CN1358570A - Modifying process for titanium-silicon molecular sieve - Google Patents
Modifying process for titanium-silicon molecular sieve Download PDFInfo
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- CN1358570A CN1358570A CN 00132121 CN00132121A CN1358570A CN 1358570 A CN1358570 A CN 1358570A CN 00132121 CN00132121 CN 00132121 CN 00132121 A CN00132121 A CN 00132121A CN 1358570 A CN1358570 A CN 1358570A
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 36
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title claims abstract 5
- 239000003513 alkali Substances 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- -1 aliphatic amine compound Chemical class 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 6
- 150000007530 organic bases Chemical class 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- 150000007529 inorganic bases Chemical class 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 239000011148 porous material Substances 0.000 abstract description 9
- 238000009792 diffusion process Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract 2
- 230000000052 comparative effect Effects 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- DTGGJUIFYJXAJI-OBGWFSINSA-N (e)-2-cyano-3-[4-(n-phenylanilino)phenyl]prop-2-enoic acid Chemical compound C1=CC(/C=C(C(=O)O)\C#N)=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 DTGGJUIFYJXAJI-OBGWFSINSA-N 0.000 description 12
- 101100510326 Caenorhabditis elegans tpa-1 gene Proteins 0.000 description 12
- 238000001179 sorption measurement Methods 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 10
- 230000001590 oxidative effect Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 8
- 238000003795 desorption Methods 0.000 description 8
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000033444 hydroxylation Effects 0.000 description 2
- 238000005805 hydroxylation reaction Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZNALFCQVQALKNH-UHFFFAOYSA-N 4-(2,4,5-tripyridin-4-ylphenyl)pyridine Chemical compound C1=NC=CC(C=2C(=CC(=C(C=3C=CN=CC=3)C=2)C=2C=CN=CC=2)C=2C=CN=CC=2)=C1 ZNALFCQVQALKNH-UHFFFAOYSA-N 0.000 description 1
- 241001502050 Acis Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229910004339 Ti-Si Inorganic materials 0.000 description 1
- 229910010978 Ti—Si Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 150000001934 cyclohexanes Chemical class 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229940043237 diethanolamine Drugs 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
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- 239000003643 water by type Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种TS－2钛硅分子筛的改性方法,其特征在于该方法包括将已经合成出的常规TS－2钛硅分子筛与一种碱溶液在50～250℃下接触1～50小时。本发明方法所得TS－2分子筛为空心结构或具有较大孔体系,有利于反应过程中分子的扩散,因而对改善反应性能有利。A method for modifying TS-2 titanium-silicon molecular sieve, which is characterized in that the method comprises contacting the synthesized conventional TS-2 titanium-silicon molecular sieve with an alkali solution at 50-250°C for 1-50 hours. The TS-2 molecular sieve obtained by the method of the present invention has a hollow structure or a relatively large pore system, which is beneficial to the diffusion of molecules during the reaction process, and thus is beneficial to improving the reaction performance.
Description
The present invention relates to the preparation method of a kind of HTS TS-2 of the MEL of having structure.
HTS is the molecular sieve that the part Si of zeolitic frameworks is replaced by Ti.Because it has the decentralized environment of rule, therefore highly homogeneous internal structure, special duct have the function of shape selective catalysis.And the titanium of introducing skeleton is to oxidant H
2O
2Activation is arranged, not to the chemical stability and the obviously influence of heat endurance generation of molecular sieve itself, kept the molecular sieve good stable simultaneously.HTS can be used as the catalyst of oxidizing hydrocarbon process.With the catalyst of this molecular sieve analog as oxidizing process, reaction mass is simple, and product is single, has simplified the accessory substance of some chemical process greatly, and does not have three waste discharge.This has not only simplified chemical process, and has greatly alleviated byproduct of reaction and treatment of wastes produced amount.Along with the continuous rise of novel oxidation technology and the raising of environmental requirement, HTS is as a kind of oxidation catalyst of excellence and be subjected to day by day paying close attention to widely and paying attention to.
