CN101798064A - Atom economic preparation method for laminated composite metal hydroxide - Google Patents
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Abstract
本发明公开了属于无机非金属功能材料的制备技术领域的一种层状复合金属氢氧化物的原子经济制备方法。本发明以金属氢氧化物、铵盐和氨水为原料，在反应器中通过原子经济反应制备层状复合金属氢氧化物。反应过程使用了铵盐和氨水，降低了反应的温度，使反应条件更加温和，易于控制；反应中使用的铵盐和氨水中的氨在后处理过程中可以回收；反应中使用了金属氢氧化物、阴离子为An-的相应铵盐，不使用NaOH等其它原料，所有原料均参加反应并生成了目标产物，原子经济性为100％，属于典型的原子经济反应。本发明生产过程中无副产物生成，产物不经过洗涤就可以进行干燥得到纯净产品，大大节约了水资源，保护了环境。
The invention discloses an atom-economic preparation method of a layered composite metal hydroxide, which belongs to the technical field of preparation of inorganic non-metallic functional materials. The invention uses metal hydroxide, ammonium salt and ammonia water as raw materials, and prepares layered composite metal hydroxide through atomic economical reaction in a reactor. The reaction process uses ammonium salt and ammonia water, which reduces the temperature of the reaction, making the reaction conditions more mild and easy to control; the ammonium salt used in the reaction and the ammonia in the ammonia water can be recovered in the post-treatment process; the reaction uses metal hydroxide The compound and the anion are the corresponding ammonium salts of An-, without using other raw materials such as NaOH, all raw materials participate in the reaction and generate the target product, and the atom economy is 100%, which belongs to a typical atom economy reaction. No by-products are generated in the production process of the invention, and the products can be dried to obtain pure products without washing, which greatly saves water resources and protects the environment.
Description
Technical field
The invention belongs to the preparing technical field of inorganic non-metallic functional materials, particularly a kind of atom economic preparation method of layered composite metal hydroxides.
Background technology
Layered composite metal hydroxides (Layered Double Hydroxides is called for short LDHs) is hydrotalcite again, is a kind of typical anionic type laminated material, and its chemical constitution formula is [M
2+ 1-xM
3+ x(OH)
2] A
N- X/nMH
2O, wherein, M
2+, M
3+Be metallic cation, A
N-Be interlayer anion, x is M
3+The ionic molar fraction, m is the quantity of crystal water.The kind of the element kind of LDHs main body laminate and proportion of composing, interlayer object and quantity is modulation in relative broad range as required, thus the material that acquisition has special construction and performance.The adjustable sex change of LDHs The Nomenclature Composition and Structure of Complexes and the multifunctionality that is caused thus make it become the type material that a class has research potential and application prospect, are widely used in fields such as catalysis, absorption, ion-exchange and functional materials.
The method for preparing LDHs mainly contains coprecipitation method, hydrothermal synthesis method, ion exchange method and roasting restoring method etc.2 tons of left and right sides sodium salts of 1 ton of LDHs product needed of produced in conventional processes by-product, and the sodium salt utility value is not high, it is big to concentrate energy consumption, generally all directly discharges, and environment has been caused pollution to a certain degree.Simultaneously contain excessive highly basic in the raw material, need to wash, water resources has been caused serious waste with the water of tens times even hundreds of times.Therefore, the technology of environmentally friendly preparation LDHs is the target that people pursue always.
Coprecipitation method is to prepare the most frequently used method of LDHs.Co-precipitation takes place with the mixing salt solution of the metal ion of formation LDHs laminate in this method under the alkali effect, wherein contain in metallic ion mixed liquor or in the alkaline solution and want synthetic interlayer anion group to some extent, throw out crystallization under certain condition can obtain target LDHs.Document (Y.Zhao, F.Li, R.Zhang, D.G.Evans, X.Duan, Preparationof layered double-hydroxide nanomaterials with a uniform crystallitesize using a new method involving separate nucleation and aging steps, Chem.Mater., 2002,14:4286-4291) reported soluble salt and Na with divalence and trivalent metal
2CO
3With NaOH the method that coprecipitation reaction prepares LDHs takes place, excessive N a has been used in reaction
2CO
3, produced a large amount of sodium salts in the reaction process, after finishing, reaction needs to wash with a large amount of water, be unfavorable for conserve water resource and environment protection.
