CN102320619B - Synthesis method of titanium silicalite TS-1 - Google Patents
Synthesis method of titanium silicalite TS-1 Download PDFInfo
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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
Technical field
The invention belongs to molecular screen material preparation field, relate to a kind of synthetic 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 catalyst system of TS-1 molecular sieve and rare hydrogen peroxide composition is widely used in selective oxidation field, has good selective oxidation reaction performance.TS-1 molecular sieve for organic oxidizing reaction, is avoided to the problem of oxidising process complex process and environmental pollution, there is unrivaled energy-conservation, the advantage such as economy and environment is friendly of conventional oxidation system, 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 Introduction of Literatures the application of TS-1 molecular sieve:
In US Patent No. P4833260 (1988-07-11), disclose taking hydrogen peroxide as oxygenant, TS-1 molecular sieve is the olefin epoxidation process of catalyzer, its temperature of reaction is 0～150 DEG C, and pressure is 1～100atm, and preferred solvent is methyl alcohol, the trimethyl carbinol, acetone.Taking rare hydrogen peroxide as oxygenant, the epoxidation of the alkene such as ethene, propylene, 2-butylene, propenyl chloride, 1-octene, has all obtained good result.
In US Patent No. P4476327 (1993-11-16), disclose the epoxidation for alkene such as propylene, propenyl chloride, vinylbenzene, tetrahydrobenzene by TS-1 molecular sieve, found that TS-1 has good epoxidation performance.
In Chinese invention patent ZL99125464.3 (Granted publication CN1097575C authorizes a day 2003-01-01), disclose and utilized TS-1 molecular sieve catalytic 4-cresols to prepare 4-methyl pyrocatechol.Find that TS-1 molecular sieve has good catalytic performance.
In Chinese invention patent ZL99103272.1 (Granted publication CN1076724C authorizes a day 2001-12-26), disclose the hydroxylation for phenol by TS-1 molecular sieve, found that TS-1 molecular sieve has good catalytic performance.
Open source literature Sudies in surface science and catalysis, 49 (1989) 69 have introduced TS-1 molecular sieve catalytic cyclohexanone-oxime oxidative ammonolysis on annual output 12kt demonstration unit, the selectivity of object product cyclohexanone-oxime 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.Producing on the full scale plant of 10kt H per year
2o
2transformation efficiency is 70%, and the transformation efficiency of phenol is 25%, and the selectivity of principal product dihydroxy-benzene is 90%, and by product tar content is little.
Open source literature chemistry journal, 58 (2000) 204-208 have introduced TS-1 molecular sieve have been reacted for cyclohexanone oxamidinating.Find to reduce concentration of hydrogen peroxide in reaction soln, increase ammonia consumption and be conducive to hydrogen peroxide utilization ratio, cyclohexanone-oxime yield and optionally improve.
Open source literature Catalysis communications, 2 (2007) 379-382 have introduced TS-1 molecular sieve in methyl alcohol and acetonitrile mixed solvent system and, for epoxidation propenyl chloride preparation table chloropharin, have found that TS-1 molecular sieve has good catalytic performance.
Following patent has also related to the application of TS-1 molecular sieve:
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Following discloses document has also related to the applied research of TS-1 molecular sieve:
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What is particularly 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 of existing technique, has huge industrial application potentiality.
By using UV Vis reflective spectrum to characterize TS-1 molecular sieve, at present, investigators generally believe that the titanium species on 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 uv atlas, the peak at 210nm place is attributed to into the 2p transition of electron of key oxygen to TiO
4+3d unoccupied orbital time, the electric charge of generation shifts, this peak has proved the existence of four-coordination skeleton titanium.The peak at 270～280nm place is attributed to the characteristic peak of amorphous hexa-coordinate titanium species.The peak at 330～350nm place is attributed to the characteristic peak of anatase titanium dioxide.In catalyzed reaction, only having four-coordination skeleton titanium is the active centre of TS-1 molecular sieve.And hexa-coordinate titanium species and anatase octahedrite to epoxidation without katalysis, but they have decomposing H
2o
2with the side effect that causes epoxidation product deep reaction.
Open source literature catalysis journal, 30 (2009) 482-484 describe 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 centre that causes acid side reaction.The existence of these amorphous hexa-coordinate extra-framework titanium species is to cause the principal element that hydrogen peroxide decomposes and side reaction occurs.Therefore, effectively avoiding the generation of amorphous extra-framework titanium, is the key that improves molecular sieve catalytic performance.
The synthetic method of TS-1 was disclosed (GB2071071A, USP4410501) first in 1981 by people such as gondola Marco Taramasso.The method is, is first made into a kind of reaction mixture that contains silicon source, titanium source, organic bases, by this reaction mixture in autoclave in 130～200 DEG C of hydrothermal crystallizings 6～30 days, then after filtration, washing, dry and roasting obtain product.Wherein silicon source can be tetraalkyl silicon ester, colloidal state SiO
2, titanium source is hydrolyzable titanium-containing compound, preferably tetraethyl titanate, and the preferred TPAOH of organic bases, following table is the feed molar composition of the synthetic TS-1 molecular sieve that provides of this patent.
