CN102659164A - Preparation method for copper and aluminium hydrotalcite - Google Patents
Preparation method for copper and aluminium hydrotalcite Download PDFInfo
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- CN102659164A CN102659164A CN2012101509058A CN201210150905A CN102659164A CN 102659164 A CN102659164 A CN 102659164A CN 2012101509058 A CN2012101509058 A CN 2012101509058A CN 201210150905 A CN201210150905 A CN 201210150905A CN 102659164 A CN102659164 A CN 102659164A
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Abstract
The invention discloses a preparation method for copper and aluminium hydrotalcite. The preparation method comprises the following steps of: (1) weighing a copper source and aluminium chloride according to a 2:1 molar ratio of Cu:Al, wherein the copper source is copper oxide or copper hydroxide, dissolving the copper oxide or copper hydroxide and the aluminium chloride in deionized water to be prepared into a mixed liquor in a reaction vessel, heating and stirring the mixed liquor at the constant temperature of 30-40 DEG C till all the copper oxide or copper hydroxide is dissolved, i.e. the color of the solution becomes blue; (2) adjusting the pH value of the solution obtained in the step (1), leading the pH value of the solution not to be higher than 8, and continuously reacting for 2-4h at the temperature of 30-40 DEG C; (3) crystallizing the slurry reacted in the step (2) at the constant temperature of 30-40 DEG C; and (4) filtering, washing, drying and grinding reaction liquid crystallized in the step (3) to obtain the copper and aluminium hydrotalcite. The preparation method has the advantages that used raw materials are low in cost and easily obtained, the conversion rate of atoms is high, and the industrialization cost can be reduced.
Description
(1) technical field
The present invention relates to a kind of preparation method of copper aluminium houghite.
(2) technical background
Hydrotalcite is to be similar to brucite Mg (OH)
2The inorganic materials of negatively charged ion stratiform structure, it has formed laminate in the limit altogether by the octahedron that metals ion and six hydroxyls constitute, between its laminate, can mix negatively charged ion or water molecules, general structure are M
2+ 1-xM
3+ x(OH)
2An
X- X/n.mH
2O, wherein M is a metallic element, it can be that trivalent also can be the metals ion of divalence; A is an interlayer anion, and x is M
3+/ (M
2++ M
3+), generally between 0.2 ~ 0.33.We can control the electric density of laminate through the ratio of allotment divalence and trivalent metal cation, thus anionic quantity between key-course, and obtain our needed hydrotalcite.In addition the interchangeability of interlayer anion also provides the supramolecule stratified material method for preparing different performance for us.
Cationic adjustable property, interlayer anion interchangeability make that hydrotalcite is able to use in many aspects on the alkalescence that has just because of hydrotalcite itself, the laminate, as can be used as environmental pollutant scavenging agent, catalyzer fire-fighting medium, acid scavenger, acid absorber, halogen-absorber, fire retardant, auxiliary ignition dope, increase polymkeric substance heat-resistant stability promotor, acid neutralizing agent, UV blocker, the anti-chlorine agent of insulation agent.
The preparation method of hydrotalcite has a lot, and coprecipitation method, nucleation crystallization isolation method, sol-gel method, hydrothermal synthesis method, electrosynthesis, roasting composite oxides restoring method, ion exchange method are arranged.The most frequently used also is to realize that the earliest industrialized is coprecipitation method; [the synthetic and catalytic activity of CuAl hydrotalcite such as Chen Hui qin for example; Synthetic chemistry; 2007 the 15th the 2nd phases of volume, 233-235 page or leaf] be that raw material adopts coprecipitation method to prepare the pillared CuAl hydrotalcite of carbanion with aluminum nitrate and cupric nitrate, owing to Cu
2+Cause tangible Jahn-Teller effect, be difficult to obtain the good product of percent crystallinity.Pang Qiuyun [preparation and the Study on adsorption properties of copper aluminium houghite; Qufu Normal University's master thesis; In April, 2009] be that raw material adopts Hydrothermal Preparation to obtain copper aluminium houghite with cupric chloride and aluminum nitrate; The hydrotalcite of Hydrothermal Preparation can the base region be told and is the hexagon sheet structure, but agglomeration is more serious.This is that the high-temperature and high-pressure conditions in the crystal growing process causes the segregation of a small amount of CuO crystal because CuAl houghite stability is lower than MgAl class.
To sum up, in the method for existing preparation copper aluminum hydrotalcite, used copper source is metal-salt mostly; It more is the metal-salt that contains a plurality of crystal water; When needs synthesized a large amount of hydrotalcites, the amount of required metal-salt was just bigger, made cost high; Atom utilization is lower, is inappropriate for industriallization and generates.And also there is the copper aluminum hydrotalcite problem of low quality that makes in hydrothermal method.