The research and development of HTS are from early eighties.People such as gondola MarcoTarramasso are open first (GB2 in 1981,071,071, USP4,410501) have a preparation method of the HTS (TS-1 has identical crystal phase structure with ZSM-5) of MFI structure, subsequently, J.S.Reddy etc. deliver (Appl.Catal., 1990,58, L1) have a preparation method of the HTS (TS-2 has identical crystal phase structure with ZSM-11) of MEL structure.TS-1 and TS-2 are respectively that the framework silicon atom is replaced the HTS with ZSM-5, ZSM-11 structure that the back forms by the titanium atom isomorphous among pure silicon molecular sieve Silicalite-1, the Silicalite-2, and their aperture is approximately below 5.5 .The aperture that TS-1, TS-2 are little limited and the reactant that its duct size is close or bigger and the diffusion velocity of product molecule, thereby limited the reaction speed of some reaction (as phenol hydroxylation, cyclohexane oxidation and cyclohexanone (alcohol) ammoxidation etc.).1992, have Beta zeolite structures HTS synthetic (M.E.Davis, Acc.Chem.Res., 26 (1993) 111 and list of references) make the aperture of this molecular sieve analog increase to about 6.5 .1994, people (Zeolites and Related Microporous Materials:State of the Art 1994 such as people such as A.Corma and O.Franke, Studies in Surface Science and Catalysis, the 84th volume, the 69th page and the 77th page) reported the synthetic of Ti-Si ultra macroporous molecular sieve with MCM-41 structure simultaneously, this class HTS has the super big hole of 15～100 , and this makes HTS become possibility as the catalyst of macromolecular organic compound selective oxidation.But, because the pore passage structure of this super macroporous molecular sieve is different with TS-1 and TS-2, thereby for some reaction,, have the selectivity different with TS-1, TS-2 as phenol hydroxylation, cyclohexane oxidation and cyclohexanone (alcohol) ammoxidation etc.
CN1245090A has proposed a kind of method of modifying of TS-1 molecular sieve, and this method comprises that TS-1 molecular sieve, acid compound and the water that will synthesize mix, and reacts 5 minutes to 6 hours down at 5～95 ℃, obtains acid-treated TS-1 molecular sieve; Gained is mixed through acid-treated TS-1 molecular sieve, organic base and water, and in sealed reactor under 120～200 ℃ temperature and self-generated pressure 2 hours to the 8 day time of reaction, then products therefrom is filtered, washing and dry; Wherein said organic base is fatty amine, alcamines or quaternary ammonium base compounds.This method gained TS-1 molecular sieve has reduced the invalid decomposition of oxidant owing to removed the outer titanium of the skeleton in the molecular sieve pore passage, thereby its catalytic oxidation activity is compared with prior art obviously improved, and has stability of catalytic activity preferably simultaneously.
Comprehensive prior art mainly concentrates on TS-1 to the preparation of HTS and the research and development of modification, and about the report of the preparation of TS-2 and modification aspect seldom.
The method of modifying that the purpose of this invention is to provide a kind of HTS (TS-2) of the MEL of having structure makes gained TS-2 molecular sieve both have the TS-2 structure, have again 6～20 than large micropore and greater than the mesopore of 20 .
The method of modifying of TS-2 HTS provided by the present invention comprises that 6～20 that do not contain that will synthesize contact 1～50 hour than the conventional TS-2 HTS that large micropore reaches greater than 20 mesopores with a kind of aqueous slkali under 50～250 ℃, preferably contact 2～40 hours down, more preferably contact 3～30 hours down at 100～200 ℃ at 80～220 ℃.
Said 6～20 that do not contain that synthesized are meant the conventional TS-2 molecular sieve for preparing according to the method in patent of having delivered or the document than the conventional TS-2 HTS that large micropore reaches greater than 20 mesopores among the preparation method provided by the invention, this molecular sieve can pass through or without calcination process, promptly can contain or not contain organic formwork agent.
Said aqueous slkali can be the aqueous solution of organic base or inorganic base in the method provided by the invention, said organic base is meant fat amine compound, quaternary ammonium base compounds or alcamine compound, or mix the mixed amine compounds of forming mutually by them, wherein preferably alcamine compound or quaternary ammonium base compounds are more preferably the quaternary amine alkali compounds with 2～4 carbon atoms; Said inorganic base is meant any water-soluble inorganic alkalis such as ammoniacal liquor, NaOH, potassium hydroxide, and wherein preferred ammoniacal liquor, NaOH or potassium hydroxide are more preferably ammoniacal liquor.