The material molar ratio composition of the synthetic TS-1 molecular sieve that table 1 patent USP4410501 provides
Wherein Me is alkali metallic sodium, potassium ion.This patent thinks, when in raw material when alkali-free sodium Metal 99.5, potassium ion, extra-framework titanium content is minimum.High-purity TPAOH of a large amount of alkali-free metal ions of synthetic TS-1 molecular sieve needs is template.
Thereby the people such as Thangaraj within 1992, disclose a kind of suppress by coupling estersil and titanium ester hydrolysis rate extra-framework titanium effectively increase skeleton in the method (Zeolites, 12 (1992), 943) of synthetic TS-1 of titanium content.The method has three main points: the one, and adopting the slower butyl (tetra) titanate of hydrolysis rate is titanium source; The 2nd, titanium source is dissolved in anhydrous isopropyl alcohol; The 3rd, adjust order of addition(of ingredients), the aqueous isopropanol in titanium source is joined in the silicone grease solution being hydrolyzed.Through the improvement of above-mentioned three aspects, the titanium amount entering in 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 be taking organo-silicon ester as silicon source, organic titanium ester as titanium source, TPAOH is the synthetic TS-1 molecular sieve of template and alkali source.
Synthetic TS-1 molecular sieve in the system that it is template that following patent and open source literature all relate in TPAOH:
Chinese invention patent ZL96110260.8 (Granted publication CN1084294C authorizes a day 2002-05-08) has disclosed a kind of synthetic method of TS-1 molecular sieve.Its technical characterictic is, tetraethoxy is hydrolyzed in TPAOH solution, then under nitrogen or oxygen protection, in above-mentioned hydrolyzed solution, adds TiCl
3make gel, by gained gel crystallization 1～5 day at 150～190 DEG C, then elimination mother liquor, washing leaching cake, and by dry at 120 DEG C filter cake, 550 DEG C of roastings 6 hours, obtain TS-1 molecular sieve.
Chinese invention patent ZL97106709.0 (Granted publication CN1079372C authorizes a day 2002-02-20) has disclosed a kind of synthetic method of TS-1 molecular sieve.Its technical characterictic is, the mixing solutions of tetraethoxy, TPAOH, tetrabutyl titanate and water composition is added in the container with whipping appts, stir and heat up 1～5 hour, pack in autoclave crystallization into 1～4 day by stirring the gel of gained, then cooling, filtration obtains filter cake, and reclaim mother liquor, then to filter cake wash, dry and roasting obtains TS-1 molecular sieve.
Chinese invention patent ZL98102391 (Granted publication CN1089274C authorizes a day 2002-08-21) has disclosed a kind of synthetic 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, at 50～100 DEG C, stirs 0.5～6 hour, then carry out hydrothermal crystallizing, more after filtration, washing, dry and roasting, obtain TS-1 molecular sieve.
Chinese invention patent CN1275530A (99107790.3 applying date of application number 1999-05-28) has disclosed a kind of synthetic method of TS-1 molecular sieve.Its technical characterictic is, the reaction mixture of silicon source, titanium source, alkali source will be contained, be positioned in autoclave, in the microwave radiation field of 600～50000MHz, under pressure 0.4～1.0MPa, crystallization 15 hours～3 days, discharge produce steam, the volume that makes steam condensate be feed intake middle water cumulative volume 60%～85%.Then by remaining crystallization product drying, roasting, obtain TS-1 molecular sieve.
Chinese invention patent ZL00116531.3 (Granted publication CN1123380C authorizes a day 2003-10-08) has disclosed a kind of synthetic method of TS-1 molecular sieve.Its technical characterictic is, taking silicon sol as silicon source, taking trivalent titanium compound as titanium source, first by after its mixing, underpressure distillation, dry pulverulent solids, at quaternary ammonium hydroxide or/and organic amine exist under crystallization, obtain synthetic product.Crystallization temperature is 120～200 DEG C, and crystallization time is 5～72 hours.This patent, because having used citric acid and ethylenediamine tetraacetic acid (EDTA) to process silicon source, causes synthetic catalyzer weak effect when for epoxidation of propylene, and 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 synthetic method of TS-1 molecular sieve.Its technical characterictic is, taking tetrabutyl titanate as titanium source, taking tetraethyl orthosilicate or silicon sol as silicon source., be made into after gel or/and organic amine is template taking quaternary ammonium hydroxide, adding phosphoric acid to synthesize TS-1 molecular sieve.This patent is found to add phosphoric acid can shorten crystallization time.But phosphoric acid is not mentioned the impact of synthetic product property.
Chinese invention patent CN1401569A (02132325.9 applying date of application number 2002-08-26) has disclosed a kind of synthetic method of TS-1 molecular sieve.Its technical characterictic is, exchange, concentrate the TPAOH aqueous solution obtaining as template taking self-control 4-propyl bromide through strongly basic anionic resin, tetraethoxy is silicon source, tetrabutyl titanate is titanium source, be made into after gel, by gained gel except alcohol 3～6 hours, crystallization 12～24 hours, after filtration, washing, dry and roasting obtain TS-1 molecular sieve.
