CN1923358A - Process for preparing Ce loading Zr crosslinking composite montmorillonoid material - Google Patents
Process for preparing Ce loading Zr crosslinking composite montmorillonoid material Download PDFInfo
- Publication number
- CN1923358A CN1923358A CNA2006100535223A CN200610053522A CN1923358A CN 1923358 A CN1923358 A CN 1923358A CN A2006100535223 A CNA2006100535223 A CN A2006100535223A CN 200610053522 A CN200610053522 A CN 200610053522A CN 1923358 A CN1923358 A CN 1923358A
- Authority
- CN
- China
- Prior art keywords
- preparation
- loading
- temperature
- hours
- hour
- 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.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention relates to a method for preparing Ce carrier Zr crosslink composite montmorillonite material. Wherein, it is characterized in that it uses cerous nitrate and sodium montmorillonite as materials, via Zr crosslink and Ce carrier, to obtain the product, which can be used in catalysis burning to eliminate VOCs.
Description
Technical field
The present invention relates to a kind of novel VOCs catalysis and eliminate material, the i.e. preparation of Ce loading Zr crosslinking composite montmorillonoid material.
Technical background
Cross-linked montmorillonite (Cross linked Montmoillonite is called for short CLM) is as a kind of porous new function material, because its particular performances becomes the focus of research in recent years.People utilize the characteristics of exchangeable cations between cheating engaging layer, mode by ion-exchange, make the cation of the original absorption of organic or inorganic IONENE G displacement surface of clay, with its 2: 1 elementary layer bridgings and strut, form " layer post " shape structure of a kind of two-dimensional channel, form cross-linked montmorillonite.It has advantages such as specific area is big, absorption property good, the aperture is big, is subjected to using widely in fields such as environmental protection, catalysis.The preparation of cross-linked montmorillonite generally is that cross-linked material is incorporated between cheating engaging layer, existing literature is reported in cross-linked material and selects for use and mainly concentrate on alkyl quaternary amine ion, bentyl cation, metal chelate and polyhydroxy metal cation etc., and wherein the most frequently used is the polyhydroxy metal cation.Drawbacks such as but the material that adopts these cross-linked materials to make often has uneven pore-size distribution, and heat endurance is good inadequately.Therefore, how to develop high stable, high performance clay material has crucial Research Significance, but rarely has report in the technology of preparing of exploitation Ce loading Zr crosslinking composite montmorillonoid and the research used it for aspect the VOCs catalysis elimination.
Chinese patent 200510060785.2 discloses a kind of preparation method of rare earth-compounded Zr cross-linked montmorillonite material, is parent material with the imvite, carries out simultaneously with rare earth is compound by Zr is crosslinked, obtains the carrier material of catalysis of removing VOCs.Its advantage is: better heat stability, after 800 ℃ of roastings, interlamellar spacing still can remain unchanged, and has improved the pore-size distribution systematicness of clay, has promoted the pore size homogenising.But it is complicated to exist the preparation method, and preparation process time is long, the deficiency that the rare earth utilization rate is low, and the VOCs that is primarily aimed at high concentration carries out catalysis and eliminates.
Summary of the invention
The objective of the invention is provides a kind of new material of catalysis of removing VOCs: the preparation method of Ce loading Zr crosslinking composite montmorillonoid material on Chinese patent 200510060785.2 bases.It is simple to adopt this method to have preparation process, and influence factor is few, is convenient to advantages such as operation, and this promotes commercial Application has very positive meaning.
The preparation method of Ce loading Zr crosslinking composite montmorillonoid material provided by the invention, total design is: with the imvite of sodium type is initiation material, adopts crosslinked and Ce load two-step method (the passing through infusion process) preparation of Zr.
