CN102925914B - A kind of method of electrochemical production nano-aluminum hydroxide powder - Google Patents
A kind of method of electrochemical production nano-aluminum hydroxide powder Download PDFInfo
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- CN102925914B CN102925914B CN201210396410.3A CN201210396410A CN102925914B CN 102925914 B CN102925914 B CN 102925914B CN 201210396410 A CN201210396410 A CN 201210396410A CN 102925914 B CN102925914 B CN 102925914B
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Abstract
The invention discloses a kind of method of electrochemical production nano-aluminum hydroxide powder, the method adopts after electrolysis of aluminum, and its electrolysate is obtained nano-aluminum hydroxide powder through washing, hydrothermal treatment consists, washing, drying, and its particle size range is 10 ~ 80nm.The present invention, by the adjustment of electric current, voltage and pH and adopt hydrothermal technology, achieves the effective control to aluminium hydroxide powder particle diameter.The preparation technology of the inventive method gained nano-aluminum hydroxide powder is simple, with short production cycle; Productive rate is high, and product stability is good; Environmentally safe.Nano-aluminum hydroxide powder prepared by the present invention is widely used in multiple industries such as chemical industry, coating, material of construction, electric wire, cable and rubber item.
Description
Technical field
The present invention relates to a kind of preparation method of aluminium hydroxide, particularly a kind of method of electrochemical production nano-aluminum hydroxide powder.
Background technology
The ultrafine particle of nano-aluminum hydroxide to be a kind of particle diameter be 1 ~ 100nm, each side has excellent characteristic, is widely used in the industries such as chemical industry, coating, material of construction, electric wire, cable and rubber item as a kind of new function material and structured material at present.In recent years, along with the development of powder surface treatment technology, the nano-aluminum hydroxide powder of surface activation is as inorganic combustion inhibitor, its application makes substantial progress, become the fire retardant kind that at present application quantity is maximum in the world, and can be used as senior filler and be widely used in the fire-retardant of macromolecular material and fill.But the technology of preparing relative progress of nano-aluminum hydroxide powder is slow, still there is numerous technical barrier, cause product performance unstable, the comparatively large and shortcoming such as wide that distributes of particle size.
Through finding the literature search of prior art, the method preparing nano-aluminum hydroxide at present has multiple, sol-gel method, conventional homogeneous precipitation method, supergravity hydrothermal method, metal alkoxide hydrolysis method etc. is patent discloses, some bibliographical informations kind point-score and carborization as existing.These methods all respectively have feature, but also there are some shortcomings, and control that is as too high in raw material preparation cost, particle size is more difficult, powder is very easily reunited, the requirement of complex operation, equipment is very high, has pollution etc. to environment.As a kind of nano material of functionalization, the industrialized difficulty of preparation technology of nano-aluminum hydroxide is comparatively large, only has minority overseas enterprise can large-scale production at present.In view of this, special proposition the present invention.
Summary of the invention
In order to overcome the shortcoming that above-mentioned prior art exists, the invention provides that a kind of cost is low, experiment condition is simple, environmentally safe, being easy to the preparation method of the nano-aluminum hydroxide of suitability for industrialized production.
The technical scheme that technical solution problem of the present invention is taked is as follows: described preparation method be using surface treatment after aluminium sheet simultaneously carry out electrolytic reaction as negative electrode and anode; Gained electrolysate is obtained nano-aluminum hydroxide powder after washing, hydrothermal treatment consists, washing, drying.
In the technical scheme of above-mentioned preparation method: described surface treatment is: first utilize caustic dip surface of aluminum plate, and then lower concentration mineral acid is utilized to clean surface of aluminum plate.Wherein, described mineral acid is selected from the one in hydrochloric acid, nitric acid and sulfuric acid, and its concentration range is 0.05 ~ 0.5mol/L; Alkali lye is selected from the one in sodium hydroxide, potassium hydroxide, and its concentration range is 0.5 ~ 2.5g/L.