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, taking organosilicon source, organic titanium source, organic bases template, water and Virahol be as raw material, through the preparation of reaction mixture solution, hydrolysis plastic, except alcohol is concentrated and hydrothermal crystallizing four steps, makes TS-1 molecular sieve.In this patent, use 3～15% lower concentration organic bases template TPAOH hydrolysis plastic, use 15～35% high density organic bases template TPAOH hydrothermal crystallizing.The method consumption of template agent is few, the hydrothermal crystallizing time is short.
Chinese invention patent ZL200410067060.1 (Granted publication CN1276874C authorizes a day 2006-09-27) has disclosed a kind of synthetic 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 and reacts 3～15 hours, and water is joined to reaction product, and the add-on of water is 3～8 times of silicon source weight, obtains glue; Glue is carried out under Time-dependent code Elevated Temperature Conditions to crystallization, then, after filtration, washing, dry and roasting obtain TS-1 molecular sieve.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 synthetic 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 to hydrothermal crystallizing, finally by filtering, wash, being dried and roasting, obtain TS-1 molecular sieve.In the method, use supersound process, can eliminate solution partial concn inequality, make the titanium dioxide that after the hydrolysis of titanium source, reunion generates certainly as far as possible few, thus the generation of minimizing extra-framework titanium.
Chinese invention patent ZL200810023174.4 (Granted publication CN101327934B authorizes a day 2010-09-15) has disclosed a kind of synthetic method of TS-1 molecular sieve.Its technical characterictic is that silicon source, titanium source, TPAOH (TPAOH) and water are mixed; Then putting into autoclave, pass into rare gas element, is 100～220 DEG C in temperature, and then the Water Under thermal crystallisation that pressure is 2.0～5.0MPa 10～72 hours, after filtration, washing, dry and roasting, obtains TS-1 molecular sieve.The method can reduce 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, taking tetraethoxy as silicon source, tetrabutyl titanate is titanium source, and TPAOH is template, and water and Virahol are solvent, H
2o
2for inorganic additives, mix, hydrothermal crystallizing 6～96 hours at 160～180 DEG C, after filtration, washing, dry and roasting obtain TS-1 molecular sieve.
Open source literature synthetic chemistry, 3 (1995) 340-344 have introduced a kind of method of synthetic TS-1 molecular sieve.Be characterized in, method one, is dissolved in H by tetrabutyl titanate
2o
2in, add TPAOH as template, then add silicon source silicon sol, mixed solution is placed 10 hours at 20 DEG C, then solution is warming up to 70-80 DEG C, stir after 6 hours, at 175 DEG C, crystallization 2-8 days in autoclave, finally by filtering, wash, being dried and roasting, obtains synthetic product; Method two, first mixes tetraethoxy with tetrabutyl titanate, stir, then add anhydrous isopropyl alcohol, TPAOH and deionized water, then mixed solution is warming up to 70-80 DEG C, stirs 6 hours at this temperature, and aftertreatment is same as method one.Experiment shows, all can synthesize TS-1 molecular sieve with two kinds of silicon sources, but use the better effects if of tetraethoxy.
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, then drip the aqueous isopropanol of tetrabutyl titanate, mixed solution is removed after alcohol, crystallization 2～5 days at 170 DEG C, finally by filtering, wash, being dried and roasting, obtain TS-1 molecular sieve.In document report, mention, utilize TiCl
3it is the effective way of synthetic TS-1 molecular sieve as titanium source; And with Ti (OR)
4for titanium source, in the time that titanium content is higher, be difficult to avoid the formation of anatase octahedrite; Show by catalyzed reaction evaluation, in the catalytic activity of TS-1 and molecular sieve, the content of titanium is proportional, and relevant to 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, taking tetraethoxy as silicon source, tetrabutyl titanate as titanium source, TPAOH is as template and alkali source, by reducing crystallization temperature, the rate of decomposition of TPAOH in Crystallization of Zeolite process reduced greatly, thus the basicity in raising system and the practical efficiency of 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 mutually, obtain uniform mixture, mixture is carried out to hydrothermal crystallizing 76 hours at 175 DEG C, filter according to a conventional method again, wash, be dried and roasting, obtain TS-1 molecular sieve.
Open source literature Journal of Molecular Catalysis, 21 (2007) 458-461 have introduced a kind of method of synthetic TS-1 molecular sieve.Be characterized in, taking silicon sol as silicon source, titanous chloride is titanium source, TPAOH is template, regulates basicity with ammoniacal liquor, and raw material is mixed, obtain uniform mixture, by mixture crystallization 76 hours at 170 DEG C, finally filter, wash, dry and roasting, obtain TS-1 molecular sieve.
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 is mixed with TPAOH, slowly drip tetrabutyl titanate, after fully stirring, add TPAOH and water, finally add H
2o
2, obtain even mixed solution, mixed solution is carried out to hydrothermal crystallizing 2 days at 200 DEG C, finally by filtering, wash, being dried and roasting, obtain 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 is dissolved in TPAOH solution, add deionized water, obtain uniform mixture, mixture is heated to 80 DEG C, stir 2 hours, then cooling mixture to 35 DEG C adds TiF under stirring in mixture
4the aqueous solution, finally final mixture is packed in autoclave, autoclave is warming up to 170 DEG C, crystallization 2 days under autogenous pressure, by end product after filtration, washing, dry and roasting, obtain 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, then in mixture, slowly add the TPAOH aqueous solution, stirring spends the night to ensure complete hydrolysis, microwave heating crystallization 0.5-2 hour at 175 DEG C again, finally separates product dialysis, wash, be dried and roasting, obtains synthetic product.
