CN102320619A - Synthesis method of titanium silicalite TS-1 - Google Patents

Synthesis method of titanium silicalite TS-1 Download PDF

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CN102320619A
CN102320619A CN201110295596A CN201110295596A CN102320619A CN 102320619 A CN102320619 A CN 102320619A CN 201110295596 A CN201110295596 A CN 201110295596A CN 201110295596 A CN201110295596 A CN 201110295596A CN 102320619 A CN102320619 A CN 102320619A
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titanium
silicon
molecular sieve
source
mixture
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CN102320619B (en
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郭洪臣
张蕾
李海龙
贾玉华
刘春燕
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Dalian University of Technology
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Abstract

The invention belongs to the field of preparation of molecular sieve material, and discloses a synthesis method of a titanium silicalite TS-1. The method is characterized by comprising the following steps of: preparing a titanium-silicon gel with a silicon source, a titanium source, a template agent, an alkaline mineralizing agent and water according to certain proportion, and introducing right amount of alkali metal salt in the gel preparation process through a direction method or an indirection method; then, executing hydrothermal crystallization at 160-180 DEG C; and obtaining the titanium silicalite TS-1 after filtering, washing, drying and roasting. With the synthesis method provided by the invention, depolymerization of the silicon source can be promoted in the gel preparation process, so that titanium can enter into a skeleton smoothly and generation of amorphous six-coordinate non-skeleton titanium can be restrained. Based on the action of alkaline metal ions and an acid site of the molecular sieve non-skeleton titanium, the acid site of the cheap titanium silicalite TS-1 is removed, and selectivity of propylene epoxide is greatly improved while taking the titanium silicalite TS-1 as the catalyst for the propylene epoxidation.

Description

A kind of compound method of titanium-silicon molecular sieve TS-1
Technical field
The invention belongs to the molecular screen material preparation field, relate to a kind of compound method of HTS (TS-1) of the MFI of having structure.
Background technology
HTS is the novel hetero-atom molecular-sieve of early eighties exploitation in last century.Wherein, the HTS titanium silicalite-1 that has MFI type structure is called for short TS-1.The catalystsystem that TS-1 molecular sieve and rare ydrogen peroxide 50 are formed is widely used in the selective oxidation field, has good selective oxidation reaction performance.The TS-1 molecular sieve is used for organic oxidizing reaction, has avoided oxidising process complex process and environmental pollution problems, have unrivaled energy-conservation, economy of conventional oxidation system and advantages of environment protection, be considered to the milestone of the zeolite catalysis eighties.Therefore, in the last thirty years, the preparation of HTS and application become a focus in zeolite catalysis field.
Following discloses patent and document have been introduced the application of TS-1 molecular sieve:
Having disclosed with the ydrogen peroxide 50 among the U.S. Pat P4833260 (1988-07-11) is oxygenant, and the TS-1 molecular sieve is the olefin epoxidation process of catalyzer, and its temperature of reaction is 0～150 ℃, and pressure is 1～100atm, and preferred solvent is methyl alcohol, the trimethyl carbinol, acetone.With rare ydrogen peroxide 50 is oxygenant, and the epoxidation of alkene such as ethene, propylene, 2-butylene, propenyl chloride, 1-octene has all obtained result preferably.
Disclosed the epoxidation that the TS-1 molecular sieve is used for alkene such as propylene, propenyl chloride, vinylbenzene, tetrahydrobenzene among the U.S. Pat P4476327 (1993-11-16), found that TS-1 has epoxidation performance preferably.
Having disclosed among the Chinese invention patent ZL99125464.3 (Granted publication CN1097575C authorizes a day 2003-01-01) utilizes TS-1 molecular sieve catalytic 4-cresols to prepare the 4-methyl pyrocatechol.Find that the TS-1 molecular sieve has catalytic performance preferably.
Disclosed the hydroxylation that the TS-1 molecular sieve is used for phenol among the Chinese invention patent ZL99103272.1 (Granted publication CN1076724C authorizes a day 2001-12-26), found that the TS-1 molecular sieve has catalytic performance preferably.
Open source literature Sudies in surface science and catalysis, 49 (1989) 69 have introduced TS-1 molecular sieve catalytic OxiKhim-Styrol oxidative ammonolysis on annual output 12kt demonstration unit, and the selectivity of purpose product OxiKhim-Styrol is 98.2%, H 2O 2Transformation efficiency be 93.2%.
Open source literature Catalysis today, 18 (1993) 163-172 have introduced TS-1 molecular sieve catalytic phenol, H 2O 2The reaction of hydroxylation preparing benzenediol.On the full scale plant of producing 10kt per year, H 2O 2Transformation efficiency is 70%, and the transformation efficiency of phenol is 25%, and the selectivity of principal product dihydroxy-benzene is 90%, and the by product tar content seldom.
Open source literature chemistry journal, 58 (2000) 204-208 have been introduced the TS-1 molecular sieve have been used for the cyclohexanone oxamidinating reaction.Find to reduce concentration of hydrogen peroxide in the reaction soln, increase the ammonia consumption and help hydrogen peroxide utilization ratio, OxiKhim-Styrol yield and optionally raising.
Open source literature Catalysis communications, 2 (2007) 379-382 have introduced in methyl alcohol and acetonitrile mixed solvent system the TS-1 molecular sieve and have been used for the epoxidation propenyl chloride and prepare Epicholorohydrin, find that the TS-1 molecular sieve has catalytic performance preferably.
Following patent has also related to the application of TS-1 molecular sieve:
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The following discloses document has also related to the applied research of TS-1 molecular sieve:
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What is worth mentioning is that the application of TS-1 molecular sieve in epoxidation of propylene is expected to thoroughly break away from the contamination type production model that has technology now, and huge industrial application potentiality are arranged.
Through using the UV, visible light reflection spectrum that the TS-1 molecular sieve is characterized, at present, investigators generally believe that the titanium species on the TS-1 molecular sieve mainly exists with three kinds of forms.Be four-coordination skeleton titanium, unbodied hexa-coordinate titanium species and anatase titanium dioxide.In the uv atlas, the peak at 210nm place ownership is into the 2p transition of electron of key oxygen to TiO 4+The 3d unoccupied orbital time, the charge transfer of generation, this peak have proved the existence of four-coordination skeleton titanium.The peak ownership at 270～280nm place is the characteristic peak of amorphous hexa-coordinate titanium species.The peak ownership at 330～350nm place is the characteristic peak of anatase titanium dioxide.In catalyzed reaction, having only four-coordination skeleton titanium is the active site of TS-1 molecular sieve.And hexa-coordinate titanium species and anatase octahedrite do not have katalysis to epoxidation, but they have decomposing H 2O 2With the spinoff that causes the epoxidation product deep reaction.
Open source literature catalysis journal, 30 (2009) 482-484 have introduced the acidity that contains different titanium species TS-1 molecular sieves in detail.Document report, the strength of acid scope of TS-1 molecular sieve is+3.3＜H 0≤+4.8, the acidity of anatase titanium dioxide is at H 0In≤+ 4.8 scopes very a little less than, can ignore.But amorphous hexa-coordinate extra-framework titanium strength of acid H 0≤+3.85, the strongest comparatively speaking.It is the main active site that causes acid side reaction.The existence of these amorphous hexa-coordinate extra-framework titanium species is the principal elements that cause hydrogen peroxide decomposition and side reaction to take place.Therefore, effectively avoiding the generation of amorphous extra-framework titanium, is the key that improves the molecular sieve catalytic performance.
