CN101913620A - Method for quickly synthesizing small-crystallite titanium-silicon molecular sieve in cheap system - Google Patents
Method for quickly synthesizing small-crystallite titanium-silicon molecular sieve in cheap system Download PDFInfo
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Abstract
The invention provides a method for preparing a small-crystallite titanium-silicon molecular sieve in a cheap system by changing the adding mode of seed crystals and by a hydrothermal process. The titanium-silicon molecular sieve is prepared by using silicon sol as a silicon source, titanium tetrachloride or tetrabutyl titanate as a titanium source, tetrapropylammonium bromide ( TPABr) as a template agent, organic amine as an alkali source and unseparated nanoscale TS-1 mother liquor as seed crystals directly and by the hydrothermal process. The grain size of the titanium-silicon molecular sieve is less than 1 micrometer, and the titanium-silicon molecular sieve has high activity for selective oxidization reactions using hydrogen peroxide as an oxidant, such as epoxidation of olefins, hydroxylation of phenol, ammoxidation of cyclohexanone and the like. The method simplifies the synthesis process of small crystallite TS-1 in the cheap system and reduces synthesis time and cost.
Description
Technical field
The present invention relates to a kind of synthetic method of HTS.
Background technology
Nineteen eighty-three, United States Patent (USP) 4410501 reported first have titanium-silicon molecular sieve TS-1 synthetic of MFI structure, it is to be the silicon source with tetraethoxy (TEOS) or silicon sol, tetraethyl titanate (TBOT) is the titanium source, TPAOH (TPAOH) is a template, under hydrothermal system, crystallization 6 ~ 30 days and getting.
Titanium-silicon molecular sieve TS-1 is in the oxidation system of forming with hydrogen peroxide, have superior catalytic performance, reaction tables such as alkene epoxidation, aromatic hydrocarbons hydroxylation, ammoxidation of cyclohexanone are revealed very high activity, and by product is a water, belong to environmentally friendly technology, therefore cause that people extensively pay attention to.
In TS-1 synthetic, restrict its industrialized major cause and be that its synthetic cost is higher, promptly need to use expensive template TPAOH; And, the operational condition harshness, step is numerous and diverse, and synthesis cycle is long, and process is wayward.
Document " catalysis journal " (2001,22 (6): 513 ~ 514) proposed a kind of method of quickly synthesizing nano level HTS, particle size is about 100nm, simplified operation steps, but still need to use TPAOH (TPAOH) as template, and need tetraethoxy (TEOS) and tetrabutyl titanate (TBOT) hydrolysis have respectively been prolonged the synthetic cycle.Use ordinary method to be difficult to Ti-Si nano molecular sieve is separated with mother liquor, this has also hindered its industrial applications.
Patent ZL01145256.0 proposed a kind of in cheap system the method for synthesizing small-crystallite titanium-silicon molecular sieve, it is HTS about 0.85 * 0.4 * 0.15 μ m that this method can synthesize particle size, but its synthesis cycle is longer, needs variable temperature crystallization.
The method that patent ZL01145256.0 provides is with TiCl
4Alcoholic solution is done the titanium source, and silicon sol is done the silicon source, at TPABr-NH
4In the OH system, be crystal seed with homemade Ti-Si nano molecular sieve, hydrothermal method synthesizes HTS, and proposes, and adds crystal seed and can significantly accelerate the TS-1 crystallization velocity, shortens crystallization time.This method gained grain-size is about 3 * 2 μ m, because particle size is bigger, for propylene ring oxidation reaction, internal diffusion is more serious to the reaction influence, and the principal product selectivity is lower.
Summary of the invention
The objective of the invention is to invent a kind of in cheap system the method for quickly synthesizing small-crystallite titanium-silicon molecular sieve, its particle size is less than 1 micron.This method may further comprise the steps:
(1) preparation of Ti-Si nano molecular sieve mother liquor (being crystal seed): with tetraethoxy (TEOS) is the silicon source, and tetrabutyl titanate (TBOT) is the titanium source, and TPAOH (TPAOH) is a template, and the mole of reactant consists of: SiO
2: TiO
2: TPAOH: H
2O=1: 0.02-0.03: 0.25-0.35: 25-40.Above-mentioned reactant took out after 170 ℃ of following crystallization 12-36 hours in having teflon-lined stainless steel crystallizing kettle, and sealing is preserved stand-by.Because the Ti-Si nano molecular sieve particle size is less, its mother liquor is a suspension liquid, can sedimentation even place for a long time also not, can take through simple agitation during use.