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 Virahol, and under vigorous stirring, this mixture is dropped in the solution of TPAOH, obtain the hydrolyzed solution of titanium, then under agitation tetraethoxy is dissolved in the aqueous solution of TPAOH, obtain the hydrolyzed solution of silicon, two kinds of mixed solutions are mixed, and heat except alcohol, and constantly add deionized water, then add S-1 that classical approach makes as crystal seed, crystallization 48 hours at 173 DEG C, finally by filtering, being dried and roasting, obtains TS-1 molecular sieve.Result shows, use S-1 pure silicon zeolite to be the TS-1 of crystal seed gained, although shape heterogeneity, but in selectivity of styrene oxidizing reaction, there is higher activity, also pointed out can have adding of crystal seed the crystallization rate of acceleration molecular sieve simultaneously, make Ti more easily enter skeleton, thereby make it have higher catalytic activity.
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 He Tai source, silicon source, TPAOH, as template, is used respectively three kinds of methods to dissolve tetrabutyl titanate: 1. make solvent with ethanol, and retain in crystallization process always; 2. make solvent with Virahol, in crystallization process, retain always; 3. make solvent with Virahol, but before crystallization, remove alcohol.Find by sign, the TS-1 skeleton titanium content that method 2 synthesizeds go out is high, shows good catalytic activity.
Following patent has also related to the improvement synthetic 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)。
Following discloses document has also related to the Study of synthesis method of carrying out TS-1 in TPAOH template system:
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; Journal of Dalian Institute of Light, 22 (2003) 243-246; Chemistry of fuel journal, 33 (2005) 112-116; Industrial Catalysis, 15 (2007) 60-63; 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 patent and the open source literature that relates to the synthetic TS-1 molecular sieve taking TPAOH as template, changes by the difference on synthesis technique, suppresses the generation of extra-framework titanium.Certainly do not introduce the common recognition that the foreign ion such as sodium ion, potassium ion is 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 TS-1 molecular sieve with the method described in patent USP4410501, has examined or check interpolation alkalimetal ion to synthetic impact.The discovery of the disclosure document, the existence of alkalimetal ion can reduce the performance of catalyzer.After pickling, the activity of catalyzer can obtain part and recover, but generally speaking performance is still undesirable.
The problem of aforesaid method is 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 the synthetic cheap law technology of what is called having formed again with non-TPAOH template of TS-1 molecular sieve.
Following patent and open source literature have related to the method with the synthetic TS-1 molecular sieve of non-TPAOH template:
US Patent No. P5688484 (1996-07-29) has disclosed a kind of synthetic method of TS-1 molecular sieve.Its technical characterictic is, tetraethoxy and tetrabutyl titanate are joined in U-4527, at room temperature stir after 30 minutes, obtain uniform mixture, mixture is cooled to 0 DEG C, then drip wherein HF and deionized water, mixture is at room temperature stirred 1 hour, add with the synthetic TS-1 molecular sieve of classical approach as crystal seed, by mixture crystallization 7 days, finally by filtering, wash, being dried and roasting, obtain TS-1 molecular sieve.
Chinese invention patent ZL97104636.0 (Granted publication CN1060411C authorizes a day 2001-1-10) has disclosed a kind of synthetic method of TS-1 molecular sieve.Its technical characterictic is, taking silica gel and butyl (tetra) titanate as He Tai source, silicon source, taking the mixture of tetraethyl ammonium hydroxide and TBAH as template.Adopt static state or dynamic method crystallization 4～6 days at 170～180 DEG C of temperature, through separating, washing, dry and roasting obtains TS-1 molecular sieve.
Chinese invention patent ZL200510111779.5 (Granted publication CN100344375C authorizes a day 2007-10-24) has disclosed a kind of synthetic method of TS-1 molecular sieve.Its technical characterictic is, uses silicon sol as silicon source, and organic titanate is as titanium source, and hexamethylene imine and piperidines be as template, hydrothermal crystallizing according to a conventional method.Through separating, washing, dry and roasting obtains TS-1 molecular sieve.
Chinese invention patent CN101913620A (201010235977.3 applying date of application number 2010-7-20) has disclosed a kind of synthetic method of TS-1 molecular sieve.Its technical characterictic is, taking silicon sol as silicon source, titanium tetrachloride or tetrabutyl titanate are titanium source, and 4-propyl bromide is template, and organic amine is alkali source, and nano level TS-1 molecular sieve and synthesis mother liquid thereof are without separating directly as crystal seed, and Hydrothermal Synthesis obtains product.
Open source literature Journal of Dalian University of Technology Total, 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 the consumption of synthetic middle template.And the order of having investigated different templates agent effect, experimental result shows: the structure-directing effect of different templates agent is by TPA
+> TBA
+> TEA
+> organic amine reduces.All can obtain the TS-1 molecular sieve of epoxidation of propylene better performances taking n-Butyl Amine 99, diethylamine, hexanediamine and TBAH as alkali source.