In preparation method of the present invention, effective constituent in the electrolytic solution that described electrolytic reaction adopts is the carbon atom number of 50 ~ 500g/L is the cats product of 5 ~ 25, and described tensio-active agent is any one in choline chloride 60, Beta-methyl choline chloride 60, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, benzyl dimethyl four decyl ammonium chloride.
In preparation method of the present invention, described electrolytic reaction adopts power supply to be direct supply.
In preparation method of the present invention, described electrolysis in pH6 ~ 10, current density 1 ~ 5A/dm
2, temperature is 30 ~ 90 DEG C, and mechanical stirring or pneumatic blending gas pushing quantity scope are carry out under the condition of 100 ~ 3000L/min.
In electrolytic reaction of the present invention, when the content of electrolysate in electrolytic solution and white aluminium hydroxide powder is 3% ~ 30%, be separated by electrolyte filtering, as by dynamic separation aluminium hydroxide powder, filtrate cycle uses.In this step, the separation method that the separation of electrolysate adopts those skilled in the art usual.
In preparation method of the present invention, described hydrothermal treatment consists is: electrolysate aluminium hydroxide powder is put into high pressure vessel, and add pure water, crystal seed and organic anion, be 100 ~ 300 DEG C in temperature, pressure is that under the condition of 1 ~ 87kg, constant temperature 1 ~ 48h carries out hydrothermal treatment consists; Wherein, the consumption of pure water is 1 ~ 8 times of aluminium hydrate powder body weight; The consumption of organic anion is 0.5 ‰ ~ 10% of aluminium hydrate powder body weight.
In above-mentioned hydrothermal treatment consists, described crystal seed particle diameter is the nano-aluminum hydroxide powder of 5 ~ 100nm, and its injected volume is aluminium hydrate powder body weight 1 ‰ ~ 10%.
In preparation method of the present invention, described organic anion is the one in tartrate or citric acid.
In preparation method of the present invention, described washing, refer to that the aluminium hydroxide powder pure water after by hydrothermal treatment consists washs, this bath water can recycle after treatment.
In preparation method of the present invention, described pure water, namely electrical resistivity range is the water of 2 ~ 10M Ω .cm.
As a kind of preferred forms of the present invention, the present invention preferably adopts following preparation method: using the aluminium sheet after surface treatment simultaneously as anodic-cathodic, being placed in containing benzyl trimethyl ammonium chloride amount is the electrolytic solution of 400g/L, in pH8 ~ 10; Current density 1A/dm
2, temperature is 30 DEG C, and pneumatic blending gas pushing quantity is electrolysis aluminium sheet under the condition of 100L/min.When powder content reaches 25% in electrolytic solution, after filtering tank liquor, obtain aluminium hydroxide powder; By aluminium hydroxide powder after washing, putting into high pressure vessel, and add the tartrate of pure water, crystal seed and aluminium hydrate powder body weight 5%, is 100 DEG C in temperature, and pressure is constant temperature 1h under the condition of 30kg.Take out aluminium hydroxide powder after washing, drying, nano-aluminum hydroxide powder can be obtained.
Adopt technique scheme, nano-aluminum hydroxide median size prepared by the present invention is 10 ~ 80nm.
Compared to existing technology, the present invention has following beneficial effect:
1. pass through the adjustment to electric current, voltage and pH and employing hydrothermal technology, achieve the effective control to nano-aluminum hydroxide particle diameter.
2. the nano-aluminum hydroxide powder of preparation, its average particle size range is 10 ~ 80nm.
3. in nano-aluminum hydroxide powder preparation process, agents useful for same is the organic composition that volatility is little, not containing inorganic additive, more environmental protection, also can not introduce impurity element simultaneously.
4. in nano-aluminum hydroxide powder preparation process, pure water used can be recycled, without a large amount of waste residue, waste gas and discharge of wastewater, extremely beneficial to environment protection, belongs to environment-friendly type technique.
