CN101182005A - Method for preparing titanium-containing zeolite molecular sieve by natural zeolite modification - Google Patents
Method for preparing titanium-containing zeolite molecular sieve by natural zeolite modification Download PDFInfo
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- CN101182005A CN101182005A CNA2007101565945A CN200710156594A CN101182005A CN 101182005 A CN101182005 A CN 101182005A CN A2007101565945 A CNA2007101565945 A CN A2007101565945A CN 200710156594 A CN200710156594 A CN 200710156594A CN 101182005 A CN101182005 A CN 101182005A
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- zeolite
- molecular sieve
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- titaniferous
- natural zeolite
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- 239000010457 zeolite Substances 0.000 title claims abstract description 105
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 104
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000010936 titanium Substances 0.000 title claims abstract description 50
- 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 32
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 31
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000012986 modification Methods 0.000 title claims abstract description 20
- 230000004048 modification Effects 0.000 title claims abstract description 20
- 238000005342 ion exchange Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000011282 treatment Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000006467 substitution reaction Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 20
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- 229910052680 mordenite Inorganic materials 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000007790 solid phase Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000005649 metathesis reaction Methods 0.000 claims description 8
- 238000012545 processing Methods 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 claims description 6
- 229910001603 clinoptilolite Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 150000003863 ammonium salts Chemical class 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 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 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 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 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 238000007669 thermal treatment Methods 0.000 claims description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- -1 through ion-exchange Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 125000005842 heteroatom Chemical group 0.000 abstract description 5
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003252 repetitive effect Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 235000008575 Pinus pinea Nutrition 0.000 description 1
- 240000007789 Pinus pinea Species 0.000 description 1
- 229910004339 Ti-Si Inorganic materials 0.000 description 1
- 229910010978 Ti—Si Inorganic materials 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- SJSWRKNSCWKNIR-UHFFFAOYSA-N azane;dihydrochloride Chemical compound N.Cl.Cl SJSWRKNSCWKNIR-UHFFFAOYSA-N 0.000 description 1
- AOFSUBOXJFKGAZ-UHFFFAOYSA-O azanium nitric acid nitrate Chemical compound [NH4+].O[N+]([O-])=O.[O-][N+]([O-])=O AOFSUBOXJFKGAZ-UHFFFAOYSA-O 0.000 description 1
- HNWVZTDQFLHVOD-UHFFFAOYSA-N azanium oxalic acid chloride Chemical compound C(C(=O)O)(=O)O.[Cl-].[NH4+] HNWVZTDQFLHVOD-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- AWADHHRPTLLUKK-UHFFFAOYSA-N diazanium sulfuric acid sulfate Chemical compound [NH4+].[NH4+].OS(O)(=O)=O.[O-]S([O-])(=O)=O AWADHHRPTLLUKK-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 1
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- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
The invention relates to a method used for preparing zeolite molecular sieve containing titanium by modification of natural zeolite, and uses the natural zeolite as a raw material and the zeolite molecular sieve containing titanium is obtained through ion exchange, chemical dealumnization treatment and gas-solid isomorphous substitution reaction. The mole ratio of Si and Ti of molecular sieve skeleton is 20 to 100. The invention brings metallic titanium which has special catalytic performance to the skeleton of the natural zeolite, which greatly promotes grade of natural zeolite products, widens the application range of the natural zeolite and provides a way with low cost, convenient operation and environment protection to prepare heteroatom zeolite molecular sieve.
Description
Technical field
The invention belongs to natural zeolite material modification technical field, relate to the method that the natural zeolite modification prepares hetero-atom molecular-sieve, particularly be specifically related to a kind of method of preparing titanium-containing zeolite molecular sieve by natural zeolite modification.
Background technology
Zeolite is that a class has the cage type of rule or the silicon aluminate crystal of pore passage structure.Just because of having the pore passage structure of this rule, spaciousness, zeolite is widely used in aspects such as catalysis, absorption, separation and Subjective and Objective assembling.Zeolite can be divided into natural zeolite and artificial synthetic zeolite.Synthetic zeolite has been compared many advantages (as the purity height, the aperture is even, ion-exchange performance good) with natural zeolite, but the production of synthetic zeolite investment is big, and cost height, mother liquor are difficult to reasons such as recovery, and it is applied on a large scale and is subjected to certain limitation.For example Ti-Si zeolite TS-1 has good selective oxidation catalytic performance and photocatalysis performance, but its price is up to 1,000,000 yuan/ton.