The preparation method of Ce loading Zr crosslinking composite montmorillonoid material provided by the invention the steps include:
1.Zr the preparation of crosslinking agent
Raw material protochloride zirconium is added the suitable quantity of water dissolving, be made into the solution that concentration is 1.0mol/L, after stirring 3--5 hour under the 60--80 ℃ of temperature conditions, under 20-25 ℃ of condition, wore out 172--184 hour, obtain the Zr crosslinking agent;
2.Ce the preparation of loading Zr crosslinking composite montmorillonoid
1. the molal weight ratio in Zr ion and imvite is: the Zr ion: the ratio of imvite=4: 1-6: 1mmol/g is measured 1 described Zr crosslinking agent, add the water wiring solution-forming, 60-80 ℃ of temperature, under the magnetic agitation condition, slowly splash into mass concentration and be in 1% the imvite suspension, constant temperature stirred 2-3 hour, and constant temperature is aging 3--5 hour then, suction filtration repeatedly washs to there not being chlorion with deionized water;
Above-mentioned presoma is dried under 100-120 ℃ of air atmosphere, under the 400-600 ℃ of air atmosphere roasting 2-3 hour, grind, 100 orders sieve, and obtain Zr cross-linked montmorillonite carrier;
2. take by weighing the nitrate raw material (is that 1: 8 molar ratio calculates by cerous nitrate and 1. described Zr ion concentration) of a certain amount of rare-earth element cerium, and add the suitable quantity of water dissolving.Adopt infusion process, with the 1. described Zr cross-linked montmorillonite of 3-5g carrier according to the above ratio incipient impregnation in solution, dipping is 1-5 hour under 20-25 ℃ of condition, then after drying by the fire 2-4 hour under the 100-120 ℃ of air atmosphere, in 400-600 ℃ of temperature, under the air atmosphere roasting 1-3 hour, make Ce loading Zr crosslinking composite montmorillonoid of the present invention.
Rare earth element nitrate raw material of the present invention is a cerous nitrate.
The whipping temp of Zr crosslinking agent of the present invention is 80 ℃, and mixing time is 4 hours, and aging temperature is 20-25 ℃, and ageing time is 184 hours.
Zr ion of the present invention with the molal weight ratio of imvite is: Zr ion: imvite=5: 1mmol/g.
The dropping temperature that Zr crosslinking agent of the present invention is added dropwise to the imvite suspension is 65 ℃, the dropping time is 1-2 hour, whipping temp is 65 ℃, mixing time is 2 hours, and aging temperature is 65 ℃, and ageing time is 3 hours, bake out temperature is 110 ℃, drying time is 2 hours, and sintering temperature is 500 ℃, and roasting time is 2 hours.
The experimental temperature of Ce loading Zr crosslinking composite montmorillonoid of the present invention is 20-25 ℃, and the time is 1-5 hour.
The bake out temperature of Ce loading Zr crosslinking composite montmorillonoid of the present invention is 110 ℃, and drying time is 3 hours, and sintering temperature is 500 ℃, and roasting time is 2 hours.
The Ce loading Zr crosslinking composite montmorillonoid that adopts the present invention to make is used for catalytic combustion elimination VOCs can obtain effect preferably.With disclosed Chinese patent 200510060785.2---rare earth-compounded Zr cross-linked montmorillonite material is compared, it is carrier that the present invention adopts the Zr cross-linked montmorillonite, it is rare earth loaded promptly to adopt infusion process to carry out after the interlamellar spacing that has increased imvite, can improve rare earth and enter amount between cheating engaging layer, clump and more activated centre is provided.Therefore reduce preparation process, also can obtain catalytic effect preferably when shortening used time of preparation.Experiment is found, in VOCs concentration in the 4.0-22.0g/M3 scope, the complete conversion temperature of acetone drops to 240 ℃ by 400 ℃ on the Ce loading Zr crosslinking composite montmorillonoid provided by the present invention, the complete conversion temperature of ethyl acetate drops to 290 ℃ by 420 ℃, and the complete conversion temperature of toluene has also descended more than 150 ℃.
The specific embodiment
Embodiment 1:
With reference to above-mentioned preparation process
1. raw material protochloride zirconium is added the suitable quantity of water dissolving, be made into the solution that concentration is 1.0mol/L, after stirring 4 hours under 80 ℃ of temperature conditions, wore out 184 hours under the 20-25 ℃ of condition, obtain the Zr crosslinking agent;
2. prepare mass percent and be 1% imvite suspension.
