CN101182044A - Method for preparing nano ferrite - Google Patents

Method for preparing nano ferrite Download PDF

Info

Publication number
CN101182044A
CN101182044A CNA2007101566859A CN200710156685A CN101182044A CN 101182044 A CN101182044 A CN 101182044A CN A2007101566859 A CNA2007101566859 A CN A2007101566859A CN 200710156685 A CN200710156685 A CN 200710156685A CN 101182044 A CN101182044 A CN 101182044A
Authority
CN
China
Prior art keywords
nitrate
preparation
ferrite
hydrate
nano ferrite
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
Application number
CNA2007101566859A
Other languages
Chinese (zh)
Other versions
CN101182044B (en
Inventor
叶瑛
吕双双
夏枚生
陈雪刚
张维睿
胡秀芳
邬黛黛
韩沉花
李秀悌
姚志通
高奇东
刘利光
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
YAN TAT CIRCUIT (SHENZHEN) CO Ltd
Zhejiang University ZJU
Original Assignee
YAN TAT CIRCUIT (SHENZHEN) CO Ltd
Zhejiang University ZJU
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by YAN TAT CIRCUIT (SHENZHEN) CO Ltd, Zhejiang University ZJU filed Critical YAN TAT CIRCUIT (SHENZHEN) CO Ltd
Priority to CN2007101566859A priority Critical patent/CN101182044B/en
Publication of CN101182044A publication Critical patent/CN101182044A/en
Application granted granted Critical
Publication of CN101182044B publication Critical patent/CN101182044B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Abstract

The invention discloses a preparation method of nanometer-ferrite. By using agricultural wastes, wood dust or sawdust as a carrier of a precursor, the ferrite precursor is obtained by a precipitation method; the ferrite precursor is formed into the nanometer-ferrite through high temperature calcinations. The preparation method of the nanometer-ferrite of the invention overcomes a plurality of deficiencies of the existing nanometer-ferrite production techniques such as irregular phase state and poorer chemical homogeneity and intractable grain size, etc., because of the different pH conditions of the different elements during the precipitation in the water solution. The obtained nanometer-ferrite has the advantages of high porosity, large specific surface area and strong catalytic activity.