Hydrothermal synthesis method is to be raw material with the insoluble oxide compound and/or the oxyhydroxide that contain the metal ion that constitutes the LDHs laminate, obtains LDHs under High Temperature High Pressure with water treatment.Present employed hydrothermal synthesis method generally uses Na
2CO
3Or NaHCO
3Deng as main raw material, be mixed with the sodium salt that reaction generates in the product, need to filter, wash and remove, environment has been caused harm.Document: Zhi Ping Xu, Guo Qing (Max) Lu, Hydrothermal Synthesis of Layered Double Hydroxides (LDHs) fromMixed MgO and Al2O3:LDH Formation Mechanism, Chem.Mater.2005.17:1055-1062 has reported with MgO and Al
2O
3Mechanical mixture be raw material, add Na
2CO
3Or NaHCO
3In 110 ℃ of preparation interlayer anion is CO
3 2-The method of MgAl-LDHs, have a large amount of Na in the product
+Ion, the unavoidably process of washing with big water gaging.
Ion exchange method is to work as M
2+And M
3+Metal ion is unstable in alkaline medium, or as negatively charged ion A
N-The salt that does not have solubility, i.e. adoptable method when co-precipitation can't be carried out.This method is to synthesize the LDHs presoma earlier, and the negatively charged ion and the LDHs interlayer anion of required insertion exchanged under certain condition, can obtain target LDHs by exchange.This method needs earlier synthetic LDHs presoma, so has by-product salt to generate in the process, and washing process is indispensable step, does not also belong to process for cleanly preparing.International monopoly PCT/CN2006/001233 has introduced a kind of method with double bond containing organic anion intercalation, earlier prepare the LDHs presoma that interlayer is a nitrate radical by coprecipitation method, filter the back with a large amount of deionized water wash and assemble, obtain double bond containing organic anion intercalation LDHs by ion-exchange.
The roasting restoring method is that LDHs that certain laminate is formed is at 500 ℃ of roasting certain hours, make sample be transformed into the composite oxides LDO of equivalent layer plate metal, join and contain in certain anionic solution medium, its structure can be recovered or part returns to the LDHs with ordered lamellar structure.Generally speaking, maturing temperature is below 500 ℃, and the recovery of structure is possible, when maturing temperature generating more than 600 ℃ when having the product of roasting of spinel structure, then cause structure forever can't recover.This method also needs synthetic in advance LDHs presoma, can not avoid the generation and the washing process of by product.Document: Jiang Wei; Nong Lanping; Lai Wenling; Chen Zeyu, with roasting restoring method intercalation assembling organic layer post double-hydroxide, chemical research and application, 2004,16 (6): 828-830, reported that a kind of elder generation adopts coprecipitation method to prepare MgAl-LDHs and ZnAl-LDHs presoma, obtained corresponding LDO, in TETRADECONIC ACID or stearic acid solution, prepared the method for TETRADECONIC ACID and stearic acid intercalation configuration LDHs then through after the roasting.In preparation presoma process, produced a large amount of by products, need water to wash.
Summary of the invention
The clean method for preparing that the purpose of this invention is to provide a kind of layered composite metal hydroxides, i.e. a kind of atom economic preparation method of layered composite metal hydroxides.This method is a raw material with metal hydroxides, ammonium salt and ammoniacal liquor, prepares LDHs by atomic economy reaction in reactor.
Negatively charged ion in metal hydroxides and the solution reacts, and realizes that the precipitation from the metal hydroxides to LDHs transforms, thereby obtains the LDHs precipitation of indissoluble more.Its reaction equation is as follows:
(1-x)M
2+(OH)
2+xM
3+(OH)
3+x/nA
n-+(m-x)H
2O→[M
2+ 1-xM
3+ x(OH)
2]A
n- x/n·mH
2O
Reaction process has been used ammonium salt and ammoniacal liquor, has reduced the temperature of reaction, makes reaction conditions gentle more, is easy to control.The ammonium salt and the ammonia in the ammoniacal liquor that use in the reaction can reclaim in last handling process, have used metal hydroxides, negatively charged ion to be A in the reaction
N-Corresponding ammonium salt, do not use other raw materials such as NaOH, all raw materials all participate in the reaction and generated target product, Atom economy is 100%, belongs to typical atomic economy reaction.