3. will be 1. described solution slowly be added drop-wise in 1% the imvite suspension, the control dropping time is 1-2 hour, the Zr crosslinking agent with the molal weight ratio of imvite is: Zr: imvite=5: 1mmol/g.Stirred 2 hours under 65 ℃ of temperature conditions, aging 3 hours, suction filtration repeatedly washed to there not being chlorion with deionized water, and baking is 2 hours under 110 ℃ air atmosphere, and roasting is 2 hours under 500 ℃ of air atmosphere, grinds, and 100 orders sieve.4. the ratio that with the mol ratio of the Zr ion in rare earth element ce and the Zr cross-linked montmorillonite is 1: 8 is calculated the weighing cerous nitrate, add the suitable quantity of water dissolving, under 20-25 ℃, with the 3. sample incipient impregnation that made in earth solution, 20-25 ℃ flooded 2-3 hour down, baking is 2 hours under 110 ℃ air atmosphere, and roasting is 2 hours under 500 ℃ of air atmosphere, makes Ce loading Zr crosslinking composite montmorillonoid of the present invention.
Embodiment 2:
A specific embodiment of Ce loading Zr crosslinking composite montmorillonoid the steps include:
1.Zr the preparation of crosslinking agent
By Zr content is the concentration of 1.0mol/L, calculates to take by weighing protochloride zirconium (ZrOCl
2) 89.06g, add water 280ml dissolving, filter, after stirring 4 hours under 80 ℃ of conditions, 20-25 ℃ was worn out 184 hours down, obtained the Zr crosslinking agent, stand-by.
2.Zr the preparation of cross-linked montmorillonite
2.1 take by weighing the 6.00g imvite, add water 600ml, under 65 ℃ of magnetic agitation conditions, make mass concentration and be 1% imvite suspension.
2.2 the molal weight ratio by zirconium crosslink agent and imvite is: Zr: imvite=5: 1mmol/g, measure the Zr crosslinking agent of 30ml, add 20ml water wiring solution-forming.Under 65 ℃ of temperature conditions, the Zr crosslinking agent slowly is added drop-wise in the above-mentioned imvite suspension, the control dropping time is 1 hour, and 65 ℃ of temperature conditions stirred 2 hours aging 3 hours down, suction filtration, repeatedly wash to there not being chlorion with deionized water, baking is 2 hours under 110 ℃ the air atmosphere, and roasting is 2 hours under 500 ℃ of air atmosphere, grind, 100 orders sieve and obtain the Zr cross-linked montmorillonite.
3.Ce the preparation of loading Zr crosslinking composite montmorillonoid
3.1 under 20-25 ℃, be 1: 8 ratio, calculate the Ce (NO that takes by weighing 0.8142g in the mol ratio of the Zr ion in rare earth element ce and the Zr cross-linked montmorillonite
3)
36H
2O adds the low amounts of water dissolving.Take by weighing Zr cross-linked montmorillonite 3.000g, slowly join in the above-mentioned earth solution, 20-25 ℃ flooded 3 hours down.
3.2 the mixture behind 3.1 dippings was dried by the fire 3 hours under 110 ℃ of air atmosphere, and roasting is 2 hours under 500 ℃ of air atmosphere, obtains the Ce loading Zr crosslinking composite montmorillonoid.