Description

A kind of preparation method of nano ferrite
Technical field
The present invention relates to the technology of preparing of nano-functional material, relate in particular to a kind of preparation method of nano ferrite.
Background technology
The wustite of manganese, zinc, cobalt, nickel is the important function material.Wherein Mn-Zn, Ni-Zn wustite are the high-frequency soft magnetic bodies of current production rate maximum in the world, are commonly used for the magneticsubstance of high-frequency transformer, inductor block and write head etc.Wustite or important catalyst, it is synthetic to be applied to synthetic ammonia, Fischer-Tropsch, and the oxidative dehydrogenation of ethylbenzene, butylene etc., and it the field such as synthesizes at chemistry and chemical industry and has broad application prospects.
In the past normally with the carbonate mixture high-temperature calcination of ferric oxide and manganese, zinc, cobalt, nickel, again through grinding the preparation wustite.This method has two shortcomings, and promptly relatively poor the and granular size of chemical uniformity is difficult to control.For overcoming above-mentioned shortcoming, coprecipitation method and alkoxide hydrolysis have been developed.Coprecipitation method iron is that solubility trivalent Fe and divalence Mn, Zn, Ni or Co are mixed with mixing solutions, forms precipitation of hydroxide through after the neutralization reaction, forms wustite through hydro-thermal reaction or calcining again.Because Fe 3+PH value when with divalent cation precipitation taking place in N-process differs greatly, so throw out and thing phase heterogeneous, thereby influences the chemical uniformity of synthetic product.And alkoxide hydrolysis need synthesize the corresponding metal alkoxide, and facility investment and production cost are all very high, and product is competitiveless on price.
For magnetic permeability and the catalytic activity that improves wustite, need preparation nano-scale wustite.The Application Areas of wustite has further been expanded in the appearance of nano-size ferrates.Be seen in a lot of of report,, explosion method synthetic, high-energy ball milling method and self propagating high temperature synthesis method etc. as wet method under chemical coprecipitation, hydrothermal method, sol-gel method, spray pyrolysis, microemulsion method, phase inversion process, supercritical methanol technology, synthesis by shock wave, the microwave field about the Preparation of Ferrite Nanocrystalline Materials method.These methods are each has something to recommend him, and how simplifying technology, reducing cost is that the nano material preparation technology is held common issue with to be solved.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of nano ferrite.
The preparation method of nano ferrite comprises the steps:
1) nitrate of iron nitrate or its hydrate and divalent cation or the ratio of its hydrate 1: 0.4 in molar ratio～0.6 are placed container, add weight and be equivalent to the alcohol of 0.8～1.5 times of the nitrate of iron nitrate or its hydrate and divalent cation or its hydrate gross weight, stir and dissolve fully until iron nitrate and nitrate;
2) in above-mentioned solution, add agricultural wastes, wood chip or the sawdust be equivalent to alcohol weight 8～16%, stir heating in water bath down, until alcohol by evaporate to dryness;
3) with mixture heating up to 600～1100 ℃, and constant temperature 2～3 hours, take out after being cooled to room temperature, obtain nano ferrite.
Described nano ferrite is the RFe of monocrystalline size 10～100 nanometers 2O 4, R is a kind of among Mn, Ni, Co, Zn, the Cu or several.Divalent cation is Mn 2+, Ni 2+, Co 2+, Zn 2+Or Cu 2+In a kind of or several.Nitrate is a kind of in manganous nitrate, nickelous nitrate, Xiao Suangu, zinc nitrate or the cupric nitrate or several.Agricultural wastes are shell, agricultural crop straw or corn cobs through pulverizing of cereal.Preferred in molar ratio 1: 0.5 of the nitrate of iron nitrate or its hydrate and divalent cation or its hydrate.
The present invention adopts the physical sedimentation method to obtain the presoma of wustite, and the phase that pH condition difference is caused when having avoided in the aqueous solution because of different elements precipitation is inhomogeneous.Adopt agricultural wastes or sawdust carrier, have wide material sources, cheap advantage as presoma.After the high-temperature calcination moulding, carrier gasifies behind combustion oxidation, and the wustite of therefore preparing has porosity height, specific surface area is big, catalytic activity is strong advantage.
Embodiment
Preparation method's the first step is that the nitrate with iron nitrate and dyad is dissolved in the alcohol, and the mol ratio of the two is 1: 0.4～0.6.Avoid making water as solvent, be because ferric iron and dyad when in the aqueous solution, precipitating pH have big difference, be difficult to form uniform precipitation, in subsequent reactions, will form independently oxide compound, rather than wustite.Recommending to use iron nitrate and manganous nitrate, is that decomposition temperature is low, can reduce alcohol consumption and energy consumption because their solubleness in alcohol is big.Said divalent cation is Mn 2+, Ni 2+, Co 2+, Zn 2+Or Cu 2+In a kind of or several; Said nitrate is a kind of in manganous nitrate, nickelous nitrate, Xiao Suangu, zinc nitrate or the cupric nitrate or several.
Preparation method's second step is that agricultural wastes, wood chip or sawdust as the presoma carrier are mixed with the spirituous solution of configuration, and with the solution evaporate to dryness.Use heating in water bath to help temperature control, to avoid overheated cause alcohol burning, the recyclable utilization of alcohol during suitability for industrialized production.The evaporate to dryness process will continue to stir, in order to avoid it is inhomogeneous precipitation to occur.Said agricultural wastes are shell, agricultural crop straw or corn cobs through pulverizing of cereal.
