CN100387519C - Prepn process of organic pillared interlayered clay material - Google Patents
Prepn process of organic pillared interlayered clay material Download PDFInfo
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- CN100387519C CN100387519C CNB2005100120451A CN200510012045A CN100387519C CN 100387519 C CN100387519 C CN 100387519C CN B2005100120451 A CNB2005100120451 A CN B2005100120451A CN 200510012045 A CN200510012045 A CN 200510012045A CN 100387519 C CN100387519 C CN 100387519C
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Abstract
The preparation process of organic pillared interlayer clay material includes the following steps: dissolving metal hydroxide in organic acid solution to obtain precursor of metal oxide, exchanging cations in clay with the precursor, ageing, filtering, washing, drying and roasting to obtain the product. The said process can introduce oxide of Co, Mn, Ce, Cr, Fe, etc into clay of laponite, montmorillonite, etc. Compared with available technology of synthesizing organic pillared interlayer clay material, the present invention has the advantages of simple technological process, wide applicable element range, and greater specific surface area and more pore structures of the product. The synthesized organic pillared interlayer laponite clay material has specific surface area of 500-640 sq m/g and organic pillared interlayer clay material has specific surface area of 200-360 sq m/g.
Description
Technical field
The present invention relates to the material technology field, particularly relate to the preparation method of organic pillared interlayered clay material.
Background technology
Organic pillared interlayered clay material is a polyporous materials that grows up in later stage nineteen seventies, this type of material has higher specific surface area, bigger pore volume and stronger surface acidity, and the aperture ratio zeolite molecular sieve is big, the relative homogeneous of pore size distribution, thereby in absorption, catalysis with the field such as separate and have higher using value.
In traditional building-up process, metal oxide precursor prepares by the partial hydrolysis soluble metal salt mostly.Because it is limited to obtain the metal-salt kind of stable product by partial hydrolysis, mainly be metal soluble salt such as aluminium, iron, chromium, titanium and zirconium, thereby the synthetic column clay mainly contains these elements.Other metal is a presoma with the polynuclear complex of complexity usually, the building-up process complexity, but these elements are in Industrial Catalysis, and often there is very important use in fields such as environment protection.
Summary of the invention
The objective of the invention is to obtain the presoma of different metal, comprise metals such as cobalt, iron, chromium, cerium, manganese, copper, lanthanum or nickel, thereby prepare the pillared clay material of different metal oxides by fairly simple method.
For achieving the above object, technical solution of the present invention provides a kind of preparation method of organic pillared interlayered clay material, can prepare the metal oxide organic pillared interlayered clay material of high-specific surface area; It obtains the presoma of metal oxide by organic acid soln dissolution of metals oxyhydroxide, exchanges positively charged ion in the clay seam with the presoma that obtains then, obtains product by ageing, filtration, washing, drying and calcination procedure.
Described method, its described metallic element comprises cobalt, iron, chromium, cerium, manganese, copper, lanthanum or nickel.
Described method, its described metal hydroxides is that the reactant aqueous solution of the aqueous solution and the sodium hydroxide or the potassium hydroxide of the soluble salt by cobalt, iron, chromium, cerium, manganese, copper, lanthanum or nickel respectively prepares.
Described method, its described organic acid comprises acetate, formic acid, propionic acid or tartrate.
Described method, the concentration of its described organic acid soln are 1%-100%.
Described method, its described clay, the mass percent concentration of its aqueous solution are 1-10%.
Described method, its metal/clay is than being 4-20mmol/g.
Described method, the digestion time during its described ion-exchange is 2-48 hour.
Described method, its described maturing temperature is 300-800 ℃.
Described method, its described clay is Laponite and montmorillonite.
Use the pillared Laponite clay material of method synthetic of the present invention after 500 ℃ of roastings specific surface area at 500m
2More than/the g, most of specific surface areas are at 400m after 700 ℃ of roastings
2More than/the g.The specific surface area of synthetic pillared montmorillonite clay material is at 200m
2More than/the g.