Open source literature Material chemistry and physics, 47 (1997) 225-230 have introduced a kind of method of synthetic TS-1 molecular sieve.When its feature, use the binary mixture of 4-propyl bromide and etamon chloride and tetrabutylammonium chloride as the synthetic TS-1 molecular sieve of structure directing agent.Its synthesis step is: Virahol, diethylamine, deionized water and tetraethoxy are mixed mutually, obtain the hydrolyzed solution of silicon, tetrabutyl titanate is mixed mutually with Virahol, obtain the hydrolyzed solution of titanium, titanium solution, except after alcohol, is mixed Yu Gui source, titanium source, stir, then add the synthetic TS-1 of classical approach to make crystal seed, finally by crossing hydrothermal crystallizing, filtration, washing, dry and roasting, obtain 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, substitute TPAOH as template with methylamine and 4-propyl bromide, and with using respectively the muriate of silicon sol or silicon and the muriate of titanium as He Tai source, silicon source, add HF simultaneously and improved Crystallization Dynamics as mineralizer.Document report, titanium stabilized implantation in the skeleton of TS-1 molecular sieve; And if in synthetic, reduce the amount of methylamine, and obviously accelerate crystallization velocity, but simultaneously, skeleton titanium content also obviously decline simultaneously in TS-1, the concentration that shows methylamine enters skeleton to titanium and plays a part very important.
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 room temperature, silicon sol, 4-propyl bromide and deionized water are mixed, stir, then drip tetrabutyl titanate solution to above-mentioned mixed solution, then under stirring, in solution, add n-Butyl Amine 99, uniform mixture, by mixture crystallization 4 days under 170 DEG C and autogenous pressure, more after filtration, washing, dry and roasting obtain TS-1 molecular sieve.
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)。Catalysis journal, 17 (1996) 173-176; Journal of Dalian University of Technology Total, 38 (1998) 363-367; Journal of Dalian University of Technology Total, 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; 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 TS-1 zeolite product is generally high than classical approach TS-1 molecular sieve, and many investigators are summed up as the foreign metal ion of bringing in the cheap raw materials such as inorganic silicon source, as Na
+, K
+, Al
3+deng.
In order to reduce the extra-framework titanium content in 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 processing step of preparation TS-1 molecular sieve, has increased cost.
As fully visible, although pass by nearly 30 years about the study on the synthesis of TS-1, synthetic high quality TS-1 molecular sieve is still a major challenge at present, and these challenge main manifestations are: in the synthetic system that TPAOH is template, the synthetic cost of molecular sieve is high; 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 improve the TS-1 Zeolite synthesis novel method of epoxidation of propylene performance.We find through large quantity research, and the existence of alkalimetal ion is not the principal element that affect titanium atom and enter 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 of amorphous extra-framework titanium generation.We further find, in synthetic TS-1 molecular sieve process, introduce appropriate an alkali metal salt, can promote the depolymerization in silicon source, are conducive to the generation that titanium enters skeleton and suppresses amorphous hexa-coordinate extra-framework titanium.Alkalimetal ion can also by with molecular sieve extra-framework titanium on the effect in acid site, eliminate the acid sites of cheap TS-1 molecular sieve, while making TS-1 molecular sieve as the catalyzer of propylene ring oxidation reaction, propylene oxide selectivity promotes greatly.
The present invention can introduce an alkali metal salt by two kinds of modes, and a kind of is directly to add appropriate an alkali metal salt (direct method) joining after glue completes; Another kind is to add alkali in silicon source, adds acid in titanium source simultaneously, with the acid-base neutralisation reaction desirable salt of generation (indirect method).
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 state form.In the time of synthesis of titanium silicon molecular sieve, easily there is following reaction in the silicate species in gel:
This reaction can cause rapid polymerization between silicate, generates the Si0 of high molecular
2micelle, is unfavorable for the combination between titanate radical species and silicate.In the time introducing appropriate bases metal ion, in alkaline environment, can there is following reaction in silicate:
Reaction (2) has suppressed the carrying out of reaction (1), thereby a large amount of silicate species can be existed with highly active oligomeric state form.In plastic and gel crystallization process, a large amount of silicate species exist with oligomeric state form, are conducive to condensation between titanate species and silicate species, make titanium enter skeleton, reduce the generation of hexa-coordinate extra-framework titanium.Meanwhile, the negatively charged ion of following alkali metal cation to introduce can also strengthen the polarity of molecular sieve structure unit, thereby promotes molecular sieve nucleus to form, accelerating growth, thus shorten the Crystallization of Zeolite time.
When adopting indirect method to introduce when alkalimetal ion, can promote reaction (2) to the alkalimetal oxide or the oxyhydroxide that add in silicon source; Can suppress the hydrolysis in titanium source to the acid adding in titanium source on the other hand, thereby promote better the reaction between silicon, titanium species.Certainly, in order to ensure crystallization condition, the alkalescence of alkalimetal oxide or oxyhydroxide neutralizes completely with the acid adding, and in addition, in the time introducing salt by direct method, adding of salt can be incorporated in silicon source before plastic, also can after plastic, introduce.And introduce when salt by indirect method, acid, alkaloid substance are introduced before being preferably in plastic.