Natural zeolite is that the mineralogist A.F.Cronsted by Sweden in 1756 at first finds, compares with synthetic zeolite, and its reserves are abundant, cost is low, and the cost that extracts " Industrial materials " from the natural zeolite rich ore only is 1% of a synthetic zeolite.China has in a large number very fine zeolite ore resources, and explored ore deposit point has surpassed 400 places, and total reserves reaches 4,000,000,000 tons, and reserves come out at the top in the world.Thereby the application problem of natural zeolite caused people's extensive attention, and carried out considerable research.Yet, but up to the present, the thumping majority natural zeolite is only used as primary products, as additive (Yin Yongzhi, CN1433992A, Wang Guilin, CN1121495, Chen Guanyi as material of construction; Zhang Xiumei etc., CN1724445), adsorbent (Chen Dongxing, CN1080209, Ma Jianzhong, CN1126094), and soil improvement agent (Cao Xiaoyan, CN1398950A, Zhang Xueying; Ma Chunmin, CN1629252) grade side.In order to improve the grade of natural zeolite product, late nineteen eighties, with ion exchange method the Jinyun mordenite is carried out modification, successfully develop NZP series organic exhaust gas and burned cleaning catalyst (CN1034319A such as Zheng Xiaoming, parasol pine longevity, CN1034494A), and realized the industrialization of this product having obtained good economic benefit and social benefit.Zhu Linzhang etc. are processed into the agent of freonll-11 highly effective drying with the Jinyun zeolite.In addition, high value-added product is very few.Therefore; the physicochemical property and the reserves that how to make full use of China's natural zeolite uniqueness enrich and cheap advantage; strengthen the study on the modification of natural zeolite; making it is the problem that needs to be resolved hurrily from the high added value new catalytic material that more single cement building material additive changes into fields such as can be used for Industrial Catalysis, environment protection, also is to realize natural zeolite resource deep development and form the key that the catalytic material industry makes a breakthrough.
Owing to the duct of natural zeolite is twisted easily usually, stopped up and with impurity, must the certain modification of process handle before the use.Usually take method of modifying such as thermal treatment, acid treatment and salt processing; through these processing; the purity of natural zeolite, the smoothness in duct and absorption property be improved significantly, but oxidation-reduction quality, solid acid alkalescence and catalytic performance also far can not satisfy industrial production and requirement on environmental protection.
Summary of the invention
The objective of the invention is with the natural zeolite is raw material, adopts gas-solid phase isomorphous method of replacement that specific metallic element titanium is incorporated on the skeleton of natural zeolite, to be prepared into the heteroatoms zeolite molecular sieve with special catalytic performance.The production cost of the hetero-atom molecular-sieve of this method preparation is low, simple to operate, as commercial catalysts and environment functional material vast market prospect is arranged.
Natural zeolite modification provided by the invention prepares the method for titaniferous zeolite molecular sieve, with the natural zeolite is raw material, through ion-exchange, chemical dealuminization is handled, steps such as gas-solid phase isomorphous replacement(metathesis)reaction are introduced zeolite framework with the metallic element titanium, obtain titaniferous zeolite molecular sieve, the Si of framework of molecular sieve and the mol ratio of Ti (Si/Ti) are 20～100, and preparation process is as follows:
● with natural zeolite, adopting ion-exchange to handle, is that the ammonium salt of 0.1～1mol/L is as ion-exchanger with concentration, the solid-to-liquid ratio of zeolite and ion-exchanger is 1: 5～25, and the exchange temperature is 70～100 ℃, 1～5 hour swap time, exchange number of times 1～4 time, washing, oven dry;
● handle with the chemical dealuminization method, as dealumination agent, acid concentration is 2～12mol/L with mineral acid or organic acid, zeolite is 1: 5～25 with the solid-to-liquid ratio of acid, and the dealuminzation temperature is 70～100 ℃, and the dealuminzation time is 1～8 hour, the dealuminzation number of times is 1～5 time, washing, oven dry;
● gas-solid phase isomorphous replacement(metathesis)reaction; will be under the protection of zeolite parent after ion-exchange and the chemical dealuminization processing at inert atmosphere; 100～200 ℃ of following thermal treatments 0.5～6 hour; with rare gas element the titanium source is brought in the reactor again; under 300～800 ℃ temperature, carried out gas-solid phase replacement(metathesis)reaction 0.5～20 hour; cooling, washing, drying obtain titaniferous zeolite molecular sieve.
