CN1207196C - Nano grade titanium silicon molecular sieve and its synthesis technology - Google Patents
Nano grade titanium silicon molecular sieve and its synthesis technology Download PDFInfo
- Publication number
- CN1207196C CN1207196C CN 01144586 CN01144586A CN1207196C CN 1207196 C CN1207196 C CN 1207196C CN 01144586 CN01144586 CN 01144586 CN 01144586 A CN01144586 A CN 01144586A CN 1207196 C CN1207196 C CN 1207196C
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- value
- sodium hydroxide
- silicon molecular
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 23
- 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 23
- 230000015572 biosynthetic process Effects 0.000 title abstract description 7
- 238000003786 synthesis reaction Methods 0.000 title abstract description 7
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 title abstract 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 9
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 3
- 239000007864 aqueous solution Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000084 colloidal system Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910004339 Ti-Si Inorganic materials 0.000 claims description 8
- 229910010978 Ti—Si Inorganic materials 0.000 claims description 8
- 239000012265 solid product Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 3
- 238000002050 diffraction method Methods 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 230000005855 radiation Effects 0.000 abstract description 4
- 230000002285 radioactive effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract description 2
- 230000002349 favourable effect Effects 0.000 abstract 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 abstract 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 abstract 1
- 210000002858 crystal cell Anatomy 0.000 abstract 1
- 238000005192 partition Methods 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 229910052792 caesium Inorganic materials 0.000 description 6
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052712 strontium Inorganic materials 0.000 description 6
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 238000003483 aging Methods 0.000 description 1
- 230000032683 aging Effects 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000012905 visible particle Substances 0.000 description 1
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention relates to a nanometer titanium-silicon molecular sieve and a synthesizing technology thereof, particularly to a titanium-silicon molecular sieve and a preparing method thereof. The molar composition of the molecular sieve is Na<1(+/-)X>Ti<1.5(+/-)Y>Si<1(+/-)Z>O5, wherein the value of X is from 0.01 to 0.2, the value of Y is from 0.1 to 0.5, and the value of Z is from 0.1 to 0.2. XRD powder diffraction peak (2theta) data comprises 11.40(+/-)0.2, 27.8(+/-)0.2, 36.2(+/-)0.5 and 46.8(+/-)0.5, and crystal cell parameters are: a=b=8.000(+/-)0.500 A, c=12.000(+/-)0.500 A. Crystal particles are tetragonal in shape and are in the size of 10 to 20 nm. Tetrabutyl titanate or tetraisopropyl titanate, ethyl orthosilicate, sodium hydroxide and water are used as raw materials, and a sol-gel method and a hydrothermal synthesizing method are jointly adopted to prepare the nanometer titanium-silicon molecular sieve. With the advantages of fine crystal particles, high reaction activity, no need of expensive templates, low synthesis cost, high exchange capacity on radioactive elements and heavy metal elements, favorable thermal stability and favorable radiation resistant performance, the molecular sieve can be widely used for removing heavy metal pollutants and radioactive pollutants in environment, purifying nuclides, etc.
Description
Technical field
The present invention relates to a kind of HTS and synthesis technique thereof, this molecular sieve is mainly used in to be removed radioactive pollutant and the heavy metal contaminants in the environment or carries out the nucleic purification, belongs to environment protection and applied chemistry technical field.
Background technology
Molecular sieve is owing to have uniform microvoid structure and can select suitable molecule to enter its skeleton inside, therefore separates with fluid molecule at gas, aspects such as ion-exchange and catalyzed reaction have wide industrial to use.Along with the continuous increase of industrial requirement, people are carrying out new design and synthetic for the skeleton structure of molecular sieve and the size shape in duct etc., and the kind of molecular sieve constantly increases, and its structure is abundanter and its performance is also more complete.The research development in recent years of HTS is very fast, at the initial stage eighties, Taramasso (the TaramassoM of Italy Enichem company, PeregoG, NotariB, US4410501,1983) etc. people's reported first synthesize the titaniferous molecular sieve TS-1 of a kind of skeleton (MFI type), because it has excellent catalytic performance in the multiple organism selective oxidation reaction that has rare hydrogen peroxide (30wt%) to participate in, be considered to a milestone of molecular sieve research field.People report in succession and synthesize Ti-β (BEA type), Ti-ZSM-12 (MTW type), Ti-M (MOR type), Ti-MCM-41 (hexagonal system), Ti-MCM-48 (isometric system) and Ti-HMS HTS such as (hexagonal systems) subsequently.