Concrete preparation method of the present invention is as follows:
A. with divalent-metal ion M
2+With trivalent metal ion M
3+Oxyhydroxide, press M
2+/ M
3+Mol ratio is that the ratio of 2-4 is mixed, and adds solid total mass 0.25-999 deionized water doubly, places reactor;
B. in reactor, the adding negatively charged ion is A
N-Corresponding ammonium salt, A
N-With M
3+Mol ratio be 1: n-10: n, do not add ammoniacal liquor or add reaction cumulative volume 0.01-0.5 ammoniacal liquor doubly, temperature of reaction 50-200 ℃, take out solid product behind the reaction 0.5-24h, under 50-120 ℃, carry out drying after the direct filtration, obtaining interlayer is A
N-LDHs.
Described M
2+Represent divalent metal Mg
2+, Zn
2+, Ca
2+, Cu
2+, Ni
2+, Co
2+, Fe
2+, Mn
2+, Cd
2+, Be
2+In one or both, preferred Mg
2+, Zn
2+, Ca
2+, Ni
2+In a kind of or two kinds.M
3+Represent trivalent metal cation Al
3+, Ni
3+, Co
3+, Fe
3+, Mn
3+, Cr
3+, V
3+, Ti
3+, In
3+, Ga
3+In one or both, preferred Al
3+, Ni
3+, Fe
3+In one or both.A
N-Be the negatively charged ion of following acid: (1) inorganic anion: F
-, Cl
-, Br
-, I
-, NO
3 -, HCO
3 -, ClO
3 -, IO
3 -, H
2PO
4 -, CO
3 2-, SO
3 2-, S
2O
3 2-, HPO
4 2-, WO
4 2-, CrO
4 2-, PO
4 3-(2) organic anion: comprise terephthaldehyde's acid group, hexanodioic acid root, succinic, dodecyl sodium sulfonate root, P-hydroxybenzoic acid root, benzoate anion; (3) with many, heteropolyacid anions: comprise Mo
7O
24 6-, V
10O
28 6-, PW
11CuO
39 6-, SiW
9V
3O
40 7-Preferred Cl
-, NO
3 -, CO
3 2-, SO
3 2-, PO
4 3-, terephthaldehyde's acid group, succinic, benzoate anion, Mo
7O
24 6-
Described interlayer is A
N-The chemical constitution formula of LDHs be:
[M
2+ 1-xM
3+ x(OH)
2]A
n- x/n·mH
2O，
Wherein, M
2+Represent divalent metal, be: Mg
2+, Zn
2+, Ca
2+, Cu
2+, Ni
2+, Co
2+, Fe
2+, Mn
2+, Cd
2+, Be
2+In one or both;
M
3+Represent trivalent metal cation, be: Al
3+, Ni
3+, Co
3+, Fe
3+, Mn
3+, Cr
3+, V
3+, Ti
3+, In
3+, Ga
3+In one or both;
A
N-Be interlayer anion, comprise (1) inorganic anion: F
-, Cl
-, Br
-, I
-, NO
3 -, ClO
3 -, IO
3 -, H
2PO
4 -, CO
3 2-, SO
3 2-, S
2O
3 2-, HPO
4 2-, WO
4 2-, CrO
4 2-Or PO
4 3-(2) organic anion: terephthaldehyde's acid group, hexanodioic acid root, succinic, dodecyl sodium sulfonate root, P-hydroxybenzoic acid root, benzoate anion; (3) with many and heteropolyanion: Mo
7O
24 6-, V
10O
28 6-, PW
11CuO
39 6-, SiW
9V
3O
40 7-
X is M
3+Ionic molar fraction, its span are 0.2≤x≤0.33;
M is the quantity of crystal water, and its span is 0≤m≤2;
N is the electrically charged number of interlayer anion.
The invention has the beneficial effects as follows that various atoms in the raw material all participate in reaction and generated target product or water molecules, no coupling product generates in the process, product just can carry out drying without washing and obtain pure product, by ammonia in the recyclable raw material of related device and recycling.The present invention has saved water resources greatly, has protected environment.
Description of drawings
Fig. 1 is embodiment 1 gained MgAl-CO
3The XRD figure of-LDHs;
Fig. 2 is embodiment 1 gained MgAl-CO
3The FT-IR spectrogram of-LDHs;
Fig. 3 is the SEM photograph of embodiment 4 gained NiFe-terephthalic acid-LDHs.