The natural zeolite of indication of the present invention is meant natural mordenite or natural clinoptilolite.
The prepared titanium-containing zeolite molecular sieve of the present invention is meant titaniferous mordenite molecular sieve or titaniferous clinoptilolite molecular sieve, and the Si of zeolite molecular sieve skeleton and the mol ratio of Ti (Si/Ti) are 20～100;
The used ion-exchanger ammonium salt of the present invention comprises: ammonium chloride (NH
4Cl), ammonium nitrate (NH
4NO
3) or ammonium sulfate ((NH
4)
2SO
4) etc., concentration is 0.5～1mol/L, and the solid-liquid preferred proportion of natural zeolite and ion-exchanger ammonium salt is 1: 10～20, and the preferable reaction conditions of ion exchange treatment is: the exchange temperature is 80 ℃, 4 hours swap times, exchanges 3 times.
The selected dealumination agent of the present invention is mainly mineral acid and organic acid: comprise hydrochloric acid (HCl), nitric acid (HNO
3), sulfuric acid (H
2SO
4), oxalic acid (COOH)
2Deng, the concentration of acid is 2～12mol/L, and natural zeolite is 1: 5～25 with the solid-to-liquid ratio of acid, and the chemical dealuminization method is handled preferable reaction conditions and is: temperature is 100 ℃, and the dealuminzation time is 8 hours, the dealuminzation number of times is 4 times.
The selected rare gas element of the present invention is nitrogen, argon gas or helium.
The selected titanium source of the present invention comprises: titanium tetrachloride (TiCl
4), tetrabutyl titanate ((C
4H
9O)
4Ti), isopropyl titanate ((C
3H
7O)
4Ti) etc., with inert atmosphere with titanium tetrachloride (TiCl
4), tetrabutyl titanate ((C
4H
9O)
4Ti), isopropyl titanate ((C
3H
7O)
4Ti) etc. the steam in titanium source is brought in the quartz reactor and is carried out gas-solid isomorphous replacement(metathesis)reaction mutually with pretreated parent.
Gas-solid phase isomorphous replacement(metathesis)reaction of the present invention; will be under the protection of zeolite parent at inert atmosphere of ion exchange treatment and chemical dealuminization processing; speed with 1～5 ℃/min is warming up to 100～200 ℃ from room temperature; thermal treatment is 0.5～6 hour under this temperature; speed with 5 ℃/min is warming up to 300 ℃～800 ℃ again; with rare gas element the titanium source is brought in the reactor, under 300～800 ℃ temperature, carried out gas-solid phase isomorphous replacement(metathesis)reaction 0.5～20 hour, cooling, washing, drying.
The invention has the beneficial effects as follows with existing natural zeolite modification technology and compare, because will have the metallic element titanium of special catalytic performance is incorporated on the skeleton of natural zeolite by isomorphous substitution, changed the one-tenth element of natural zeolite skeleton group, thereby the zeolite molecular sieve product that the present invention obtains has good oxidation reductibility, solid acid alkalescence and photocatalysis performance, thereby greatly improved the natural zeolite value-added content of product, can be used as commercial catalysts and environment functional material; The present invention simultaneously also provides a kind of preparation cost the method for preparing HTS cheap, simple to operate, for the hetero-atom molecular-sieve catalyst heavy industrialization is provided by the practicable approach that provides.
