CN100522813C - 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
- Publication number
- CN100522813C CN100522813C CNB2007101565945A CN200710156594A CN100522813C CN 100522813 C CN100522813 C CN 100522813C CN B2007101565945 A CNB2007101565945 A CN B2007101565945A CN 200710156594 A CN200710156594 A CN 200710156594A CN 100522813 C CN100522813 C CN 100522813C
- Authority
- CN
- China
- Prior art keywords
- zeolite
- molecular sieve
- natural
- titanium
- ion
- 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
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.But up to the present yet, the thumping majority natural zeolite is only used as primary products, as the additive of material of construction (Yin Yongzhi, CN 1433992A, Wang Guilin, CN 1121495, Chen Guanyi; Zhang Xiumei etc., CN 1724445), adsorbent (Chen Dongxing, CN 1080209, Ma Jianzhong, CN 1126094), and soil improvement agent (Cao Xiaoyan, CN 1398950A, 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 (CN 1034319A such as Zheng Xiaoming, parasol pine longevity, CN 1034494A), 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 the method for gas-solid phase isomorphous substitution 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, gas-steps such as solid phase isomorphous substitution reaction 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 (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 substitution 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 of the present invention-solid phase isomorphous substitution reaction; 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 substitution and reacted cooling, washing, drying 0.5～20 hour.
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 (8)
1, a kind of method of 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-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 mordenite zeolite or using natural clinoptilolite, adopt ion-exchange to handle, with concentration is that the ammonium salt of 0.1～1mol/L is as ion-exchanger, the solid-to-liquid ratio of zeolite and ion-exchanger is 1:5～25, 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 substitution reaction; will be through the zeolite parent after ion-exchange and the chemical dealuminization processing; under the protection of a kind of indifferent gas in nitrogen, argon gas or helium,, with above-mentioned a kind of indifferent gas 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-solid phase replacement(metathesis)reaction 0.5～20 hour, cooling, washing; drying promptly obtains titaniferous zeolite molecular sieve.
2, the method for preparing titanium-containing zeolite molecular sieve by natural zeolite modification according to claim 1 is characterized in that the titaniferous zeolite molecular sieve for preparing is: titaniferous mordenite or titaniferous clinoptilolite.
3, the method for preparing titanium-containing zeolite molecular sieve by natural zeolite modification according to claim 1 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, the method for preparing titanium-containing zeolite molecular sieve by natural zeolite modification according to claim 1 is characterized in that the dealumination agent that described chemical dealuminization method is handled is: a kind of in hydrochloric acid, nitric acid, sulfuric acid, the oxalic acid.
5, the method for preparing titanium-containing zeolite molecular sieve by natural zeolite modification according to claim 1 is characterized in that described titanium source is: a kind of in titanium tetrachloride, tetrabutyl titanate, the isopropyl titanate.
6, the method for preparing titanium-containing zeolite molecular sieve by natural zeolite modification according to claim 1 is characterized in that the exchange temperature that described ion-exchange is handled is 80 ℃, 4 hours swap times, exchanges 3 times.
7, the method for preparing titanium-containing zeolite molecular sieve by natural zeolite modification according to claim 1 is characterized in that the temperature that described chemical dealuminization method is handled is 100 ℃, and the dealuminzation time is 8 hours, and the dealuminzation number of times is 4 times.
8; the method of preparing titanium-containing zeolite molecular sieve by natural zeolite modification according to claim 1; it is characterized in that described gas-solid phase isomorphous substitution reaction is: will be through the zeolite parent after ion-exchange and the chemical dealuminization processing at nitrogen; under the protection of a kind of indifferent gas in argon gas or the helium; 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 above-mentioned a kind of 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 above-mentioned a kind of indifferent gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101565945A CN100522813C (en) | 2007-11-09 | 2007-11-09 | Method for preparing titanium-containing zeolite molecular sieve by natural zeolite modification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007101565945A CN100522813C (en) | 2007-11-09 | 2007-11-09 | Method for preparing titanium-containing zeolite molecular sieve by natural zeolite modification |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101182005A CN101182005A (en) | 2008-05-21 |
| CN100522813C true CN100522813C (en) | 2009-08-05 |
Family
ID=39447449
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007101565945A Expired - Fee Related CN100522813C (en) | 2007-11-09 | 2007-11-09 | Method for preparing titanium-containing zeolite molecular sieve by natural zeolite modification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100522813C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101678A (en) * | 2010-12-07 | 2011-06-22 | 浙江大学 | Method for preparing titanium-silicon molecular sieve by virtue of liquid-solid phase replacement and modification of natural zeolite |
| US11130118B2 (en) * | 2017-11-02 | 2021-09-28 | Tubitak | Preparation of natural zeolite catalyst and the method of producing dimethyl ether from methyl alcohol using this catalyst |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102049239A (en) * | 2010-12-07 | 2011-05-11 | 浙江大学 | Nitrogen oxide adsorbent prepared through ion exchange modification of natural zeolite |