Embodiment
Embodiment 1:
Steps A: with Mg (OH)
2And Al (OH)
3Press Mg
2+/ Al
3+Mol ratio is 3: 1 a mixed, gets the 10g mixture and places the 90g deionized water, is added in the reactor again;
Step B: in reactor, add 1.27g bicarbonate of ammonia and 10ml ammoniacal liquor, be warming up to 100 ℃, reacted 2 hours, with the product that obtains centrifugal after directly in 70 ℃ of dryings 8 hours, obtaining molecular formula is Mg
6Al
2(OH)
12CO
34H
2The LDHs product of O, i.e. MgAl-CO
3-LDHs.
Adopting day XRD-6000 type X-ray powder diffraction instrument of island proper Tianjin company that sample is carried out crystalline structure characterizes.Fig. 1 is the XRD spectra of embodiment 1 gained sample, as can be seen from the figure, 003,006 and 009 crystal face diffraction peak of reflection laminate structure appears at 2 θ=11.7 ° respectively, 23.4 ° and about 34.5 ° locate, each characteristic diffraction peak peak shape point is alarmmed, baseline is low flat, and the inclusion-free peak occurs, and the interpret sample crystalline phase is single and have a complete layered crystal structure.
Adopt the German Bruker Vector22 of company type Fourier transformation infrared spectrometer that sample is carried out qualitative analysis.By the Fourier transform spectrum FT-IR spectrogram of embodiment 1 gained sample, as shown in Figure 2,1361cm
-1The strong absorption peak at place can belong to and is magnalium carbonate LDHs interlayer anion CO
3 2-Feature symmetrical stretching vibration absorption peak.From figure, it can also be seen that the appearance at inclusion-free peak.
Embodiment 2:
Steps A: with Zn (OH)
2, Mg (OH)
2And Al (OH)
3Press Zn
2+: Mg
2+: Al
3+Mol ratio is 1: 3: 2 a mixed, gets the 15g mixture and places the 80g deionized water, is added in the reactor again;
Step B: in reactor, add 1.27g bicarbonate of ammonia and 20ml ammoniacal liquor, be warming up to 200 ℃, reacted 1 hour, with the product that obtains centrifugal after directly in 70 ℃ of dryings 8 hours, obtaining molecular formula is ZnMg
3Al
2(OH)
12CO
34H
2The LDHs product of O.
Embodiment 3:
Steps A: with Ca (OH)
2And Al (OH)
3Press Ca
2+: Al
3+Mol ratio is 3: 1 a mixed, gets the 20g mixture and places the 80g deionized water, is added in the reactor again;
Step B: add 1.27g bicarbonate of ammonia and 30ml ammoniacal liquor in reactor, be warming up to 200 ℃, reacted 1 hour, with the product centrifugation that obtains, directly in 70 ℃ of dryings 8 hours, obtaining molecular formula was Ca
4Al
2(OH)
12CO
34H
2The LDHs product of O.
Adopt day island proper Tianjin ICPS-7500 type elemental analyser that the constituent content of sample is analyzed.The sample of embodiment 3 preparation is carried out ultimate analysis show Ca in the product: Al=3: 1, and do not contain Na in the product
+Deng hetero-ion.
Embodiment 4:
Steps A: with Ni (OH)
2And Fe (OH)
3Press Ni
2+/ Fe
3+Mol ratio is 4: 1 a mixed, gets the 5g mixture and places the 90g deionized water, is added in the reactor again;
Step B: in reactor, add 0.58g terephthalic acid ammonium and 20ml ammoniacal liquor, be warming up to 160 ℃, reacted 6 hours, with the product that obtains centrifugal after directly in 70 ℃ of dryings 8 hours, obtaining molecular formula is Ni
8Fe
2(OH)
20(C
8H
4O
4) 4H
2The LDHs product of O, i.e. NiFe-terephthalic acid-LDHs.
Adopt the pattern of Japanese HITACHI S-3500N type scanning electronic microscope SEM observing samples, Fig. 3 is the SEM photograph of the sample of embodiment 4 preparations, and as seen from the figure, the LDHs that makes is the hexagon flaky substance.