(2) preparation of small-crystallite titanium-silicon molecular sieve in the cheap system: adopting silicon sol is the silicon source, titanium tetrachloride or tetrabutyl titanate (TBOT) are the titanium source, 4-propyl bromide (TPABr) is a template, organic amine is an alkali source, organic amine comprises: methylamine, ethamine, diethylamine, triethylamine, propylamine, n-Butyl Amine 99 etc., the mole of reactant consists of: SiO
2: TiO
2: TPABr: organic amine: H
2O=1: 0.01-0.03: 0.1-0.3: 0.1-3.0: 30-60.As crystal seed, the quality of the contained Ti-Si nano molecular sieve of this mother liquor kind is m (nano-TS-1), then m (SiO in the reactant with the Ti-Si nano molecular sieve mother liquor
2): m (nano-TS-1)=15-30: 1.In having teflon-lined stainless steel crystallizing kettle, after 150-180 ℃ of following crystallization 12-36 hour, take out mother liquor and leave standstill natural subsidence, washing, drying, 540 ℃ of roastings 6 hours.
The synthetic method of HTS provided by the present invention has following beneficial effect:
(1) in cheap system, synthesizes, greatly reduce the synthetic cost of HTS;
(2) with the Ti-Si nano molecular sieve mother liquor as crystal seed, not only can accelerate crystallization velocity, and compare as crystal seed with the Ti-Si nano molecular sieve powder, can obtain littler particle size.This method is applicable to that a plurality of needs add the synthetic system of crystal seed;
(3) because the Ti-Si nano molecular sieve particle size is very little, separation difficulty directly uses the Ti-Si nano molecular sieve mother liquor as crystal seed, has avoided the separation to mother liquor, has shortened synthesis cycle;
(4) leave standstill can natural layering for the little crystal grain TS-1 of this method institute synthetic mother liquor, has simplified separating technology.
Description of drawings
Below in conjunction with drawings and Examples the present invention is done description in further detail.
Fig. 1 is X-ray powder diffraction (XRD) spectrogram of HTS provided by the invention (embodiment 1), shows that it has the MFI structure.
Fig. 2 is fourier-transform infrared (FT-IR) spectrogram of HTS provided by the invention (embodiment 1), shows the existence of four-coordination skeleton titanium.
Fig. 3 is ultraviolet-visible absorption spectroscopy (UV-Vis) spectrogram of HTS provided by the invention (embodiment 1), shows the existence of skeleton titanium and a small amount of extra-framework titanium.
Fig. 4 is uv raman spectroscopy (UV-Raman) spectrogram of HTS provided by the invention (embodiment 1), shows the existence of skeleton titanium.
Fig. 5 is scanning electron microscope (SEM) photo of HTS provided by the invention (embodiment 1), even particle size as can be seen, and particle size is 600 * 400 * 250nm.
Fig. 6 is that particle size is 2 * 1 * 0.5 μ m as can be seen according to scanning electron microscope (SEM) photo of the embodiment 2 described HTS (Comparative Examples 3) of patent ZL01145256.0.
Fig. 7 is that (2001,22 (6): 513 ~ 514) scanning electron microscope (SEM) photo of disclosed method synthetic Ti-Si nano molecular sieve (Comparative Examples 1), particle size is 100 ~ 200nm as can be seen according to document " catalysis journal ".
Fig. 8 is scanning electron microscope (SEM) photo of HTS provided by the invention (embodiment 4), and particle size is 1.7 * 0.6 * 0.3 μ m.
Fig. 9 is that (1998,38 (3): 363) scanning electron microscope (SEM) photo of disclosed method synthetic HTS (Comparative Examples 4), particle size is 2.5 * 1.2 * 0.3 μ m according to " Dalian University of Technology's journal ".
Embodiment
Comparative Examples 1
According to document " catalysis journal " (2001,22 (6): 513 ~ 514) disclosed method, the 50g tetraethoxy is added in the there-necked flask of strap clamp cover, under 25 ℃, magnetic agitation, add the 45g TPAOH aqueous solution (20wt%) and 40g deionized water, make teos hydrolysis 90min, continue heat temperature raising to 85 ℃ then; The 15g anhydrous isopropyl alcohol is joined in the 2g tetrabutyl titanate, add the TPAOH aqueous solution (20wt%) 17g and deionized water 20g successively under stirring, at room temperature hydrolysis 30min obtains the tetrabutyl titanate hydrolysis thing; The tetrabutyl titanate hydrolysis thing is mixed with the teos hydrolysis thing, and it is following to pure 6h at 85 ℃, the settled solution that obtains is put into the stainless steel crystallizing kettle that has poly-tetrafluoro liner, 170 ℃ of crystallization 24h, crystallization product is after washing, drying, at 540 ℃ of roasting 5h, the TS-1 that obtains is numbered A with it.
