assistant-modified titanium-silicon molecular sieve-supported gold catalyst and preparation method and application thereof |
| CN115283012A (en) * | 2022-08-25 | 2022-11-04 | 华东理工大学 | Roasting method for reducing titanium species outside framework of titanium-silicon molecular sieve, titanium-silicon molecular sieve and application of titanium-silicon molecular sieve |
| CN115283011A (en) * | 2022-08-25 | 2022-11-04 | 华东理工大学 | Method for improving dispersity of gold nanoparticles of titanium-silicon molecular sieve supported gold catalyst and application of gold nanoparticles |
| CN115518683A (en) * | 2021-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | Supported catalyst, preparation method and application thereof, and method for synthesizing pyromellitic anhydride by durene gas-phase oxidation |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107265474B (en) * | 2017-05-26 | 2019-12-20 | 中国石油大学(华东) | Honeycomb hexagonal titanium-silicon molecular sieve and preparation method and application thereof |
| CN107265474A (en) * | 2017-05-26 | 2017-10-20 | 中国石油大学(华东) | A kind of honeycomb hexagon HTS and its production and use |
| CN111924852A (en) * | 2019-04-26 | 2020-11-13 | 中国石油大学(华东) | Preparation method of titanium-silicon molecular sieve |
| CN111924852B (en) * | 2019-04-26 | 2023-11-03 | 中国石油大学(华东) | Preparation method of titanium-silicon molecular sieve |
| CN112279267A (en) * | 2019-07-23 | 2021-01-29 | 南京理工大学 | Preparation method of TS-1 molecular sieve with high titanium content |
| CN112279267B (en) * | 2019-07-23 | 2023-11-03 | 南京理工大学 | Preparation method of TS-1 molecular sieve with high titanium content |
| CN115518683A (en) * | 2021-06-24 | 2022-12-27 | 中国石油化工股份有限公司 | Supported catalyst, preparation method and application thereof, and method for synthesizing pyromellitic anhydride by durene gas-phase oxidation |
| CN115518683B (en) * | 2021-06-24 | 2024-02-02 | 中国石油化工股份有限公司 | Supported catalyst, preparation method and application thereof, and method for synthesizing pyromellitic dianhydride by gas-phase oxidation of durene |
| WO2023160593A1 (en) * | 2022-02-28 | 2023-08-31 | 华东理工大学 | Physically mixed catalyst for epoxidation of propylene using hydrogen and oxygen, and preparation method therefor and use thereof |
| CN114471700A (en) * | 2022-02-28 | 2022-05-13 | 华东理工大学 | Physical mixed catalyst for propylene hydrogen oxygen epoxidation and preparation method and application thereof |
| CN115155653A (en) * | 2022-08-12 | 2022-10-11 | 华东理工大学 | Sulfur-assistant-modified titanium-silicon molecular sieve-supported gold catalyst and preparation method and application thereof |
| CN115283011A (en) * | 2022-08-25 | 2022-11-04 | 华东理工大学 | Method for improving dispersity of gold nanoparticles of titanium-silicon molecular sieve supported gold catalyst and application of gold nanoparticles |
| CN115283012A (en) * | 2022-08-25 | 2022-11-04 | 华东理工大学 | Roasting method for reducing titanium species outside framework of titanium-silicon molecular sieve, titanium-silicon molecular sieve and application of titanium-silicon molecular sieve |
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| CN103395799B (en) | 2015-10-21 |
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