Embodiment 5:
Steps A: with Co (OH)
2And Ni (OH)
3Press Co
2+: Ni
3+Mol ratio is 4: 1 a mixed, gets the 2g mixture and places the 400g deionized water, is added in the reactor again;
Step B: in reactor, add 0.73g (NH
4)
6Mo
7O
24, be warming up to 120 ℃, reacted 8 hours, with the product centrifugation that obtains, directly in 70 ℃ of dryings 8 hours, obtaining molecular formula was Co
24Ni
6(OH)
60(Mo
7O
24) 4H
2The LDHs product of O.
Embodiment 6:
Steps A: with Mg (OH)
2And Fe (OH)
3Press Mg
2+: Fe
3+Mol ratio is 2: 1 a mixed, gets the 4g mixture and puts in the 600g deionized water, is added in the reactor again;
Step B: in reactor, add 0.58g (NH
4)
3PO
4, be warming up to 150 ℃, reacted 8 hours, with the product centrifugation that obtains, directly in 70 ℃ of dryings 8 hours, obtaining molecular formula was Mg
6Fe
3(OH)
18(PO
4) 4H
2The LDHs product of O.
Embodiment 7:
Steps A: with Co (OH)
2And Ni (OH)
3Press Zn
2+: Fe
3+Mol ratio is 3: 1 a mixed, gets the 5g mixture and puts in the 30g deionized water, is added in the reactor again;
Step B: in reactor, add 5.6g (NH
4)
6PW
11CuO
39, be warming up to 200 ℃, reacted 1 hour, with the product centrifugation that obtains, directly in 70 ℃ of dryings 8 hours, obtaining molecular formula was Co
4Ni
2(OH)
12CO
34H
2The LDHs product of O.
Claims (6)
1. the atom economic preparation method of a layered composite metal hydroxides is characterized in that, its concrete preparation process is:
A. with divalent-metal ion M
2+With trivalent metal ion M
3+Oxyhydroxide, press M
2+/ M
3+Mol ratio is that the ratio of 2-4 is mixed, and adds solid total mass 0.25-999 deionized water doubly, places reactor;
B. in reactor, the adding negatively charged ion is A
N-Corresponding ammonium salt, A
N-With M
3+Mol ratio be 1: n-10: n, do not add ammoniacal liquor or add reaction cumulative volume 0.01-0.5 ammoniacal liquor doubly, temperature of reaction 50-200 ℃, take out solid product behind the reaction 0.5-24h, under 50-120 ℃, carry out drying after the direct filtration, obtaining interlayer is A
N-LDHs.
2. the atom economic preparation method of a kind of layered composite metal hydroxides according to claim 1 is characterized in that, described M
2+Represent divalent metal Mg
2+, Zn
2+, Ca
2+, Cu
2+, Ni
2+, Co
2+, Fe
2+, Mn
2+, Cd
2+, Be
2+In one or both; M
3+Represent trivalent metal cation Al
3+, Ni
3+, Co
3+, Fe
3+, Mn
3+, Cr
3+, V
3+, Ti
3+, In
3+, Ga
3+In one or both; A
N-Be the negatively charged ion of following acid: (1) inorganic anion: F
-, Cl
-, Br
-, I
-, NO
3 -, HCO
3 -, ClO
3 -, IO
3 -, H
2PO
4 -, CO
3 2-, SO
3 2-, S
2O
3 2-, HPO
4 2-, WO
4 2-, CrO
4 2-, PO
4 3-(2) organic anion: comprise terephthaldehyde's acid group, hexanodioic acid root, succinic, dodecyl sodium sulfonate root, P-hydroxybenzoic acid root, benzoate anion; (3) with many, heteropolyacid anions: comprise Mo
7O
24 6-, V
10O
28 6-, PW
11CuO
39 6-, SiW
9V
3O
40 7-
3. the atom economic preparation method of a kind of layered composite metal hydroxides according to claim 1 is characterized in that, described interlayer is A
N-The chemical constitution formula of LDHs be:
[M
2+ 1-xM
3+ x(OH)
2]A
n- x/n·mH
2O，
Wherein, M
2+Represent divalent metal, be: Mg
2+, Zn
2+, Ca
2+, Cu
2+, Ni
2+, Co
2+, Fe
2+, Mn
2+, Cd
2+, Be
2+In one or both;
M
3+Represent trivalent metal cation, be: Al
3+, Ni
3+, Co
3+, Fe
3+, Mn
3+, Cr
3+, V
3+, Ti
3+, In
3+, Ga
3+In one or both;
A
N-Be interlayer anion, comprise (1) inorganic anion: F
-, Cl
-, Br
-, I
-, NO
3 -, ClO
3 -, IO
3 -, H
2PO
4 -, CO
3 2-, SO
3 2-, S
2O
3 2-, HPO
4 2-, WO
4 2-, CrO
4 2-Or PO
4 3-(2) organic anion: terephthaldehyde's acid group, hexanodioic acid root, succinic, dodecyl sodium sulfonate root, P-hydroxybenzoic acid root, benzoate anion; (3) with many and heteropolyanion: Mo
7O
24 6-, V
10O
28 6-, PW
11CuO
39 6-, SiW
9V
3O
40 7-
X is M
3+Ionic molar fraction, its span are 0.2≤x≤0.33;
M is the quantity of crystal water, and its span is 0≤m≤2;
N is the electrically charged number of interlayer anion.