| CN102091592A (en) * | 2010-12-07 | 2011-06-15 | 浙江大学 | Nitric oxide adsorbent prepared by supercritically modifying natural zeolite |
| CN102101679A (en) * | 2010-12-07 | 2011-06-22 | 浙江大学 | Method for preparing titanium-silicalite molecular sieve from natural zeolite through supercritical replacement and modification |
| CN103252252B (en) * | 2013-04-24 | 2015-07-08 | 华东师范大学 | Preparation method of non-binder titaniferous mercerizing molecular sieve catalyst |
| CN104860329B (en) * | 2015-05-11 | 2017-03-15 | 华东师范大学 | A kind of preparation method of super-hydrophobicity containing Ti nano mordenite molecular sieves |
| CN105195171A (en) * | 2015-11-03 | 2015-12-30 | 海南中航特玻科技有限公司 | Honeycombed catalyst for low-temperature denitration and preparation method |
| CN106818675A (en) * | 2017-01-20 | 2017-06-13 | 唐成康 | The application and method of modifying of zeolite molecular sieve or modified zeolite molecular sieve in mosquito is caught |
| CN107008493B (en) * | 2017-04-12 | 2020-05-22 | 中国天辰工程有限公司 | Preparation method of titanium-containing catalyst for olefin epoxidation or ketone ammoximation |
| CN108906119A (en) * | 2018-05-29 | 2018-11-30 | 河南师范大学 | A kind of preparation method of SAPO-34 composite molecular screen |
| CN112408417B (en) * | 2019-08-22 | 2022-07-01 | 中国科学院大连化学物理研究所 | Modified mordenite molecular sieve and preparation method thereof |
| CN110668463B (en) * | 2019-11-06 | 2021-04-02 | 中国天辰工程有限公司 | Method for preparing titanium-containing mordenite with high silicon-aluminum ratio |
| CN112221537B (en) * | 2020-11-05 | 2021-07-06 | 大连理工大学 | Using white carbon black and TiCl4Method for preparing high-activity propylene and hydrogen peroxide gas phase epoxidation catalyst by gas-solid phase reaction |
| CN114350182A (en) * | 2021-12-17 | 2022-04-15 | 沈阳市津浩科技有限公司 | Preparation method of modified zeolite for environment-friendly high-performance interior wall coating |
-
2007
- 2007-11-09 CN CNB2007101565945A patent/CN100522813C/en not_active Expired - Fee Related
Non-Patent Citations (4)
| Title |
|---|
| 催化新材料-钛硅分子筛合成及应用研究. 周继承，王祥生.化学进展，第10卷第4期. 1998 |
| 催化新材料-钛硅分子筛合成及应用研究. 周继承，王祥生.化学进展，第10卷第4期. 1998 * |
| 钛硅沸石的研究现状及工业化前景. 王祥生.精细化工，第13卷第1期. 1996 |
| 钛硅沸石的研究现状及工业化前景. 王祥生.精细化工，第13卷第1期. 1996 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102101678A (en) * | 2010-12-07 | 2011-06-22 | 浙江大学 | Method for preparing titanium-silicon molecular sieve by virtue of liquid-solid phase replacement and modification of natural zeolite |
| US11130118B2 (en) * | 2017-11-02 | 2021-09-28 | Tubitak | Preparation of natural zeolite catalyst and the method of producing dimethyl ether from methyl alcohol using this catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101182005A (en) | 2008-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100522813C (en) | Method for preparing titanium-containing zeolite molecular sieve by natural zeolite modification | |
| CN103818927B (en) | The method of the synthetic high hydrothermal stability cupric CHA type molecular sieve of one-step method | |
| CN102049239A (en) | Nitrogen oxide adsorbent prepared through ion exchange modification of natural zeolite | |
| DK2823900T3 (en) | Process for the preparation of solid nitrosyl ruthenium nitrate using a waste catalyst containing ruthenium | |
| CN106475105A (en) | A kind of double-perovskite type O composite metallic oxide catalyst and preparation method and application | |
| CN104291349A (en) | Method for preparing P type molecular sieve by using coal ash as raw material | |
| CN105540606B (en) | It is a kind of using clay mineral as the method for raw material uninanned platform MFI type zeolite | |
| CN105347318B (en) | A kind of green synthesis method of hydroxylamine salt | |
| CN104709920A (en) | Tin-containing heteroatomic functional molecular sieve and synthesis and application thereof | |
| CN108246334A (en) | A kind of functionalization tri compound catalysis material and preparation method thereof and purposes | |
| CN107008473A (en) | A kind of three-dimensional structure bismuth titanates nanometer sheet/perite nanometer piece composite photo-catalyst and preparation method thereof | |
| CN102101678A (en) | Method for preparing titanium-silicon molecular sieve by virtue of liquid-solid phase replacement and modification of natural zeolite | |
| CN106006665B (en) | A kind of preparation method of titanium-silicon molecular sieve TS-1 | |
| CN110272058A (en) | A kind of MCM-41 ordered mesoporous material and preparation method thereof | |
| CN104803827A (en) | Method for preparing 2,6-dichlorotoluene by catalyzing o-chlorotoluene with ionic liquid | |
| CN110451520A (en) | A kind of magnetic molecule sieve/straw charcoal composite material and preparation method and application | |
| CN107008493A (en) | A kind of preparation method for alkene epoxidation or the titanium-containing catalyst of ketone oxamidinating | |
| CN112642427A (en) | Metal M-doped titanium dioxide photocatalyst and application thereof in photocatalytic nitrogen fixation | |
| CN104192829A (en) | Multidimensional-hierarchical porous SiO2/C composite powder and preparation method thereof | |
| CN103170313A (en) | Heavy metal modified bioadsorbent and preparation method thereof as well as application of heavy metal modified bioadsorbent in tungsten-containing waste water treatment | |
| CN104926689A (en) | Method for preparing cyclohexanone-oxime in solvent-free mode | |
| CN107983398A (en) | A kind of production method of the nano-attapulgite clay compounded catalyst prepared for 3- picolines | |
| CN102872898B (en) | Preparation method for Fe-containing mesoporous mordenite with high catalytic activity | |
| CN102101679A (en) | Method for preparing titanium-silicalite molecular sieve from natural zeolite through supercritical replacement and modification | |
| CN112675868A (en) | High-efficiency response optical coupling denitration catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090805 Termination date: 20091209 |