CN1257134C - Method for preparing porous oxide molecular sieve using plant template - Google Patents
Method for preparing porous oxide molecular sieve using plant template Download PDFInfo
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- CN1257134C CN1257134C CN 200410054211 CN200410054211A CN1257134C CN 1257134 C CN1257134 C CN 1257134C CN 200410054211 CN200410054211 CN 200410054211 CN 200410054211 A CN200410054211 A CN 200410054211A CN 1257134 C CN1257134 C CN 1257134C
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- chloride
- nitrate
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- molecular sieve
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Abstract
The present invention relates to a method for preparing a porous oxide molecular sieve by using a plant template, which belongs to the field of inorganic ceramic materials. The method comprises the following steps: (1) selecting the type of plant material powder, soaking the plant material powder in an ammonia water solution for 1 to 24 hours to deglue, and drying; (2) soaking the plant material powder in the water solution of strong acid salt of metal M for 1 to 24 hours, and taking out for drying; (3) processing the plant material powder processed by the step (2) at high temperatures in oxidizing atmosphere at a temperature rise rate of 1 to 20 DEG C / minute within the range of 200 to 1200 DEG C, and obtaining the porous oxide MxOy molecular sieve material of the metal M after 1 to 10 hours of heat preservation, wherein the pore diameter of the material is centralized within the range of 2 to 50 nm, M is one of Ni, Fe, Co, Zn, Al, Ce, Y, Mn, Zr, Cr, La and Ti, X is one of 1, 2 and 3, and Y is one of 1, 2, 3 and 4. The present invention has the characteristics of low cost, wide sources and simple manufacturing process.
Description
Technical field
The present invention relates to the preparation method of a kind of inorganic ceramic material field porous material, particularly a kind of method of utilizing the plant template to prepare the porous oxide molecular sieve.
Background technology
The oxide material powder can be widely used in makes magnetic material, materials of electronic components, coating, pottery and the pigment of glass and the raw material of catalyst, and according to the difference of oxide kind, can present different unique function and efficacies such as unique INFRARED ABSORPTION, electromagnetic wave shielding and absorption, ultraviolet screener.Along with the continuous development and the maturation of oxide material technology of preparing, people can prepare various types of oxide compounds of different-grain diameter, different components, different structure.
Find that by literature search the preparation method around oxide compound has many bibliographical informations, as Chinese patent CN1112520A, name is called: " a kind of preparation method of ultramicro particle nickel oxide ".The technical characterstic of this patent is nickel salt with after bicarbonate of ammonia or carbonic acid ammonia mix, and adds water, stirring reaction to pH value is 6.5-7.5, and slurry is carried out solid-liquid separation, and filter residue washing oven dry back is 400-1000 ℃ of pyrolysis.This technology can obtain median size at the uniform nickel oxide powder of nano-scale particle size, but the nickel oxide powder that this technology obtains does not have the porous feature, simultaneously the technical matters relative complex.
Summary of the invention
The present invention is directed to the deficiencies in the prior art and defective, a kind of method of utilizing the plant template to prepare the porous oxide molecular sieve is provided, make the oxide powder of preparation not only have the porous feature, density is low, and its pore size distribution is concentrated in a certain scope, the while is with low cost, technology is simple relatively.
The present invention is achieved by the following technical solutions, and method steps is as follows:
1). select vegetable material powder kind, at first the vegetable material powder flood processing of coming unstuck in 1-24 hour in ammoniacal liquor after, drying;
2). then, again the vegetable material powder is flooded pre-treatment 1-24 hour in the aqueous solution of the strong acid salt of metal M after, take out dry;
3). at last more further with step 2) in the vegetable material powder processed in oxidizing atmosphere with 1-20 ℃/minute programming rate, be raised to a certain temperature in the 200-1200 ℃ of scope, and namely obtain the concentrated porous oxide M that is distributed in the metal M in the 2-50nm scope in aperture after 1-10 hour in this temperature insulation
xO
yMolecular screen material, wherein: M is a kind of among metal Ni, Fe, Co, Zn, Al, Ce, Y, Mn, Zr, Cr, La and the Ti, and X is in 1,2,3, and Y is in 1,2,3,4.