The synthetic method of HTS mainly contains following two kinds at present:
(1) isomorphous substitution method
Isomorphous substitution method is with TiCl
4For the vapor phase process in titanium source and with (NH
4)
2TiF
6Deng the liquid phase method that is the titanium source, claim gas-solid phase isomorphous replacement process (Thangaraj A, Kumar R, et al.Appl.Catal., 1990,57,1～3) again.This method is raw materials used to be generally high silicon or the total silicon zeolite molecular sieve is made silicon source material, with TiCl
4Be the titanium source material.Isomorphous substitution is reflected in the silica tube fixed-bed reactor and carries out, and uses N
2Gas is with TiCl
4Bring reactor into, under 400～700 ℃, carry out the isomorphous substitution certain hour, can obtain HTS (TS), do not change the skeleton structure of zeolite in the isomorphous substitution process, do the silicon source with ZSM-5, ZSM-11 type supersiliceous zeolite molecular sieve with MFI, MEL structure and carry out isomorphous substitution and can obtain corresponding TS-1 and TS-2.The shortcoming of this synthetic method mainly contains the following aspects: the service temperature height, and power consumption is big; Belong to gas-solid and operate mutually, the difficult control of reaction, complex process; To the equipment requirements height, reliability is little; Sample crystal grain is big; Also be difficult to realize industrialization at present.
(2) hydrothermal synthesis method
Hydrothermal synthesis method claims direct synthesis technique again, is present the most frequently used HTS synthetic method.Generally mix by a certain percentage with template, carry out hydrothermal mutually and synthetic by titanium source and silicon source material.Its process normally stirs above-mentioned mixed sols under 70～90 ℃, behind the hydrolysis certain hour, go in the autoclave, in 90 ℃ of ageings 1～2 day, crystallization 2～10 days under 170 ℃ of autogenous pressures again, after the gained crystal washed, filters, dries,, promptly get the former powder of HTS (Reddy J S at 550 ℃ of following roasting 5～10h, Kumar R.Zeolites, 1992,12,95～100).
Used silicon source material is tetraethoxy (TEOS), butyl silicate (TBOS) in the synthesis material; Titanium source material has positive titanium ethanolate (TEOT), positive butyl (tetra) titanate (TBOT); Template is used TPAOH (TPAOH), TBAH (TBAOH) etc. usually.The difference of template causes the difference (Esposito A, Taramasso M, etal.USP4396783,1983) of crystalline structure.When using TPAOH to make template, the synthetic HTS has the MFI structure of ZSM-5 type, i.e. TS-1 (claiming Ti-ZSM-5 again); When being template with TBAOH, the synthetic HTS has the MEL structure of ZSM-11 zeolite type, i.e. TS-2 (claiming Ti-ZSM-11 again).
The shortcoming of this synthetic method mainly contains following several respects at present:
(1) needs to use in a large number the TPAOH template of expensive price in the building-up process.
(2) the HTS particle diameter is more little, and activity is good more.Therefore it is most important to control the HTS grain size, generally should be less than 0.2 μ m, and still the HTS particle diameter that synthesizes at present is many more than 1 μ m.
(3) loading capacity is low, and thermostability and radiation-resistant property are poor.
Summary of the invention
Purpose of the present invention and task provide a kind of Ti-Si nano molecular sieve and synthesis technique thereof, make it in synthetic, need not to re-use expensive template, the synthetic zeolite crystal is tiny, and radioelement and heavy metal element had very high exchange capacity, thermostability and radiation-resistant property are good.