Claims (6)
1, a kind of preparation method of Ce loading Zr crosslinking composite montmorillonoid material is an initiation material with the imvite of sodium type, adopts the crosslinked and Ce load two-step method preparation of Zr, the steps include:
● the preparation of Zr crosslinking agent
Raw material protochloride zirconium is added the suitable quantity of water dissolving, be made into the solution that concentration is 1.0mol/L, after stirring 3--5 hour under the 60--80 ℃ of temperature conditions, under 20-25 ℃ of condition, wore out 172--184 hour, obtain the Zr crosslinking agent;
● the preparation of Zr cross-linked montmorillonite carrier
Molal weight ratio in Zr ion and imvite is: the Zr ion: the ratio of imvite=4: 1-6: 1mmol/g is measured described Zr crosslinking agent, add the water wiring solution-forming, 60-80 ℃ of temperature, under the magnetic agitation condition, slowly splash into mass concentration and be in 1% the imvite suspension, constant temperature stirred 2-3 hour, and constant temperature is aging 3--5 hour then, suction filtration repeatedly washs to there not being chlorion with deionized water;
Above-mentioned presoma is dried under 100-120 ℃ of air atmosphere, under the 400-600 ℃ of air atmosphere roasting 2-3 hour, grind, 100 orders sieve, and obtain Zr cross-linked montmorillonite carrier;
● the preparation of Ce loading Zr crosslinking composite montmorillonoid
Taking by weighing the nitrate raw material of a certain amount of rare-earth element cerium, is 1: 8 molar ratio calculating by cerous nitrate and described Zr ion concentration, and adds the suitable quantity of water dissolving; With the described Zr cross-linked montmorillonite of 3-5g carrier according to the above ratio incipient impregnation in solution, dipping is 1-5 hour under 20-25 ℃ of condition, then after drying by the fire 2-4 hour under the 100-120 ℃ of air atmosphere, in 400-600 ℃ of temperature, under the air atmosphere roasting 1-3 hour, make Ce loading Zr crosslinking composite montmorillonoid of the present invention.
2, the preparation method of Ce loading Zr crosslinking composite montmorillonoid material according to claim 1, the whipping temp of the described Zr crosslinking agent preparation of its feature is 80 ℃, and mixing time is 4 hours, and aging temperature is 20-25 ℃, and ageing time is 184 hours.
3, the preparation method of Ce loading Zr crosslinking composite montmorillonoid material according to claim 1, the described Zr ion of its feature with the molal weight ratio of imvite is: Zr ion: imvite=5: 1mmol/g.
4, the preparation method of Ce loading Zr crosslinking composite montmorillonoid material according to claim 1, in the preparation of the described Zr cross-linked montmorillonite of its feature carrier, the dropping temperature that the Zr crosslinking agent splashes in the imvite suspension is 65 ℃, and the dropping time is 1-2 hour, whipping temp is 65 ℃, mixing time is 2 hours, and aging temperature is 65 ℃, and ageing time is 3 hours, bake out temperature is 110 ℃, drying time is 2 hours, and sintering temperature is 500 ℃, and roasting time is 2 hours.
5, the preparation method of Ce loading Zr crosslinking composite montmorillonoid material according to claim 1, the described Ce load temperature of its feature is 20-25 ℃, load time is 3 hours.
6, the preparation method of Ce loading Zr crosslinking composite montmorillonoid material according to claim 1, the bake out temperature of the described Ce loading Zr crosslinking composite montmorillonoid of its feature is 110 ℃, drying time is 3 hours, and sintering temperature is 500 ℃, and roasting time is 2 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100535223A CN100421785C (en) | 2006-09-22 | 2006-09-22 | Process for preparing Ce loading Zr crosslinking composite montmorillonoid material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100535223A CN100421785C (en) | 2006-09-22 | 2006-09-22 | Process for preparing Ce loading Zr crosslinking composite montmorillonoid material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1923358A true CN1923358A (en) | 2007-03-07 |
| CN100421785C CN100421785C (en) | 2008-10-01 |
Family
ID=37816289
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006100535223A Expired - Fee Related CN100421785C (en) | 2006-09-22 | 2006-09-22 | Process for preparing Ce loading Zr crosslinking composite montmorillonoid material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100421785C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618325B (en) * | 2008-07-01 | 2011-06-08 | 浙江大学 | Method for preparing zirconium-yttrium composite pillared montmorillonite supported cobalt catalyst |
