CN103395799B - A kind of HTS preparation method and purposes - Google Patents
A kind of HTS preparation method and purposes Download PDFInfo
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- CN103395799B CN103395799B CN201310342500.9A CN201310342500A CN103395799B CN 103395799 B CN103395799 B CN 103395799B CN 201310342500 A CN201310342500 A CN 201310342500A CN 103395799 B CN103395799 B CN 103395799B
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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 invention discloses a kind of HTS and its production and use.Described HTS is non-roasting titanium-silicon molecular sieve TS-1.The invention also discloses a kind of raw catalyst being applied to the direct gas-phase epoxidation of propylene and preparing propylene oxide system, described catalyzer with non-roasting titanium-silicon molecular sieve TS-1 provided by the invention for carrier to load metal particle.
Description
Technical field
The present invention relates to catalyzer, particularly relate 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., and be also the main raw material of forth generation washing composition nonionogenic tenside, oil field demulsifier, farm chemical emulgent etc., development prospect is wide.At present, the main method of producing PO in industry is chlorohydrination and conjugated oxidation.But chlorohydrination produces a large amount of waste water and chlorine byproducts in process of production, and large to equipment corrosion, do 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 product.Under coexistence of hydrogen gas and oxygen condition, method has environmental protection, simple to operate, selectivity the is high advantages such as (>90%) of working load gold catalyst catalyzing preparing epoxypropane by epoxidation of propene, is subject to domestic and international extensive concern.In the middle of this system, although traditional HTS (TS-1) has stronger hydrophobicity compared with other carriers, the desorption of product propene oxide can be promoted thus improve the stability of catalyzer and activity, but still there is significant deactivation prob (document 1:J.Catal.2012 in catalyzer, 287,178 – 189).Although have report recently about the load gold catalyst using solid-state polishing to prepare high stability, but catalyzer needs to use expensive presoma, and gold grain cannot optionally be deposited near the active sites titanium of HTS by this preparation method, waste part gold, also invisiblely catalyzer cost (document 2:Appl.Catal.B:Environ.2010 is added, 95,430 – 438).Therefore, while guarantee catalyzer low cost, 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 prepares the purposes of propylene oxide system at the direct gas-phase epoxidation of propylene.
In a first aspect of the present invention, provide a kind of preparation method of titanium-silicon molecular sieve TS-1, described method comprises step:
(1) silicon source is mixed with the mixing solutions 1 containing micropore template, tensio-active agent and water, obtain mixing solutions 2;
(2) mixing solutions 2 is mixed with the mixing solutions 3 containing titanium source and Virahol, obtain solution A; With
(3) solution A is carried out, except alcohol, centrifugal after crystallization, washing and dry, obtain the titanium-silicon molecular sieve TS-1 of non-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, is more preferably 0.2-0.5ml/ minute, most preferably is 0.1-0.2ml/ minute.
In another preference, in step (3), mixed solution A is removed alcohol 2-6 hour; More preferably except alcohol 2-4 hour; Most preferably except alcohol 4-6 hour.
In a second aspect of the present invention, provide the titanium-silicon molecular sieve TS-1 of the non-roasting that a kind of use preparation method provided by the invention as above prepares, described molecular sieve pore passage is blocked by micropore template, and molecular sieve is exposed outer surface only.
In a third aspect of the present invention, provide a kind of low charge capacity catalyzer, described catalyzer with non-roasting HTS provided by the invention as above for 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, provide a kind of preparation method of catalyzer provided by the invention as above, described method comprises step: will non-roasting HTS provided by the invention and chlorauric acid solution mix as above, mineral alkali or organic bases is used 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, centrifugation rotating speed is 4000 revs/min.
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 and prepare propylene oxide activity and the method for stability, use catalyzer provided by the invention as above.
Accordingly, provide a kind of solve ensure catalyzer low cost while, improve the scheme of the activity of catalyzer, the problem of stability.
Accompanying drawing explanation
Fig. 1 is the x-ray diffraction pattern of the titanium-silicon molecular sieve TS-1 that in embodiment 1, micropore is blocked.
Fig. 2 is the UV-vis figure of the titanium-silicon molecular sieve TS-1 that in embodiment 1, micropore is blocked.
Fig. 3 is that the transmission electron microscope TEM of the titanium-silicon molecular sieve TS-1 that in embodiment 1, micropore is blocked schemes.
Fig. 4 is the scanning electron microscope sem figure of the titanium-silicon molecular sieve TS-1 that in embodiment 1, micropore is blocked.
