CN1796283A - Method and technique for preparing Nano type sol of polyaluminium chloride in high purity - Google Patents
Method and technique for preparing Nano type sol of polyaluminium chloride in high purity Download PDFInfo
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- CN1796283A CN1796283A CN 200410101786 CN200410101786A CN1796283A CN 1796283 A CN1796283 A CN 1796283A CN 200410101786 CN200410101786 CN 200410101786 CN 200410101786 A CN200410101786 A CN 200410101786A CN 1796283 A CN1796283 A CN 1796283A
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- aluminium hydroxide
- basicity
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Abstract
This invention describes a process for preparing high-purity nanoscale polyalumina sols. This invention uses active aluminum hydroxide and industrial hydrochloric acid as raw materials, and adopts a two-stage reverse stripping process to produce a solution of polyaluminum chloride with an alkalinity higher than 50%, which is then increased to 70% or higher using high-purity calcium aluminate as the alkalizer. The process ensures complete stripping of the aluminum hydroxide raw material at normal atmosphere and a low temperature, thus obtaining a high-purity product. In addition, in the produced polyaluminum chloride sols the total content of nanoscale Al13 and Al30 having Keggin structure is higher than 70%, the alkalinity is 70-85% and the aluminum concentration is 10-19% (measured as Al2O3). The product is widely used as raw material for modern fine chemical binders, gluing agent for neutral paper manufacturing, intermediate or additive for modern pharmaceutical technology, coupling agent and catalyst for chemical production and flocculant for water treatment, and has potential applications in such emerging fields as inorganic nanocomposites and inorganic membrane materials.
Description
Technical field
The present invention relates to the preparation method and the technology of inorganic polymer sol of polyaluminium chloride, particularly a kind of have high-basicity and a nanometer Keggin structure Al
13And Al
30The preparation method of the Nano type sol of polyaluminium chloride in high purity that form content is high and technology, product is widely used in the raw material of fine chemistry industry caking agent, neutral glue used in paper-making, pharmacy and makeup intermediate or additive, Chemical Manufacture coupling agent and catalyzer, and water treatment flocculant.In addition, it has more potential using value in inorganic nano composite material, the inorganic material film field of rising in recent years.
Background technology
Sol of polyaluminium chloride is under artificial forced hydrolysis reaction conditions, high density chlorination aluminum solutions (＞2mol/L) a kind of colloidal sol goods of obtaining of hydrolytic-polymeric reaction.High density, highly purified sol of polyaluminium chloride are widely used in the raw material of fine chemistry industry caking agent in recent years, neutral glue used in paper-making, pharmacy and makeup intermediate or additive, the coupling agent of chemical process and catalyzer raw material, and water treatment flocculant.Especially Nano type sol of polyaluminium chloride in high purity has the potential using value in inorganic nano composite material, the inorganic material film field of rising in recent years.
20th century, be limited to nuclear magnetic resonance spectrometer resolving power precision (
27Al NMR), can't crack the colloidal sol form in the high density polymeric aluminum solution, think Al always with Keggin structure
13The hydrolytic polymerization form is the advantage form in the polymeric aluminum chlorides solution, has ignored Al
13Assemble the colloidal sol morphological significance that forms, thereby limited the range of application of high density polymeric aluminum colloidal sol goods.
21 century is initial, and along with the modern industry fast development, the high density polymeric aluminum chlorides solution is more and more in the application in fields such as modern fine chemistry industry, papermaking, medicine, matrix material, mineral membrane.Simultaneously, the raising along with nuclear magnetic resonance spectrometer resolving power precision studies confirm that Al
30Form and accumulation shape thereof are advantage forms in the high density polymeric aluminum solution, and it is the Al of Keggin structure under the hot conditions
13The result that the further polymerization of form transforms.Al
30Form has 18 positive charges, and the unit particle diameter is about 2.0nm, has the Al of ratio
13Higher charge neutrality ability and morphological stability, its content height directly influences the performance of goods.Therefore, high density, high purity, high Al
30The polymeric aluminum colloidal sol goods of form are the dreamboats that high-purity nm type polymeric aluminum colloidal sol production technique is pursued.