Preparation method's the 3rd step is that the carrier that is equipped with iron nitrate and other nitrate is calcined under preset temperature.Nitrate decomposes earlier in calcination process, and further reaction forms wustite then, and is sintered into the shape of carrier.Calcining temperature should be regulated according to the purposes of the finished product, can select lower calcining temperature as the product of magneticsubstance, should select higher calcining temperature as the product of catalyzer.
The present invention is further described in conjunction with following example, but content of the present invention is not limited only to content related among the embodiment.
Embodiment 1: the preparation of ferrous acid manganese
1) takes by weighing Fe (NO respectively 3) 39H 2O 404 gram and Mn (NO 3) 24H 2O 125.5 grams place reaction flask, add 423.6 gram industrial spirit, stir and dissolve fully until iron nitrate and manganous nitrate;
2) add 34 gram powdered rice hulls, stir heating in water bath down, until alcohol by evaporate to dryness;
3) mixture is taken out from reaction flask, place muffle furnace, be warmed up to 600 ℃, constant temperature 2 hours takes out after being cooled to room temperature, promptly obtains nanometer～submicron order ferrous acid manganese.
Embodiment 2: the preparation (Mn of ferrous acid MnZn 0.6Zn 0.4Fe 2O 4)
1) takes by weighing Fe (NO respectively 3) 39H 2O 404 grams, Mn (NO 3) 24H 2O 75.3 gram and Zn (NO 3) 26H 2The O59.5 gram places reaction flask, adds 808.2 gram raw spirits, stirs and dissolves fully until iron nitrate, manganous nitrate and zinc nitrate;
2) add 129.3 gram corn cob meals, stir heating in water bath down, until alcohol by evaporate to dryness;
3) mixture is taken out from reaction flask, place muffle furnace, be warmed up to 1100 ℃, constant temperature 3 hours takes out after being cooled to room temperature, promptly obtains nanometer～submicron order ferrous acid MnZn.
Embodiment 3: the preparation of cobalt ferrite
1) takes by weighing Fe (NO respectively 3) 39H 2O 404 gram and Co (NO 3) 26H 2O 145.02 grams place reaction flask, add 549 gram industrial spirit, stir and dissolve fully until iron nitrate and manganous nitrate;
2) add 55 gram corn stalk powders, stir heating in water bath down, until alcohol by evaporate to dryness;
3) mixture is taken out from reaction flask, place muffle furnace, be warmed up to 900 ℃, constant temperature 2.5 hours takes out after being cooled to room temperature, promptly obtains nanometer～submicron order cobalt ferrite.
Embodiment 4: the preparation of nickel ferrite based magnetic loaded
1) takes by weighing Fe (NO respectively 3) 39H 2O 404 gram and Ni (NO 3) 26H 2O 145.4 grams place reaction flask, add 600 gram industrial spirit, stir and dissolve fully until iron nitrate and nickelous nitrate;
2) add 70 gram corn stalk powders, stir heating in water bath down, until alcohol by evaporate to dryness;
3) mixture is taken out from reaction flask, place muffle furnace, be warmed up to 850 ℃, constant temperature 2.5 hours takes out after being cooled to room temperature, promptly obtains nanometer～submicron order nickel ferrite based magnetic loaded.
Embodiment 5: the preparation of coppeferrite
1) takes by weighing Fe (NO respectively 3) 39H 2O 404 gram and Cu (NO 3) 23H 2O 120.8 grams place reaction flask, add 630 gram industrial spirit, stir and dissolve fully until iron nitrate and cupric nitrate;
2) add 58 gram wheat bran, stir heating in water bath down, until alcohol by evaporate to dryness;
3) mixture is taken out from reaction flask, place muffle furnace, be warmed up to 1000 ℃, constant temperature 2.5 hours takes out after being cooled to room temperature, promptly obtains nanometer～submicron order coppeferrite.
Embodiment 6: the preparation (Ni of cobalt ferrite nickel 0.6Co 0.4Fe 2O 4)
1) takes by weighing Fe (NO respectively 3) 39H 2O 404 grams, Co (NO 3) 26H 2O 58 gram and Ni (NO 3) 26H 2The O87.2 gram places reaction flask, adds 670 gram raw spirits, stirs and dissolves fully until iron nitrate, Xiao Suangu and nickelous nitrate;
2) add 80 gram sawdust powder, stir heating in water bath down, until alcohol by evaporate to dryness;
3) mixture is taken out from reaction flask, place muffle furnace, be warmed up to 950 ℃, constant temperature 3 hours takes out after being cooled to room temperature, promptly obtains nanometer～submicron order cobalt ferrite nickel.
Embodiment 7: the preparation of zinc ferrite
1) takes by weighing Fe (NO respectively 3) 39H 2O 404 gram and Zn (NO 3) 26H 2O 148.7 grams place reaction flask, add 550 gram industrial spirit, stir and dissolve fully until iron nitrate and zinc nitrate;
2) add 50 gram wood dusts, stir heating in water bath down, until alcohol by evaporate to dryness;
3) mixture is taken out from reaction flask, place muffle furnace, be warmed up to 750 ℃, constant temperature 2.2 hours takes out after being cooled to room temperature, promptly obtains nanometer～submicron order zinc ferrite.
Embodiment 8: the preparation of zinc ferrite
1) takes by weighing Fe (NO respectively 3) 39H 2O 404 gram and Zn (NO 3) 26H 2O 178.4 grams place reaction flask, add 800 gram industrial spirit, stir and dissolve fully until iron nitrate and zinc nitrate;
2) add 120 gram wood dusts, stir heating in water bath down, until alcohol by evaporate to dryness;
3) mixture is taken out from reaction flask, place muffle furnace, be warmed up to 600 ℃, constant temperature 2 hours takes out after being cooled to room temperature, promptly obtains nanometer～submicron order zinc ferrite.
Embodiment 9: the preparation of zinc ferrite
1) takes by weighing Fe (NO respectively 3) 39H 2O 404 gram and Zn (NO 3) 26H 2O 118.9 grams place reaction flask, add 420 gram industrial spirit, stir and dissolve fully until iron nitrate and zinc nitrate;
2) add 40 gram wood dusts, stir heating in water bath down, until alcohol by evaporate to dryness;
3) mixture is taken out from reaction flask, place muffle furnace, be warmed up to 1000 ℃, constant temperature 3 hours takes out after being cooled to room temperature, promptly obtains nanometer～submicron order zinc ferrite.