Its general formula of said fat amine compound is R
1(NH
2)
n, R wherein
1For having the alkyl of 1～6 carbon atom, n=1 or 2, wherein preferred fat amine compound is ethamine, n-butylamine, butanediamine or hexamethylene diamine.
Its general formula of said alcamine compound is (HOR
2)
mN, wherein R
2For having the alkyl of 1～4 carbon atom, m=1～3, wherein preferred alcamine compound is MEA, diethanol amine or triethanolamine.
The concentration of said aqueous slkali has no particular limits in the method provided by the invention, is preferably 0.2～50 weight %, more preferably 1～30 weight %.
The ratio of said molecular sieve, alkali and water is molecular sieve (gram) in the method provided by the invention: alkali (mole): water (mole)=100: (0.0050～0.50): (5～200) are preferably 100: (0.010～0.15): (20～80).
Fig. 1 is the X-ray diffractogram of Comparative Examples 1 gained sieve sample (CB-2).
Fig. 2 is the transmission electron microscope photo (50,000 times) of Comparative Examples 1 gained sieve sample (CB-2).
Fig. 3 is the adsorption isotherm and the desorption isotherm of the cryogenic nitrogen absorption of Comparative Examples 1 gained sieve sample (CB-2).
Fig. 4 is the transmission electron microscope photo (50,000 times) of embodiment 1 gained sieve sample (TPA-1).
Fig. 5 is the transmission electron microscope photo (50,000 times) of embodiment 2 gained sieve samples (TBA-1).
Fig. 6 is the transmission electron microscope photo (30,000 times) of embodiment 3 gained sieve samples (AMO-1).
Fig. 7 is the adsorption isotherm and the desorption isotherm of the cryogenic nitrogen absorption of embodiment 1 gained sieve sample (TPA-1).
Fig. 8 is the adsorption isotherm and the desorption isotherm of the cryogenic nitrogen absorption of embodiment 3 gained sieve samples (AMO-1).
Fig. 9 is the transmission electron microscope photo (50,000 times) of embodiment 4 gained sieve samples (TPA-2).
Figure 10 is the transmission electron microscope photo (50,000 times) of embodiment 5 gained sieve samples (TPA-3).
Figure 11 is the transmission electron microscope photo (50,000 times) of embodiment 6 gained sieve samples (TPA-4).
Figure 12 is the transmission electron microscope photo (40,000 times) of embodiment 7 gained sieve samples (TPA-5).
The HTS of the TS-2 structure that method provided by the invention obtains be hollow-core construction or have 6～20 than large micropore and greater than the middle pore system of 20 . This hollow-core construction and larger pore system are conducive to the diffusion of molecule in the course of reaction, thereby favourable to improving reactivity worth; For example the result from the reaction of the cyclohexane selectively oxidizing of Comparative Examples 2 and embodiment 10～14 can find out, compares with conventional TS-2 molecular sieve through its reaction conversion ratio of TS-2 molecular sieve after the inventive method modification and improves a lot.
There is hysteresis loop between the adsorption isotherm of the nitrogen absorption under low temperature of the HTS of the TS-2 structure that method provided by the invention obtains and the desorption isotherm. Study discovery through the inventor, the hollow-core construction of this hysteresis loop and molecular sieve or relevant than large micropore; Basically do not have hysteresis loop between the adsorption isotherm of conventional its nitrogen absorption under low temperature of TS-2 molecular sieve of the prior art and the desorption isotherm, and all there is said hysteresis loop to some extent in the TS-2 molecular sieve after the modification among the present invention; The size of the cavity part of hollow crystal grain is larger, and then its said hysteresis loop is also larger.
The following examples will the present invention is further illustrated.
Comparative Examples 1
The synthetic TS-2 molecular sieve of the method that the explanation of this Comparative Examples proposes according to people such as J.S.Reddy (Appl.Catal., 1990, the 58 volumes, the L1～L4 page or leaf).