Ti-Si nano molecular sieve of the present invention is characterized in that this Ti-Si nano molecular sieve demonstrates following physicochemical characteristic:
(1) its mole consists of Na
1 ± XTi
1.5 ± YSi
1 ± ZO
5, wherein the X value is 0.01～0.2, and the Y value is 0.1～0.5, and the Z value is 0.1～0.2;
(2) XRD powdery diffractometry peak (2 θ) data are: 11.40 ± 0.2,27.8 ± 0.2,36.2 ± 0.5,46.8 ± 0.5;
(3) unit cell parameters is a=b=8.000 ± 0.500 , c=12.000 ± 0.500 ;
(4) crystal grain is square, is of a size of 10～20 nanometers
(5) outward appearance: white powder.
Above-mentioned nano silicone titanium molecular sieve synthetic process is as follows: with titanium isopropylate ([(CH
3)
2CHO]
4Ti), 5%～15% tetraethoxy ([C
2H
5]
4SiO
4), 1%～10% sodium hydroxide, 65%～80% water is synthetic raw material (above all be weight percentage, starting material are analytical pure), adopts sol-gel method and hydrothermal synthesis method to finish jointly, its synthetic in turn including the following steps:
(1) by weight percentage the sodium hydroxide of 65%～80% water and 1%～10% is mixed with the aqueous solution of sodium hydroxide;
(2) under continue stirring, be that 5%～15% titanium isopropylate is added drop-wise in the aqueous solution of sodium hydroxide with weight percent, the pH value of solution is controlled at 10～12;
(3) be that 5%～15% tetraethoxy is added drop-wise in the above-mentioned mixed solution with 0.01 milliliters/second～0.1 milliliters/second speed with weight percent, obtain white colloid;
(4) white colloid is transferred in the easy reaction autoclave, carried out hydro-thermal reaction 3～10 days, obtain solid product at 140～250 ℃;
(5) above-mentioned solid product is used acetone and deionized water wash respectively, obtain the white powder sample in drying in oven after the centrifugation.
The present invention synthesizes a kind of Ti-Si nano molecular sieve by using the better starting material of hydrolysis property, adjustment raw material ratio and interpolation order and methods such as pH value of solution value, control rate of addition and hydro-thermal synthesis temperature.This zeolite crystal is tiny, between 10～20nm, has greatly improved the reactive behavior of product; In synthetic, need not to re-use expensive template in addition, significantly reduced synthetic cost; This kind HTS has very high exchange capacity to heavy metal element and radioelement, and thermostability and radiation-resistant property are good, can be widely used in removing heavy metal contaminants and radioactive pollutant and nucleic purification etc. in the environment.
Description of drawings
Fig. 1 is SEM figure of the present invention.Sample particle is very thin as can be seen among the figure, and powder is of a size of nano level.Because nanocrystal has bigger specific surface area and surface free energy, therefore be aggregating state basically, so can not from the SEM photo, find out the concrete pattern of particulate.
Fig. 2 is TEM figure of the present invention.As can be seen from the figure visible particle is the cubic crystal grain of rule, and particle grain size is about 10～20nm.
Embodiment
Embodiment 1:
6% sodium hydroxide joined in 76% the water, under continuing to stir, earlier 8% titanium isopropylate is added drop-wise in the aqueous solution of sodium hydroxide, again 10% tetraethoxy is added drop-wise in the mixed solution with 0.06ml/s speed, obtain white colloid.Then colloid is transferred in the simple and easy autoclave, under 190 ℃ temperature condition, carried out hydro-thermal reaction 4 days.The solid product that obtains is used acetone and deionized water wash respectively, obtains required sample in drying in oven after the centrifugation.
Adopt atomic absorption spectrum (AAS) to measure this sample at 0.1M HNO
3, the 100ppm caesium the aqueous solution in, can be to the partition ratio of caesium up to 36500ml/g; In the aqueous solution of 0.1M NaOH, 100ppm strontium, can be to the partition ratio of strontium up to 9000ml/g; In the aqueous solution of 0.1M NaOH, 100ppm lithium, can reach 800ml/g to the partition ratio of lithium.