| CN105694009A (en) * | 2014-11-25 | 2016-06-22 | 上海凯众材料科技股份有限公司 | Zirconium/cerium-montmorillonite composite catalyst, and preparation method for polyester glycol |
| CN108164902A (en) * | 2018-01-26 | 2018-06-15 | 中山职业技术学院 | Modified montmorillonite used dispersion liquid, 3D printing dusty material and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2589143B1 (en) * | 1985-10-28 | 1990-06-01 | Elf France | BRIDGE CLAYS WITH IMPROVED THERMAL STABILITY, PROCESS FOR THEIR PREPARATION AND THEIR USE AS CATALYSTS |
| US6521559B1 (en) * | 1999-09-27 | 2003-02-18 | The Regents Of The University Of Michigan | Superior pillared clay catalysts for selective catalytic reduction of nitrogen oxides for power plant emission control |
| CN1803610A (en) * | 2005-09-15 | 2006-07-19 | 浙江大学 | Method for preparing rare earth-compounded Zr cross-linked montmorillonite material |
-
2006
- 2006-09-22 CN CNB2006100535223A patent/CN100421785C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101618325B (en) * | 2008-07-01 | 2011-06-08 | 浙江大学 | Method for preparing zirconium-yttrium composite pillared montmorillonite supported cobalt catalyst |
| CN105694009A (en) * | 2014-11-25 | 2016-06-22 | 上海凯众材料科技股份有限公司 | Zirconium/cerium-montmorillonite composite catalyst, and preparation method for polyester glycol |
| CN108164902A (en) * | 2018-01-26 | 2018-06-15 | 中山职业技术学院 | Modified montmorillonite used dispersion liquid, 3D printing dusty material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100421785C (en) | 2008-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5629042B2 (en) | Porous silica powder | |
| CN1923358A (en) | Process for preparing Ce loading Zr crosslinking composite montmorillonoid material | |
| CN1803610A (en) | Method for preparing rare earth-compounded Zr cross-linked montmorillonite material | |
| RU2748350C2 (en) | Molecularly imprinted polymer granules for extraction of lithium, mercury and scandium | |
| CN101992083B (en) | Composite cerium-zirconium solid solution with high oxygen storage capability and preparation method thereof | |
| CN106824068A (en) | A kind of bamboo source multiporous biological matter charcoal fuel oil high-selectivity adsorption desulfurizing agent | |
| CN101053832A (en) | Magnenese-cerium composite oxide supported catalyst for purifying formaldehyde in the indoor air | |
| JP2006503698A5 (en) | ||
| CN105664909A (en) | Ordered macroporous/ordered mesoporous composite-pore Ce/Zr metal oxide catalyst | |
| CN1919412A (en) | Active carbon fabric composite filter element and production method thereof | |
| CN106430304A (en) | Preparation method of high-specific surface and high-temperature-resistant ceria-zirconia solid solution | |
| CN110813275A (en) | Titanium-based nano catalytic oxidation catalyst and preparation method and application thereof | |
| CN104475086B (en) | 3DOM oxide supported alkali/manganese metal oxide catalyst as well as preparation method and application thereof | |
| CN112121788A (en) | Preparation method and application of B-modified vanadium-titanium low-temperature SCR catalyst | |
| CN113996319B (en) | Low-temperature wear-resistant honeycomb catalyst for cement kiln, preparation method and application thereof | |
| CN105032344A (en) | Carbon-doped nano-titanium dioxide adsorbing material for reducing harmful components of cigarettes | |
| Hemström et al. | Polymer‐based monolithic microcolumns for hydrophobic interaction chromatography of proteins | |
| WO2023123139A1 (en) | Preparation method for composite microspheres, composite microspheres prepared thereby and use | |
| CN1234808C (en) | Desulfate adsorbing agent for deep purifying sulfide in fuel oil and preparation process thereof | |
| CN115106013A (en) | Reverse extrusion type granulation forming method | |
| CN1091650C (en) | Catalyst for reducing nitrogen monoxide with carbon monoxide | |
| CN110787811B (en) | Solid super acid and preparation method thereof, glycerol cyclohexanone ketal and preparation method thereof | |
| Kanwal et al. | Isothermal Investigation of Copper (II) and Nickel (II) Adsorption from Water by Novel Synthesized Polyaniline Composites with Polyalthia longifolia and Alastonia scholaris Dried Leaves | |
| CN102381978B (en) | Method for synthesizing vinyl benzoate | |
| CN1628904A (en) | Highly effective catalyst for purifying automobile exhaust and its preparing process |
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: 20081001 Termination date: 20091022 |