4. the atom economic preparation method of a kind of layered composite metal hydroxides according to claim 1 is characterized in that, described M
2+Represent divalent metal Mg
2+, Zn
2+, Ca
2+, Ni
2+In a kind of or two kinds.
5. the atom economic preparation method of a kind of layered composite metal hydroxides according to claim 1 is characterized in that, described M
3+Represent trivalent metal cation Al
3+, Ni
3+, Fe
3+In one or both.
6. the atom economic preparation method of a kind of layered composite metal hydroxides according to claim 1 is characterized in that, described A
N-Be Cl
-, NO
3 -, CO
3 2-, SO
3 2-, PO
4 3-, terephthaldehyde's acid group, succinic, benzoate anion or Mo
7O
24 6-
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| CN101913570A (en) * | 2010-09-02 | 2010-12-15 | 东北林业大学 | Pillared hydrotalcite and its preparation method |
| CN102372275A (en) * | 2010-08-16 | 2012-03-14 | 中国科学院大连化学物理研究所 | Preparation method of inorganic phosphatic crystal material |
| CN102627261A (en) * | 2012-04-23 | 2012-08-08 | 上海大学 | Laminated bimetal oxide material prepared by using main laminate cation exchange way and method for preparing laminated bimetal oxide material |
| CN103028479A (en) * | 2012-11-08 | 2013-04-10 | 北京泰克来尔科技有限公司 | Multi-stage continuous refiner set and application of the multi-stage continuous refiner set in clean preparation of layer-like composite metal hydroxide |
| CN103232104A (en) * | 2013-05-17 | 2013-08-07 | 上海大学 | Treatment method of electroplating wastewater containing cyanogen/zinc |
| WO2014071726A1 (en) * | 2012-11-09 | 2014-05-15 | 北京化工大学 | Self-balance high-pressure high-cutting reaction kettle and application thereof in laminated composite metal hydroxide preparation |
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| CN106517304A (en) * | 2016-11-11 | 2017-03-22 | 中国科学院青海盐湖研究所 | Preparation method of three-dimensional LDHs (layered double hydroxides) |
| CN106517274A (en) * | 2016-11-11 | 2017-03-22 | 中国科学院青海盐湖研究所 | Comprehensive utilization method of byproduct magnesium hydroxide |
| CN107128879A (en) * | 2017-05-17 | 2017-09-05 | 北京师范大学 | A kind of preparation method of layered double hydroxide and its product of preparation |
| CN108246311A (en) * | 2018-01-24 | 2018-07-06 | 济南大学 | A kind of metal simple-substance is inserted into the preparation method of layered double-hydroxide interlayer porous material |
| CN111606338A (en) * | 2020-05-26 | 2020-09-01 | 陈豫镇 | Clean production preparation method of hydrotalcite for plastic processing |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5728365A (en) * | 1994-04-29 | 1998-03-17 | Aluminum Company Of America | Two powder synthesis of hydrotalcite and hydrotalcite-like compounds with divalent inorganic anions |
| CN1994888A (en) * | 2007-01-12 | 2007-07-11 | 北京化工大学 | Cleaning preparation method of sheet-like composite oxide powder |
-
2010
- 2010-03-15 CN CN2010101263415A patent/CN101798064B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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