Influence nano shape Al in the polymeric aluminum solution
13And Al
30The principal element of content has basicity, and preparation temperature adds alkali speed etc., and its best basicity is about 75%, and preparation temperature is low more, helps preventing Al more
13And Al
30Transform Deng to high polymeric species, add alkali at a slow speed and help Al
13And Al
30Generation, but the too slow alkali speed that adds can make equipment capacity descend, and increases production cost.
At present, high-purity sol of polyaluminium chloride mainly adopts metallic aluminium and hydrochloric acid or the long-time back flow reaction of aluminum trichloride solution high temperature to make (USP3535268, USP3340205), but this production method is because speed of reaction is uncontrollable, heat-up time is long, superpolymer content height in the prepared sol of polyaluminium chloride, nano shape Al
13And Al
30Content low, and adopt rafifinal to make raw material production cost height.Chinese patent CN1101622A has reported employing Al
2O
3H
2O makes raw material, separate through mixture acidolysis, the glue of mineral acid, organic acid or mineral acid and storng-acid cation exchange resin and to make polymeric aluminum colloidal sol, but this preparation method's long reaction time, prepared product al species size distribution is inhomogeneous, particle size distribution range 10～350nm.Chinese patent CN1445167A report adopts aluminum oxide or aluminium hydroxide or boehmite to make aluminium source and hydrochloric acid or aluminum trichloride solution prepared in reaction aluminium colloidal sol under High Temperature High Pressure, but this preparation needs reaction under high pressure, severe reaction conditions.
In addition, production field at high-purity flocculant of polymeric aluminium chloride generally adopts the acid pasting preparation of one step of industrial aluminium hydroxide gel, be the solubility rate of assurance aluminium hydroxide and the basicity of product, reaction must be carried out in autoclave, and temperature of reaction is more than 150 ℃, more than the reaction pressure 0.3MPa, and long reaction time generally needed 6～8 hours just can finish severe reaction conditions, and the basicity of product can only reach 45～55%, Al
13And Al
30Content only 20～30%.
Chinese patent CN1508292, CN1177653 have reported that respectively the employing aluminum chloride is an electrolytic solution, and aluminium sheet is an anode, and iron plate is a negative electrode, separate the aqueous solution of prepared in reaction polymerize aluminum chloride, the Al of product by low voltage, large-current electric
13Content can reach more than 70%, but this production method needs the consumable anode aluminium sheet, and the product cost height only is suitable for small-scale production and uses.
The present invention is just for addressing the above problem the preparation method and the technology of a kind of high-purity nano polyaluminium chloride colloidal sol that proposes, adopt two sections reverse dissolving-out process of active aluminium hydroxide, can under normal pressure, low temperature, realize the high solubility rate of aluminium hydroxide, and the basicity of solution is higher, has avoided the molten technology of conventional hot-press to cause Al because of the heat overlong time
13And Al
30, adopt high-purity calcium aluminate to make basifier simultaneously and regulate basicity to the defective that high polymeric species transforms etc. nano shape, satisfied the requirement that adds alkali at a slow speed, can effectively prevent the generation of aluminum hydroxide gel.
Summary of the invention
Purpose of the present invention mainly is to provide a kind of high-basicity, nano shape Al
13And Al
30The content height, the preparation method and the technology of the high-purity nano polyaluminium chloride colloidal sol of preparation condition gentleness.
Major technique content of the present invention is: under condition of normal pressure, adopt active aluminium hydroxide and technical hydrochloric acid to make raw material, adopt two sections reverse stripping methods to prepare basicity greater than 50% polymeric aluminum chlorides solution, adopt high-purity calcium aluminate to make basifier then, more than the basicity to 70% of regulator solution, make high density, high-basicity, high Al
13And Al
30High-purity sol of polyaluminium chloride of content.
All reaction process of the present invention are all carried out under normal pressure, and conversion unit is simple, and cost is low.
Active aluminium hydroxide of the present invention is an amorphousness aluminium hydroxide, compares with the prepared crystalloid aluminium hydroxide of kind of point-score, has better solubility in acid.
The mass concentration of technical hydrochloric acid of the present invention is 15～35%.
The mol ratio of molten process active aluminium hydroxide of two sections acid of the present invention and hydrochloric acid is 1: 1.4～2.0.