In the step 1), described vegetable material refers to timber, bamboo, straw shell, straw, cavings, jowar shell.
Step 2) in, the vegetable material powder that can handle coming unstuck in the step 1) earlier for the impregnation rate of the strong acid salt solution that improves metal M is raised to vegetable material porous carbon that 250 ℃ of a certain temperature in-650 ℃ of temperature ranges and insulation handle to obtain in the 1-8 hour strong acid salt aqueous solution of impregnating metal M again with 1-20 ℃/minute heat-up rate under non-oxygen condition;
Step 2) in, the vegetable material powder that can handle coming unstuck in the step 1) for the impregnation rate of the strong acid salt solution that improves metal M is placed in the strong acid salt aqueous solution that adds the alcoholic acid metal M and floods;
Step 2) in, the salt of described metal M refers to a kind of in the nitrate, chlorate of metal M especially refer to nickel nitrate [Ni (NO
3)
2], ferric nitrate [Fe (NO
3)
3], cobalt nitrate [Co (NO
3)
3], zinc nitrate [Zn (NO
3)
2], aluminum nitrate [Al (NO
3)
3], cerous nitrate [Ce (NO
3)
3], yttrium nitrate [Y (NO
3)
3], manganese nitrate [Mn (NO
3)
2], zirconium nitrate [Zr (NO
3)
2], chromic nitrate [Cr (NO
3)
3], lanthanum nitrate [La (NO
3)
3], nickel chloride [NiCl
2], iron chloride [FeCl
3], frerrous chloride [FeCl
2], cobalt chloride [CoCl
3], zinc chloride [ZnCl
2], aluminium chloride [AlCl
3], cerium chloride [CeCl
3], yttrium chloride [YCl
3], manganese chloride [MnCl
2], zirconium chloride [ZrCl
2], chromium chloride [CrCl
3], lanthanum chloride [LaCl
3], titanium tetrachloride (TiCl
4) in a kind of;
Step 3) in, the porous oxide M of described metal M
xO
y, refer to NiO, Ni
2O
3, FeO, Fe
2O
3, Fe
3O
4, Co
3O
4, ZnO, Al
2O
3, CeO
2, Y
2O
3, MnO
2, ZrO
2, Cr
2O
3, La
2O
3, TiO
2In a kind of;
Step 3) in, the porous oxide M of described metal M
xO
yThe aperture of molecular screen material is concentrated and is distributed in the 2-50nm scope, and the aperture that is distributed in this scope accounts for the percentage in all apertures more than 70%.
The present invention is based on following principle: natural living body material, there is a large amount of holes such as wood materials-plant structure inside, especially have the abundant nanoaperture of quantity, it can be with the 1nm-100nm different scale, with three-dimensional, bidimensional, one dimension or zero dimension, multi-form being present in the different plant structures such as continuous or discontinuous.The present invention is a template with the nanostructure hole in the wood materials such as plant structure, its structure of heredity, and its component that makes a variation realizes that the variation of component transforms.
The present invention can obtain most of aperture and concentrate the porous oxide molecular screen material that is distributed in the 2-500nm scope by selection, control technology and the heat decomposition temperature condition of vegetable material, and pore-size distribution can be regulated arbitrarily in this scope simultaneously.
The present invention has substantive distinguishing features and marked improvement, the present invention adopts, and vegetable materials with low cost, wide material sources are raw material and template, processing is burnt till in aqueous solution impregnation process and the oxidation of the strong acid salt of metal M under the process certain condition, and namely obtaining composition constitutional chemistry formula is M
xO
yThe porous oxide molecular screen material, technology is simple, selective scope is wide, has the advantages that density is low, in light weight, pore-size distribution is concentrated.It is that the porous oxide molecular screen material of template preparation can be applied to different field such as electromagnetic wave absorbent material field, electrostatic shielding, field of magnetic material, electronic material device and support of the catalyst good prospects for application is arranged that the present invention adopts vegetable material.
