CN104418343B - A kind of TS-1 HTS and its preparation method and application - Google Patents
A kind of TS-1 HTS and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of TS-1 molecular sieve, and it is prepared by following methods: with substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide for template, be dissolved in template aqueous solution by titanium source, and stirring 1-1.5h obtains settled solution; Settled solution adds positive esters of silicon acis, stirring hydrolysis 1.5-5.5h at 5-55 DEG C, then it is incubated 1-3h, then remove the alcohol of generation, obtain Zeolite synthesis liquid, and in the synthesis liquid described in control, each component molar ratio meets the following conditions: SiO2:TiO2=8��250, H2O:SiO2=0.6��60, and NRRTPAOH:SiO2=0.01��0.5; Will synthesis liquid in 130��200 DEG C of hydrothermal crystallizings 1��30 day, then filter according to a conventional method, washing, dry and roasting, obtain described TS-1 molecular sieve. The TS-1 molecular sieve structure of the present invention is stable, and degree of crystallinity is high, reproducible, it is easy to industrially popularization and application. The present invention also provides for the preparation method and application of described TS-1 molecular sieve.
Description
Technical field
The present invention relates to silicate field, be specifically related to a kind of molecular sieve, particularly relate to a kind of HTS, and its preparation method and application.
Background technology
HTS is the novel hetero-atom molecular-sieve that early eighties starts exploitation. The TS-2 of TS-1, the MFL type structure having MFI type structure synthesized at present, and there is the TS-48 etc. of large hole structure. This molecular sieve analog is to there being H2O2The many organic oxidizing reactions participated in, the epoxidation of such as alkene, arene hydroxylation, Ketohexamethylene oximate, alcohol the reaction such as oxidation there is excellent catalysis activity and selective paraffin oxidation performance, they have a good application prospect as redox-type molecular sieve catalyst.
The synthetic method of TS-l is first public (GB2071071A, USP4,410,501) in 1981 by MarcoTaramasso of Italy et al.. The method is first to prepare a kind of reactant mixture containing silicon source, titanium source, organic base (RN+) and/or basic anhydride, by this reactant mixture in autoclave in 130��200 DEG C of hydrothermal crystallizings 1-20 days, be then peeled off, wash, dry, roasting and product, silicon source therein can be tetraalkyl titanate, colloidal state SiO2Or alkali silicate, titanium source can be hydrolyzable titanium compound, it is preferable that Ti (OC2H5)4, the preferred TPAOH of organic base, wherein the molar composition ranges of reactant mixture is:
Owing to the molecular sieve that the method for M.Taramasso et al. synthesizes being incorporated into the TiO of skeleton2Seldom, A.Thangaraj of India et al. disclosed a kind of method (Zelites, 1992, VoL12, P943) being considered as presently the most effectively to synthesize TS-1 to amount in 1992.The method is that appropriate TPAOH (TPAOH) aqueous solution is joined stirring and dissolving certain time in ethyl silicate solution, is then slowly added to the aqueous isopropanol of butyl titanate with vigorous stirring and obtains the liquid mixture of clarification and (must be slowly added dropwise to prevent tetrabutyl titanate hydrolysis too fast and form white TiO2Precipitation), after stirring 15 minutes, it is slow added into appropriate TPAOH aqueous solution, after then reactant mixture being caught up with alcohol 3��6 hours in 75��80 DEG C, is transferred in autoclave at 170 DEG C hydrothermal crystallizing 3��6 days, wherein mole the consisting of of reactant mixture: SiO2: (0.01��0.10) TiO2:0.36TPAOH:35H2O. The X-ray diffraction crystalline phase figure of the TS-1 molecular sieve synthesized similar with the Silicalite-1 of pure silicon (MFI structure), its infrared absorption spectroscopy (IR) is at 950��970cm-1Place occurs in that the unexistent characteristic absorption peak of Silicalite-1, and this is the result causing Si-O key antisymmetric stretching vibration after entering framework of molecular sieve due to Ti, it is believed that be the Ti evidence entering framework of molecular sieve.