(3) summary of the invention
The preparation method who the purpose of this invention is to provide a kind of copper aluminium houghite, the used low in raw material cost of this method is easy to get, and the atom transformation efficiency is high, can reduce the industriallization cost.
For realizing the foregoing invention purpose, the present invention adopts following technical scheme:
A kind of preparation method of copper aluminium houghite, said preparation method carries out according to the following step:
(1) takes by weighing copper source and aluminum chloride by Cu:Al mol ratio 2:1; Described copper source is cupric oxide or verditer; In reaction vessel, be dissolved in deionized water and be made into mixed solution, the gained mixed solution is stirred to cupric oxide or verditer all dissolves (ie in solution color become blue) in 30 ~ 40 ℃ of thermostatically heating;
(2) the pH value of solution value that obtains of regulating step (1) makes it not to be higher than 8, continues at 30 ~ 40 ℃ of reaction 2 ~ 4h down;
(3) with the reacted slurries of step (2) at 30 ~ 40 ℃ of following thermostatic crystallization 12 ~ 24h;
(4) with reacting liquid filtering, washing, drying, grinding after step (3) crystallization, obtain copper aluminium houghite.
Among the preparation method according to the invention, the pH value in the synthesis temperature in the step (1), the step (2), the crystallization temperature in the step (3) etc. are the key factors that influences hydrotalcite structure.
In the said step (1), the consumption of said deionized water is counted 5 ~ 15mL/g with the quality of aluminum chloride.。
In the said step (2), the pH value of solution value can not be higher than 8, if pH is too high, can make the copper source all become CuO, and the solution blackening is difficult to dissolving, preferred regulator solution pH value to 7.5 ~ 8.The present invention can use sodium hydroxide solution regulator solution pH value, can make that product percent crystallinity is better, and crystalline phase is single.
In the said step (3), drying temperature is 30 ~ 100 ℃, and be 12 ~ 24 hours time of drying.
The copper aluminium houghite that the present invention makes can be used as acid absorber, halogen-absorber etc.
Compared with prior art, beneficial effect of the present invention is:
1) copper of the present invention source is cheap and easy to get, can synthesize required hydrotalcite in a large number, and atom utilization is high, can reduce the industriallization cost.
2) the present invention is through the optimization to reaction conditions (especially pH value of solution value), and it is better to have obtained percent crystallinity, and the single copper aluminium of crystalline phase houghite.
(4) description of drawings
Fig. 1 is the XRD figure of the copper aluminium houghite that makes of embodiment 5.From figure, can know; Institute's synthetic copper aluminum hydrotalcite possesses the stratiform of hydrotalcite diffractive features and crystalline structure is arranged; Point is arranged and strong diffraction peak in 2 θ value lowers, the existence of laminate structure has been explained corresponding to 003 crystal face in this peak; Peak type point in the spectrogram and the narrow percent crystallinity of having explained is better, and crystalline phase is single.
Fig. 2 is the XRD figure of the copper aluminium houghite that makes of embodiment 3.The intensity at 006 peak is apparently higher than the intensity at 003 peak, and crystal formation does not have obviously that Fig. 1's is good.
Fig. 3 is the XRD figure of the copper aluminium houghite that makes of embodiment 6.Comparison diagram 1 can significantly be found it except the characteristic peak of hydrotalcite, also has other explanations to also have other impurity to exist, and crystalline phase is not single.
(5) embodiment
With specific embodiment technical scheme of the present invention is further specified below, but protection scope of the present invention is not limited thereto:
Embodiment one
Take by weighing the AlCl of 6g
3Cu (OH) with 4.9g
2In there-necked flask, be dissolved in the deionized water of 50ml, be made into mixed solution.30 ℃ of electronic stirrings of following constant temperature.Solution turned blue about 30 minutes.Survey its pH=3, continue stirring reaction 3h, then at 30 ℃ of following crystallization 24h, back suction filtration, and with deionized water wash 3 times, after putting into 40 ℃ of loft drier then and drying 24h, grinding promptly gets Cu/Al hydrotalcite powder.
Embodiment two
Take by weighing the AlCl of 6g
3Cu (OH) with 4.9g
2In there-necked flask, be dissolved in the deionized water of 50ml, be made into mixed solution.In 35 ℃ of electronic stirrings of following constant temperature, solution turned blue about 30 minutes.Take by weighing the NaOH of 5g, be dissolved in the deionized water of 50ml, be made into 0.1g/ml solution; And its part added in the above-mentioned blue solution, regulate pH=6, continue stirring reaction 3h then at 35 ℃ of following crystallization 18h; Back suction filtration, and with deionized water wash 3 times, put into 40 ℃ of loft drier oven dry 24h then after; Grind, promptly get Cu/Al hydrotalcite powder.