Under agitation to containing 45.0 gram tetraethylorthosilicise, 25.0 slowly add the aqueous solution that contains 10.0 gram TBAHs (TBAOH) in the solution of gram isopropyl alcohol and 25.0 gram redistilled waters, make the TEOS partial hydrolysis, under vigorous stirring, in the gained mixed solution, drip aqueous isopropanol 10.0 grams that contain 1.13 gram butyl titanates then very lentamente, with the limpid liquid mixture of gained 57 ℃ of following stir abouts 1 hour, make esters of silicon acis and titanate esters complete hydrolysis, add the aqueous solution 70.0 grams that contain 40.0 gram TBAHs again, the stirring under 75～80 ℃ of gained mixture was caught up with alcohol 8 hours, change autoclave then over to and after 8 days, obtain the mixture of crystallization product in 170 ℃ of crystallization; This mixture is filtered, is washed with water to pH is 6～8, and in 110 ℃ of dryings 60 minutes, obtains the TS-2 molecular screen primary powder.With the former powder of this TS-2 in 550 ℃ of following roastings 3 hours, the TS-2 molecular sieve, it is numbered CB-2, the peak type of its XRD crystalline phase figure diffraction maximum and peak position as shown in Figure 1, its transmission electron microscope photo as shown in Figure 2, its N
2Adsorption isotherm as shown in Figure 3.
Embodiment 1～3
These embodiment illustrate preparation method and the crystal structure and the pore structure characteristics of HTS of the present invention (promptly have the TS-2 crystal structure and greater than the pore canal system of 6 ).
Get 3 parts of Comparative Examples, 1 gained CB-2 sample, every part of CB-2 is 3 grams, be immersed in the TPAOH of 2.1 grams, 20 weight % respectively, in the aqueous solution of TBAOH and ammoniacal liquor, in sealing autoclave, under 165 ℃ and self-generated pressure, handled 24 hours, then the gained mixture is filtered, it is 6～8 that solid product is washed with water to pH, in 110 ℃ of dryings 60 minutes, 550 ℃ of following roastings 3 hours, get Different Alkali and handle sample, it is numbered TPA-1 respectively, TBA-1 and AMO-1, the peak type of its XRD crystalline phase figure diffraction maximum is similar to Fig. 1 with peak position, and its transmission electron microscope photo is respectively as Fig. 4,5, shown in 6, the N of TPA-1 and TBA-1
2Adsorption isotherm is basic identical, wherein the N of TPA-1
2Adsorption isotherm as shown in Figure 7, the N of AMO-1
2Adsorption isotherm as shown in Figure 8.Because TPA-1, TBA-1 have the XRD spectrum similar to CB-2 with AMO-1, illustrate that they have the MEL type crystal structure of TS-2.Comparison diagram 2 and 4～6 is not difficult to find that the granularity of molecular sieve and pattern almost do not change after the WITH AMMONIA TREATMENT; After TPAOH and TBAOH processing, although molecular sieve does not change on granularity, tangible depression or cavity have appearred in molecular sieve, and its size is 6～about 1000 .Comparison diagram 3 and 7～8 can be found, CB-2 presents the absorption and the desorption isotherm of conventional TS-2 structure molecular screen, at p/p
0There is a high pressure hysteresis loop at＞0.9 place, and this is because due to the accumulation hole between sieve particle.TPA-1 of the present invention, TBA-1 and AMO-1 are at p/p
0Be 0.1～0.2 a low pressure hysteresis loop to have occurred, this hysteresis loop appearance, illustrating has existing than large micropore of 6～20 in TPA-1, TBA-1 and AMO-1.In addition, in TPA-1 and TBA-1, high pressure hysteresis loop closing point relative pressure p/p
0Appear at 0.45, and the area of hysteresis loop increases considerably.This shows the mesopore that has 6 a large amount of～about 1000 in TPA-1 and TBA-1.
Embodiment 4～7
These embodiment illustrate preparation method and the crystal structure and the pore structure characteristics of HTS of the present invention (promptly have the TS-2 crystal structure and greater than the pore canal system of 6 ).
Get 4 parts of Comparative Examples, 1 gained CB-2 sample, every part of CB-2 is 3 grams, step according to embodiment 1～3 contacts with 4 kinds of TPAOH aqueous solution, the concentration and the consumption of these four kinds of solution are respectively: the TPAOH of 6.3 grams, 6.6 weight %, 14.7 restrain the TPAOH of 2.8 weight %, 1.5 restrain the TPAOH of 20 weight %, 3.0 restrain the TPAOH of 20 weight %, all the other conditions are identical, obtain four samples, it is numbered TPA-2 respectively, TPA-3, TPA-4 and TPA-5, the peak type of its XRD crystalline phase diffraction maximum is similar to Fig. 1 with peak position, its transmission electron microscope photo such as Fig. 9,10,11, shown in 12, its N
2Adsorption isotherm and Fig. 7 are similar.This result shows, TPA-2, TPA-3, TPA-4 and TPA-5 have simultaneously TS-2 MEL type crystal structure, 6～20 than large micropore with greater than the mesopore of 20 .
Embodiment 8
With Comparative Examples 1 gained CB-2 sieve sample according to molecular sieve (gram): triethanolamine (mole): TPAOH (mole): water (mole)=100: 0.20: 0.15: 180 ratio mixes, put into the stainless steel sealed reactor, constant temperature is placed 0.5 day time under 190 ℃ temperature and self-generated pressure, after the cooling release, filter according to a conventional method, wash, drying, and 550 ℃ of following air atmosphere roastings 3 hours, obtain the TS-2 molecular sieve of modification of the present invention, the adsorption isotherm of its cryogenic nitrogen absorption and desorption isotherm and Fig. 7 are similar.
Embodiment 9
With Comparative Examples 1 gained CB-2 sieve sample according to molecular sieve (gram): n-butylamine (mole): the ratio of water (mole)=100: 0.18: 30 mixes, put into the stainless steel sealed reactor, constant temperature was placed 40 hours under 90 ℃ temperature, after the cooling, filter according to a conventional method, wash, drying, and, obtaining the TS-2 molecular sieve of modification of the present invention 500 ℃ of following air atmosphere roastings 4 hours, the adsorption isotherm of its cryogenic nitrogen absorption and desorption isotherm and Fig. 8 are similar.
Comparative Examples 2
The effect of cyclohexane selectively oxidizing reaction is carried out in the explanation of this Comparative Examples with conventional TS-2 molecular sieve.
CB-2 with Comparative Examples 1 preparation makes catalyst, carries out cyclohexane selectively oxidizing reaction preparing cyclohexanone (alcohol), and specific implementation process is as follows:
With 9 milliliters of acetone, 5.5 ml concns is that pack into inner liner polytetrafluoroethylene, volume of 30% aqueous hydrogen peroxide solution, 2 milliliters of cyclohexanes and 0.1 gram CB-1 is 50 milliliters Pressure solution bullet, under stirring, magnetic heats up, after oil bath temperature reaches 373K, isothermal reaction 8 hours, products therefrom carries out quantitative analysis with gas-chromatography.Obtain conversion of cyclohexane thus and see Table 1.
Embodiment 10-14
These embodiment explanations are carried out the effect that cyclohexane selectively oxidizing reacts with the TS-2 molecular sieve of the inventive method preparation.
TPA-1, TBA-1, AMO-1, TPA-2 and TPA-3 with embodiment 1～5 preparation make catalyst, carry out cyclohexane selectively oxidizing reaction preparing cyclohexanone and cyclohexanol, and reactions steps and Comparative Examples 2 are identical.Obtain conversion of cyclohexane thus and see Table 1.
The conversion ratio of table 1 cyclohexane selectively oxidizing reaction on different catalysts
| Comparative Examples 2 | Embodiment 10 | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | |
| Molecular sieve | CB-2 | ?TPA-1 | ?TPB-1 | ?AMO-1 | ?TPA-2 | ?TPA-3 |
| Conversion ratio/% | 29.2 | ?66.1 | ?63.1 | ?47.4 | ?53.2 | ?46.6 |
As can be seen from Table 1, its reaction conversion ratio of TS-2 molecular sieve after the modification of process the inventive method is compared with conventional TS-2 molecular sieve and is improved a lot.
Claims (10)
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