Technical scheme of the present invention is as follows:
The first step, prepares titanium silicon gel
Prepare titanium silicon gel and take direct method and indirect method: directly adding an alkali metal salt joining after glue completes, is exactly direct method; In silicon source, add alkali, add acid in titanium source, with the required salt of acid-base neutralisation reaction generation, be exactly indirect method simultaneously.The mode adding adopts following three kinds:
The first: direct method is introduced an alkali metal salt
(1) under agitation, silicon source is mixed with water, an alkali metal salt, template, make raw silicon.
(2) under agitation, titanium source is mixed with complexing agent, make raw material titanium.
(3) under agitation, raw silicon is mixed with raw material titanium, and then add wherein alkaline mineralizer, this mixture is stirred, make titanium silicon gel.
The second: 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 is mixed with complexing agent, make raw material titanium.
(3) under agitation, raw silicon is mixed with raw material titanium, and then add successively an alkali metal salt wherein, alkaline mineralizer, this mixture is stirred, make titanium silicon gel.
The third: indirect method is introduced an alkali metal salt, provides required an alkali metal salt by the neutralization reaction of alkali-metal oxide compound or oxyhydroxide and corresponding acid solution
(1) under agitation, silicon source is mixed with water, alkali-metal oxide compound or oxyhydroxide and template, make raw silicon.
(2) under agitation, titanium source is mixed with acid solution and complexing agent, make raw material titanium.
(3) under agitation, raw silicon is mixed with raw material titanium, and then add wherein alkaline mineralizer, this mixture is stirred, make titanium silicon gel.
Second step, makes HTS
By the above-mentioned titanium silicon gel preparing hydrothermal crystallizing under state static or that stir, crystallization temperature scope is 120～200 DEG C, and preferably 160～180 DEG C, crystallization time scope is 1h～168h, preferably 2～3 days.The steps such as the feed liquid after crystallization is passed through solid-liquid separation and is dried, roasting process HTS.
Silicon source adopts one or two or more kinds mixture in silica gel, silicon sol, white carbon black;
Titanium source adopts one or two or more kinds mixture in tetrabutyl titanate, titanium tetrachloride, titanous chloride, titanium sulfate;
An alkali metal salt adopts the above mixture of any one or two kinds in sodium sulfate, sodium-chlor, SODIUMNITRATE, sodium phosphate, sodium acetate, potassium sulfate, Repone K, saltpetre, potassiumphosphate, potassium acetate, Lithium Sulphate, lithium chloride, lithium nitrate, Trilithium phosphate, lithium acetate, and also can carry out neutralization reaction by 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 one or two or more kinds mixture in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid.。
Template adopts one or two or more kinds mixture in tetrapropyl Neutral ammonium fluoride, 4-propyl ammonium chloride, 4-propyl bromide;
Alkalescence mineralizer adopts one or two or more kinds mixture in ammoniacal liquor, methylamine, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, quadrol, diethylamine, hexanediamine;
Titanium complexing agent adopts a kind of or its mixture in methyl ethyl diketone, Virahol.
Above-mentioned titanium silicon gel has following composition: aSiO
2: b TiO
2: c Me:d SDA:e K:fL:g H
2o, wherein, Me, SDA, K, L represent respectively 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.
The invention has the beneficial effects as follows by introduce appropriate bases metal-salt in titanium silicon gel, on the one hand, suppressed the generation of amorphous hexa-coordinate extra-framework titanium in 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 by method of the present invention, be conducive to further reduce the cost of TS-1 molecular sieve.
Embodiment
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention.Wherein in embodiment, reagent used is commercially available chemical reagent.
Brief description of the drawings
Fig. 1 is Fourier's infrared spectrum of comparative example's 1 sample.
In Fig. 2, a line is the uv-vis spectra spectrogram of comparative example's 1 sample, and b line is the uv-vis spectra spectrogram of embodiment 1 sample.
Comparative example 1
Get 220ml deionized water and join in 225g silicon sol (20%wt), stir after 10 minutes, 20.4g 4-propyl bromide is added in 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, stir 15 minutes, make raw material titanium solution; Get the prepared raw material titanium solution of 14.7ml and join in raw silicon solution, stir after 30 minutes, add 54ml n-Butyl Amine 99, continue to stir 15 minutes, obtain even gel; Then gained gel is joined in 2L stainless steel cauldron to crystallization 48 hours at autogenous pressure and 170 DEG C; Product filters through ordinary method, and washing is to neutral, dry at 110 DEG C, and 540 DEG C of roastings 6 hours, remove template, obtain sieve sample A.
Fourier's infrared spectrum as shown in Figure 1, in infrared spectrum at 960cm
-1near there is the unexistent infrared absorption peak of silica zeolite, show that titanium has entered skeleton.Uv-vis spectra is as shown in a line in Fig. 2, and in uv atlas, there is wide absorption peak at 270～280nm place, shows to have the non-skeleton of amorphous hexa-coordinate to exist.There is not the absorption band of anatase octahedrite in 330nm place.
Embodiment 1
Get 220ml deionized water and join in 225g silicon sol (20%wt), and add 5.3g sodium sulfate, stir after 10 minutes, 20.4g 4-propyl bromide is added in 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, stir 15 minutes, make raw material titanium; Get the prepared raw material titanium solution of 14.7ml and join in raw silicon solution, stir after 30 minutes, add 54ml n-Butyl Amine 99, continue to stir 15 minutes, obtain even gel; Then gained gel is joined in 2L stainless steel cauldron to crystallization 48 hours under autogenous pressure and at 170 DEG C; Product filters through ordinary method, and washing is to neutral, dry at 110 DEG C, and 540 DEG C of roastings 6 hours, remove template, obtain sieve sample B.