Two sections reverse stripping methods of the present invention are meant according to active aluminium hydroxide solubility in acid difference, utilize active aluminium hydroxide to make basifier, the polymeric aluminum chlorides solution reaction of the low basicity that in one section molten still of acid, prepares with two sections molten stills of acid, the basicity of solution is brought up to more than 50%, unreacted aluminium hydroxide returns two sections molten stills of acid after filtering and makes raw material, with the hydrochloric acid reaction of high density.
Total solubility rate that aluminium hydroxide of the present invention is two sections is 100%.
The stripping temperature of active aluminium hydroxide of the present invention is 85～100 ℃, and it is 80～90 ℃ that calcium aluminate is transferred the alkali temperature.
High-purity calcium aluminate of the present invention is that solugastril makes 1300～1500 ℃ of left and right sides roastings, and the granularity of calcium aluminate is 30～80 orders, and wherein the mole proportioning of lime carbonate and aluminium hydroxide is 1: 1.0～3.0.
One, two section dissolution time of active aluminium hydroxide of the present invention is 2～3hr, and it is 1～2hr that calcium aluminate is transferred the alkali time.
The present invention adjusts the required high-purity calcium aluminate (CaOnAl of basicity
2O
3) quality can estimate by following formula:
B wherein
1, B
2Be respectively the basicity of transferring alkali front and back solution, C is Al in the solution
3+Mole number, n is Al in the calcium aluminate
2O
3With the mol ratio of CaO, η is the solubility rate of calcium aluminate.
Nano shape Al in the prepared sol of polyaluminium chloride of the present invention
13And Al
30The content sum greater than 70%, basicity is 70～85%, total aluminium concentration is 10～19% (with Al
2O
3Meter).
Description of drawings
Accompanying drawing 1 is the technological process of production synoptic diagram of sol of polyaluminium chloride of the present invention.Among the figure: 1a is two sections molten stills of acid, and 1b is one section molten still of acid, and 1c is for transferring the alkali still, and 2a, 2b, 2c are reflux exchanger, and 3a, 3b are filtering basin, and 4a is low basicity polymerize aluminum chloride storage tank, and 4b is a high-basicity polymerize aluminum chloride storage tank.
Accompanying drawing 2 is prepared sol of polyaluminium chloride
27The AlNMR spectrogram.
Among the figure: the peak at 80ppm, 4ppm (broad peak) and 0ppm place is represented internal standard substance sodium aluminate, dimer and aluminium monomer (Al respectively
m) resonance peak; 62.5ppm and 70ppm (broad peak) represents Al respectively
13And Al
30The resonance peak of middle aluminum-oxygen tetrahedron, the broad peak at 10～12ppm place is represented Al
13, Al
30Reach the resonance peak of alumina octahedral in other form.
Embodiment
Production method example below in conjunction with Nano type sol of polyaluminium chloride of the present invention illustrates the specific embodiment of the present invention.
Example 1:
With 225L concentration is that 31% hydrochloric acid adds two sections molten still 1a of acid, adds the aluminium hydroxide that 78kg is returned by filtering basin 3a simultaneously, stirs and is warming up to 95 ℃, reaction 2hr; Reaction finishes reactant is put into one section molten still 1b of acid, add the 115kg active aluminium hydroxide, stir and be warming up to 95 ℃ of reaction 1hr, add the total aluminium concentration that 445kg water is adjusted solution, continue stirring reaction 1hr down at 95 ℃, react the cooling that finishes, filter in filtering basin 3a, filter residue returns two sections and proceeds sour molten reaction, make filtrate 818kg, put into low basicity polymerize aluminum chloride storage tank 4a, total aluminium concentration is 9.2%, and basicity is 51.8%; The low basicity polymerize aluminum chloride of 818kg is pumped into accent alkali still 1c, add the high-purity calcium aluminate of 64kg, stirring is warming up to 90 ℃ of reaction 1.5hr cooling, be put among the filtering basin 3b and filter, filter residue returns next batch and transfers alkali to continue to use, and makes filtrate 868kg, and total aluminium concentration is 13.0%, basicity is 75.1%, puts into high-basicity polymerize aluminum chloride storage tank 4b; The product warp
27AlNMR analyzes, Al
13Content is 22.6%, Al
30Content is 50.6%, Al
13And Al
30The content sum is 73.2%.