Embodiment three
Take by weighing the AlCl of 6g
3Cu (OH) with 4.9g
2In there-necked flask, be dissolved in the deionized water of 50ml, be made into mixed solution.In 35 ℃ of electronic stirrings of following constant temperature, solution turned blue about 30 minutes.Take by weighing the NaOH of 5g, be dissolved in the deionized water of 50ml, be made into 0.1g/ml solution; And its part added in the above-mentioned blue solution, regulate pH=6, continue stirring reaction 3h then at 40 ℃ of following crystallization 20h; Back suction filtration, and with deionized water wash 3 times, put into 60 ℃ of loft drier oven dry 24h then after; Grind, promptly get Cu/Al hydrotalcite powder, its XRD figure is as shown in Figure 2.
Embodiment four
Take by weighing the AlCl of 6g
3Cu (OH) with 4.9g
2In there-necked flask, be dissolved in the deionized water of 50ml, be made into mixed solution.40 ℃ of electronic stirrings of following constant temperature.Solution turned blue about 30 minutes.Take by weighing the NaOH of 5g, be dissolved in the deionized water of 50ml, be made into 0.1g/ml solution; And its part added in the above-mentioned blue solution, regulate pH=6, continue stirring reaction 3h then at 40 ℃ of following crystallization 20h; Back suction filtration, and with deionized water wash 3 times, put into 100 ℃ of loft drier oven dry 24h then after; Grind, promptly get Cu/Al hydrotalcite powder.
Embodiment five
Take by weighing the AlCl of 6g
3Cu (OH) with 4.9g
2In there-necked flask, be dissolved in the deionized water of 50ml, be made into mixed solution.In 35 ℃ of electronic stirrings of following constant temperature, solution turned blue about 30 minutes.Take by weighing the NaOH of 5g, be dissolved in the deionized water of 50ml, be made into 0.1g/ml solution; And its part added in the above-mentioned blue solution, regulate pH=8, continue stirring reaction 3h then at 35 ℃ of following crystallization 20h; Back suction filtration, and with deionized water wash 3 times, put into 60 ℃ of loft drier oven dry 24h then after; Grind, promptly get Cu/Al hydrotalcite powder, its XRD figure is as shown in Figure 1.
Embodiment six
Take by weighing the AlCl of 6g
3Cu (OH) with 4.9g
2In there-necked flask, be dissolved in the deionized water of 50ml, be made into mixed solution.In 35 ℃ of electronic stirrings of following constant temperature, solution turned blue about 30 minutes.Take by weighing the NaOH of 5g, be dissolved in the deionized water of 50ml, be made into 0.1g/ml solution; And its part added in the above-mentioned blue solution, regulate pH=9, continue stirring reaction 3h then at 40 ℃ of following crystallization 20h; Back suction filtration, and with deionized water wash 3 times, put into 60 ℃ of loft drier oven dry 24h then after; Grind, promptly get Cu/Al hydrotalcite powder, its XRD figure is as shown in Figure 3.
Claims (4)
1. the preparation method of a copper aluminium houghite is characterized in that said preparation method carries out according to the following step:
(1) takes by weighing copper source and aluminum chloride by Cu:Al mol ratio 2:1; Described copper source is cupric oxide or verditer; In reaction vessel, be dissolved in deionized water and be made into mixed solution, the gained mixed solution is stirred to cupric oxide or verditer all dissolves in 30 ~ 40 ℃ of thermostatically heating, and it is blue that the ie in solution color becomes;
(2) the pH value of solution value that obtains of regulating step (1) makes it not to be higher than 8, continues at 30 ~ 40 ℃ of reaction 2 ~ 4h down;
(3) with the reacted slurries of step (2) at 30 ~ 40 ℃ of following thermostatic crystallization 12 ~ 24h;
(4) with reacting liquid filtering, washing, drying, grinding after step (3) crystallization, obtain copper aluminium houghite.
2. the preparation method of copper aluminium houghite as claimed in claim 1 is characterized in that: in the said step (2), and regulator solution pH value to 7.5 ~ 8.
3. the preparation method of copper aluminium houghite as claimed in claim 2 is characterized in that: in the said step (2), use sodium hydroxide solution regulator solution pH value.