Fig. 5 is N2 physical adsorption and the graph of pore diameter distribution of the titanium-silicon molecular sieve TS-1 that in embodiment 1, micropore is blocked.
Fig. 6 is the different activity of embodiment oxypropylene (PO) and the difference of stability.
Embodiment
Contriver is through extensive and deep research, find that namely a kind of catalyst stability that improves prepares the blocked titanium-silicon molecular sieve TS-1 of micropore with active method, simultaneously use deposition-precipitation can selectivity by deposition of gold near the outside surface active sites titanium of TS-1, therefore, under the prerequisite ensureing low charge capacity, catalyst activity and life-span can be improved.On this basis, the present invention is completed.
As used herein, " room temperature " refers to 15-30 DEG C, preferred 20-25 DEG C.
The titanium-silicon molecular sieve TS-1 that micropore is blocked
The invention provides the titanium-silicon molecular sieve TS-1 that a kind of micropore is blocked, compared to HTS of the prior art, its micropore by template or other inert substances block, main expose its outside surface.
The blocked titanium-silicon molecular sieve TS-1 of micropore provided by the invention is prepared by following step:
The first step, adds micropore template in the mixing solutions containing tensio-active agent and water, obtains alkaline mixed solution 1;
Second step, is added to silicon source in mixing solutions 1, obtains mixing solutions 2;
3rd step, mixes titanium source with Virahol, obtains mixing solutions 3;
4th step, adds to mixing solutions 3 in mixing solutions 2, obtains mixed solution A;
5th step, by mixed solution A except alcohol;
6th step, by the solution crystallization after alcohol, centrifuge washing, drying, obtains the titanium-silicon molecular sieve TS-1 of non-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, is preferably 1:0.15.
Titanium source described in above-mentioned preparation method is selected from titanium-containing compound that is 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 that is 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, the 4th step of above-mentioned preparation method is slowly added by the mixing solutions 3 containing titanium source and Virahol in mixing solutions 2 thus obtains mixed solution A; Described adding is the form dripped, and speed is 0.1-0.5ml/ minute, is preferably 0.2-0.5ml/ minute, is more preferably 0.1-0.2ml/ minute.
In one embodiment of the invention, the mixed solution A the 4th step of above-mentioned preparation method obtained removes alcohol 2-6 hour in 80 degree; Preferably except alcohol 2-4 hour; More preferably, except alcohol 4-6 hour.
In one embodiment of the invention, the 6th step of above-mentioned preparation method be mixed solution A is placed in include 10mL water autoclave at 160-180 DEG C of crystallization 18-48 hour, preferably 170 DEG C of crystallization 18 hours.
In one embodiment of the invention, obtain after the 6th step crystallization of above-mentioned preparation method solid particulate 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 preparing loaded metal.
In one embodiment of the invention, by mineral alkali as precipitation agent, the titanium-silicon molecular sieve TS-1 outside surface utilizing deposition-precipitation gold to be loaded to micropore to be blocked by template, and then prepare catalyzer.
In one embodiment of the invention, by organic bases (urea) as precipitation agent, the titanium-silicon molecular sieve TS-1 outside surface utilizing deposition-precipitation gold to be loaded to micropore to be blocked by template, and then prepare catalyzer.
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 blocked by template by micropore provided by the invention and chlorauric acid solution mix, and make pH be 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; Centrifugation rotating speed is 4000 revs/min; 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 blocked by template by micropore provided by the invention 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; Centrifugation rotating speed is 4000 revs/min; At room temperature vacuum-drying 12 hours; The concentration of hydrochloro-auric acid is 0.001-0.05mol/L.
Be loaded on meso-porous nano titanium-silicon molecular sieve TS-1 by deposition-precipitation by gold, the catalyzer of preparation passes through test, when low charge capacity 0.1wt%, and air speed 14000mLh
-1g
cat -1under, Propylene Selectivity is greater than 90%, and propylene oxide generating rate can reach 130g
pOh
-1g
cat -1, activity can maintain 50 hours; Improve charge capacity to 0.2wt%, propylene oxide generating rate can reach 160g
pOh
-1g
cat -1, charge capacity is higher than 0.3% then activity decrease.
The catalyzer provided by the invention obtained by aforesaid method can be used for various catalyzed reaction, is 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, above-mentioned catalyzer provided by the invention is used to react in the present invention, 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, and reaction product is by gas chromatographic analysis.