Claims (6)

1. the preparation method of a nano ferrite is characterized in that it comprises the steps:
1) nitrate of iron nitrate or its hydrate and divalent cation or the ratio of its hydrate 1: 0.4 in molar ratio～0.6 are placed container, add weight and be equivalent to the alcohol of 0.8～1.5 times of the nitrate of iron nitrate or its hydrate and divalent cation or its hydrate gross weight, stir and dissolve fully until iron nitrate and nitrate;
2) in above-mentioned solution, add agricultural wastes, wood chip or the sawdust be equivalent to alcohol weight 8～16%, stir heating in water bath down, until alcohol by evaporate to dryness;
3) with mixture heating up to 600～1100 ℃, and constant temperature 2～3 hours, take out after being cooled to room temperature, obtain nano ferrite.
2. the preparation method of a kind of nano ferrite according to claim 1 is characterized in that described nano ferrite is the RFe of monocrystalline size 10～100 nanometers 2O 4, R is a kind of among Mn, Ni, Co, Zn, the Cu or several.
3. the preparation method of a kind of nano ferrite according to claim 1 is characterized in that described divalent cation is Mn 2+, Ni 2+, Co 2+, Zn 2+Or Cu 2+In a kind of or several.
4. the preparation method of a kind of nano ferrite according to claim 1 is characterized in that described nitrate is a kind of in manganous nitrate, nickelous nitrate, Xiao Suangu, zinc nitrate or the cupric nitrate or several.
5. the preparation method of a kind of nano ferrite according to claim 1 is characterized in that described agricultural wastes are shell, agricultural crop straw or corn cobs through pulverizing of cereal.
6. the preparation method of a kind of nano ferrite according to claim 1 is characterized in that the nitrate of described iron nitrate or its hydrate and divalent cation or its hydrate 1: 0.5 in molar ratio.
CN2007101566859A 2007-11-12 2007-11-12 Method for preparing nano ferrite Expired - Fee Related CN101182044B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2007101566859A CN101182044B (en) 2007-11-12 2007-11-12 Method for preparing nano ferrite