5. preparation technology of the present invention is simple, and with short production cycle, production cost is lower, and scale and benefit are strong, facility of expanding production.
Embodiment
Embodiment 1
The preparation method of the nano-aluminum hydroxide of present embodiment carries out in accordance with the following steps: using the aluminium sheet after surface treatment simultaneously as negative electrode and anode, be placed in the benzyl trimethyl ammonium chloride electrolytic solution that content is 200g/L, be 7 ~ 8 at pH, current density is 3A/dm
2, temperature is 60 DEG C, and mechanical stirring gas pushing quantity is electrolysis aluminium sheet under the condition of 800L/min.When solids content reaches 28% in electrolytic solution, after filtering tank liquor, obtain aluminium hydroxide powder; By aluminium hydroxide powder after washing, put into high pressure vessel, and add the citric acid of pure water, crystal seed and filter cake weight 5%; Temperature be 200 DEG C, pressure be the condition of 12kg under constant temperature 6h carry out hydrothermal treatment consists; Wherein the consumption of pure water is 4 times of aluminium hydrate powder body weight; The nano-aluminum hydroxide powder of crystal seed to be particle diameter be 50nm, its injected volume is aluminium hydrate powder body weight 5%; Tartaric consumption is 6% of aluminium hydrate powder body weight.Take out after hydrothermal treatment consists and can obtain nano-aluminum hydroxide powder after washing, drying.
Through above-mentioned preparation process, the median size of the nano-aluminum hydroxide powder finally obtained is 50nm, Granular composite and size is even.
Embodiment 2
The preparation method of the nano-aluminum hydroxide of present embodiment carries out in accordance with the following steps:
Using the aluminium sheet after surface treatment simultaneously as anodic-cathodic, being placed in chloride containing choline amount is the electrolytic solution of 400g/L, at pH 8 ~ 10; Current density 1A/dm
2, temperature is 30 DEG C, electrolysis aluminium sheet under the condition of pneumatic blending gas pushing quantity 100L/min.When solids content reaches 25% in electrolytic solution, after filtering tank liquor, obtain aluminium hydroxide powder; By aluminium hydroxide powder after washing, putting into high pressure vessel, and add the citric acid of pure water, crystal seed and aluminium hydrate powder body weight 5%, is 100 DEG C in temperature, and pressure is that under the condition of 10kg, constant temperature 1h carries out hydrothermal treatment consists; Wherein the consumption of pure water is 3 times of aluminium hydrate powder body weight; Crystal seed is the nano-aluminum hydroxide powder of particle diameter 5nm, and its injected volume is aluminium hydrate powder body weight 1 ‰; The consumption of citric acid is 6% of aluminium hydrate powder body weight.Take out after hydrothermal treatment consists through washing, after drying, nano-aluminum hydroxide powder can be obtained.
The median size of nano-aluminum hydroxide powder prepared by the present embodiment is 30nm.
Embodiment 3
The preparation method of the nano-aluminum hydroxide of present embodiment carries out in accordance with the following steps:
Using the aluminium sheet after surface treatment simultaneously as anodic-cathodic, being placed in containing benzyltriethylammoinium chloride content is the electrolytic solution of 400g/L, at pH 8 ~ 10, current density 5A/dm
2, temperature is 90 DEG C, and mechanical stirring gas pushing quantity is electrolysis aluminium sheet under the condition of 1000L/min.When aluminium hydrate powder body burden reaches 30% in electrolytic solution, after being filtered by tank liquor, obtain aluminium hydroxide powder; After being washed by aluminium hydroxide powder, putting into high pressure vessel, and add the tartrate of pure water, crystal seed and aluminium hydrate powder body weight 10%, is 300 DEG C in temperature; Pressure is that under the condition of 87kg, constant temperature 30h carries out hydrothermal treatment consists; Wherein the consumption of pure water is 5 times of aluminium hydrate powder body weight; Crystal seed is the nano-aluminum hydroxide powder of particle diameter 100nm, and its injected volume is aluminium hydrate powder body weight 10%; Tartaric consumption is 2% of aluminium hydrate powder body weight.Take out after hydrothermal treatment consists through pure water, after drying, nano-aluminum hydroxide powder can be obtained.