Embodiment
Provide following three embodiment in conjunction with content of the present invention:
Embodiment one
Choosing dry wood materials-China fir powder is starting material, and in ammoniacal liquor 1 hour after drying of dip treating, and then in the aqueous solution of nickelous nitrate the dipping 1 hour after drying, then further in oxidizing atmosphere the heat-up rate with 1 ℃/minute carry out pyroprocessing, promptly obtain porous nickel oxide (NiO) molecular screen material that the aperture mainly is distributed in 2nm 200 ℃ of insulations after 10 hours, in the 100MHZ-1.5GHZ scope, have good absorption of electromagnetic wave effect.
Embodiment two
Choosing dry wood materials-paulownia powder is raw material, and impregnation process is dry after 12 hours in ammoniacal liquor, and then at yttrium nitrate [Y (NO
3)
3] the aqueous solution in dipping dry after 12 hours, then further in oxidizing atmosphere the programming rate with 10 ℃/minute carry out high-temperature process, namely obtain the porous oxidation yttrium (Y that the aperture mainly is distributed in 26nm 700 ℃ of insulations after 5 hours
2O
3) molecular screen material, in visible-range, have good assimilation effect.
Embodiment three
Choosing dry wood materials-kahikatea powder is raw material, and impregnation process is dry after 24 hours in ammoniacal liquor, and then at zirconium nitrate [Zr (NO
3)
2] the aqueous solution in dipping dry after 24 hours, then further in oxidizing atmosphere the programming rate with 20 ℃/minute carry out high-temperature process, namely obtain the porous zirconia (ZrO that the aperture mainly is distributed in 50nm 1200 ℃ of insulations after 1 hour
2) molecular screen material, in the ultraviolet frequencies scope, have good ultraviolet shielded effect.
Embodiment four
Choosing dry wood materials-tamarack powder is starting material, and in ammoniacal liquor 1 hour after drying of dip treating, under the non-oxygen condition with 1 ℃/minute heat-up rate 250 ℃ handle 8 hours after, then at zinc chloride (ZnCl
2) (water+ethanol) solution in the dipping 1 hour after drying, and then further in oxidizing atmosphere the heat-up rate with 1 ℃/minute carry out pyroprocessing, promptly obtain porous zinc bloom (ZnO) molecular screen material that the aperture mainly is distributed in 2nm 200 ℃ of insulations after 1O hour, in ultraviolet ray range, have good shield effectiveness.
Embodiment five:
Choosing dried plant material-bamboo powder is raw material, and impregnation process is dry after 12 hours in ammoniacal liquor, under the non-oxygen condition with 1O ℃/minute programming rate 450 ℃ process 4 hours after, then at lanthanum chloride (LaCl
3) (water+ethanol) solution in dipping dry after 12 hours, and then further in oxidizing atmosphere the programming rate with 10 ℃/minute carry out high-temperature process, namely obtain the porous oxidation lanthanum (La that the aperture mainly is distributed in 26nm 700 ℃ of insulations after 5 hours
2O
3) molecular screen material, in the far infrared scope, have good assimilation effect.
Embodiment six:
Choosing dried plant material-jowar shell powder is raw material, and impregnation process is dry after 24 hours in ammoniacal liquor, under the non-oxygen condition with 20 ℃/minute programming rate 650 ℃ process 1 hour after, then at iron chloride (FeCl
3) (water+ethanol) solution in dipping dry after 24 hours, and then further in oxidizing atmosphere the programming rate with 20 ℃/minute carry out high-temperature process, namely obtain the porous ferric oxide (Fe that the aperture mainly is distributed in 50nm 1200 ℃ of insulations after 1 hour
2O
3) molecular screen material, in the 100M-1.5GHZ scope, have good effectiveness.