In the prior art of above-mentioned all synthesis TS-1, generally all adopt expensive organic base TPAOH (TPAOH) as template, and the more difficult synthesis of TPAOH, the market price is per ton more than 1,000,000 yuan. Additionally at normal crystallization temperature (150-185 degree Celsius), TPAOH (TPAOH) just has decomposition to occur, not only increase the consumption of TPAOH, and decompose the tri-n-butylamine of generation and propanol is easily caused TS-1 molecular sieve defect, cause crystallization product defective and yield rate is low, therefore the TS-1 molecular sieve synthesized costly so that it is application prospect is restricted.
Summary of the invention
It is an object of the invention to overcome the shortcoming of prior art, it is provided that a kind of TS-1 molecular sieve, have Stability Analysis of Structures, degree of crystallinity is high, reproducible feature.
The preparation method that it is a further object to provide described TS-1 molecular sieve so that the TS-l molecular sieve prepared is less costly and has higher activity and stability.
It is also another object of the present invention to provide the application of described TS-1 molecular sieve.
The purpose of the present invention is achieved through the following technical solutions:
Thering is provided a kind of TS-1 molecular sieve, it is prepared by following methods:
1) with substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide for template, titanium source is dissolved in substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide aqueous solution, stirs 1-1.5h, obtain settled solution;
Described substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide, molecular formula is denoted as NRRTPAOH, and shown in structure such as following formula (I), wherein R1 is the alkyl of C1��C3; R2 is the alkyl of C2��C4;
2) in the settled solution that step 1) obtains, positive esters of silicon acis is added, stirring hydrolysis 1.5-5.5h at 5-55 DEG C, then it is incubated 1-3h, then remove the alcohol of generation, obtain containing SiO2��TiO2��H2The synthesis liquid of O and NRRTPAOH, and in the synthesis liquid described in control, each component molar ratio meets the following conditions:
SiO2:TiO2=8��250, H2O:SiO2=0.6��60, and NRRTPAOH:SiO2=0.01��0.5;
3) by step 2) the synthesis liquid that obtains in 130��200 DEG C of hydrothermal crystallizings 1��30 day, then filter according to a conventional method, washing, dry and roasting, obtain described TS-1 molecular sieve.
The present invention also provides for a kind of method preparing described TS-1 molecular sieve, comprises the following steps:
1) with substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide for template, titanium source is dissolved in substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide aqueous solution, stirs 1-1.5h, obtain settled solution;
Described substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide, molecular formula is denoted as NRRTPAOH, and shown in structure such as following formula (I), wherein R1 is the alkyl of C1��C3; R2 is the alkyl of C2��C4;
2) in the settled solution that step 1) obtains, positive esters of silicon acis is added, stirring hydrolysis 1.5-5.5h at 5-55 DEG C, then it is incubated 1-3h, then remove the alcohol of generation, obtain containing SiO2��TiO2��H2The synthesis liquid of O and NRRTPAOH, and in the synthesis liquid described in control, each component molar ratio meets the following conditions:
SiO2:TiO2=8��250, H2O:SiO2=0.6��60, and NRRTPAOH:SiO2=0.01��0.5;
3) by step 2) the synthesis liquid that obtains in 130��200 DEG C of hydrothermal crystallizings 1��30 day, then filter according to a conventional method, washing, dry and roasting, obtain described TS-1 molecular sieve.
Substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide template of step 1) of the present invention, it is preferable that in described formula (I), R1 is methyl or ethyl, and R2 is the compound of ethyl, n-pro-pyl, normal-butyl or isobutyl group; Specifically include:
R1It is methyl, R2N-methyl-N ethyl nafoxidine ammonium hydroxide (NMETPAOH) when being ethyl;
R1It is methyl, R2N-methyl-N-n-propyl nafoxidine ammonium hydroxide (NMPTPAOH) when being n-pro-pyl;
R1It is methyl, R2N-methyl-N-normal-butyl nafoxidine ammonium hydroxide (NMBTPAOH) when being normal-butyl;
R1It is methyl, R2N-methyl-N-isopropyl butyl nafoxidine ammonium hydroxide (NMIBTPAOH) when being isobutyl group;
R1It is ethyl, R2N, N-diethyl nafoxidine ammonium hydroxide (NEETPAOH) when being ethyl;
R1It is ethyl, R2N-ethyl-N-propyl group nafoxidine ammonium hydroxide (NEPTPAOH) when being propyl group;
R1It is ethyl, R2N-ethyl-N-normal-butyl nafoxidine ammonium hydroxide (NEBTPAOH) when being normal-butyl;
Or,
R1It is ethyl, R2N-ethyl-N-isobutyl group nafoxidine ammonium hydroxide (NEITBPAOH) when being isobutyl group.
Step 1) of the present invention most preferred substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide template is N-methyl-N-normal-butyl nafoxidine ammonium hydroxide (NMBTPAOH) shown in structural formula such as following formula (II)
Titanium source described in step 1) is hydrolyzable titanium compound, or the ��-TiO being hydrolyzed by titanium compound and obtaining2, for instance tetraalkyl titanate Ti (alkoxy)4��TiCl4��TiOCl2��Ti(SO4)2��TiOSO4Deng or their hydrolyzate; Wherein it is preferred that tetraalkyl titanate Ti (alkoxy)4, the carbon number of alkyl therein is 1��6; Most preferably tetraethyl titanate or butyl titanate.
Titanium source is dissolved in substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide aqueous solution described in step 1), it is preferable that being slowly added dropwise in titanium source to substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide aqueous solution, rate of addition controls at 0.01��0.2mol/h.
Step 2) described in the preferred methyl silicate of positive esters of silicon acis, tetraethyl orthosilicate, positive silicic acid propyl ester or butyl silicate, it is most preferred that tetraethyl orthosilicate.
Step 2) described in synthesis liquid in each component molar ratio be preferably controlled in: SiO2:TiO2=10��150, H2O:SiO2=10��45, and NRRTPAOH:SiO2=0.03��0.4.
The preferred crystallization temperature of step 3) is 150��180 DEG C; Most preferably 170-180 DEG C.
The hydrothermal crystallizing time described in step 3) is preferably 36��192 hours.
Substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide (NRRTPAOH) used in the inventive method is existing compound, or can synthesize according to existing method.
The template compound that the inventive method uses has good heat stability, for N-methyl-N-normal-butyl nafoxidine ammonium hydroxide (NMBTPAOH) template, find that it and TPAOH of the prior art are that template is compared heat stability and significantly improved after measured, be specifically compared as follows table 1:
Table 1.20% quaternary ammonium base aqueous solution, 4 hours resolving times latter two template heat stability contrasts
| Decomposition temperature | TPAOH resolution ratio | NMBTPAOH resolution ratio |
| 100�� | 3.1% | 0 |
| 120�� | 10.4% | 0 |
| 150�� | 18.9% | 0 |
| 170�� | 52.1% | 0.3% |
| 200�� | 89.0% | 1.5% |
Therefore, the method preparing TS-1 molecular sieve provided by the present invention is compared with prior art, owing to it using substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide (NRRTPAOH) template, this template is cheap and easy to get, and high-temperature stable, so the HTS Stability Analysis of Structures of synthesis, degree of crystallinity is high, reproducible, it is easy to industrially popularization and application.
The present invention also provide for described TS-1 molecular sieve as catalyst aldehyde ketone ammoxidation, alkene epoxidation, oxidation of alkanes, aromatic hydrocarbon hydroxylating or alcohol aoxidize in application.
Described aldehyde ketone ammoxidation refers mainly to aliphatic aldehydes and alkanones or beta-branched side aldehyde ketone ammoxidation, wherein preferred acetaldehyde, propionic aldehyde, butyraldehyde, acetone, butanone, Ketohexamethylene, benzaldehyde, citronellal.