Comparative Examples 2
Embodiment 1 described method according to patent ZL01145256.0, getting the 10g deionized water joins in the 15g 30wt% silicon sol, after stirring 30min, splash into the alcoholic solution of 1.4g titanium tetrachloride, continue to stir 30min, then with the 3g 4-propyl bromide, 10g 65wt% ethylamine solution, join in the glue successively, stir 60min, add the 30g deionized water, the gained glue is added in the stainless steel crystallizing kettle that has poly-tetrafluoro liner, earlier 100 ℃ of crystallization 9 days, be warming up to 120 ℃ again and continued crystallization 9 days, crystallization product is through washing, after the drying, at 540 ℃ of roasting 6h, the TS-1 that obtains is numbered B with it.
Comparative Examples 3
Embodiment 2 described methods according to patent ZL01145256.0, the 81mL deionized water is added in the 100mL 30wt% silicon sol, stir 10min, again with after the alcoholic solution of 14mL titanium tetrachloride mixes, stir 30min, add the 24g 4-propyl bromide more successively, 50mL 65wt% ethylamine solution, 1g Ti-Si nano molecular sieve powder, and 78mL deionized water, after stirring 30min, glue is added in the stainless steel crystallizing kettle that has poly-tetrafluoro liner 170 ℃ of crystallization 48h, crystallization product is through washing, after the drying, at 540 ℃ of roasting 6h, the TS-1 that obtains is numbered C with it.
Comparative Examples 4
According to " Dalian University of Technology's journal " (1998,38 (3): the 363) method that is provided,, 10.2g TPABr is dissolved in the 88mL water, join then in the 43mL silicon sol, stirred 20 minutes, under agitation condition, drip 4.16mL metatitanic acid four
The methyl ethyl diketone solution of butyl ester adds the 16mL n-Butyl Amine 99 more successively, and 2.4g Ti-Si nano molecular sieve powder stirred 20 minutes as crystal seed, 170 ℃ of crystallization 48h, and crystallization product is after washing, drying, and at 540 ℃ of roasting 6h, the TS-1 that obtains is numbered D with it.
Embodiment 1
The 1.4mL titanium tetrachloride is splashed in the 12mL Virahol, be stirred to the HCl volatilization fully, obtain the aqueous isopropanol of titanium tetrachloride.The 81mL deionized water is added in the 100mL 30wt% silicon sol, stir 10min, again with after the alcoholic solution of titanium tetrachloride mixes, stir 30min, add the 24g 4-propyl bromide more successively, 50mL 65wt% ethylamine solution, 12mL Ti-Si nano molecular sieve mother liquor, and 78mL deionized water are behind the stirring 30min, glue is added in the stainless steel crystallizing kettle that has poly-tetrafluoro liner, 170 ℃ of crystallization 24h, crystallization product is after washing, drying, at 540 ℃ of roasting 6h, the TS-1 that obtains is numbered E with it.Its X-ray diffraction (XRD) spectrum as shown in Figure 1, its fourier-transform infrared (FT-IR) spectrum as shown in Figure 2, its scanning electron microscope (SEM) photo is as shown in Figure 3.
Embodiment 2
All raw materials compositions and batching operating process are all identical with embodiment 1, and the titanium silicone fluid that just obtains passes through identical last handling process again at 170 ℃ of following crystallization 60h, the TS-1 that obtains, it is numbered F, and XRD spectrum and Fig. 1 are similar, and just relative crystallinity is higher; IR spectrum and Fig. 2 are similar, and the skeleton titanium content does not have to change substantially; SEM photo and Fig. 3 are similar, and grain-size does not have considerable change.
Embodiment 3
Owing to contain excessive template TPAOH in the Ti-Si nano molecular sieve mother liquor, may produce certain influence to crystallization process, so change crystal seed into the Ti-Si nano molecular sieve powder, when little crystal grain TS-1 is synthetic, add a certain amount of TPAOH again, investigation causes the less reason of little crystal grain TS-1 crystal grain.The 81mL deionized water is added in the 100mL 30wt% silicon sol, stir 10min, again with after the alcoholic solution of 14mL titanium tetrachloride mixes, stir 30min, add the 24g 4-propyl bromide more successively, the 50mL65wt% ethylamine solution, 1g Ti-Si nano molecular sieve powder, 25mL 0.12mol/L TPAOH, and 55mL deionized water, after stirring 30min, glue is added in the stainless steel crystallizing kettle that has poly-tetrafluoro liner 170 ℃ of crystallization 36h, crystallization product is after washing, drying, at 540 ℃ of roasting 6h, the TS-1 that obtains is numbered G with it.