The above-mentioned feature that the present invention mentions, or the feature that embodiment is mentioned can arbitrary combination.All features that this case specification sheets discloses can with any composition forms and use, each feature disclosed in specification sheets, anyly can provide identical, alternative characteristics that is impartial or similar object replaces.Therefore apart from special instruction, the feature disclosed is only general example that is impartial or similar features.
Major advantage of the present invention is:
1, the present invention adopts template original position to block the duct of titanium-silicon molecular sieve TS-1, the titanium-silicon molecular sieve TS-1 that the micropore of synthesis only containing tetrahedral framework titanium is blocked by template.
2, the main exposed outer surface of titanium-silicon molecular sieve TS-1 that blocked by template of micropore provided by the invention, therefore when using deposition-precipitation method to carry out the load of gold grain, gold grain is made to be carried on carrier outer surface, efficient hardening reaction product spreads, reduce coking rate, and then the extending catalyst life-span;
3, Au catalyst preparation method provided by the invention, uses hydrochloro-auric acid cheap and easy to get as presoma, prepares low charge capacity catalyzer, while reduction catalyzer cost, improve catalyst activity and stability.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, the usually conveniently conditioned disjunction condition of advising according to manufacturer.Unless otherwise indicated, otherwise all percentage ratio, ratio, ratio or number by weight.
Unit in percent weight in volume in the present invention is well-known to those skilled in the art, such as, refer to the weight of solute in the solution of 100 milliliters.
Unless otherwise defined, all specialties used in literary composition and scientific words and one skilled in the art the same meaning be 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 blocked by template
Get 1.5g tween 20,25g deionized water is placed in beaker mix and blend, obtain mixing solutions 1.Get 66g tetraethoxy, 26g TPAOH add in solution 1 stir within 30 minutes, obtain mixing solutions 2.Get 20mL Virahol and 0.22g tetrabutyl titanate mix and blend 1 hour, obtain mixing solutions 3.Solution 3 is added in solution 2 with the speed of 0.5ml/ minute and stirs 1 hour, obtain solution A.Mixed solution A removes alcohol 2 hours in 80 degree.Solution after alcohol is placed in autoclave, crystallization 18 hours under 160 degree of conditions, takes out washing drying.
Embodiment 2
The preparation of the titanium-silicon molecular sieve TS-1 that micropore is blocked by template
Get 10g tween 20,100g deionized water is placed in beaker mix and blend, obtain mixing solutions 1.Get 66g tetraethoxy, 52g TPAOH add in solution 1 stir within 30 minutes, obtain mixing solutions 2.Get 20mL Virahol and 3.08g tetrabutyl titanate mix and blend 1 hour, obtain mixing solutions 3.Solution 3 is added in solution 2 with the speed of 0.1ml/ minute and stirs 1 hour, obtain solution A.Mixed solution A removes alcohol 6 hours in 80 degree.Solution after alcohol is placed in autoclave, crystallization 48 hours under 180 degree of conditions, takes out washing drying.
Embodiment 3
Carrier 0.5g in Example 1 is placed in 250mL beaker, adds the chlorauric acid solution that 10mL concentration is 0.001mol/L wherein, stirs after 30 minutes and regulates pH to 7 with 1mol/L sodium hydroxide, and aging 6 hours; Centrifugation also, after washing, by catalyzer dried in vacuo overnight under 30 degree, obtains low charge capacity 0.1% catalyzer.
Embodiment 4
Carrier 0.5g in Example 1 is placed in 250mL beaker, adds 0.001g hydrochloro-auric acid and 0.3g urea wherein, is spent by solution warms to 90, and aging 6 hours; Centrifugation also, after washing, by catalyzer dried in vacuo overnight under 30 degree, obtains low charge capacity 0.1% catalyzer.
Embodiment 5(contrasts)
Carrier 0.5g in Example 1 is placed in 250mL beaker, adds the chlorauric acid solution that 10mL concentration is 0.005mol/L wherein, stirs after 30 minutes and regulates pH to 7 with 1mol/L sodium hydroxide, and aging 16 hours; Centrifugation also, after washing, by catalyzer dried in vacuo overnight under 30 degree, obtains high capacity amount 1% catalyzer.