Described alkene epoxidation refers mainly to aliphatic alkene epoxidation, it is preferable that propylene, n-butene, isobutene., positive amylene, iso-amylene, cyclopentenes, cyclohexene.
Described oxidation of alkanes refers mainly to acyclic straight hydrocarbon and cycloalkanes oxidation, it is preferable that propane, normal butane, pentane, isopentane, Pentamethylene., hexamethylene, 4-methoxycyclohexyl alkane.
Described aromatic hydrocarbon hydroxylating refers mainly to phenol and fortified phenol, it is preferable that the hydroxylating of phenol.
Described alcohol oxidation refers mainly to aliphatic primary alcohol and secondary alcohol, it is preferable that isopropanol, sec-butyl alcohol, amylalcohol, methoxypropanol, to methoxycyclohexanol.
Accompanying drawing explanation
Fig. 1 is the XRD crystalline phase figure of the obtained product of example 1.
Fig. 2 is the transmission electron microscope picture of the obtained product of example 1.
Fig. 3 is the XRD crystalline phase figure of the obtained product of example 2.
Detailed description of the invention
The present invention is described further for the following examples. But it is not limited only to following instance.
Preparation embodiment 1
First 12.65 grams of 40%N-methyl-N-normal-butyl nafoxidine ammonium hydroxide (NMBTPAOH) and 30.24 grams of water are joined in the glass kettle of 500ml and start to stir. Then being slowly added dropwise TBOT (butyl titanate) 2.67 grams, within about 0.5 hour, add, stirring is until clear liquid about 0.5 hour. Add TEOS(tetraethyl orthosilicate) 48.98 grams, 45.0 grams of water, stirring reaction 2 hours, 50 DEG C are incubated 2 hours, are warming up to 78 DEG C except ethanol, until it reaches gross weight 85 grams. Then synthesis liquid is transferred in the autoclave of 300ml, 170 DEG C of thermostatic crystallization 144h. In shown synthesis liquid, each component molar ratio is as follows:
SiO2/TiO2=30, NMBTPAOH/SiO2=0.15, H2O/SiO2=17
The complete reactant liquor of crystallization is filtered by the ceramic-film tube of 50nm, 120 DEG C of drying, after 550 DEG C of roastings a kind of TS-1 molecular sieve of the present invention. Its XRD spectra as it is shown in figure 1, transmission electron microscope picture as shown in Figure 2.
Preparation embodiment 2
Being slowly added dropwise TBOT (butyl titanate) 2.67 grams, changing into and be slowly added dropwise TEOT (tetraethyl titanate) 1.78 grams, other preparations are with preparation embodiment 1. Its gained HTS XRD spectra is as shown in Figure 3.
Preparation embodiment 3
" 12.65 grams of 40%N methyl N normal-butyl nafoxidine ammonium hydroxide (NMBTPAOH) " is changed into " N methyl N ethyl nafoxidine ammonium hydroxide (NMETPAOH) of 10.42 gram 40% ", and other preparations are with preparation embodiment 1.
Preparation embodiment 4
" 12.65 grams of 40%N-methyl-N-normal-butyl nafoxidine ammonium hydroxide (NMBTPAOH) change " N methyl N n-pro-pyl nafoxidine ammonium hydroxide (NMPTPAOH) of 11.70 gram 40% " into, and other preparations are with preparation embodiment 1.
Preparation embodiment 5
" 12.65 grams of 40%N-methyl-N-normal-butyl nafoxidine ammonium hydroxide (NMBTPAOH) " is changed into " N, the N diethyl nafoxidine ammonium hydroxide (NEETPAOH) of 11.7 gram 40% ", and other preparations are with preparation embodiment 1.