The compound method of TS-1 disclosed (GB2071071A, USP4410501) first by people such as gondola Marco Taramasso in 1981.This method is, is made into a kind of reaction mixture that contains silicon source, titanium source, organic bases earlier, with this reaction mixture in autoclave in 130～200 ℃ of hydrothermal crystallizings 6～30 days, obtain product through filtration, washing, drying and roasting then.Wherein the silicon source can be the tetraalkyl silicon ester, colloidal state SiO 2, the titanium source is hydrolyzable titanium-containing compound, preferred tetraethyl titanate, and the preferred TPAOH of organic bases, following table is formed for the feed molar of the synthetic TS-1 molecular sieve that this patent provides.
The material molar ratio of the synthetic TS-1 molecular sieve that table 1 patent USP4410501 provides is formed
Figure BDA0000095160350000051
Wherein Me is alkali metallic sodium, potassium ion.This patent thinks, when in the raw material when alkali-free sodium Metal 99.5, potassium ion, extra-framework titanium content is minimum.It is template that promptly synthetic TS-1 molecular sieve needs high-purity TPAOH of a large amount of alkali-free metals ions.
Thereby people such as Thangaraj disclose in 1992 and have a kind ofly suppressed extra-framework titanium through coupling estersil and titanium ester hydrolysis rate and effectively increase the method for the synthetic TS-1 of titanium content in the skeleton (Zeolites, 12 (1992), 943).This method has three main points: the one, and adopting the slower butyl(tetra)titanate of hydrolysis rate is the titanium source; The 2nd, the titanium source is dissolved in the anhydrous isopropyl alcohol; The 3rd, adjustment order of addition(of ingredients) joins the aqueous isopropanol in titanium source in the silicone grease solution of hydrolysis.Through the improvement of above-mentioned three aspects, the titanium amount that gets in the framework of molecular sieve improves, and has obtained the TS-1 molecular sieve of better performances.
The above-mentioned method that relates to synthetic TS-1 molecular sieve, we are referred to as classical approach.Its common feature is to be that silicon source, organic titanium ester are that titanium source, TPAOH are the synthetic TS-1 molecular sieve of template and alkali source with the organo-silicon ester.
It is synthetic TS-1 molecular sieve in the system of template that following patent and open source literature all relate at TPAOH:
Chinese invention patent ZL96110260.8 (Granted publication CN1084294C authorizes a day 2002-05-08) has disclosed a kind of compound method of TS-1 molecular sieve.Its technical characterictic is with tetraethoxy hydrolysis in TPAOH solution, under nitrogen or oxygen protection, in above-mentioned hydrolyzed solution, to add TiCl then 3Make gel, with the gained gel 150～190 ℃ of following crystallization 1～5 day, elimination mother liquor then, washing leaching cake, and with filter cake 120 ℃ of dry down, 550 ℃ of roastings 6 hours, obtain the TS-1 molecular sieve.
Chinese invention patent ZL97106709.0 (Granted publication CN1079372C authorizes a day 2002-02-20) has disclosed a kind of compound method of TS-1 molecular sieve.Its technical characterictic is; The mixing solutions that tetraethoxy, TPAOH, tetrabutyl titanate and water are formed is added in the container of band whipping appts; Stir to heat up 1～5 hour, and with pack in autoclave crystallization 1～4 day of the gel that stirs gained, cooled off then, filter and obtain filter cake; And the recovery mother liquor, then to filter cake wash, drying and roasting obtain the TS-1 molecular sieve.
Chinese invention patent ZL98102391 (Granted publication CN1089274C authorizes a day 2002-08-21) has disclosed a kind of compound method of TS-1 molecular sieve.Its technical characterictic is, silicon sol, TPAOH and water are mixed, and makes the hydrolyzed solution of silicon, then organic titanium ester, Virahol, TPAOH mixed with water, makes the hydrolyzed solution of titanium.The hydrolyzed solution of titanium is joined in the hydrolyzed solution of silicon, stirred 0.5～6 hour down, carry out hydrothermal crystallizing then,, obtain the TS-1 molecular sieve again through filtration, washing, drying and roasting in 50～100 ℃.
Chinese invention patent CN1275530A (99107790.3 applying date of application number 1999-05-28) has disclosed a kind of compound method of TS-1 molecular sieve.Its technical characterictic is; To contain the reaction mixture of silicon source, titanium source, alkali source, be positioned in the autoclave, in the microwave radiation field of 600～50000MHz; Under pressure 0.4～1.0MPa; Crystallization 15 hours～3 days, the steam that discharge to produce, the volume that makes steam condensate be water in feeding intake TV 60%～85%.Then with remaining crystallization product through dry, roasting, obtain the TS-1 molecular sieve.
Chinese invention patent ZL00116531.3 (Granted publication CN1123380C authorizes a day 2003-10-08) has disclosed a kind of compound method of TS-1 molecular sieve.Its technical characterictic is, is the silicon source with the silicon sol, is the titanium source with the trivalent titanium compound, earlier with behind its mixing, underpressure distillation, dry the pulverulent solids, at quaternary ammonium hydroxide or/and crystallization in the presence of the organic amine obtains synthetic product.Crystallization temperature is 120～200 ℃, and crystallization time is 5～72 hours.This patent is handled the silicon source because of having used Hydrocerol A and YD 30, causes synthetic catalyzer weak effect when being used for epoxidation of propylene, and the propylene oxide selectivity is lower than 75%.
Chinese invention patent ZL01132199.7 (Granted publication CN1169623C authorizes a day 2004-10-06) has disclosed a kind of compound method of TS-1 molecular sieve.Its technical characterictic is, is the titanium source with the tetrabutyl titanate, is the silicon source with tetraethyl orthosilicate or silicon sol.Or/and organic amine is a template, after being made into gel, add the synthetic TS-1 molecular sieve of phosphoric acid with quaternary ammonium hydroxide.This patent finds to add phosphoric acid can shorten crystallization time.But phosphoric acid is not mentioned the influence of synthetic product property.
Chinese invention patent CN1401569A (02132325.9 applying date of application number 2002-08-26) has disclosed a kind of compound method of TS-1 molecular sieve.Its technical characterictic is; Is template with the self-control 4-propyl bromide through strongly basic anionic resin exchange, the concentrated TPAOH aqueous solution that obtains, and tetraethoxy is the silicon source, and tetrabutyl titanate is the titanium source; After being made into gel; The gained gel was removed alcohol 3～6 hours, and crystallization 12～24 hours obtains the TS-1 molecular sieve through filtration, washing, drying and roasting.
Chinese invention patent ZL03129657.0 (Granted publication CN1234458C authorizes a day 2006-01-04) has disclosed a kind of method of synthetic TS-1 molecular sieve.Its technical characterictic is, is raw material with organosilicon source, organic titanium source, organic bases template, water and Virahol, through the preparation of reaction mixture solution, be hydrolyzed into glue, remove alcohol and concentrate and four steps of hydrothermal crystallizing, makes the TS-1 molecular sieve.Use 3～15% lower concentration organic bases template TPAOH to be hydrolyzed into glue in this patent, use 15～35% high concentration organic alkali template TPAOH hydrothermal crystallizing.This method consumption of template agent is few, the hydrothermal crystallizing time short.