Embodiment 6(contrasts)
Get common HTS carrier 0.5g and be placed in 250mL beaker, add the chlorauric acid solution that 10mL concentration is 0.003mol/L wherein, stir after 30 minutes and regulate pH to 7 with 1mol/L sodium hydroxide, and aging 3 hours; After centrifugation is also washed, by catalyzer at room temperature dried in vacuo overnight.Catalyzed reaction the results are shown in Figure 5.
The result of contrast shows, the Au catalyst of titanium-silicon molecular sieve TS-1 load using micropore to be blocked by template carries out propylene gas-phase epoxidation to be prepared propylene oxide and have higher stability with active; When charge capacity is too high, catalyst activity and stability decline.
The foregoing is only preferred embodiment of the present invention, and be not used to limit substantial technological context of the present invention, substantial technological content of the present invention is broadly defined in the right of application, any technology entities that other people complete or method, if with application right define identical, also or a kind of change of equivalence, be all covered by being regarded as among this right.
Claims (15)
1. a catalyzer, is characterized in that, described catalyzer with non-roasting HTS for carrier to load metal particle; Described metallic particles is gold nano grain; The charge capacity of described catalyzer is 0.02-0.3%;
Described non-roasting HTS duct is blocked by micropore template, and molecular sieve is exposed outer surface only, is prepared by following step:
(1) silicon source is mixed with the mixing solutions 1 containing micropore template, tensio-active agent and water, obtain mixing solutions 2;
(2) mixing solutions 2 is mixed with the mixing solutions 3 containing titanium source and Virahol, obtain solution A;
(3) solution A is carried out, except alcohol, centrifugal after crystallization, washing and dry, obtain the titanium-silicon molecular sieve TS-1 of non-roasting.
2. catalyzer as claimed in claim 1, it is characterized in that, the charge capacity of described catalyzer is 0.02-0.1%.
3. catalyzer as claimed in claim 1, it is characterized in that, the charge capacity of described catalyzer is 0.1-0.3%.
4. catalyzer as claimed in claim 1, it 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.
5. catalyzer as claimed in claim 4, it is characterized in that, described tensio-active agent is tween 20; In mixing solutions 1, tween 20 is 2.5-10g, water 40-100g.
6. catalyzer as claimed in claim 4, it is characterized in that, described tensio-active agent is tween 20; In mixing solutions 1, tween 20 is 2g, water 25-40g.
7. catalyzer as claimed in claim 1, it 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.
8. catalyzer as claimed in claim 1, it 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.
9. catalyzer as claimed in claim 8, it is characterized in that, in step (2), mixing solutions 3 drops in solution 2 and obtains solution A, and drop rate is 0.2-0.5ml/ minute.
10. catalyzer as claimed in claim 8, it is characterized in that, in step (2), mixing solutions 3 drops in solution 2 and obtains solution A, and drop rate is 0.1-0.2ml/ minute.
11. catalyzer as claimed in claim 1, is characterized in that, in step (3), mixed solution A are removed alcohol 2-6 hour.
12. catalyzer as claimed in claim 11, is characterized in that, in step (3), mixed solution A are removed alcohol 2-4 hour.
13. catalyzer as claimed in claim 11, is characterized in that, in step (3), mixed solution A are removed alcohol 4-6 hour.
The preparation method of 14. 1 kinds of catalyzer as described in any one of claim 1-13, it is characterized in that, described method comprises step: by non-roasting HTS and chlorauric acid solution mixing, mineral alkali or organic bases is used to reconcile pH, aging rear centrifugal, dry, obtain the catalyzer as described in any one of claim 1-13.
15. 1 kinds are improved propylene gas-phase epoxidation and prepare propylene oxide activity and the method for stability, it is characterized in that, use the catalyzer as described in any one of claim 1-13.
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| 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 |
| CN111924852B (en) * | 2019-04-26 | 2023-11-03 | 中国石油大学(华东) | Preparation method of titanium-silicon molecular sieve |
| 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 |
| 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 |
| 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 |
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| CN1260241A (en) * | 1998-04-10 | 2000-07-19 | 中国石油化工总公司 | Preparation method for Ti-Si molecular sieve |
| CN101670298A (en) * | 2008-09-11 | 2010-03-17 | 中国石油化工股份有限公司 | Method for modifying titanium silicalite zeolite |
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| CN1260241A (en) * | 1998-04-10 | 2000-07-19 | 中国石油化工总公司 | Preparation method for Ti-Si molecular sieve |
| CN101670298A (en) * | 2008-09-11 | 2010-03-17 | 中国石油化工股份有限公司 | Method for modifying titanium silicalite zeolite |
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