Claims (7)
1, a kind of method of utilizing the plant template to prepare the porous oxide molecular sieve is characterized in that method steps is as follows:
1). select vegetable material powder kind, at first the vegetable material powder flood processing of coming unstuck in 1-24 hour in ammoniacal liquor after, drying;
2). then, again the vegetable material powder is flooded pre-treatment 1-24 hour in the aqueous solution of the strong acid salt of metal M after, take out dry;
3). last, again further with step 2) in the vegetable material powder handled in oxidizing atmosphere with 1-20 ℃/minute heat-up rate, be raised to a certain temperature in the 200-1200 ℃ of scope, and promptly obtain the aperture after 1-10 hour in the insulation of this temperature and concentrate the porous oxide MxOy molecular screen material that is distributed in the metal M in the 2-50nm scope
Wherein: M is a kind of among metal Ni, Fe, Co, Zn, Al, Ce, Y, Mn, Zr, Cr, La and the Ti, and X is in 1,2,3, and Y is in 1,2,3,4.
2, the method for utilizing the plant template to prepare the porous oxide molecular sieve according to claim 1 is characterized in that, in the step 1), described vegetable material refers to timber, bamboo, straw shell, straw, cavings, jowar shell.
3, the method for utilizing the plant template to prepare the porous oxide molecular sieve according to claim 1, it is characterized in that, step 2) in, be the impregnation rate of the strong acid salt solution that improves metal M, perhaps the vegetable material powder of handling coming unstuck in the step 1) earlier is raised to 250 ℃ of a certain temperature in-650 ℃ of temperature ranges with 1-20 ℃/minute heat-up rate and is incubated vegetable material porous carbon that processing obtained in the 1-8 hour strong acid salt aqueous solution of impregnating metal M again under non-oxygen condition; Perhaps the vegetable material powder of handling coming unstuck in the step 1) is placed in the strong acid salt aqueous solution that adds the alcoholic acid metal M and floods.
4, the method for utilizing the plant template to prepare the porous oxide molecular sieve according to claim 1 is characterized in that step 2) in, the strong acid salt of described metal M refers to a kind of in the nitrate, chlorate of metal M.
5, according to claim 1 or the 4 described methods of utilizing the plant template to prepare the porous oxide molecular sieve, it is characterized in that step 2) in, the strong acid salt of described metal M refers to nitric acid nickel (NO
3)
2, ferric nitrate Fe (NO
3)
3, cobalt nitrate Co (NO
3)
3, zinc nitrate Zn (NO
3)
2, aluminum nitrate Al (NO
3)
3, cerous nitrate Ce (NO
3)
3, yttrium nitrate Y (NO
3)
3, manganese nitrate Mn (NO
3)
2, zirconium nitrate Zr (NO
3)
2, chromic nitrate Cr (NO
3)
3, lanthanum nitrate La (NO
3)
3, nickel chloride NiCl
2, iron chloride FeCl
3, frerrous chloride FeCl
2, cobalt chloride CoCl
3, zinc chloride ZnCl
2, aluminium chloride AlCl
3, cerium chloride CeCl
3, yttrium chloride YCl
3, manganese chloride MnCl
2, zirconium chloride ZrCl
2, chromium chloride CrCl
3, lanthanum chloride LaCl
3, titanium tetrachloride TiCl
4In a kind of.
6, the method for utilizing the plant template to prepare the porous oxide molecular sieve according to claim 1 is characterized in that step 3) in, the porous oxide M of described metal M
xO
y, refer to NiO, Ni
2O
3, FeO, Fe
2O
3, Fe
3O
4, Co
3O
4, ZnO, Al
2O
3, CeO
2, Y
2O
3, MnO
2, ZrO
2, Cr
2O
3, La
2O
3, TiO
2In a kind of.
7, the method for utilizing the plant template to prepare the porous oxide molecular sieve according to claim 1, it is characterized in that, in the step 3), the aperture of the porous oxide MxOy molecular screen material of described metal M is concentrated and is distributed in the 2-50nm scope, and the aperture that is distributed in this scope accounts for the per-cent in all apertures more than 70%.
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