Embodiment
In the inventive method, the aqueous solution of the soluble salt by cobalt, iron, chromium, cerium, manganese, copper, lanthanum or nickel etc. prepares corresponding oxyhydroxide with the reactant aqueous solution of an amount of sodium hydroxide or potassium hydroxide, be that the organic acid soln of 1-100% comes the dissolved hydrogen oxide compound with concentration then, obtain the corresponding metal presoma.Clay is dissolved in obtains the solution that mass percent concentration is 1-10% in the water.Keep metal/clay than being 4-20mmol/g.Metal precursor solution contacts the back and stirred 1-3 hour with clayish solution, after still aging then 2-48 hour, through processes such as filtration, washing, drying and roastings, obtain organic pillared interlayered clay material.
Embodiment 1: by the pillared Laponite clay material of acetate approach synthetic iron oxide
Iron nitrate is dissolved in the water, adds proper amount of sodium hydroxide solution while stirring, iron nitrate: the mol ratio of sodium hydroxide is 1/2-1/6.With the ferric hydroxide precipitate centrifugation that obtains, adding concentration in precipitation is the acetic acid solution of 30-100%, stirs one hour, obtains the precursor solution of iron rapidly.In water, concentration is 1-5% with the Laponite clay dispersion, stirs more than one hour, obtains clayish solution.The precursor solution of iron with after clayish solution mixes, was stirred 1-3 hour, still aging then after, through filtration, washing, dry, behind 400-800 ℃ of roasting supervisor, obtain the pillared Laponite clay material of ferric oxide, finished color is a brown.The material specific surface area that obtains through 500 ℃ of roastings in the present embodiment is 510m
2/ g, the specific surface area of the material that obtains through 700 ℃ of roastings is 380m
2/ g.
Embodiment 2: by the synthetic pillared Laponite clay material of chromic oxide of acetate approach
Chromium nitrate is dissolved in the water, adds proper amount of sodium hydroxide solution while stirring, chromium nitrate: the mol ratio of sodium hydroxide is 1/2-1/6.With the chromium hydroxide precipitation centrifugation that obtains, adding concentration in precipitation is the acetic acid solution of 20-100%, stirs one hour, obtains the precursor solution of chromium rapidly.Remaining program is with embodiment 1.The color of the pillared Laponite clay material of the chromic oxide that obtains finished product is a yellow-green colour.The material specific surface area that obtains through 500 ℃ of roastings in the present embodiment is 625m
2/ g, the specific surface area of the material that obtains through 700 ℃ of roastings is 487m
2/ g.
Embodiment 3: by the synthetic pillared Laponite clay material of cerium oxide of acetate approach
Cerous nitrate is dissolved in the water, adds proper amount of sodium hydroxide solution while stirring, cerous nitrate: the mol ratio of sodium hydroxide is 1/2-1/6.With the cerous hydroxide precipitation and centrifugal separation that obtains, adding concentration in precipitation is the acetic acid solution of 20-100%, stirs one hour, obtains the precursor solution of cerium rapidly.Remaining program is with embodiment 1.The color of the pillared Laponite clay material of the cerium oxide that obtains finished product is light yellow.The material specific surface area that obtains through 500 ℃ of roastings in the present embodiment is 594m
2/ g, the specific surface area of the material that obtains through 700 ℃ of roastings is 444m
2/ g.
Embodiment 4: by the synthetic pillared Laponite clay material of manganese oxide of acetate approach
Manganous nitrate is dissolved in the water, adds proper amount of sodium hydroxide solution while stirring, manganous nitrate: the mol ratio of sodium hydroxide is 1/2-1/6.With the manganous hydroxide precipitation and centrifugal separation that obtains, adding concentration in precipitation is the acetic acid solution of 30-100%, stirs one hour, obtains the precursor solution of manganese rapidly.Remaining program is with embodiment 1.The color of the pillared Laponite clay material of the manganese oxide that obtains finished product is a chocolate.The material specific surface area that obtains through 500 ℃ of roastings in the present embodiment is 595m
2/ g, the specific surface area of the material that obtains through 700 ℃ of roastings is 472m
2/ g.