Embodiment
Embodiment 1
● the 30g natural mordenite zeolite is placed in the 500ml three footpath bottles, add 300ml, the NH of 0.8M
4Cl solution stirred 2 hours down at 80 ℃, washing, oven dry, repetitive operation 2 times;
● get natural mordenite zeolite that 25g handles through (1) in 500ml three footpath bottles, add 300ml, the HCl solution of 6M stirred 8 hours down at 100 ℃, washing, oven dry, repetitive operation 3 times;
● get 3g in the sample of (2) processing is packed crystal reaction tube into, speed with 5 ℃/min rises to 120 ℃ from room temperature, at 120 ℃ with nitrogen treatment 2 hours, speed with 2 ℃/min rises to 400 ℃ from 120 ℃ again, bring the steam of titanium tetrachloride into crystal reaction tube with nitrogen, and reacted 8 hours down, stop logical titanium tetrachloride vapors at 400 ℃, continue to purge 3 hours under this temperature with nitrogen, cooling, washing, drying obtain the titanium-containing zeolite sieve sample;
● sample characterizes through powder x-ray diffraction analysis (XRD), and the XRD spectra of the sample of this law preparation is consistent with the absorption figure of the standard x RD spectrum of mordenite, shows the skeleton structure that still keeps natural zeolite with the sample of method for preparing; Si/Ti ratio in inductively coupled plasma (ICP) working sample is 80, and the uv-vis spectra of sample (UV-vis) figure has absorption at the 212nm place, show in the sample of this law preparation to contain titanium, and titanium has successfully entered the skeleton of mordenite.
Embodiment 2
● with embodiment 1;
● get the sample that 25g handles through (1), in 500ml three footpath bottles, add 300ml, the HCl solution of 8M stirred 6 hours down at 100 ℃, washing, oven dry, repetitive operation 3 times;
● get 3g in the sample of (1), (2) processing is packed crystal reaction tube into, temperature rise rate with 3 ℃/min is heated to 180 ℃ from 30 ℃, under this temperature, kept 2 hours, be raised to 500 ℃ with 5 ℃/min from 180 ℃ again, with argon gas the steam of isopropyl titanate is brought in the silica tube, reacted 10 hours down, continue under this temperature, to purge 3 hours with argon gas at 500 ℃, the titanium-containing zeolite sieve sample is washed, is drying to obtain in cooling; Obtain titaniferous mordenite sample; This sample is through phenetic analysis such as XRD, ICP and UV-Vis, and the result shows that titanium has successfully entered the skeleton of natural zeolite in the sample of preparation, and the ratio of the Si/Ti in the sample is 75.
Embodiment 3-6
Press embodiment 1 at the different ions exchanger, the Si/Ti ratio of the titanium-containing zeolite sieve sample of dealumination agent preparation sees Table 1
| Natural zeolite | Ion-exchanger | Dealumination agent | Solid-to-liquid ratio | Si/Ti |
| Natural mordenite zeolite | Ammonium chloride | Hydrochloric acid | 1∶5 | 80 |
| Using natural clinoptilolite | Ammonium chloride | Oxalic acid | 1∶25 | 90 |
| Using natural clinoptilolite | Ammonium sulfate | Sulfuric acid | 1∶10 | 85 |
| Natural mordenite zeolite | Ammonium nitrate | Nitric acid | 1∶15 | 85 |
Embodiment 7-10
See Table 2 by embodiment 1 at the Si/Ti ratio of the titanium-containing zeolite sieve sample of different chemical dealuminzation condition preparation
| Temperature of reaction (℃) | Reaction times (hour) | Reaction times | Si/Ti |
| 70 | 1 | 1 | 100 |
| 80 | 2 | 2 | 95 |
| 90 | 3 | 3 | 90 |
| 100 | 8 | 4 | 80 |
Embodiment 11-13
The Si/Ti ratio with the titanium-containing zeolite sieve sample of different titaniums source preparation by embodiment 1 sees Table 3
| The titanium source | Temperature of reaction (℃) | Reaction times (hour) | Si/Ti |
| Titanium tetrachloride | 500 | 8 | 75 |
| Tetrabutyl titanate | 500 | 8 | 90 |
| Isopropyl titanate | 500 | 8 | 80 |
Embodiment 14-20
Si/Ti ratio by the titanium-containing zeolite sieve sample of the different gas-solid phase conditions of replacement reaction preparation of embodiment 1 sees Table 4
| The titanium source | Temperature of reaction (℃) | Reaction times (hour) | Si/Ti |
| Titanium tetrachloride | 400 | 8 | 80 |
| Titanium tetrachloride | 400 | 15 | 70 |
| Titanium tetrachloride | 500 | 8 | 75 |
| Titanium tetrachloride | 500 | 15 | 65 |
| Titanium tetrachloride | 600 | 8 | 55 |
| Titanium tetrachloride | 600 | 15 | 40 |
| Titanium tetrachloride | 700 | 8 | 50 |
| Titanium tetrachloride | 700 | 15 | 55 |
| Titanium tetrachloride | 800 | 8 | 70 |
| Titanium tetrachloride | 800 | 15 | 80 |
Claims (9)