Chinese invention patent ZL200410067060.1 (Granted publication CN1276874C authorizes a day 2006-09-27) has disclosed a kind of compound method of TS-1 molecular sieve.Its technical characterictic is, the alcoholic solution in titanium source joined in the mixing solutions of silicon source and template to react 3～15 hours, and water is joined reaction product, and the add-on of water is 3～8 times of silicon source weight, obtains glue; Glue is carried out crystallization under unsteady state temperature programming condition, then, obtain the TS-1 molecular sieve through filtration, washing, drying and roasting.The present invention adopts the program control method of unsteady state that the particle diameter of HTS is increased, and has eliminated filtration resistance, has improved filtration velocity, has reduced the loss of catalyzer.
Chinese invention patent CN101190792A (200610144213.7 applying date of application number 2006-11-30) has disclosed a kind of compound method of TS-1 molecular sieve.Its technical characterictic is, tetraethoxy and tetrabutyl titanate are successively joined in the aqueous solution of TPAOH, carries out supersound process; Mix; Then mixed solution is carried out hydrothermal crystallizing,, obtain the TS-1 molecular sieve at last through filtration, washing, drying and roasting.Use supersound process in this method, it is uneven to eliminate the solution partial concn, makes the titanium oxide that generates from reuniting after the hydrolysis of titanium source few as far as possible, thereby reduces the generation of extra-framework titanium.
Chinese invention patent ZL200810023174.4 (Granted publication CN101327934B authorizes a day 2010-09-15) has disclosed a kind of compound method of TS-1 molecular sieve.Its technical characterictic is that silicon source, titanium source, TPAOH (TPAOH) and water are mixed; Putting into autoclave then, feed rare gas element, is 100～220 ℃ in temperature, and pressure is hydrothermal crystallizing 10～72 hours under the condition of 2.0～5.0MPa, then, through filtration, washing, drying and roasting, obtains the TS-1 molecular sieve.This method can reduce the template consumption, shortens the generated time of molecular sieve.
Chinese invention patent CN101696019A (200910217756.0 applying date of application number 2009-10-26) has disclosed a kind of method of synthetic TS-1 molecular sieve.Its technical characterictic is, is the silicon source with the tetraethoxy, and tetrabutyl titanate is the titanium source, and TPAOH is a template, and water and Virahol are solvent, H 2O 2Be inorganic additives, mix,, obtain the TS-1 molecular sieve through filtration, washing, drying and roasting 160～180 ℃ of following hydrothermal crystallizings 6～96 hours.
The open source literature synthetic chemistry, 3 (1995) 340-344 have introduced a kind of method of synthetic TS-1 molecular sieve.Be characterized in that method one is dissolved in H with tetrabutyl titanate 2O 2In, add TPAOH as template, add silicon source silicon sol then; Mixed solution in 20 ℃ of held 10 hours, is warming up to 70-80 ℃ with solution again, stirs after 6 hours; Under 175 ℃; In autoclave crystallization 2-8 days, pass through filtration, washing, drying and roasting at last, obtain synthetic product; Method two at first mixes tetraethoxy with tetrabutyl titanate, stir, and adds anhydrous isopropyl alcohol, TPAOH and deionized water again, then mixed solution is warming up to 70-80 ℃, under this temperature, stirs 6 hours, and aftertreatment is same as method one.Experiment shows, all can synthesize the TS-1 molecular sieve with two kinds of silicon sources, but is to use the better effects if of tetraethoxy.
The open source literature Journal of Molecular Catalysis, 10 (1996) 25-32 have introduced a kind of method of synthetic TS-1 molecular sieve.Be characterized in, tetraethoxy is mixed with TPAOH, add Virahol; The aqueous isopropanol of dropwise adding tetrabutyl titanate then, mixed solution removed alcohol after, in 170 ℃ of following crystallization 2～5 days; Through filtration, washing, drying and roasting, obtain the TS-1 molecular sieve at last.Mention in the document report, utilize TiCl 3As the titanium source is the effective way of synthetic TS-1 molecular sieve; And with Ti (OR) 4Be the titanium source, when titanium content is higher, be difficult to avoid the formation of anatase octahedrite; Show that through the catalyzed reaction evaluation content of titanium is proportional in the catalytic activity of TS-1 and the molecular sieve, and relevant with the preparation method of molecular sieve.
Open source literature petroleum journal (refining of petroleum), 20 (2004) 26-31 have introduced a kind of method of synthetic TS-1 molecular sieve.Be characterized in; With the tetraethoxy is that silicon source, tetrabutyl titanate are that titanium source, TPAOH are template and alkali source; Through reducing crystallization temperature; The rate of decomposition of TPAOH in the molecular sieve crystallization process reduced greatly, thus the practical efficiency of basicity in the raising system and TPAOH.
Open source literature organic chemical industry and catalysis, 14 (2006) 38-40 have introduced a kind of method of synthetic TS-1 molecular sieve.Be characterized in; Silicon sol, TPAOH, titanous chloride and ammoniacal liquor are mixed each other, get uniform mixture, mixture was carried out hydrothermal crystallizing 76 hours under 175 ℃; Again by ordinary method filter, wash, drying and roasting, obtain the TS-1 molecular sieve.
The open source literature Journal of Molecular Catalysis, 21 (2007) 458-461 have introduced a kind of method of synthetic TS-1 molecular sieve.Being characterized in, is the silicon source with the silicon sol, and titanous chloride is the titanium source; TPAOH is a template, uses ammoniacal liquor to regulate basicity, and raw material is mixed; Get uniform mixture; Mixture in 170 ℃ of following crystallization 76 hours, is filtered at last, washs, drying and roasting, obtain the TS-1 molecular sieve.
The open source literature Chinese Journal of Inorganic Chemistry, 26 (2010) 1711-1714 have introduced a kind of method of synthetic TS-1 molecular sieve.Be characterized in, tetraethoxy mixed with TPAOH that slowly dropwise adding tetrabutyl titanate after fully stirring, adds TPAOH and water, adds H at last 2O 2, get uniform mixing liquid, mixed solution was carried out hydrothermal crystallizing 2 days under 200 ℃, at last through filtration, washing, drying and roasting, obtain the TS-1 molecular sieve.
Open source literature Zeolites, 19 (1997) 238-245 have introduced a kind of method of synthetic TS-1 molecular sieve.Be characterized in, tetraethoxy be dissolved in the TPAOH solution, add deionized water, uniform mixture, with mixture heating up to 80 ℃, stirred 2 hours, cooling mixture to 35 ℃ stirs the following TiF that in mixture, adds then 4The aqueous solution, at last final mixture is packed in the autoclave, autoclave is warming up to 170 ℃, crystallization is 2 days under autogenous pressure, and end product through filtration, washing, drying and roasting, is obtained the TS-1 molecular sieve.
Open source literature Microporous and mesoporous material, 66 (2003) 143-156 have introduced a kind of method of synthetic TS-1 molecular sieve.Be characterized in; Tetraethyl silicate is mixed with tetrabutyl titanate, at room temperature stir, in mixture, slowly add the TPAOH aqueous solution then; Stirred overnight is to guarantee complete hydrolysis; In 175 ℃ of following microwave heating crystallization 0.5-2 hour, with product dialysis separation, washing, drying and roasting, obtain synthetic product at last again.