Embodiment 5: by the synthetic pillared Laponite clay material of cobalt oxide of acetate approach
Rose vitriol is dissolved in the water, adds proper amount of sodium hydroxide solution while stirring, rose vitriol: the mol ratio of sodium hydroxide is 1/2-1/6.With the cobaltous hydroxide suspension liquid stirring centrifugation after 15 minutes that obtains, after the washing, adding concentration in precipitation is the acetic acid solution of 4-100%, stirs one hour, obtains the precursor solution of cobalt.Remaining program is with embodiment 1.The color of the pillared Laponite clay material of the cobalt oxide that obtains finished product is a black.The material specific surface area that obtains through 500 ℃ of roastings in the present embodiment is 639m
2/ g, the specific surface area of the material that obtains through 700 ℃ of roastings is 495m
2/ g.
Embodiment 6: by the synthetic pillared Laponite clay material of cobalt oxide of formate transporters
Rose vitriol is dissolved in the water, adds proper amount of sodium hydroxide solution while stirring, rose vitriol: the mol ratio of sodium hydroxide is 1/2-1/6.With the cobaltous hydroxide suspension liquid stirring centrifugation after 15 minutes that obtains, after the washing, adding concentration in precipitation is the formic acid solution of 2-30%, stirs one hour, obtains the precursor solution of cobalt.Remaining program is with embodiment 1.The material specific surface area that obtains through 500 ℃ of roastings in the present embodiment is 582m
2/ g.
Embodiment 7: by the synthetic pillared Laponite clay material of chromic oxide of tartrate approach
Chromium nitrate is dissolved in the water, adds proper amount of sodium hydroxide solution while stirring, chromium nitrate: the mol ratio of sodium hydroxide is 1/2-1/6.With the chromium hydroxide precipitation centrifugation that obtains, adding concentration in precipitation is the tartaric acid solution of 4-20%, stirs one hour, obtains the precursor solution of chromium rapidly.Remaining program is with embodiment 1.The material specific surface area that obtains through 500 ℃ of roastings in the present embodiment is 626m
2/ g.
Embodiment 8: by acetate approach synthetic iron oxide pillared montmorillonite clay material
The preparation method of the precursor solution of iron is with embodiment 1.Montmorillonitic clay is dispersed in the water, and concentration is 1-5%, stirs more than one hour, obtains clayish solution.The precursor solution of iron with after montmorillonitic clay solution mixes, was stirred 1-3 hour, still aging then after, through filtration, washing, dry, behind 300-600 ℃ of roasting supervisor, obtain ferric oxide pillared montmorillonite clay material.The material specific surface area that obtains through 400 ℃ of roastings in the present embodiment is 252m
2/ g.
Embodiment 9: by the synthetic cobalt oxide pillared montmorillonite clay material of acetate approach
The preparation method of the precursor solution of cobalt is with embodiment 6.Montmorillonitic clay is dispersed in the water, and concentration is 1-5%, stirs more than one hour, obtains clayish solution.The precursor solution of cobalt with after montmorillonitic clay solution mixes, was stirred 1-3 hour, still aging then after, through filtration, washing, dry, behind 300-600 ℃ of roasting supervisor, obtain cobalt oxide pillared montmorillonite clay material.The material specific surface area that obtains through 400 ℃ of roastings in the present embodiment is 286m
2/ g.
Claims (8)
1. the preparation method of an organic pillared interlayered clay material can prepare the metal oxide organic pillared interlayered clay material of high-specific surface area; It is characterized in that, obtain the presoma of metal oxide by the oxyhydroxide of acetate, formic acid, propionic acid or tartaric acid solution dissolved cobalt, iron, chromium, cerium, manganese, copper, lanthanum or nickel, exchange positively charged ion in the clay seam with the presoma that obtains then, obtain product by ageing, filtration, washing, drying and calcination procedure.