Embodiment 2:
2% sodium hydroxide joined in 80% the water, under continuing to stir, earlier 5% titanium isopropylate is added drop-wise in the aqueous solution of sodium hydroxide, again 13% tetraethoxy is added drop-wise in the mixed solution with 0.02ml/s speed, obtain white colloid.Then colloid is transferred in the easy reaction still, under 140 ℃ of temperature condition, carried out hydro-thermal reaction 10 days.The solid product that obtains is used acetone and deionized water wash respectively, obtains required sample in drying in oven after the centrifugation.
Adopt atomic absorption spectrum (AAS) to measure this sample at 0.1M HNO
3, the 100ppm caesium the aqueous solution in, can be to the partition ratio of caesium up to 10000ml/g.In the aqueous solution of 0.1M NaOH, 100ppm strontium, can be to the partition ratio of strontium up to 15000ml/g.In the aqueous solution of 0.1M NaOH, 100ppm lithium, can reach 600ml/g to the partition ratio of lithium.
Embodiment 3:
10% sodium hydroxide joined in 70% the water, under continuing to stir, earlier 15% titanium isopropylate is added drop-wise in the aqueous solution of sodium hydroxide, again 5% tetraethoxy is added drop-wise in the mixed solution with 0.09ml/s speed, obtain white colloid.Then colloid is transferred in the easy reaction still, under 250 ℃ of temperature condition, carried out hydro-thermal reaction 4 days.The solid product that obtains is used acetone and deionized water wash respectively, obtains required sample in drying in oven after the centrifugation.
Adopt atomic absorption spectrum (AAS) to measure this sample at 0.1M HNO
3, the 100ppm caesium the aqueous solution in, can be to the partition ratio of caesium up to 11000ml/g.In the aqueous solution of 0.1M NaOH, 100ppm strontium, can be to the partition ratio of strontium up to 8000ml/g.In the aqueous solution of 0.1M NaOH, 100ppm lithium, can reach 1033ml/g to the partition ratio of lithium.
Claims (2)
1. Ti-Si nano molecular sieve is characterized in that this Ti-Si nano molecular sieve demonstrates following physicochemical characteristic:
(1) its mole consists of Na
1 ± XTi
1.5 ± YSi
1 ± ZO
5, wherein the X value is 0.01～0.2, and the Y value is 0.1～0.5, and the Z value is 0.1～0.2;
(2) XRD powdery diffractometry peak (2 θ) data are: 11.40 ± 0.2,27.8 ± 0.2,36.2 ± 0.5,46.8 ± 0.5;
(3) unit cell parameters is a=b=8.000 ± 0.500 , c=12.000 ± 0.500 ;
(4) crystal grain is square, is of a size of 10～20 nanometers;
(5) outward appearance: white powder.