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2007101566859A CN101182044B (en) 2007-11-12 2007-11-12 Method for preparing nano ferrite

Publications (2)

Publication Number Publication Date
CN101182044A true CN101182044A (en) 2008-05-21
CN101182044B CN101182044B (en) 2010-06-02

Family

ID=39447489

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2007101566859A Expired - Fee Related CN101182044B (en) 2007-11-12 2007-11-12 Method for preparing nano ferrite

Country Status (1)

Country Link
CN (1) CN101182044B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102275999A (en) * 2011-05-27 2011-12-14 山东大学 Network cobalt ferrite for anode material for lithium ion battery and use thereof
CN102790211A (en) * 2012-08-23 2012-11-21 山东大学 Preparation method of high-performance copper ferrite ultrafine powder for lithium ion battery cathode materials
CN102815762A (en) * 2012-08-30 2012-12-12 浙江大学 Method for absorbing precipitation by nano iron and removing phosphate in water by magnetic separation technology
CN103466715A (en) * 2013-09-16 2013-12-25 华北电力大学 Method for preparing nano-copper ferrite composite oxygen carrier by microwave hydrothermal method
CN103657680A (en) * 2012-09-26 2014-03-26 上海华谊丙烯酸有限公司 Ferrate catalyst, preparation method and application of ferrate catalyst
CN105118691A (en) * 2015-09-14 2015-12-02 南京大学 Foamed nickel-supported cobalt acid ferrous submicron tube electrode material and preparation method thereof
CN106277065A (en) * 2015-06-05 2017-01-04 颜笑天 A kind of preparation method of nano ferrite
CN109399725A (en) * 2017-08-15 2019-03-01 中国石油化工股份有限公司 A kind of preparation method and applications of the nano-structure array of dregs containing zinc
CN110038324A (en) * 2019-04-26 2019-07-23 河南大学 A kind of magnetism fire resisting oil absorbing porous silastic material and its preparation method and application

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1065836C (en) * 1998-09-18 2001-05-16 清华大学 Technology for preparing plane haxagon structural soft ferrimagnetics high activity superfine powder by gel method
CN1189962C (en) * 2002-07-30 2005-02-16 复旦大学 Nano anode material for Li-ion battery and its preparing process

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102275999B (en) * 2011-05-27 2013-06-19 山东大学 Network cobalt ferrite for anode material for lithium ion battery and use thereof
CN102275999A (en) * 2011-05-27 2011-12-14 山东大学 Network cobalt ferrite for anode material for lithium ion battery and use thereof
CN102790211B (en) * 2012-08-23 2014-10-29 山东大学 Preparation method of high-performance copper ferrite ultrafine powder for lithium ion battery cathode materials
CN102790211A (en) * 2012-08-23 2012-11-21 山东大学 Preparation method of high-performance copper ferrite ultrafine powder for lithium ion battery cathode materials
CN102815762A (en) * 2012-08-30 2012-12-12 浙江大学 Method for absorbing precipitation by nano iron and removing phosphate in water by magnetic separation technology
CN103657680A (en) * 2012-09-26 2014-03-26 上海华谊丙烯酸有限公司 Ferrate catalyst, preparation method and application of ferrate catalyst
CN103657680B (en) * 2012-09-26 2015-04-08 上海华谊丙烯酸有限公司 Ferrate catalyst, preparation method and application of ferrate catalyst
CN103466715A (en) * 2013-09-16 2013-12-25 华北电力大学 Method for preparing nano-copper ferrite composite oxygen carrier by microwave hydrothermal method
CN103466715B (en) * 2013-09-16 2016-01-13 华北电力大学 A kind of microwave-hydrothermal method prepares the method for nano-copper ferrite composite oxygen carrier
CN106277065A (en) * 2015-06-05 2017-01-04 颜笑天 A kind of preparation method of nano ferrite
CN105118691A (en) * 2015-09-14 2015-12-02 南京大学 Foamed nickel-supported cobalt acid ferrous submicron tube electrode material and preparation method thereof
CN105118691B (en) * 2015-09-14 2018-01-23 南京大学 Nickel foam supports ferrous sub-micron tube electrode material of cobalt acid and preparation method thereof
CN109399725A (en) * 2017-08-15 2019-03-01 中国石油化工股份有限公司 A kind of preparation method and applications of the nano-structure array of dregs containing zinc
CN109399725B (en) * 2017-08-15 2021-04-13 中国石油化工股份有限公司 Preparation method and application of zinc ferrite-containing nano-structure array
CN110038324A (en) * 2019-04-26 2019-07-23 河南大学 A kind of magnetism fire resisting oil absorbing porous silastic material and its preparation method and application