Open source literature Chemical engineering journal, 147 (2009) 316-322 have introduced a kind of method of synthetic TS-1 molecular sieve.Be characterized in, tetrabutyl titanate is dissolved in the Virahol, and under vigorous stirring; This mixture is dropped in the solution of TPAOH, obtain the hydrolyzed solution of titanium, under agitation tetraethoxy is dissolved in the aqueous solution of TPAOH then; Obtain the hydrolyzed solution of silicon, two kinds of mixed solutions are mixed, and heating removes alcohol; And constantly add deionized water, add S-1 that classical approach makes then, in 173 ℃ of following crystallization 48 hours as crystal seed; Pass through filtration, drying and roasting at last, obtain the TS-1 molecular sieve.The result shows; Use S-1 pure silicon zeolite to be the TS-1 of crystal seed gained; Though the shape heterogeneity has higher activity in the selectivity of styrene oxidizing reaction, the while has pointed out that also the adding of crystal seed can have the crystallization rate of acceleration molecular sieve; Make Ti get into skeleton more easily, thereby make it that higher catalytic activity arranged.
Open source literature Catalysis today, 158 (2010) 510～514 have introduced a kind of method of synthetic TS-1 molecular sieve.Be characterized in, use tetraethyl orthosilicate and tetrabutyl titanate respectively as silicon source and titanium source, TPAOH uses three kinds of method dissolving tetrabutyl titanates respectively: 1. make solvent with ethanol, and in crystallization process, keep always as template; 2. make solvent with Virahol, in crystallization process, keep always; 3. make solvent with Virahol, but before crystallization, remove alcohol.Find that through characterizing the TS-1 skeleton titanium content that method 2 is synthesized is high, shows good catalytic activity.
Following patent has also related to the improvement compound method of TS-1 in TPAOH template system:
CN1169952A(1996-07-10)，CN1239015A(1998-16-12)，CN1245089A(1998-08-18)，CN1247771A(1998-09-17)，CN1275529A(1999-05-28)，CN1294030A(1999-10-27)，CN1328878A(2000-06-15)，CN1327947A(2001-06-13)，CN1475442A(2002-08-15)，CN1482062A(2003-07-18)，CN1634765A(2003-12-28)，CN1902187A(2004-12-13)，CN101134575A(2006-08-31)，CN101291877A(2006-09-12)，CN1935651A(2006-10-19)，CN1830564A(2006-04-24)，CN101434400A(2007-11-15)，CN101696019A(2009-10-26)，USP5656252(1995-01-30)，USP5688484(1997-11-18)，USP5977009(1999-11-02)，USP6387349(2002-058-14)，WO2009077086(2008-12-03)。
The following discloses document has also related to the Study of synthesis method of in TPAOH template system, carrying out TS-1:
Petroleum chemistry (petrochemical complex), 14 (1998) 40-44; Oil refinery and chemical industry, 31 (2000) 33-37; Maoming College's journal, 11 (2001) 1-7; The Dalian Polytechnic College journal, 22 (2003) 243-246; The chemistry of fuel journal, 33 (2005) 112-116; Industrial Catalysis, 15 (2007) 60-63; The catalysis journal, 28 (2007) 895-899; SCI, 29 (2008) 1926-1929; Journal of Physics and Chemistry of Solids, 69 (2008) 1136-1138; Journal of American Chemistry Society, 130 (2008) 10150-10164; Microporous and mesoporous materials, 122 (2009) 301-308; Materials research bulletin, 46 (2011) 698～701.
Above-mentioned relating to the TPAOH is the patent and the open source literature of the synthetic TS-1 molecular sieve of template, changes through the difference on the synthesis technique, suppresses the generation of extra-framework titanium.Certainly not introducing foreign ions such as sodium ion, potassium ion is the common recognition of these previous methods.Such as document Journal of catalysis, 151 (1995) 77-86 have introduced a kind of method of the TS-1 of preparation molecular sieve.It has synthesized the TS-1 molecular sieve with the method described in the patent USP4410501, has examined or check the interpolation alkalimetal ion to synthetic influence.This open source literature finds that the existence of alkalimetal ion can reduce the performance of catalyzer.After pickling, activity of such catalysts can obtain part and recover, but generally speaking performance is still undesirable.
The problem of aforesaid method is to need to use highly purified TPAOH, and the synthetic cost of molecular sieve is high.In order to reduce the synthetic cost of molecular sieve, Many researchers attempts replacing the synthetic TS-1 molecular sieve of TPAOH with other template, thereby makes synthesizing of TS-1 molecular sieve form the so-called cheap law technology with non-TPAOH template again.
Following patent and open source literature have related to the method with the synthetic TS-1 molecular sieve of non-TPAOH template:
U.S. Pat P5688484 (1996-07-29) has disclosed a kind of compound method of TS-1 molecular sieve.Its technical characterictic is, tetraethoxy and tetrabutyl titanate are joined in the U-4527, at room temperature stir 30 minutes after; Get uniform mixture, mixture is cooled to 0 ℃, then to wherein dripping HF and deionized water; Mixture was at room temperature stirred 1 hour, add with classical approach synthetic TS-1 molecular sieve, with mixture crystallization 7 days as crystal seed; Pass through filtration, washing, drying and roasting at last, obtain the TS-1 molecular sieve.
Chinese invention patent ZL97104636.0 (Granted publication CN1060411C authorizes a day 2001-1-10) has disclosed a kind of compound method of TS-1 molecular sieve.Its technical characterictic is, is silicon source and titanium source with silica gel and butyl(tetra)titanate, is template with the mixture of tetraethyl ammonium hydroxide and TBAH.Adopt static state or dynamic method crystallization 4～6 days under 170～180 ℃ of temperature, through separating, washing, drying and roasting obtain the TS-1 molecular sieve.
Chinese invention patent ZL200510111779.5 (Granted publication CN100344375C authorizes a day 2007-10-24) has disclosed a kind of compound method of TS-1 molecular sieve.Its technical characterictic is, uses silicon sol as the silicon source, and organic titanate is as the titanium source, and hexamethylene imine and piperidines are pressed the ordinary method hydrothermal crystallizing as template.Through separating, to wash, drying and roasting obtain the TS-1 molecular sieve.
Chinese invention patent CN101913620A (201010235977.3 applying date of application number 2010-7-20) has disclosed a kind of compound method of TS-1 molecular sieve.Its technical characterictic is, is the silicon source with the silicon sol, and titanium tetrachloride or tetrabutyl titanate are the titanium source, and 4-propyl bromide is a template, and organic amine is an alkali source, and nano level TS-1 molecular sieve and synthesis mother liquid thereof are without separating directly as crystal seed the synthetic product that obtains of hydro-thermal.
Open source literature Dalian University of Technology journal, 40 (2000) 155-159 have introduced a kind of method of synthetic TS-1 molecular sieve.Be characterized in, use 4-propyl bromide to replace TPAOH, and can reduce synthetic middle template agent.And investigated the order of different templates agent effect, experimental result shows: the structure-directing effect of different templates agent is pressed TPA +＞TBA +＞TEA +＞organic amine reduces.With n-Butyl Amine 99, diethylamine, hexanediamine and TBAH is the TS-1 molecular sieve that alkali source all can obtain the epoxidation of propylene better performances.