Embodiment 4
According to " Dalian University of Technology's journal " (1998,38 (3): the 363) method that is provided, 10.2g TPABr is dissolved in the 88mL water, join then in the 43mL silicon sol, stirred 20 minutes, drip the methyl ethyl diketone solution of 4.16mL tetrabutyl titanate under agitation condition, add the 16mL n-Butyl Amine 99 more successively, 20mL Ti-Si nano molecular sieve mother liquor is as crystal seed, stirred 20 minutes, 170 ℃ of crystallization 48h, crystallization product is after washing, drying, at 540 ℃ of roasting 6h, the TS-1 that obtains is numbered H with it.
In 0.4L stainless steel intermittent kettle reactor, add 24mL acetone, 8mL methyl alcohol, 1.6mL 30wt% hydrogen peroxide, the back that stirs adds the 0.4g catalyzer, and the envelope still feeds propylene, keeps propylene pressure 0.4MPa, stirs following 60 ℃ of reactions 1 hour.The transformation efficiency of iodometric determination hydrogen peroxide, the selectivity of gas chromatographic analysis propylene oxide.Reaction result such as table 1.Wherein, X
H2O2Be H
2O
2Transformation efficiency, S
POSelectivity for propylene oxide.
Table 1TS-1 catalytic epoxidation of propone reactivity worth
As can be seen from Table 1, react for catalytic epoxidation of propone, small-crystallite titanium-silicon molecular sieve E provided by the invention and A (being to use TPAOH in the Comparative Examples 1 as template synthetic Ti-Si nano molecular sieve) performance is approaching, the selectivity of propylene oxide obviously is better than synthetic TS-1 in other cheap systems, H
2O
2Transformation efficiency a little less than G; The catalytic reaction activity of HTS F is the highest.
Embodiment 6
In the 50mL round-bottomed flask, add 4g phenol, 24mL acetone, 1.6mL 30wt% hydrogen peroxide, the following 80 ℃ of reactions of magnetic agitation 6 hours.The transformation efficiency of iodometric determination hydrogen peroxide, the transformation efficiency of gas chromatographic analysis phenol and each product selectivity.Reaction result such as table 2.Wherein, X
H2O2Be H
2O
2Transformation efficiency, X
PHEBe the transformation efficiency of phenol, S
HQBe the selectivity of pyrocatechol, S
CATBe the selectivity of Resorcinol, S
PBQSelectivity for para benzoquinone.
Table 2TS-1 catalysis of phenol hydroxylating performance
As can be seen from Table 2, small-crystallite titanium-silicon molecular sieve F provided by the invention is for the catalysis of phenol hydroxylating, approaching with use TPAOH in the Comparative Examples 1 as template synthetic Ti-Si nano molecular sieve performance, and HTS E, the performance of F all is better than other TS-1 of synthetic in the cheap system.
Claims (2)
1. the method for quickly synthesizing small-crystallite titanium-silicon molecular sieve in the cheap system is characterized in that this method is finished by following steps:
(1) preparation of Ti-Si nano molecular sieve mother liquor: with the tetraethoxy is the silicon source, and tetrabutyl titanate is the titanium source, and TPAOH is a template, and the mole of reactant consists of: SiO
2: TiO
2: TPAOH: H
2O=1: 0.02-0.03: 0.25-0.35: 25-40, above-mentioned reactant took out after 170 ℃ of following crystallization 12-36 hours in having teflon-lined stainless steel crystallizing kettle, and sealing is preserved stand-by;
(2) preparation of small-crystallite titanium-silicon molecular sieve in the cheap system: adopting silicon sol is the silicon source, 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 the mole of reactant consists of: SiO
2: TiO
2: TPABr: organic amine: H
2O=1: 0.01-0.03: 0.1-0.3: 0.1-3.0: 30-60; As crystal seed, the quality of contained Ti-Si nano molecular sieve is m (nano-TS-1) in this mother liquor, then m (SiO in the reactant with the Ti-Si nano molecular sieve mother liquor
2): m (nano-TS-1)=15-30: 1, in having teflon-lined stainless steel crystallizing kettle, after 150-180 ℃ of following crystallization 12-36 hour, take out mother liquor and leave standstill natural subsidence, washing, drying, 540 ℃ of following roastings 6 hours.
2. according to the method for quickly synthesizing small-crystallite titanium-silicon molecular sieve in the described a kind of cheap system of claim 1, it is characterized in that described organic amine is methylamine, ethamine, diethylamine, triethylamine, propylamine or n-Butyl Amine 99.
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