Preparation embodiment 6
" 12.65 grams of 40%N-methyl-N-normal-butyl nafoxidine ammonium hydroxide (NMBTPAOH) " is changed into " N ethyl n propyl group nafoxidine ammonium hydroxide (NEPTPAOH) of 12.65 gram 40% ", and other preparations are with preparation embodiment 1.
Preparation embodiment 7
" 12.65 grams of 40%N-methyl-N-normal-butyl nafoxidine ammonium hydroxide (NMBTPAOH) " is changed into " N ethyl n normal-butyl nafoxidine ammonium hydroxide (NEBTPAOH) of 13.60 gram 40% ", and other preparations are with preparation embodiment 1.
Preparation embodiment 8
" 12.65 grams of 40%N-methyl-N-normal-butyl nafoxidine ammonium hydroxide (NMBTPAOH) " is changed into " N methyl N isobutyl group nafoxidine ammonium hydroxide (NMIBTPAOH) of 12.65 gram 40% ", and other preparations are with preparation embodiment 1.
Preparation embodiment 9
" 12.65 grams of 40%N-methyl-N-normal-butyl nafoxidine ammonium hydroxide (NMBTPAOH) " is changed into " N ethyl n isobutyl group nafoxidine ammonium hydroxide (NEITBPAOH) of 13.60 gram 40% ", and other preparations are with preparation embodiment 1.
Application example 1 ammoxidation of cyclohexanone
In the 100ml glass reaction bottle with sieve plate filter, it is initially charged the tertiary butanol aqueous solution 60ml of 75%, adds 3 grams of the TS-1 molecular sieve of preparation embodiment 1 preparation, be warmed up to 76-80 DEG C. Then simultaneously hydrogen peroxide to pass into 27% for 24.5-26ml/ hour, passes into the mixture of Ketohexamethylene and the tert-butyl alcohol for 90ml/ hour, and the ammonia of 190ml/ hour, after stable reaction, every two hours sample analysis.
Reaction result is as follows: the conversion ratio 99.2% of Ketohexamethylene, and the selectivity 99.5% of Ketohexamethylene, the utilization rate of hydrogen peroxide is more than 96%.
Application example 2 isobutene. epoxidation
Taking 20 grams of the TS-1 molecular sieve of preparation embodiment 1 preparation, the Ludox and the 0.5 gram of sesbania gum that add 10 gram 30% are mixed together, then extruded moulding on little banded extruder. Then dry, roasting, obtain the catalyst of silica gel molding. Take 10 grams of Catalyst packings to internal diameter 12mm, in the stainless steel reactor of height 500mm, with heating in water bath to 35-40 DEG C. Then pass into the hydrogen peroxide of 35% with 5.4 Grams Per Hours, 25 Grams Per Hours pass into methanol, the isobutene. of 6 Grams Per Hours, after stable reaction, every two hours sample analysis simultaneously.
Reaction result is as follows: the conversion ratio 28% of isobutene., and the selectivity 98% of isobutene., the utilization rate of hydrogen peroxide is more than 92%.
Application example 3 Pentamethylene. aoxidizes
10 grams of the TS-1 molecular sieve taking preparation embodiment 2 preparation is placed in the autoclave of 2 liters, adds methanol 400 grams, Pentamethylene. 350 grams, closes autoclave, be warmed up to 80-90 DEG C, then squeezed into the hydrogen peroxide 315 grams of 35% in 4 hours with constant-flux pump. After having reacted, cooling, sample analysis.
Reaction result is as follows: the conversion ratio of Pentamethylene. is more than 62%, and the selectivity of Pentamethylene. is more than 96%, and the utilization rate of hydrogen peroxide is more than 89%.
Application example 4 phenol hydroxylation
In four mouthfuls of reaction bulbs of 500ml, add the mixture of 100 grams of acetone and 84 grams of phenol, add 2.5 grams of the TS-1 molecular sieve of preparation embodiment 9 preparation, be warmed up to 60-70 DEG C, in 2 hours, then drip the hydrogen peroxide of 40 gram 27%. After dripping, insulation reaction 0.5 hour. Then sample analysis.