Open source literature Material chemistry and physics, 47 (1997) 225-230 have introduced a kind of method of synthetic TS-1 molecular sieve.During its characteristics, the two-component mixture that uses 4-propyl bromide and etamon chloride and tetrabutylammonium chloride is as the synthetic TS-1 molecular sieve of structure directing agent.Its synthesis step is: Virahol, diethylamine, deionized water and tetraethoxy are mixed each other, obtain the hydrolyzed solution of silicon, tetrabutyl titanate is mixed with Virahol each other; Obtain the hydrolyzed solution of titanium, titanium solution except that behind the alcohol, is mixed the titanium source with the silicon source; Stir; Add classical approach synthetic TS-1 then and make crystal seed, pass through hydrothermal crystallizing, filtration, washing, drying and roasting at last, obtain the TS-1 molecular sieve.
Open source literature Zeolites, 19 (1997) 246-252 have introduced a kind of method of synthetic TS-1 molecular sieve.Be characterized in, use methylamine and 4-propyl bromide to substitute TPAOH as template, and with the muriate of muriate that uses silicon sol or silicon respectively and titanium as silicon source and titanium source, add HF simultaneously and improved crystallization kinetics as mineralizer.Document report, titanium stabilized implantation in the skeleton of TS-1 molecular sieve; And if in synthesizing, reduce the amount of methylamine, obviously accelerated crystallization velocity, but simultaneously, the skeleton titanium content descends obviously also simultaneously among the TS-1, show that the concentration of methylamine plays a part very important to titanium entering skeleton.
Open source literature Catalysis today, 74 (2002) 65-75 have introduced a kind of method of synthetic TS-1 molecular sieve.Be characterized in, under the room temperature, silicon sol, 4-propyl bromide and deionized water mixed; Stir, then in dropwise adding tetrabutyl titanate solution to the above-mentioned mixed solution, under the restir; In solution, add n-Butyl Amine 99; Uniform mixture, with mixture crystallization 4 days under 170 ℃ and autogenous pressure, obtain the TS-1 molecular sieve through filtration, washing, drying and roasting again.
Following patent and open source literature have also related to the method with the synthetic TS-1 molecular sieve of non-TPAOH template:
CN100457622A(2001-12-28)，CN1212892A(2002-12-31)，CN100344375A(2005-12-21)，CN101428814A(2007-11-07)，CN101767036A(2009-12-25)。The catalysis journal, 17 (1996) 173-176; Dalian University of Technology's journal, 38 (1998) 363-367; Dalian University of Technology's journal, 38 (1998) 354-358; Acta PhySico-Chimica Sinica, 14 (1998) 906-912; Petroleum journal (petrochemical complex), 14 (1998) 35-39; Petroleum journal (refining of petroleum), 15 (1999) 90-93; Journal of Molecular Catalysis, 14 (2000) 363-367; The catalysis journal, 22 (2001) 92-94; Material chemistry and physics, 47 (1997) 225-230; Microporous materials, 12 (1997) 141-148.
The inexpensive method of above-mentioned synthetic TS-1 obviously can reduce the synthetic cost of TS-1 molecular sieve.But the extra-framework titanium content in the TS-1 zeolite product is generally high than classical approach TS-1 molecular sieve, and many investigators are summed up as it in foreign metal ion of bringing in cheap raw material such as inorganic silicon source, like Na +, K +, Al 3+Deng.
In order to reduce the extra-framework titanium content in the cheap TS-1 molecular sieve, improve the catalytic activity of TS-1 molecular sieve, many investigators have carried out the post-modification research of TS-1 molecule.Following patent relates to the post-modification method of TS-1 molecular sieve:
CN1245090A(1998-08-18)，CN1421389A(2001-11-29)，CN1413768A(2002-11-17)，CN1555923A(2004-01-10)，CN101658791A(2008-08-26)，CN101658798A(2008-08-29)，CN101653734A(2008-08-22)，CN101623653A(2008-07-10)，CN101618338A(2008-06-30)，CN101618339A(2008-06-30)，CN101537372A(2008-03-20)，CN101602013A(2008-06-12)，CN101537371A(2008-03-20)，CN101786638A(2009-12-25)，USP5646314(1995-02-28)，USP5675026(1996-06-21)，USP6103915(1998-12-30)。But post-modification has increased the process step of preparation TS-1 molecular sieve, has increased cost.
To sum up visible, although the study on the synthesis of relevant TS-1 has been pass by nearly 30 years, synthetic at present high quality TS-1 molecular sieve is still a major challenge, and these challenges mainly show as: TPAOH is the synthetic cost height of molecular sieve in the synthetic system of template; Replace the synthetic TS-1 molecular sieve of TPAOH body can increase the content of amorphous hexa-coordinate extra-framework titanium with other template, be unfavorable for catalytic applications; Post-modification method weak effect and increased the cost of TS-1 molecular sieve.
Summary of the invention
The invention provides a kind of with cheap raw material and can reduce extra-framework titanium content and the TS-1 molecular sieve new synthetic method that improves the epoxidation of propylene performance.We are through discover in a large number, and the existence of alkalimetal ion is not to influence the principal element that titanium atom gets into framework of molecular sieve, and the hydrolysis rate in the hydrolysis rate in silicon source and titanium source can not mate, and is the principal element that amorphous extra-framework titanium produces.We further find, in synthetic TS-1 molecular sieve process, introduce an amount of an alkali metal salt, can promote the depolymerization in silicon source, help titanium and get into skeleton and the generation that suppresses amorphous hexa-coordinate extra-framework titanium.Alkalimetal ion can also through with the molecular sieve extra-framework titanium on the effect in acid site, eliminate the acid sites of cheap TS-1 molecular sieve, when making the TS-1 molecular sieve as the catalyzer of propylene ring oxidation reaction, the propylene oxide selectivity promotes greatly.
The present invention can introduce an alkali metal salt through dual mode, and a kind of is after joining the glue completion, directly to add an amount of an alkali metal salt (direct method); Another kind is in the silicon source, to add alkali, in the titanium source, adds acid simultaneously, produces desirable salt (indirect method) with the acid-base neutralisation reaction.
Key of the present invention is, utilizes alkalimetal ion to reduce the condensation degree in silicon source, and a large amount of silicate species are existed with highly active oligomeric attitude form.When synthesis of titanium silicon molecular sieve, following reaction takes place in silicate species in the gel easily:
Figure BDA0000095160350000121
This reaction can cause rapid polymerization between the silicate, generates high-molecular weight SiO 2Micelle is unfavorable for combining between titanate radical species and the silicate.When introducing the appropriate bases metals ion, in alkaline environment, following reaction can take place in silicate:
Figure BDA0000095160350000131
Reaction (2) has suppressed the carrying out of reaction (1), thereby a large amount of silicate species can be existed with highly active oligomeric attitude form.In becoming glue and gel crystallization process, a large amount of silicate species exist with oligomeric attitude form, help condensation between titanate species and the silicate species, make titanium get into skeleton, reduce the generation of hexa-coordinate extra-framework titanium.Simultaneously, the negatively charged ion of following alkali metal cation to introduce can also strengthen the unitary polarity of molecular sieve structure, thereby promotes the molecular sieve nucleus to form, accelerating growth, thus shorten the molecular sieve crystallization time.
When adopting indirect method to introduce alkalimetal ion, alkalimetal oxide that in the silicon source, adds or oxyhydroxide can promote reaction (2); The acid that in the titanium source, adds on the other hand can suppress the hydrolysis in titanium source, thereby promotes the reaction between silicon, the titanium species better.Certainly, in order to guarantee crystallization condition, the alkalescence of alkalimetal oxide or oxyhydroxide will use the acid of adding to neutralize fully, and in addition, when introducing salt with direct method, the adding of salt can be incorporated in the silicon source before becoming glue, also can after becoming glue, introduce.And when introducing salt with indirect method, acid, alkaloid substance are introduced before being preferably in into glue.
Technical scheme of the present invention is following:
The first step, preparation titanium silicon gel
Preparation titanium silicon gel is taked direct method and indirect method: after joining the glue completion, directly adding an alkali metal salt, is exactly direct method; In the silicon source, adding alkali, in the titanium source, add acid simultaneously, produce required salt with the acid-base neutralisation reaction, is exactly indirect method.The mode that adds adopts following three kinds:
First kind: direct method is introduced an alkali metal salt
(1) under agitation, silicon source and water, an alkali metal salt, template are mixed, make raw silicon.
(2) under agitation, titanium source and complexing agent are mixed, make the raw material titanium.
(3) under agitation, raw silicon and raw material titanium are mixed, and then, this mixture is stirred, promptly make titanium silicon gel to wherein adding alkaline mineralizer.
Second kind: direct method is introduced an alkali metal salt
(1) under agitation, silicon source, water and template are mixed, make raw silicon.
(2) under agitation, titanium source and complexing agent are mixed, make the raw material titanium.
(3) under agitation, raw silicon and raw material titanium are mixed, and then, this mixture is stirred, promptly make titanium silicon gel to wherein adding an alkali metal salt, alkaline mineralizer successively.
The third: indirect method is introduced an alkali metal salt, and promptly the neutralization reaction with alkali-metal oxide compound or oxyhydroxide and corresponding acid solution provides required an alkali metal salt
(1) under agitation, silicon source and water, alkali-metal oxide compound or oxyhydroxide and template are mixed, make raw silicon.
(2) under agitation, titanium source and acid solution and complexing agent are mixed, make the raw material titanium.
(3) under agitation, raw silicon and raw material titanium are mixed, and then, this mixture is stirred, promptly make titanium silicon gel to wherein adding alkaline mineralizer.
In second step, make HTS
With the above-mentioned titanium silicon gel for preparing hydrothermal crystallizing under the state of static or stirring, the crystallization temperature scope is 120～200 ℃, and preferred 160～180 ℃, the crystallization time scope is 1h～168h, preferred 2～3 days.Feed liquid after the crystallization processes HTS through solid-liquid separation and steps such as drying, roasting.
A kind of in silica gel, silicon sol, the WHITE CARBON BLACK adopted or mixture more than two kinds in the silicon source;
A kind of in tetrabutyl titanate, titanium tetrachloride, titanous chloride, the titanium sulfate adopted or mixture more than two kinds in the titanium source;
An alkali metal salt adopts any in sodium sulfate, sodium-chlor, SODIUMNITRATE, sodium phosphate, sodium acetate, vitriolate of tartar, Repone K, saltpetre, potassiumphosphate, potassium acetate, Lithium Sulphate, lithium chloride, lithium nitrate, Trilithium phosphate, the lithium acetate or mixture more than two kinds, and also can carry out neutralization reaction with the oxyhydroxide of the oxide compound of the oxyhydroxide of the oxide compound of the oxyhydroxide of the oxide compound of sodium, sodium, lithium, lithium, potassium, potassium and acid solution provides above-mentioned salt or its mixture; Described acid solution adopts a kind of in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, the acetate or mixture more than two kinds.。
Template adopts a kind of in tetrapropyl Neutral ammonium fluoride, 4-propyl ammonium chloride, the 4-propyl bromide or mixture more than two kinds;
The alkalescence mineralizer adopts a kind of in ammoniacal liquor, methylamine, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, quadrol, diethylamine, the hexanediamine or mixture more than two kinds;
The titanium complexing agent adopts a kind of or its mixture in methyl ethyl diketone, the Virahol.
Above-mentioned titanium silicon gel has following composition: aSiO 2: bTiO 2: c Me:d SDA:e K:fL:g H 2O, wherein, Me, SDA, K, L represent alkalimetal ion, template, alkaline mineralizer, titanium complexing agent, a=1, b=0.01～0.03, c=0.01～0.2, d=0.05～0.5, e=0.1～3.0, f=0.01～0.5, g=30～100 respectively.
The invention has the beneficial effects as follows through in titanium silicon gel, introducing the appropriate bases metal-salt; On the one hand; Suppressed the generation of amorphous hexa-coordinate extra-framework titanium in the TS-1 molecular sieve, the acid site of having reduced makes the cheap TS-1 molecular sieve in propylene ring oxidation reaction, show high reactivity and highly selective.On the other hand, can relax the particularly purity requirement in silicon source of TS-1 synthesis material, help further reducing the cost of TS-1 molecular sieve with method of the present invention.
Description of drawings
Fig. 1 is Fourier's infrared spectrum of comparative example's 1 sample.
The a line is the uv-vis spectra spectrogram of comparative example's 1 sample among Fig. 2, and the b line is the uv-vis spectra spectrogram of embodiment 1 sample.
Embodiment
Following embodiment will be further described the present invention, but therefore not limit the present invention.Wherein used reagent is commercially available chemical reagent among the embodiment.
The comparative example 1
Get the 220ml deionized water and join in the 225g silicon sol (20%wt), stir after 10 minutes, the 20.4g 4-propyl bromide is added in the glue, continue to stir 20 minutes, make raw silicon solution; Tetrabutyl titanate and methyl ethyl diketone are mixed with mass ratio at 1: 0.9, stirred 15 minutes, make the raw material titanium solution; Get the prepared raw material titanium solution of 14.7ml and join in the raw silicon solution, stir after 30 minutes, add the 54ml n-Butyl Amine 99, continue to stir 15 minutes, get even gel; Then the gained gel is joined in the 2L stainless steel cauldron, autogenous pressure and 170 ℃ of following crystallization 48 hours; Product filters through conventional method, and washing is to neutral, and 110 ℃ are dry down, and template is removed in 540 ℃ of roastings 6 hours, sieve sample A.
Fourier's infrared spectrum is as shown in Figure 1, in the infrared spectrum at 960cm -1Near the unexistent infrared absorption peak of total silicon molecular sieve appears, show that titanium has got into skeleton.Uv-vis spectra is shown in Fig. 2 (a), and there is wide absorption peak at 270～280nm place in the uv atlas, and showing has the non-skeleton of amorphous hexa-coordinate to exist.The absorption band of anatase octahedrite does not appear in the 330nm place.
Embodiment 1
Get the 220ml deionized water and join in the 225g silicon sol (20%wt), and add 5.3g sodium sulfate, stir after 10 minutes, the 20.4g 4-propyl bromide is added in the glue, continue to stir 20 minutes, make raw silicon solution; Tetrabutyl titanate and methyl ethyl diketone are mixed with mass ratio at 1: 0.9, stirred 15 minutes, make the raw material titanium; Get the prepared raw material titanium solution of 14.7ml and join in the raw silicon solution, stir after 30 minutes, add the 54ml n-Butyl Amine 99, continue to stir 15 minutes, get even gel; Then the gained gel is joined in the 2L stainless steel cauldron, under autogenous pressure with 170 ℃ of following crystallization 48 hours; Product filters through conventional method, and washing is to neutral, and 110 ℃ are dry down, and template is removed in 540 ℃ of roastings 6 hours, sieve sample B.
Its Fourier's infrared spectrum and Fig. 1 are similar, in the infrared spectrum at 960cm -1Near the unexistent infrared absorption peak of total silicon molecular sieve appears, show that titanium has got into skeleton.Uv-vis spectra is shown in Fig. 2 (b), and the absorption peak strength at 270～280nm place in the uv atlas is compared with uv-vis spectra spectrogram Fig. 2 (a) of Comparative Examples, obviously weakens.Show that the non-skeleton content of amorphous hexa-coordinate obviously reduces.The absorption band of anatase octahedrite does not appear in the 330nm place.
Embodiment 2
Get the 220ml deionized water and join in the 225g silicon sol (20%wt), stir after 10 minutes, the 20.4g 4-propyl bromide is added in the glue, continue to stir 20 minutes, make raw silicon solution; Tetrabutyl titanate and methyl ethyl diketone are mixed with mass ratio at 1: 0.9, stirred 15 minutes, make the raw material titanium; Get the prepared raw material titanium solution of 14.7ml and join in the raw silicon solution, stir after 30 minutes, add 5.3g sodium sulfate, stirred 5 minutes, add the 54ml n-Butyl Amine 99, continue to stir 10 minutes, get even gel; Then the gained gel is joined in the 2L stainless steel cauldron, autogenous pressure and 170 ℃ of following crystallization 48 hours; Product filters through conventional method, and washing is to neutral, and 110 ℃ are dry down, and template is removed in 540 ℃ of roastings 6 hours, sieve sample.Gained sample epoxidation of propylene performance is all suitable with sample B.
Its Fourier's infrared spectrum and Fig. 1 are similar, and uv-vis spectra and Fig. 2 (b) are similar.The absorption peak strength at 270～280nm place in the uv atlas is compared with uv-vis spectra spectrogram Fig. 2 (a) of Comparative Examples, obviously weakens.The non-skeleton content of amorphous hexa-coordinate obviously reduces.The absorption band of anatase octahedrite does not appear in the 330nm place.
Embodiment 3
Repeat embodiment 1, but wherein the add-on of sodium sulfate becomes 10.6g, 2.65g, 0.53g.Be c=0.2,0.05,0.01, then obtain sieve sample C, D, E successively.
Its Fourier's infrared spectrum is all similar with Fig. 1, and uv-vis spectra and Fig. 2 (b) are similar, and the non-skeleton content of amorphous hexa-coordinate obviously reduces.The absorption band of anatase octahedrite does not appear in the 330nm place.
Embodiment 4
Repeat embodiment 1; But change salt wherein into sodium-chlor, SODIUMNITRATE, sodium phosphate, sodium acetate, vitriolate of tartar, Repone K, saltpetre, potassiumphosphate, potassium acetate, Lithium Sulphate, lithium chloride, lithium nitrate, Trilithium phosphate, lithium acetate; The relative molar content of component is consistent with embodiment 1; Be c=0.1, then obtain sieve sample successively.Gained sample epoxidation of propylene performance is all suitable with sample B.
Its Fourier's infrared spectrum is all similar with Fig. 1, and uv-vis spectra and Fig. 2 (b) are similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.The absorption band of anatase octahedrite does not appear in the 330nm place.
Embodiment 5
Repeat embodiment 1, but change silicon sol wherein into silica gel, WHITE CARBON BLACK respectively.The relative molar content of component is consistent with embodiment 1, then obtains sieve sample successively, and gained sample epoxidation of propylene performance is all suitable with sample B.
Its Fourier's infrared spectrum is all similar with Fig. 1, and uv-vis spectra and Fig. 2 (b) are similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.The absorption band of anatase octahedrite does not appear in the 330nm place.
Embodiment 6
Repeat embodiment 1 operation, but change titanium source wherein into titanium tetrachloride, titanous chloride, titanium sulfate respectively.The relative molar content of component is consistent with embodiment 1, and promptly b=0.03 obtains sieve sample successively, and gained sample epoxidation of propylene performance is all suitable with sample B.
Its Fourier's infrared spectrum is all similar with Fig. 1, and uv-vis spectra and Fig. 2 (b) are similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.The absorption band of anatase octahedrite does not appear in the 330nm place.
Embodiment 7
Repeat embodiment 1, but change n-Butyl Amine 99 wherein into ammoniacal liquor, methylamine, ethamine, Tri N-Propyl Amine, quadrol, diethylamine, hexanediamine respectively, the relative molar content of component is consistent with embodiment 1, and promptly e=0.73 gets sieve sample.Gained sample epoxidation of propylene performance is all suitable with sample B.
Its Fourier's infrared spectrum is all similar with Fig. 1, and uv-vis spectra and Fig. 2 (b) are similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.The absorption band of anatase octahedrite does not appear in the 330nm place.
Embodiment 8
Get the 220ml deionized water and join in the 225g silicon sol (20%wt), add 3g sodium hydroxide, stir after 10 minutes, with the 5.4g crystal seed, the 20.4g 4-propyl bromide adds in the glue, continues to stir 20 minutes, makes raw silicon solution; Tetrabutyl titanate and methyl ethyl diketone are mixed with mass ratio at 1: 0.9, add 3.7g sulfuric acid, stirred 15 minutes, make the raw material titanium; Get the prepared raw material titanium solution of 14.7ml and join in the raw silicon solution, stir after 30 minutes, add the 54ml n-Butyl Amine 99, continue to stir 15 minutes, get even gel; Then the gained gel is joined in the 2L stainless steel cauldron, autogenous pressure and 170 ℃ of following crystallization 48 hours; Product filters through conventional method, and washing is to neutral, and 110 ℃ are dry down, and template is removed in 540 ℃ of roastings 6 hours, the molecular sieve sample F.
Its Fourier's infrared spectrum is all similar with Fig. 1, and uv-vis spectra and Fig. 2 (b) are similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.The absorption band of anatase octahedrite does not appear in the 330nm place.
Embodiment 9
Repeat embodiment 8, wherein the sulfuric acid add-on changes 7.4g into, 1.85g, and 0.37g, addition amount of sodium hydroxide changes 6g into, 0.75g, 0.3g.Be c=0.2,0.05,0.01, then obtain sieve sample successively and be followed successively by G, H, I.
Its Fourier's infrared spectrum is all similar with Fig. 1, and uv-vis spectra and Fig. 2 (b) are similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.The absorption band of anatase octahedrite does not appear in the 330nm place.