Its Fourier's infrared spectrum and Fig. 1 are similar, in infrared spectrum at 960cm
-1near there is the unexistent infrared absorption peak of silica zeolite, show that titanium has entered skeleton.Uv-vis spectra is as shown in b line in Fig. 2, and the absorption peak strength at 270～280nm place in uv atlas, compared with a line in uv-vis spectra spectrogram Fig. 2 of comparative example, obviously weakens.Show that the non-skeleton content of amorphous hexa-coordinate obviously reduces.There is not the absorption band of anatase octahedrite in 330nm place.
Embodiment 2
Get 220ml deionized water and join in 225g silicon sol (20%wt), stir after 10 minutes, 20.4g 4-propyl bromide is added in 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, stir 15 minutes, make raw material titanium; Get the prepared raw material titanium solution of 14.7ml and join in raw silicon solution, stir after 30 minutes, add 5.3g sodium sulfate, stir 5 minutes, add 54ml n-Butyl Amine 99, continue to stir 10 minutes, obtain even gel; Then gained gel is joined in 2L stainless steel cauldron to crystallization 48 hours at autogenous pressure and 170 DEG C; Product filters through ordinary method, and washing is to neutral, dry at 110 DEG C, and 540 DEG C of roastings 6 hours, remove template, obtain 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 in uv-vis spectra and Fig. 2, b line is similar.The absorption peak strength at 270～280nm place in uv atlas, compared with a line in uv-vis spectra spectrogram Fig. 2 of comparative example, obviously weakens.The non-skeleton content of amorphous hexa-coordinate obviously reduces.There is not the absorption band of anatase octahedrite in 330nm place.
Embodiment 3
Repeat embodiment 1, but the add-on of sodium sulfate is wherein become to 10.6g, 2.65g, 0.53g.Be c=0.2,0.05,0.01, obtain successively sieve sample C, D, E.
Its Fourier's infrared spectrum is all similar with Fig. 1, and in uv-vis spectra and Fig. 2, b line is similar, and the non-skeleton content of amorphous hexa-coordinate obviously reduces.There is not the absorption band of anatase octahedrite in 330nm place.
Embodiment 4
Repeat embodiment 1, but change salt wherein into sodium-chlor, SODIUMNITRATE, sodium phosphate, sodium acetate, potassium sulfate, 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, obtain successively 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 in uv-vis spectra and Fig. 2, b line is similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.There is not the absorption band of anatase octahedrite in 330nm place.
Embodiment 5
Repeat embodiment 1, but change respectively silicon sol wherein into silica gel, white carbon black.The relative molar content of component is consistent with embodiment 1, obtains successively sieve sample, 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 in uv-vis spectra and Fig. 2, b line is similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.There is not the absorption band of anatase octahedrite in 330nm place.
Embodiment 6
Repeat embodiment 1 and operate, but change respectively titanium source wherein into titanium tetrachloride, titanous chloride, titanium sulfate.The relative molar content of component is consistent with embodiment 1, i.e. 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 in uv-vis spectra and Fig. 2, b line is similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.There is not the absorption band of anatase octahedrite in 330nm place.
Embodiment 7
Repeat embodiment 1, but change respectively n-Butyl Amine 99 wherein into ammoniacal liquor, methylamine, ethamine, Tri N-Propyl Amine, quadrol, diethylamine, hexanediamine, the relative molar content of component is consistent with embodiment 1, i.e. e=0.73, obtains 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 in uv-vis spectra and Fig. 2, b line is similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.There is not the absorption band of anatase octahedrite in 330nm place.
Embodiment 8
Get 220ml deionized water and join in 225g silicon sol (20%wt), add 3g sodium hydroxide, stir after 10 minutes, by 5.4g crystal seed, 20.4g 4-propyl bromide adds in 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, stir 15 minutes, make raw material titanium; Get the prepared raw material titanium solution of 14.7ml and join in raw silicon solution, stir after 30 minutes, add 54ml n-Butyl Amine 99, continue to stir 15 minutes, obtain even gel; Then gained gel is joined in 2L stainless steel cauldron to crystallization 48 hours at autogenous pressure and 170 DEG C; Product filters through ordinary method, and washing is to neutral, dry at 110 DEG C, and 540 DEG C of roastings 6 hours, remove template, obtain molecular sieve sample F.
Its Fourier's infrared spectrum is all similar with Fig. 1, and in uv-vis spectra and Fig. 2, b line is similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.There is not the absorption band of anatase octahedrite in 330nm place.
Embodiment 9
Repeat embodiment 8, wherein sulphuric acid 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, obtain successively sieve sample and be followed successively by G, H, I.
Its Fourier's infrared spectrum is all similar with Fig. 1, and in uv-vis spectra and Fig. 2, b line is similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.There is not the absorption band of anatase octahedrite in 330nm place.