Also Published As

Publication number Publication date
CN101182044B (en) 2010-06-02

Similar Documents

Publication Publication Date Title
CN101182044B (en) Method for preparing nano ferrite
JP6304830B2 (en) Catalyst for butadiene production by oxidative dehydrogenation of butene used in fluidized bed reactor, and production method and use thereof
CN104039445B (en) The method for preparing reforming catalyst and reforming methane
CN105948085B (en) A kind of preparation method of magnetic hydrotalcite
CN102107910B (en) Preparation method of nano magnesium ferrite
CN101549890B (en) Solvothermal synthesis method of nickel cobaltate nano particles
Bhavani et al. Okra (Abelmoschus esculentus) plant extract-assisted combustion synthesis and characterization studies of spinel ZnAl2O4 nano-catalysts
CN104039452B (en) Produce the method for methanation catalyst and the method for synthesis gas methanation
Kumar et al. Synergic effect of manganese oxide on ceria based catalyst for direct conversion of CO2 to green fuel additive: Catalyst activity and thermodynamics study
CN101905861A (en) Preparation method of nanometer laminated composite metal hydroxide
CN100395852C (en) Method for synthesizing series single-dispersed ferrite nanometer magnetic beads
CN103934003A (en) Nano silver catalyst for catalyzing hydrolysis of amino borane and preparation method thereof
CN108927139A (en) Nano bar-shape Nb-CeO2Material preparation method and products thereof and application
CN102371162B (en) High stability iron / manganese catalyst for fluidized bed Fischer-Tropsch synthesis and preparation method thereof
CN112517012A (en) CO (carbon monoxide)2Preparation method and application of catalyst for preparing methanol by hydrogenation
Randhawa et al. Synthesis of lithium ferrite by precursor and combustion methods: A comparative study
Fang et al. NiCo2O4 nanoparticles: an efficient and magnetic catalyst for Knoevenagel condensation
CN100577576C (en) Simple method for ozone oxidation preparation of alpha-FeOOH, beta-MnO2 and Co3O4 nano material
CN1986426A (en) Preparing process of nano Mn-Zn ferrite material
CN106693985A (en) Preparation method of sheet spinel structure cobalt-manganese composite oxide
Shang et al. Insights into the Mn-doping effects on the catalytic performance of ZnCrAlOy/SAPO-34 bifunctional catalyst for the direct conversion of syngas to light olefins
Jaiswal et al. Studies on role of support metal in glycerol conversion to glycerol carbonate through Mg/MnO2 and Mg/CuO heterogeneous catalyst
CN102491421B (en) Nesting doll-shaped manganese oxide nanocrystalline grain composite particle and preparation method thereof
CN107790138B (en) A kind of copper zinc catalyst and preparation method thereof
CN106277065A (en) A kind of preparation method of nano ferrite

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: 20100602

Termination date: 20111112