4. like the preparation method of the described copper aluminium of one of claim 1 ~ 3 houghite, it is characterized in that: in the said step (3), drying temperature is 30 ~ 100 ℃, and be 12 ~ 24 hours time of drying.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921417A (en) * | 2012-10-25 | 2013-02-13 | 常州大学 | Method for preparing nanometer copper oxide catalyst |
| CN103318977A (en) * | 2013-05-23 | 2013-09-25 | 北京化工大学 | Method for preparing hydrotalcite-based supercapacitor material through amorphous aluminum precursor induction |
| CN104030337A (en) * | 2014-06-18 | 2014-09-10 | 江苏隆昌化工有限公司 | Method for preparing copper-aluminum hydrotalcite from copper-containing wastewater |
| CN104944508A (en) * | 2015-05-27 | 2015-09-30 | 浙江工业大学 | Photocatalytic degradation method of low-concentration mixture dye |
| CN106024404A (en) * | 2016-04-29 | 2016-10-12 | 上海大学 | Copper aluminum hydrotalcite like material preparation method and applications thereof |
| CN107419125A (en) * | 2017-06-30 | 2017-12-01 | 常州市顺旭商贸有限公司 | A kind of preparation method of high stable type copper-based electric contact material |
| CN109046355A (en) * | 2018-09-07 | 2018-12-21 | 湘潭大学 | A kind of copper-based houghite catalyzes and synthesizes 3,3 ', 5,5 '-tetramethyls -4,4 '-biphenyl diquinone method |
| CN110577380A (en) * | 2019-09-05 | 2019-12-17 | 中南林业科技大学 | Silicotungstic acid intercalated multi-element hydrotalcite-like light heat-insulating material and preparation method thereof |
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| CN1962453A (en) * | 2006-11-22 | 2007-05-16 | 天津化工研究设计院 | Process for producing hydrotalcite-like layered hydroxide |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102921417B (en) * | 2012-10-25 | 2014-04-09 | 常州大学 | Method for preparing nanometer copper oxide catalyst |
| CN102921417A (en) * | 2012-10-25 | 2013-02-13 | 常州大学 | Method for preparing nanometer copper oxide catalyst |
| CN103318977A (en) * | 2013-05-23 | 2013-09-25 | 北京化工大学 | Method for preparing hydrotalcite-based supercapacitor material through amorphous aluminum precursor induction |
| CN103318977B (en) * | 2013-05-23 | 2015-02-18 | 北京化工大学 | Method for preparing hydrotalcite-based supercapacitor material through amorphous aluminum precursor induction |
| CN104030337A (en) * | 2014-06-18 | 2014-09-10 | 江苏隆昌化工有限公司 | Method for preparing copper-aluminum hydrotalcite from copper-containing wastewater |
| CN104944508B (en) * | 2015-05-27 | 2017-11-07 | 浙江工业大学 | A kind of photocatalytic degradation method of low concentration mixed dye |
| CN104944508A (en) * | 2015-05-27 | 2015-09-30 | 浙江工业大学 | Photocatalytic degradation method of low-concentration mixture dye |
| CN106024404A (en) * | 2016-04-29 | 2016-10-12 | 上海大学 | Copper aluminum hydrotalcite like material preparation method and applications thereof |
| CN106024404B (en) * | 2016-04-29 | 2018-04-06 | 上海大学 | The preparation method and applications of copper aluminium hydrotalcite-like materials |
| CN107419125A (en) * | 2017-06-30 | 2017-12-01 | 常州市顺旭商贸有限公司 | A kind of preparation method of high stable type copper-based electric contact material |
| CN107419125B (en) * | 2017-06-30 | 2018-12-04 | 泉州天泉信息科技有限公司 | A kind of preparation method of high stable type copper-based electric contact material |
| CN109046355A (en) * | 2018-09-07 | 2018-12-21 | 湘潭大学 | A kind of copper-based houghite catalyzes and synthesizes 3,3 ', 5,5 '-tetramethyls -4,4 '-biphenyl diquinone method |
| CN109046355B (en) * | 2018-09-07 | 2021-09-07 | 湘潭大学 | Method for synthesizing 3,3',5,5' -tetramethyl-4, 4' -biphenyl diquinone by catalysis of copper-based hydrotalcite |
| CN110577380A (en) * | 2019-09-05 | 2019-12-17 | 中南林业科技大学 | Silicotungstic acid intercalated multi-element hydrotalcite-like light heat-insulating material and preparation method thereof |
| CN110577380B (en) * | 2019-09-05 | 2021-11-23 | 中南林业科技大学 | Silicotungstic acid intercalated multi-element hydrotalcite-like light heat-insulating material and preparation method thereof |
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Address after: 221000 Datun Street Office Industrial Park, Peixian County, Xuzhou City, Jiangsu Province Patentee after: Xuzhou Hongyang New Material Technology Co.,Ltd. Address before: 221000 Hanyuan Street Office, Peixian County, Xuzhou City, Jiangsu Province Patentee before: XUZHOU HONGYANG NEW MATERIAL TECHNOLOGY CO.,LTD. |