The median size of nano-aluminum hydroxide powder prepared by the present embodiment is 70nm.
Embodiment 4
The preparation method of the nano-aluminum hydroxide of present embodiment carries out in accordance with the following steps:
Using the raw material aluminium sheet after surface treatment simultaneously as negative electrode and anode, be placed in the Beta-methyl choline chloride 60 electrolytic solution that content is 50g/L, at pH 7 ~ 8, current density 3A/dm
2, temperature is 60 DEG C, and pneumatic blending gas pushing quantity is electrolysis aluminium sheet under the condition of 3000L/min.When solids content reaches 3% in electrolytic solution, after filtering tank liquor, obtain aluminium hydroxide powder; By aluminium hydroxide powder after washing, putting into high pressure vessel, and add pure water, crystal seed and tartrate, is 100 DEG C in temperature, and pressure is that under the condition of 32kg, constant temperature 24h carries out hydrothermal treatment consists; Wherein, the consumption of pure water is 8 times of aluminium hydrate powder body weight; Crystal seed is the nano-aluminum hydroxide powder of particle diameter 50nm, and its injected volume is aluminium hydrate powder body weight 5%; Tartaric consumption is 0.5 ‰ of aluminium hydrate powder body weight.Take out after hydrothermal treatment consists, through pure water, after drying, nano-aluminum hydroxide powder can be obtained.
The median size of nano-aluminum hydroxide powder prepared by the present embodiment is 10nm.
Embodiment 5
The preparation method of the nano-aluminum hydroxide of present embodiment carries out in accordance with the following steps:
Using the raw material aluminium sheet after surface treatment simultaneously as negative electrode and anode, be placed in the benzyl trimethyl ammonium chloride electrolytic solution that content is 500g/L, at pH 6 ~ 7, current density 5A/dm
2, temperature is 30 DEG C, and mechanical stirring gas pushing quantity is electrolysis aluminium sheet under the condition of 2000L/min.When solids content reaches 10% in electrolytic solution, after filtering tank liquor, obtain aluminium hydroxide powder; By aluminium hydroxide powder after washing, putting into high pressure vessel, and add pure water, crystal seed and citric acid, is 300 DEG C in temperature, and pressure is that under the condition of 7kg, constant temperature 48h carries out hydrothermal treatment consists; Wherein, the consumption of pure water is 1 times of aluminium hydrate powder body weight; Crystal seed is the nano-aluminum hydroxide powder of particle diameter 30nm, and its injected volume is aluminium hydrate powder body weight 6%; The consumption of citric acid is 5% of aluminium hydrate powder body weight.Take out after hydrothermal treatment consists, through pure water, after drying, nano-aluminum hydroxide powder can be obtained.
The median size of nano-aluminum hydroxide powder prepared by the present embodiment is 80nm.
Embodiment 6
The preparation method of the nano-aluminum hydroxide of present embodiment carries out in accordance with the following steps:
Using the raw material aluminium sheet after surface treatment simultaneously as negative electrode and anode, be placed in the benzyl dimethyl four decyl ammonium chloride electrolytic solution that content is 300g/L, in pH8 ~ 10, current density 5A/dm
2, temperature is 30 DEG C, and pneumatic blending gas pushing quantity is electrolysis aluminium sheet under the condition of 100L/min.When solids content reaches 20% in electrolytic solution, after filtering tank liquor, obtain aluminium hydroxide powder; By aluminium hydroxide powder after washing, putting into high pressure vessel, and add pure water, crystal seed and tartrate, is 100 DEG C in temperature, and pressure is that under the condition of 37kg, constant temperature 48h carries out hydrothermal treatment consists; Wherein, the consumption of pure water is 2 times of aluminium hydrate powder body weight; Crystal seed is the nano-aluminum hydroxide powder of particle diameter 60nm, and its injected volume is aluminium hydrate powder body weight 1%; Tartaric consumption is 10% of aluminium hydrate powder body weight.Take out after hydrothermal treatment consists, through pure water, after drying, nano-aluminum hydroxide powder can be obtained.