1. the method for a preparing titanium-containing zeolite molecular sieve by natural zeolite modification, it is characterized in that with the natural zeolite being raw material, through ion-exchange, chemical dealuminization is handled, gas one solid phase isomorphous substitution reactions steps is introduced zeolite framework with the metallic element titanium, obtains titaniferous zeolite molecular sieve, the Si of framework of molecular sieve and the mol ratio of Ti are 20～100, and preparation process is as follows:
● with natural zeolite, adopting ion-exchange to handle, is that the ammonium salt of 0.1～1mol/L is as ion-exchanger with concentration, the solid-to-liquid ratio of zeolite and ion-exchanger is 1: 5～25, and the exchange temperature is 70～100 ℃, 1～5 hour swap time, exchange number of times 1～4 time, washing, oven dry;
● handle with the chemical dealuminization method, as dealumination agent, acid concentration is 2～12mol/L with mineral acid or organic acid, zeolite is 1: 5～25 with the solid-to-liquid ratio of acid, and the dealuminzation temperature is 70～100 ℃, and the dealuminzation time is 1～8 hour, the dealuminzation number of times is 1～5 time, washing, oven dry;
● the reaction of gas one solid phase isomorphous substitution; will be through the zeolite parent after ion-exchange and the chemical dealuminization processing; under the protection of inert atmosphere,, with rare gas element the titanium source is brought in the reactor again 100～200 ℃ of following thermal treatments 0.5～6 hour; under 300～800 ℃ temperature; carried out gas one solid phase replacement(metathesis)reaction 0.5～20 hour, cooling, washing; drying promptly obtains titaniferous zeolite molecular sieve.
2. natural zeolite modification according to claim 1 prepares the method for titaniferous zeolite molecular sieve, it is characterized in that described natural zeolite is: natural mordenite or natural clinoptilolite, the titaniferous zeolite molecular sieve of preparation is: titaniferous mordenite or titaniferous clinoptilolite.
3. natural zeolite modification according to claim 1 prepares the method for titaniferous zeolite molecular sieve, it is characterized in that described ion-exchanger ammonium salt is: a kind of in ammonium chloride, ammonium nitrate or the ammonium sulfate, the solid-to-liquid ratio of zeolite and ion-exchanger is 1: 10～20.
4. natural zeolite modification according to claim 1 prepares the method for titaniferous zeolite molecular sieve, it is characterized in that the used acid of described chemical dealuminization is: a kind of in hydrochloric acid, nitric acid, sulfuric acid, the oxalic acid.
5. natural zeolite modification according to claim 1 prepares the method for titaniferous zeolite molecular sieve, it is characterized in that described inert atmosphere is meant a kind of in nitrogen, argon gas or the helium.
6. natural zeolite modification according to claim 1 prepares the method for titaniferous zeolite molecular sieve, it is characterized in that described titanium source is: a kind of in titanium tetrachloride, tetrabutyl titanate, the isopropyl titanate.
7. natural zeolite modification according to claim 1 prepares the method for titaniferous zeolite molecular sieve, it is characterized in that described ion exchange treatment reaction conditions is: the exchange temperature is 80 ℃, 4 hours swap times, exchanges 3 times.
8. natural zeolite modification according to claim 1 prepares the method for titaniferous zeolite molecular sieve, and it is characterized in that described chemical dealuminization method handles preferable reaction conditions and be: temperature is 100 ℃, and the dealuminzation time is 8 hours, and the dealuminzation number of times is 4 times.
9. natural zeolite modification according to claim 1 prepares the method for titaniferous zeolite molecular sieve; it is characterized in that described gas-solid phase isomorphous replacement(metathesis)reaction is: will be under the protection of zeolite parent after ion-exchange and the chemical dealuminization processing at inert atmosphere; speed with 1～5 ℃/min is heated to 100 ℃～200 ℃ from room temperature; under this temperature, kept 2 hours; speed with 1～5 ℃/min is warming up to 300 ℃～800 ℃ again; with indifferent gas the steam in titanium source is brought in the silica tube; reacted 0.5～20 hour down at 300 ℃～800 ℃, continue under this temperature, to purge 3 hours with indifferent gas.
Priority Applications (1)
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