Embodiment 10
Repeat embodiment 8, but change sulfuric acid wherein into hydrochloric acid, nitric acid, phosphoric acid, acetate respectively, add-on is followed successively by 7.8g, 4.8g, and 2.9g, 4.5g, promptly c=0.1 gets sieve sample.Gained sample epoxidation of propylene performance is all suitable with sample F.
Its Fourier's infrared spectrum is all similar with Fig. 1, and uv-vis spectra and Fig. 2 (b) are similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.The absorption band of anatase octahedrite does not appear in the 330nm place.
Embodiment 11
Repeat embodiment 8, but change sodium hydroxide wherein into Pottasium Hydroxide, Lithium Hydroxide MonoHydrate, add-on is followed successively by 4.2g, 1.8g, promptly c=0.1 obtains sieve sample.Gained sample epoxidation of propylene performance is all suitable with sample F.
Its Fourier's infrared spectrum is all similar with Fig. 1, and uv-vis spectra and Fig. 2 (b) are similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.The absorption band of anatase octahedrite does not appear in the 330nm place.
Embodiment 12
Repeat embodiment 8, but change silicon sol wherein into silica gel, WHITE CARBON BLACK respectively.The relative molar content of component is consistent with embodiment 8, then gets sieve sample successively, and gained sample epoxidation of propylene performance is all suitable with sample F.
Its Fourier's infrared spectrum is all similar with Fig. 1, and uv-vis spectra and Fig. 2 (b) are similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.The absorption band of anatase octahedrite does not appear in the 330nm place.
Embodiment 13
Repeat embodiment 8, but change titanium source wherein into titanium tetrachloride, titanous chloride, titanium sulfate respectively.The relative molar content of component is consistent with embodiment 1, and promptly b=0.03 then obtains sieve sample successively, and gained sample epoxidation of propylene performance is all suitable with sample F.
Its Fourier's infrared spectrum is all similar with Fig. 1, and uv-vis spectra and Fig. 2 (b) are similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.The absorption band of anatase octahedrite does not appear in the 330nm place.
Embodiment 14
Repeat embodiment 8, but change n-Butyl Amine 99 wherein into ammoniacal liquor, methylamine, ethamine, Tri N-Propyl Amine, quadrol, diethylamine, hexanediamine respectively, the relative molar content of component is consistent with embodiment 8, and promptly e=0.73 then gets sieve sample successively.Gained sample epoxidation of propylene performance is all suitable with sample F.
Its Fourier's infrared spectrum is all similar with Fig. 1, and uv-vis spectra and Fig. 2 (b) are similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.The absorption band of anatase octahedrite does not appear in the 330nm place.
Embodiment 15
In 400ml stainless steel high pressure batch reactor, add the 0.2g catalyst A, 30ml methyl alcohol; The ydrogen peroxide 50 of 2ml30% stirs and feeds propylene, propylene pressure 0.4MPa down; 50 ℃ of temperature of reaction, the sampling when reaction times is 60 minutes, iodimetry,iodometry is surveyed the transformation efficiency of ydrogen peroxide 50.The selectivity of gas chromatographic analysis propylene oxide and the effective rate of utilization of hydrogen peroxide.Replace A respectively with catalyst B～I, carry out above-mentioned reaction, reaction result is listed in table 1.
The epoxidation of propylene performance of table 1 part sieve sample
Figure BDA0000095160350000181
Can find out that from table 1 the epoxidation of propylene performance of the TS-1 molecular sieve that the present invention obtains is compared with not introducing an alkali metal salt synthetic TS-1 molecular sieve, propylene oxide selectivity and effective utilization ratio of hydrogen peroxide all obviously improve.

Claims (8)

1. the compound method of a titanium-silicon molecular sieve TS-1 is characterized in that comprising the steps:
The first step, take a kind of preparation titanium silicon gel in following three kinds of methods: after joining the glue completion, directly adding an alkali metal salt, is exactly direct method; In the silicon source, adding alkali, in the titanium source, add acid simultaneously, produce required salt with the acid-base neutralisation reaction, is exactly indirect method;
First kind: direct method is introduced an alkali metal salt
(1) under agitation, silicon source and water, an alkali metal salt, template are mixed, make raw silicon;
(2) under agitation, titanium source and complexing agent are mixed, make the raw material titanium;
(3) under agitation, raw silicon and raw material titanium are mixed, and then, this mixture is stirred, promptly make titanium silicon gel to wherein adding alkaline mineralizer;
Second kind: direct method is introduced an alkali metal salt
(1) under agitation, silicon source, water and template are mixed, make raw silicon;
(2) under agitation, titanium source and complexing agent are mixed, make the raw material titanium;
(3) under agitation, raw silicon and raw material titanium are mixed, and then, this mixture is stirred, promptly make titanium silicon gel to wherein adding an alkali metal salt, alkaline mineralizer successively;
The third: indirect method is introduced an alkali metal salt, when promptly required an alkali metal salt being provided with alkali-metal oxide compound or oxyhydroxide and the neutralization reaction of acid solution accordingly,
(1) under agitation, silicon source and water, alkali-metal oxide compound or oxyhydroxide and template are mixed, make raw silicon;
(2) under agitation, titanium source and acid solution and complexing agent are mixed, make the raw material titanium;
(3) under agitation, raw silicon and raw material titanium are mixed, and then, this mixture is stirred, promptly make titanium silicon gel to wherein adding alkaline mineralizer;
In second step, make HTS
With the above-mentioned titanium silicon gel for preparing hydrothermal crystallizing under the state of static or stirring, the crystallization temperature scope is 120～200 ℃, and the crystallization time scope is 1h～168h; Feed liquid after the crystallization processes HTS through solid-liquid separation and dry, roasting.
2. the method for closing according to claim 1 is characterized in that, described silicon source is a kind of in silica gel, silicon sol, the WHITE CARBON BLACK or mixture more than two kinds.
3. compound method according to claim 1 is characterized in that, described titanium source is a kind of in tetrabutyl titanate, titanium tetrachloride, titanous chloride, the titanium sulfate or mixture more than two kinds.
4. compound method according to claim 1; It is characterized in that; Described an alkali metal salt is any in sodium sulfate, sodium-chlor, SODIUMNITRATE, sodium phosphate, sodium acetate, vitriolate of tartar, Repone K, saltpetre, potassiumphosphate, potassium acetate, Lithium Sulphate, lithium chloride, lithium nitrate, Trilithium phosphate, the lithium acetate or mixture more than two kinds, or carries out neutralization reaction with the oxyhydroxide of the oxide compound of the oxyhydroxide of the oxide compound of the oxyhydroxide of the oxide compound of sodium, sodium, lithium, lithium, potassium, potassium and acid solution and make.
5. compound method according to claim 1 is characterized in that, described acid solution is a kind of in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, the acetate or mixture more than two kinds.
6. compound method according to claim 1 is characterized in that, described alkaline mineralizer is a kind of in ammoniacal liquor, methylamine, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, quadrol, diethylamine, the hexanediamine or mixture more than two kinds.
7. compound method according to claim 1 is characterized in that, described complexing agent is for adopting a kind of or its mixture in methyl ethyl diketone, the Virahol.
8. compound method according to claim 1 is characterized in that, template is a kind of in tetrapropyl Neutral ammonium fluoride, 4-propyl ammonium chloride, the 4-propyl bromide or mixture more than two kinds.
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