2. by the described method of claim 1, it is characterized in that described metal hydroxides is that the reactant aqueous solution of the aqueous solution and the sodium hydroxide or the potassium hydroxide of the soluble salt by cobalt, iron, chromium, cerium, manganese, copper, lanthanum or nickel respectively prepares.
3. by the described method of claim 1, it is characterized in that the concentration of described organic acid soln is 1%-100%.
4. by the described method of claim 1, it is characterized in that described clay, the mass percent concentration of its aqueous solution are 1-10%.
5. by the described method of claim 1, it is characterized in that metal/clay is than being 4-20mmol/g.
6. by the described method of claim 1, it is characterized in that the digestion time during described ion-exchange is 2-48 hour.
7. by the described method of claim 1, it is characterized in that described maturing temperature is 300-800 ℃.
8. by the described method of claim 1, it is characterized in that described clay is Laponite or montmorillonite.
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| CN100387519C true CN100387519C (en) | 2008-05-14 |
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| CN102728378B (en) * | 2011-04-13 | 2014-07-02 | 中国科学院过程工程研究所 | Coal tar hydrocracking catalyst with pillared clay as vector and preparation method thereof |
| CN102351680A (en) * | 2011-11-04 | 2012-02-15 | 广西大学 | Synthesis technique of chromium propionate |
| CN102698595A (en) * | 2012-05-25 | 2012-10-03 | 中国科学院生态环境研究中心 | Application of supported pillared clay catalyst in selective oxidization process of hydrogen sulphide |
| CN103272553B (en) * | 2013-05-16 | 2015-05-13 | 武汉大学 | Preparation method of magnetic nanometer iron oxide adsorbent for removing arsenic from water |
| CN103357375B (en) * | 2013-07-23 | 2015-07-15 | 武汉大学 | Magnetic mesoporous silica adsorbent for removing organic pollutants in water body and preparation method and application thereof |
| CN103738976B (en) * | 2013-12-19 | 2015-09-23 | 绍兴文理学院 | AlCr composite axis system, preparation method and application thereof |
| CN105709750B (en) * | 2014-12-04 | 2018-01-16 | 中国石油化工股份有限公司 | A kind of copper pillared montmorillonite catalyst and its preparation method and application |
| CN106111143A (en) * | 2016-06-27 | 2016-11-16 | 郭迎庆 | A kind of preparation method of near infrared light catalysis column clay catalyst |
| CN106566585A (en) * | 2016-11-10 | 2017-04-19 | 临沂大学 | Natural gas synergist |
| CN106423045B (en) * | 2016-11-23 | 2019-07-09 | 兰州理工大学 | A kind of modified montmorillonoid sorbent preparation method of Treatment of Zinc-containing Wastewater |
| CN108097287B (en) * | 2016-11-25 | 2021-04-30 | 中国石油天然气股份有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN108273470A (en) * | 2018-02-24 | 2018-07-13 | 高姌 | Transition metal modified montmorillonite dephosphorization adsorbent based on deposition method preparation of reporting to the leadship after accomplishing a task |
| CN109355119B (en) * | 2018-11-20 | 2020-12-25 | 杭州勃扬能源设备有限公司 | Desulfurization process for petroleum associated gas |
| CN112108105B (en) * | 2020-10-19 | 2023-01-31 | 江苏中烟工业有限责任公司 | Adsorbing material for reducing HCN and phenol in cigarette smoke and application thereof |
| CN113368856B (en) * | 2021-06-03 | 2022-09-13 | 华南师范大学 | Preparation method and application of iron pillared montmorillonite composite catalyst |
Citations (1)
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|---|---|---|---|---|
| CN1508069A (en) * | 2002-12-17 | 2004-06-30 | ϣ���ٹɷݹ�˾ | Method for preparing layer silicate intercalation compound, the intercalation compound obtained therefrom and use thereof |
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| CN1508069A (en) * | 2002-12-17 | 2004-06-30 | ϣ���ٹɷݹ�˾ | Method for preparing layer silicate intercalation compound, the intercalation compound obtained therefrom and use thereof |
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