The median size of nano-aluminum hydroxide powder prepared by the present embodiment is 60nm.
Embodiment in above-described embodiment can combine further or replace; and embodiment is only be described the preferred embodiments of the present invention; not the spirit and scope of the present invention are limited; under the prerequisite not departing from design philosophy of the present invention; the various changes and modifications that in this area, professional and technical personnel makes technical scheme of the present invention, all belong to protection scope of the present invention.
Claims (7)
1. a preparation method for nano-aluminum hydroxide, is characterized in that, described preparation method be using surface treatment after raw material aluminium sheet simultaneously carry out electrolytic reaction as negative electrode and anode; Gained electrolysate is obtained nano-aluminum hydroxide powder after washing, hydrothermal treatment consists, washing, drying; In the electrolytic solution that described electrolytic reaction adopts, effective constituent is the carbon atom number of 50 ~ 500g/L is the cats product of 5 ~ 25, and described tensio-active agent is any one in choline chloride 60, Beta-methyl choline chloride 60, benzyl trimethyl ammonium chloride, benzyltriethylammoinium chloride, benzyl dimethyl four decyl ammonium chloride; Described hydrothermal treatment consists is: put into high pressure vessel after being filtered by electrolysate aluminium hydroxide powder, and add pure water, crystal seed and organic anion, be 100 ~ 300 DEG C in temperature, pressure is that under the condition of 1 ~ 87kg, constant temperature 1 ~ 48h carries out hydrothermal treatment consists; Wherein, the consumption of pure water is 1 ~ 8 times of aluminium hydrate powder body weight; The consumption of organic anion is 0.5 ‰ ~ 10% of aluminium hydrate powder body weight.
2. preparation method according to claim 1, is characterized in that, described electrolytic reaction adopts power supply to be direct supply.
3. preparation method according to claim 1, is characterized in that, described electrolytic reaction at pH 6 ~ 10, current density 1 ~ 5A/dm
2, temperature is 30 ~ 90 DEG C, and mechanical stirring or pneumatic blending gas pushing quantity are carry out under the condition of 100 ~ 3000L/min.
4. preparation method according to claim 1, is characterized in that, when in electrolytic solution, the content of electrolysate white aluminium hydroxide powder is 3% ~ 30%, is separated by electrolyte filtering.
5. preparation method according to claim 1, is characterized in that, described crystal seed is the nano-aluminum hydroxide powder of particle diameter 5 ~ 100nm, and the injected volume of crystal seed is 1 ‰ ~ 10% of aluminium hydrate powder body weight.
6. preparation method according to claim 1, is characterized in that, described organic anion is the one in tartrate or citric acid.
7. preparation method according to claim 1, it is characterized in that, described preparation method is: using the aluminium sheet after surface treatment simultaneously as anodic-cathodic, being placed in containing benzyl trimethyl ammonium chloride amount is the electrolytic solution of 400g/L, in pH8 ~ 10, current density 1A/dm
2, temperature is 30 DEG C, and pneumatic blending gas pushing quantity is electrolysis aluminium sheet under the condition of 100L/min, when powder content reaches 25% in electrolytic solution, obtains aluminium hydroxide powder after filtering tank liquor; By aluminium hydroxide powder after washing, putting into high pressure vessel, and add the tartrate of pure water, crystal seed and aluminium hydrate powder body weight 5%, is 100 DEG C in temperature, and pressure is constant temperature 1h under the condition of 30kg; Take out and can obtain nano-aluminum hydroxide powder after washing, drying.
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| TWI548779B (en) * | 2014-12-01 | 2016-09-11 | 國立雲林科技大學 | Method for preparing metal compounds |
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