2. synthetic method of Ti-Si nano molecular sieve according to claim 1, its method in turn includes the following steps:
(1) by weight percentage the sodium hydroxide of 65%～80% water and 1%～10% is mixed with the aqueous solution of sodium hydroxide;
(2) under continue stirring, be that 5%～15% titanium isopropylate is added drop-wise in the aqueous solution of sodium hydroxide with weight percent, the pH value of solution is controlled at 10～12;
(3) be that 5%～15% tetraethoxy is added drop-wise in the above-mentioned mixed solution with 0.01 milliliters/second～0.1 milliliters/second speed with weight percent, obtain white colloid;
(4) white colloid is transferred in the easy reaction autoclave, carried out hydro-thermal reaction 3～10 days, obtain solid product at 140～250 ℃;
(5) above-mentioned solid product is used acetone and deionized water wash respectively, obtain the white powder sample in drying in oven after the centrifugation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01144586 CN1207196C (en) | 2001-12-21 | 2001-12-21 | Nano grade titanium silicon molecular sieve and its synthesis technology |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01144586 CN1207196C (en) | 2001-12-21 | 2001-12-21 | Nano grade titanium silicon molecular sieve and its synthesis technology |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1426962A CN1426962A (en) | 2003-07-02 |
| CN1207196C true CN1207196C (en) | 2005-06-22 |
Family
ID=4677695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01144586 Expired - Fee Related CN1207196C (en) | 2001-12-21 | 2001-12-21 | Nano grade titanium silicon molecular sieve and its synthesis technology |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1207196C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321062C (en) * | 2005-06-23 | 2007-06-13 | 复旦大学 | Process for synthesizing microporous titanium silicon fluorite ETS-10 |
| CN105540943B (en) * | 2015-10-30 | 2018-03-20 | 中国石油化工股份有限公司 | The processing method of silicon-containing wastewater and the Application way of silicon-containing wastewater and molecular sieve preparation method |
| CN107867698A (en) * | 2017-11-20 | 2018-04-03 | 广西师范大学 | A kind of preparation method using the molecular sieves of sol-gal process selectivity synthesis pure phase MCM 48 |
| CN108793179B (en) * | 2017-12-15 | 2021-04-09 | 中国科学院大连化学物理研究所 | Titanium-silicon molecular sieve and preparation and application thereof |
-
2001
- 2001-12-21 CN CN 01144586 patent/CN1207196C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1426962A (en) | 2003-07-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Ren et al. | A seed surface crystallization approach for rapid synthesis of submicron ZSM-5 zeolite with controllable crystal size and morphology | |
| CN101062475B (en) | Metasilicate hole material assembled nano titanium oxide composite material and preparation method thereof | |
| CN1226874A (en) | Preparation of Y zeolite | |
| CN105347359A (en) | Synthesis and application of zeolite molecular sieve with solid acid contained in porous channels | |
| CN104707648B (en) | A kind of ion hot post-synthesis of complex functionality hetero-atom molecular-sieve | |
| CN106044793A (en) | Method for synthesis of nanometer ZSM-5 molecular sieve from mother liquor flocculate | |
| CN109502601B (en) | Titanium-silicon molecular sieve and preparation method and application thereof | |
| CN1168860A (en) | Process for prepn. of crystalline microporous and mesoporous metal silicates, products obtainable by said process and their use | |
| CN102674389B (en) | Preparation method of titanium-containing nano-mordenite molecular sieve | |
| CN100488621C (en) | Method for synthesizing soluble titanium dioxide nano crystal in low temperature | |
| CN108383131B (en) | Method for preparing different zeolites from fly ash by solid phase conversion method | |
| CN1207196C (en) | Nano grade titanium silicon molecular sieve and its synthesis technology | |
| CN1235799C (en) | Method for synthesizing new titanium-silicone metapore molecular sieve | |
| CN112158856B (en) | Method for preparing Ti-MWW molecular sieve | |
| Xia et al. | Preparation and catalysis in epoxidation of allyl chloride of zeolitic titanosilicate-1/smectitic clay minerals | |
| JPS62216914A (en) | Zeolite and manufacture | |
| CN110745864B (en) | Perovskite type lanthanum titanate material and preparation method and application thereof | |
| CN1035668C (en) | Method No.1 for synthesizing beta zealite | |
| CN101863490A (en) | Method for synthesizing full-silicon beta zeolite with small crystal grains | |
| CN108298551A (en) | A kind of preparation method of core-shell structure copolymer-nuclear structure mesoporous molecular sieve nanocomposite | |
| CN105621449A (en) | NaY type molecular sieve and preparation method thereof | |
| Chatterjee et al. | Synthesis, characterization and catalytic properties of two novel vanado-aluminosilicates with EU-1 and ZSM-22 structures | |
| CN113830780B (en) | MTT molecular sieve and synthesis method and application thereof | |
| CN105084388A (en) | Method for preparing and modifying Y-type molecular sieve | |
| CN1089279C (en) | Synthesis of titania-silica molecular sieve |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |