CN1048228C - titanium silicate zeolite molecular sieve crystal and preparation method thereof - Google Patents
titanium silicate zeolite molecular sieve crystal and preparation method thereof Download PDFInfo
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- CN1048228C CN1048228C CN95119388A CN95119388A CN1048228C CN 1048228 C CN1048228 C CN 1048228C CN 95119388 A CN95119388 A CN 95119388A CN 95119388 A CN95119388 A CN 95119388A CN 1048228 C CN1048228 C CN 1048228C
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- molecular sieve
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Abstract
The present invention relates to a novel titanium silicate zeolite molecular sieve crystal, and a preparation method thereof. The preparation method comprises the steps as follows: silica resource, titanium resource, alkali metal hydroxide, water, etc. are heated and crystallized at a pH value more than 12.5 at 100 to 300 DEG C to synthesis a novel stable ST-series titanium silicate molecular sieve crystal. The ST-series titanium silicate molecular sieve crystal can be used for adsorption, ion exchange, catalysis, etc.
Description
The invention belongs to zeolite molecular sieve crystal and preparation method thereof, particularly two kinds of Novel Titanium silicate zeolite molecular sieve crystals and preparation method thereof.
Use present method and can synthesize a kind of stable New type of S T series titanosilicate molecular sieve crystal.ST series titanosilicate molecular sieve crystal can be applied to aspects such as absorption, ion-exchange and catalysis.
Since the later stage fifties, people such as Milton find in the silico-aluminate system can polymerization to generate uniform pore size, internal charge equilibrated and nature find be of a sort molecular sieve zeolites after, molecular sieve zeolites has obtained application (U.S.Pat.Nos.2882243 and 2882244) widely at aspects such as catalyzer, sorbent material, ion-exchangers.The crystal of this skeleton structure has huge specific surface area and uniform duct.In this crystalline structure, Al
3+Ion is to link to each other with oxygen to be tetrahedral structure, makes skeleton present superfluous electronegativity, therefore, exists a large amount of active charge positions in crystal, and they play an important role to absorption and catalysis.In addition, the effect of the positively charged ion of balancing charge effect and skeleton negative charge is not a covalency, and therefore, it can be exchanged by other positively charged ion, thereby changes crystalline character, makes this material have adjustable sex change, has expanded their range of application.
The prior art the most approaching with the present invention is the U.S.Pat.No.4938939 patent (open day Jul.3,1990) of Kuznicki application, and the chemical formula of given titanosilicate molecular sieve crystal is:
1.0±0.25M
2/nO：TiO
2：ySiO
2：zH
2O
Wherein M is that valency is the positively charged ion of n, n=1,2, M can be the monovalence metal, divalent metal, the mixture of one or more of ammonium etc., y=1.0-10, z=0-100, its X-ray powder diffraction compose as table 3: d value (dust) I/I that table 3 is main
011.65 ± 0.25 S-VS6.95 ± 0.25 S-VS5.28 ± 0.15 M-S4.45 ± 0.15 W-M2.98 ± 0.05 VS wherein: the preparation method of this molecular sieve crystal of VS=50-100S=30-70M=15-50W=5-30 (being referred to as ETS-4) is roughly with TiCl3, Ti
2O
3Be titanium source, SiO
2Be the silicon source, with Hybrid Heating such as alkali metal hydroxide, fluorochemical and water, temperature of reaction is 100 ℃ to 300 ℃, and the reaction times is 8 hours to 40 days, and the pH value of reaction mixture is 10.45-11.0 ± 0.1.Product is an ETS-4 series titanosilicate molecular sieve.
The objective of the invention is to adopt unlike the prior art the titanium source and the pH value of mixture, synthesize two kinds of novel molecular sieve crystal, can be applied to aspects such as absorption, ion-exchange and catalysis.
New titanium-silicone hydrochlorate molecular sieve crystal of the present invention is called ST series titanosilicate molecular sieve crystal, particularly ST-16 and two kinds of ST-30 and the diverse molecular sieve crystal of prior art.Its chemical formula is
xM
2/nO∶TiO
2∶ySiO
2∶zH
2O
Wherein M is that electric charge is a kind of positively charged ion of monovalence metal, divalent metal, ammonium of n etc. or cationic mixture more than two kinds, x=0.5-5, y=1-50, z=0-100.The characteristic X-ray powdery diffractometry spectrum of two kinds of new titanium-silicone hydrochlorate molecular sieve crystals is respectively shown in table 1 and 2:
XRD powder spectrum (0-40 ° of 2theta) main d value (dust) I/I of table 1 ST-16
010.72±0.5 S-VS 5.35±0.5 VS 4.33±0.3 M-S 3.57±0.3 S-VS 3.49±0.3 M 3.21±0.3 M 3.15±0.3 M-S 2.56±0.3 M-S
XRD powder spectrum (0-40 ° of 2theta) main d value (dust) I/I of table 2 ST-30
014.81 ± 0.5 VS 4.88 ± 0.5 W-M 4.42 ± 0.5 W-M 3.78 ± 0.3 W-M 3.04 ± 0.3 S 2.74 ± 0.3 S
Wherein: VS=50-100 S=30-70 M=15-50 W=5-30
The listed d Value Data in the data of table 1 and table 2 and back all is to record with Japanese D/MAX-111A type X-ray diffractometer of science, is that interior mark is proofreaied and correct with KCl.Peak intensity directly records from peak heights.ST series molecular sieve has orderly crystalline structure, by the crystal that different positively charged ion M obtain, and strong little the changing in its peak position and peak, but its crystalline structure is constant.
Adopt switching technology, original cationic M can to small part by other cationic exchange.These positively charged ions can be hydrogen ion, ammonium ion, rare earth ion and their mixture etc.ST series molecular sieve can be stabilized to 500 ℃.ST series molecular sieve can planar water.Normal hexane etc.
The preparation method of ST series molecular sieve crystal of the present invention uses hydrothermal crystallization method, that is:
Heating crystallization comprises silicon source, titanium source, alkali metal hydroxide and water etc., and the mole ratio range of each material is as follows:
SiO
2/TiO
2：1-60
H
2O/SiO
2：3-3000
Mn/SiO
2：0.001-10
Wherein M is that valency is the metallic cation of n.Temperature of reaction is 100 ℃ to 300 ℃, and the reaction times is 4 hours to 50 days.Resultant is after cooling, filtration, washing, and is at room temperature dry.The invention is characterized in that said titanium source comprises titanic compound; The pH value of reaction mixture is 12.5～14.Except that can synthesizing two kinds of novel molecular sieve crystal of ST-16 and ST-30, also can synthesize the ETS-4 molecular sieve crystal, the main d value of its characteristic X-ray powder diffraction spectra is identical with the table 3 of prior art.
The ST molecular sieve can be by titaniferous raw material such as titanium dioxide, titanium sesquioxide, titanous chloride, titanium tetrachloride, titanyl sulfate, tetrabutyl titanate, titanium ethanolate etc., and siliceous raw material such as silicon-dioxide, water glass, silicon sol, water glass and basic metal oxygen oxide compound, water, alkali metal halide etc. make by the molar ratio hybrid reaction in the table 4.
The mole ratio range of the various materials of table 4
Scope optimum range ST-16 molecular sieve SiO
2/ Ti 1-60 2-10
H
2O/SiO
2?3-1000 10-100
Mn/SiO
20.08-0.75 0.3-0.6EST-4 molecular sieve SiO
2/ Ti 1-20 2-5
H
2O/SiO
2 3-1000 10-100
Mn/SiO
20.76-1.1 0.8-1ST-30 molecular sieve SiO
2/ Ti 1-60 5-10
H
2O/SiO
2 3-1000 10-100
Mn/SiO
2 1.11-2.4 1.5-2.0
Wherein M is that valent state is the amount that the positively charged ion of n is equivalent to alkali metal cation.The pH value of reaction mixture is 12.5-14, can be synthetic under greater than 13 condition in the pH value.Reaction mixture carries out hydrothermal crystallizing reaction at 100 ℃ to 300 ℃ scope internal heating, the temperature of reaction height, and crystallization time is short, as more than 180 ℃, i.e. 180 ℃ to 300 ℃ scopes.Reaction times is 4 hours to 50 days or longer.Resultant is after cooling, filtration, washing, and is at room temperature dry.
The reaction raw materials that is used to prepare the ST compound is widely.In reaction mixture, can add fluorochemical and regulate the solvability of titanium etc.
The titanium source can be titanous and titanic, for example titanium dioxide, titanium sesquioxide, titanous chloride, titanium tetrachloride, titanyl sulfate, tetrabutyl titanate, titanium ethanolate etc.
The silicon source can be silicon-dioxide, water glass, silicon sol, water glass etc.
Alkali-metal raw material often is the aqueous solution of alkali metal hydroxide.Its effect is that alkali metal cation, the acid-basicity of regulation system on the other hand are provided on the one hand.The pH value of reaction mixture can be 12.5-14.
The synthetic HTS has ion-exchange character.Adopt conventional switching technology, can be exchanged into hydrogen ion, ammonium ion, alkylamine, aromatic perfume amine, metal ion etc.After for example hydrogen type molecular sieve can be exchanged into ammonium ion by sodium ion, make 300 ℃ of calcinations.
With sodium is cationic ST-16 HTS, although ratio can great changes have taken place for titanium silicon, its X-ray powder diffraction spectrogram is identical substantially, shown in table 1-3.
As catalyzer, this HTS can be used together with other material, so that adapt to various conditional requests.This knot material can be active or inactive, for example clay, silicon-dioxide, metal oxide, molecular sieve etc.
For essence of the present invention and the repeatability in experiment are described better, list some experiment embodiments below.
Synthesizing of example 1. ST-16 HTS
Reactant feed is as follows:
1.6 gram TiO
2
18.8 gram SiO
2
7.1 gram NaOH
100 gram H
2O
Wherein: Ti/Si=0.06
Na/Si＝0.6
H
2O/Si＝18
Above-mentioned reactant feed in the reactor of packing into, 240 ℃ of following crystallization 10 days, obtains the ST-16 crystal after electronic mixing.Its X-ray powder diffraction spectrogram (XRD) is as shown in table 5: table 5. is X-ray powder diffraction spectrum d (A) I/I of cationic ST-16 HTS with sodium
010.72 696.08 45.35 1004.33 373.57 583.49 183.21 183.15 372.82 82.61 42.56 202.52 72.38 4
Its main d value is identical with table 1.
Product has following composition (weight percent)
SiO
2：58％
TiO
2：24％
Na
2O：13％
Si/Ti＝3
Synthesizing of example 2. ST-16 HTS
Reactant feed is as follows:
3.5 gram TiO
2
18.8 gram SiO
2
7.1 gram NaOH
100 gram H
2O
Wherein: Ti/Si=0.13
Na/Si＝0.6
H
2O/Si＝18
Above-mentioned reactant feed in the reactor of packing into, 240 ℃ of following crystallization 2 days, obtains the ST-16 crystal after electronic mixing.The main d value of its X-ray powder diffraction spectrogram (XRD) is as shown in table 1.
Synthesizing of example 3. ST-16 HTS
Reactant feed is as follows:
14 gram TiO
2
18.8 gram SiO
2
7.1 gram NaOH
100 gram H
2O
Wherein: Ti/Si=0.5
Na/Si＝0.6
H
2O/Si＝18
Above-mentioned reactant feed in the reactor of packing into, 200 ℃ of following crystallization 10 days, obtains the ST-16 crystal after electronic mixing.The main d value of its X-ray powder diffraction spectrogram (XRD) is as shown in table 1.Product has following composition (weight percent):
SiO
2：35％
TiO
2：42％
Na
2O：13％
Si/Ti＝1∶1
Synthesizing of example 4. ETS-4 HTS
Reactant feed is as follows:
5.8 gram TiO
2
18.8 gram SiO
2
13.1 gram NaOH
100 gram H
2O
Wherein: Ti/Si=0.24
Na/Si＝1.0
H
2O/Si＝18
Above-mentioned reactant feed in the reactor of packing into, 240 ℃ of following crystallization 10 days, obtains the ETS-4 crystal after electronic mixing.Its X-ray powder diffraction spectrogram (XRD) is as shown in the table: d (A) I/I
011.6 1006.9 945.27 284.45 393.61 193.45 283.38 313.07 922.98 812.90 472.76 282.64 222.59 582.43 28
Its main d value is identical with table 3.
Synthesizing of example 5. ST-30 HTS
Reactant feed is as follows:
5.9 gram TiO
2
18.8 gram SiO
2
25.1 gram NaOH
100 gram H
2O
Wherein: Ti/Si=0.24
Na/Si＝2.0
H
2O/Si＝18
Above-mentioned reactant feed in the reactor of packing into, 240 ℃ of following crystallization 7 days, obtains the ST-30 crystal after electronic mixing.Its X-ray powder diffraction spectrogram (XRD) is as shown in the table: d (A) I/I
014.81 1004.88 144.42 154.32 94.05 83.78 143.25 103.04 432.74 322.57 112.45 11
Its main d value is identical with table 2.
The absorption property of example 6. ST-16 HTS
ST-16 crystalline absorption property is measured on U.S. Cahr-2000 vacuum electronic balance.Sample, is measured in balance system after 5 hours through 300 ℃ of burnings.Its adsorptive capacity to water is (weight percent) 13.1%.
ST series molecular sieve crystal of the present invention has bigger uniform pore size and higher thermostability, is suitable for the application at aspects such as absorption, ion-exchange and catalysis.The preparation method of ST series molecular sieve crystal of the present invention is owing to the popularity of material, and pH value wide ranges can be synthesized under greater than 13 condition, thereby is suitable for producing.