Embodiment 10
Repeat embodiment 8, but change respectively sulfuric acid wherein into hydrochloric acid, nitric acid, phosphoric acid, acetic acid, add-on is followed successively by 7.8g, 4.8g, and 2.9g, 4.5g, i.e. 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 in uv-vis spectra and Fig. 2, b line is similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.There is not the absorption band of anatase octahedrite in 330nm place.
Embodiment 11
Repeat embodiment 8, but change sodium hydroxide wherein into potassium hydroxide, lithium hydroxide, add-on is followed successively by 4.2g, 1.8g, i.e. 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 in uv-vis spectra and Fig. 2, b line is similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.There is not the absorption band of anatase octahedrite in 330nm place.
Embodiment 12
Repeat embodiment 8, but change respectively silicon sol wherein into silica gel, white carbon black.The relative molar content of component is consistent with embodiment 8, obtains successively sieve sample, 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 in uv-vis spectra and Fig. 2, b line is similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.There is not the absorption band of anatase octahedrite in 330nm place.
Embodiment 13
Repeat embodiment 8, but change respectively titanium source wherein into titanium tetrachloride, titanous chloride, titanium sulfate.The relative molar content of component is consistent with embodiment 1, i.e. b=0.03 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 in uv-vis spectra and Fig. 2, b line is similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.There is not the absorption band of anatase octahedrite in 330nm place.
Embodiment 14
Repeat embodiment 8, but change respectively n-Butyl Amine 99 wherein into ammoniacal liquor, methylamine, ethamine, Tri N-Propyl Amine, quadrol, diethylamine, hexanediamine, the relative molar content of component is consistent with embodiment 8, i.e. e=0.73 obtains 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 in uv-vis spectra and Fig. 2, b line is similar.The non-skeleton content of amorphous hexa-coordinate obviously reduces.There is not the absorption band of anatase octahedrite in 330nm place.
Embodiment 15
In 400ml stainless steel high pressure batch reactor, add 0.2g catalyst A, 30ml methyl alcohol, the hydrogen peroxide of 2ml30%, passes into propylene under stirring, propylene pressure 0.4MPa, 50 DEG C of temperature of reaction, the sampling when reaction times is 60 minutes, iodimetry,iodometry is surveyed the transformation efficiency of hydrogen peroxide.The selectivity of gas chromatographic analysis propylene oxide and the effective rate of utilization of hydrogen peroxide.Replace respectively A 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
As can be seen from Table 1, compared with the epoxidation of propylene performance of the TS-1 molecular sieve that the present invention the obtains TS-1 molecular sieve synthetic with not introducing an alkali metal salt, propylene oxide selectivity and effective utilization ratio of hydrogen peroxide all obviously improve.
Claims (8)
1. a synthetic method for titanium-silicon molecular sieve TS-1, is characterized in that comprising the steps:
The first step, takes following method to prepare titanium silicon gel: in silicon source, add alkali, add acid in titanium source, with the required salt of acid-base neutralisation reaction generation, be exactly indirect method simultaneously; Described indirect method is as follows:
Indirect method is introduced an alkali metal salt, with alkali-metal oxide compound or oxyhydroxide with when the neutralization reaction of acid solution provides required an alkali metal salt accordingly,
(1) under agitation, silicon source is mixed with water, alkali-metal oxide compound or oxyhydroxide and template, make raw silicon; (2) under agitation, titanium source is mixed with acid solution and complexing agent, make raw material titanium;
(3) under agitation, raw silicon is mixed with raw material titanium, and then add wherein alkaline mineralizer, this mixture is stirred, make titanium silicon gel;
Second step, makes HTS
By the above-mentioned titanium silicon gel preparing hydrothermal crystallizing under state static or that stir, crystallization temperature scope is 120～200 DEG C, and crystallization time scope is 1h～168h; Feed liquid after 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 one or two or more kinds mixture in silica gel, silicon sol, white carbon black.
3. synthetic method according to claim 1, is characterized in that, described titanium source is one or two or more kinds mixture in tetrabutyl titanate, titanium tetrachloride, titanous chloride, titanium sulfate.
4. synthetic method according to claim 1, it is characterized in that, described an alkali metal salt is the above mixtures of any one or two kinds in sodium sulfate, sodium-chlor, SODIUMNITRATE, sodium phosphate, sodium acetate, potassium sulfate, Repone K, saltpetre, potassiumphosphate, potassium acetate, Lithium Sulphate, lithium chloride, lithium nitrate, Trilithium phosphate, lithium acetate, or carries out neutralization reaction by 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. synthetic method according to claim 1, is characterized in that, described acid solution is one or two or more kinds mixture in sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, acetic acid.
6. synthetic method according to claim 1, is characterized in that, described alkaline mineralizer is one or two or more kinds mixture in ammoniacal liquor, methylamine, ethamine, Tri N-Propyl Amine, n-Butyl Amine 99, quadrol, diethylamine, hexanediamine.
7. synthetic method according to claim 1, is characterized in that, described complexing agent is a kind of or its mixture adopting in methyl ethyl diketone, Virahol.
8. synthetic method according to claim 1, is characterized in that, template is one or two or more kinds mixture in tetrapropyl Neutral ammonium fluoride, 4-propyl ammonium chloride, 4-propyl bromide.
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