Reaction result is as follows: the conversion ratio 28% of phenol, and the selectivity 98% of phenol, the utilization rate of hydrogen peroxide is more than 96%.
Claims (10)
1. a preparation method method for TS-1 molecular sieve, comprises the following steps:
1) with substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide for template, titanium source is dissolved in substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide aqueous solution, stirs 1-1.5h, obtain settled solution; Described substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide, molecular formula is denoted as NRRTPAOH, and shown in structure such as following formula (I), wherein R1 is the alkyl of C1��C3; R2 is the alkyl of C2��C4;
2) in step 1) settled solution that obtains adds positive esters of silicon acis, stirring hydrolysis 1.5-2.5h at 5-55 DEG C, then it is incubated 1-3h, then remove the alcohol of generation, obtain containing SiO2��TiO2��H2The synthesis liquid of O and NRRTPAOH, and in the synthesis liquid described in control, each component molar ratio meets the following conditions:
SiO2:TiO2=8��250, H2O:SiO2=0.6��60, and NRRTPAOH:SiO2=0.01��0.5;
3) by step 2) the synthesis liquid that obtains in 130��200 DEG C of hydrothermal crystallizings 1��30 day, then filter according to a conventional method, washing, dry and roasting, obtain described TS-1 molecular sieve.
2. method according to claim 1, it is characterized in that: step 1) described in any one in the following compound of substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide template: N-methyl-N ethyl nafoxidine ammonium hydroxide, N-methyl-N-n-propyl nafoxidine ammonium hydroxide, N-methyl-N-normal-butyl nafoxidine ammonium hydroxide, N-methyl-N-isopropyl butyl nafoxidine ammonium hydroxide, N, N-diethyl nafoxidine ammonium hydroxide, N-ethyl-N-propyl group nafoxidine ammonium hydroxide, N-ethyl-N-normal-butyl nafoxidine ammonium hydroxide or N-ethyl-N-isobutyl group nafoxidine ammonium hydroxide.
3. method according to claim 1, it is characterised in that: step 1) described in substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide template be the N-methyl-N-normal-butyl nafoxidine ammonium hydroxide shown in structural formula such as following formula (II)
4. method according to claim 1, it is characterized in that: step 1) described in titanium source is dissolved in substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide aqueous solution, being be slowly added dropwise in titanium source to substituted-tetrahydro pyrroles's quaternary ammonium base ammonium hydroxide aqueous solution, rate of addition controls at 0.01��0.2mol/h.
5. method according to claim 1, it is characterised in that: step 1) described in titanium source be tetraalkyl titanate, the carbon number of alkyl therein is 1��6; Step 2) described in positive esters of silicon acis selected from methyl silicate, tetraethyl orthosilicate, positive silicic acid propyl ester or butyl silicate.
6. method according to claim 1, it is characterised in that: step 1) described in titanium source be tetraethyl titanate or butyl titanate; Step 2) described in positive esters of silicon acis be tetraethyl orthosilicate.
7. method according to claim 1, it is characterised in that: step 2) described in synthesis liquid in each component molar ratio control: SiO2:TiO2=10��150, H2O:SiO2=10��45, and NRRTPAOH:SiO2=0.03��0.4.
8. method according to claim 1, it is characterised in that: step 3) described in hydrothermal crystallizing temperature be 150��180 DEG C;Step 3) described in the hydrothermal crystallizing time be 36��192 hours.
9. a TS-1 molecular sieve, it is characterised in that be prepared by the method described in any one of claim 1-8 and obtain.
10. the TS-1 molecular sieve described in claim 9 as catalyst aldehyde ketone ammoxidation, alkene epoxidation, oxidation of alkanes, aromatic hydrocarbon hydroxylating or alcohol aoxidize in application.
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| CN102530980A (en) * | 2012-01-13 | 2012-07-04 | 大连理工大学 | Hierarchical zeolite, preparation and application thereof |
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