Claims (5)
1. titanium silicate zeolite molecular sieve crystal, its chemical formula is
xM
2/nO：TiO
2：ySiO
2：ZH
2O
Wherein M is that electric charge is a kind of positively charged ion of monovalence metal, divalent metal, ammonium of n etc. or cationic mixture more than two kinds, x=0.5-5, y=1-50, z=0-100: it is characterized in that this crystal is ST-16 or ST-30, its characteristic X-ray powder spectrum is as follows when being 0～40 ° at 2 θ angles:
XRD powder diffraction data and the relative intensity of ST-16
Main d value (dust) I/I
0
10.72±0.5 S-VS
5.35±0.5 VS
4.33±0.3 M-S
3.57±0.3 S-VS
3.49±0.3 M
3.21±0.3 M
3.15±0.3 M-S
2.56±0.3 M-S
XRD powder diffraction data and the relative intensity of ST-30
Main d value (dust) I/l
0
14.81±0.5 VS
4.88±0.5 W-M
4.42±0.5 W-M
3.78±0.3 W-M
3.04±0.3 S
2.74±0.3 S
Wherein:
VS＝50-100
S＝30-70
M＝15-50
W＝5-30
2. the preparation method of claim 1 titanium silicate zeolite molecular sieve crystal, its process are the hydrothermal crystallizing reaction, and material comprises silicon source, titanium source, alkali metal hydroxide and water etc., and the mole ratio range of each material is as follows:
SiO
2/TiO
2：1-60
H
2O/SiO
2：3-3000
Mn/SiO
2：0.001-10
Wherein M is that valency is a kind of positively charged ion of monovalence metal, divalent metal, ammonium of n etc. or cationic mixture more than two kinds, and temperature of reaction is 100 ℃ to 300 ℃, and the reaction times is 4 hours to 50 days; Resultant is after cooling, filtration, washing, and is at room temperature dry; It is characterized in that said titanium source is titanic compound; The pH value of reaction mixture is 12.5～14.
3. press the preparation method of the described titanium silicate zeolite molecular sieve crystal of claim 2, it is characterized in that said titanium source comprises titanium dioxide, titanium tetrachloride, titanyl sulfate, tetrabutyl titanate, titanium ethanolate, said silicon source comprises silicon-dioxide, water glass, silicon sol, water glass.
4. must ask the preparation method of 2 or 3 described titanium silicate zeolite molecular sieve crystals by power, it is characterized in that the mole ratio range that each material represents with oxide compound is as follows:
SiO
2/TiO
2：2-10
H
2O/SiO
2：10-100
Mn/SiO
2：0.3-0.6
Products therefrom is a ST-16 titanosilicate molecular sieve crystal.
5. by the preparation method of claim 2 or 3 described titanium silicate zeolite molecular sieve crystals, it is characterized in that the mole ratio range that each material represents with oxide compound is as follows:
SiO
2/TiO
2：5-10
H
2O/SiO
2：10-100
Mn/SiO
2：1.5-2.0
Products therefrom is a ST-30 titanosilicate molecular sieve crystal.
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|---|---|---|---|---|
| CN1089279C (en) * | 1998-09-17 | 2002-08-21 | 中国石油化工集团公司 | Synthesis of titania-silica molecular sieve |
| CN100457622C (en) * | 2001-12-28 | 2009-02-04 | 大连理工大学 | Prepn. of small-grain Ti-Si molecular sieve in cheap hydrothermal system and its application |
| CN103420392B (en) * | 2012-05-23 | 2016-01-13 | 中国石油化工股份有限公司 | Containing the HTS and its preparation method and application of rare earth |
| CN103395800B (en) * | 2013-07-19 | 2014-12-10 | 吉林大学 | Phosphorous acid titanium with three-dimensional open-framework structure and preparation method thereof |
| JP6025795B2 (en) * | 2014-10-02 | 2016-11-16 | 日本化学工業株式会社 | Method for producing crystalline silicotitanate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4853202A (en) * | 1987-09-08 | 1989-08-01 | Engelhard Corporation | Large-pored crystalline titanium molecular sieve zeolites |
| EP0372132A1 (en) * | 1988-12-06 | 1990-06-13 | Engelhard Corporation | Small-pored crystalline titanium molecular sieve zeolites |
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1995
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4853202A (en) * | 1987-09-08 | 1989-08-01 | Engelhard Corporation | Large-pored crystalline titanium molecular sieve zeolites |
| US5011591A (en) * | 1987-09-08 | 1991-04-30 | Engelhard Corporation | Large-pored crystalline titanium molecular sieve zeolites |
| EP0372132A1 (en) * | 1988-12-06 | 1990-06-13 | Engelhard Corporation | Small-pored crystalline titanium molecular sieve zeolites |
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