Example 2:
With 365L concentration is that 20% hydrochloric acid adds two sections molten still 1a of acid, adds the aluminium hydroxide that 78kg is returned by filtering basin 3a simultaneously, stirs and is warming up to 95 ℃, reaction 2.5hr; Reaction finishes reactant is put into one section molten still 1b of acid, add the 115kg active aluminium hydroxide, stir and be warming up to 90 ℃ of reaction 1.5hr, add 330kg water and adjust solution to required total aluminium concentration, continue stirring reaction 1hr down at 90 ℃, react the cooling that finishes, filter in filtering basin 3a, filter residue returns two sections and proceeds sour molten reaction, make filtrate 843kg, put into low basicity polymerize aluminum chloride storage tank 4a, total aluminium concentration is 8.6%, and basicity is 52.6%; The low basicity polymerize aluminum chloride of 843kg is pumped into accent alkali still 1c, add the high-purity calcium aluminate of 75.7kg, stirring is warming up to 80 ℃ of reaction 2hr, cooling is put among the filtering basin 3b and filters, and filter residue returns next batch and transfers alkali to continue to use, get filtrate 900kg, total aluminium concentration is 12.7%, and basicity is 78.0%, puts into high-basicity polymerize aluminum chloride storage tank 4b; The product warp
27AlNMR analyzes, Al
13Content is 25.4%, Al
30Content is 46.3%, Al
13And Al
30The content sum is 71.7%.
Claims (9)
1, a kind of preparation method of Nano type sol of polyaluminium chloride in high purity and technology, it is characterized in that: under condition of normal pressure, adopt active aluminium hydroxide and technical hydrochloric acid to make raw material, adopt two sections reverse stripping methods to prepare basicity greater than 50% polymeric aluminum chlorides solution, adopt high-purity calcium aluminate to make basifier then, the regulator solution basicity makes Nano type sol of polyaluminium chloride in high purity.
2, Nano type sol of polyaluminium chloride in high purity according to claim 1 is characterized in that: nano shape Al in the polymerize aluminum chloride
13And Al
30The content sum greater than 70%, basicity is 70～85%, total aluminium concentration is 10～19% (with Al
2O
3Meter).
3, active aluminium hydroxide raw material according to claim 1 is characterized in that: used aluminium hydroxide is amorphousness aluminium hydroxide.
4, technical hydrochloric acid according to claim 1 is characterized in that: its mass concentration is 15～35%.
5, the production technique of polymerize aluminum chloride according to claim 1 is characterized in that: the mole proportioning of two sections molten process active aluminium hydroxides of reverse acid and hydrochloric acid is 1: 1.4～2.0.
6, two sections reverse stripping methods according to claim 1, it is characterized in that: adopt active aluminium hydroxide to make basifier, the polymeric aluminum chlorides solution reaction of the low basicity that in one section molten still of acid, prepares with two sections molten stills of acid, improve the solution basicity, unreacted aluminium hydroxide returns two sections molten stills of acid after filtering and makes raw material, continues reaction with concentrated hydrochloric acid.
7, the production technique of sol of polyaluminium chloride according to claim 1, it is characterized in that: the stripping temperature of active aluminium hydroxide is 85～100 ℃, one, two section dissolution time of active aluminium hydroxide is 2～3hr, and total solubility rate that active aluminium hydroxide is two sections is 100%.
8, the production technique of sol of polyaluminium chloride according to claim 1 is characterized in that: it is 80～90 ℃ that calcium aluminate is transferred the alkali temperature, and it is 1～2hr that calcium aluminate is transferred the alkali time.
9, high-purity calcium aluminate according to claim 1, it is characterized in that: high-purity calcium aluminate is that solugastril makes 1300～1500 ℃ of left and right sides roastings, the granularity of calcium aluminate is 30～80 orders, and wherein the mole proportioning of lime carbonate and aluminium hydroxide is 1: 1.0～3.0.
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| CN100453474C (en) * | 2006-09-07 | 2009-01-21 | 中国科学院生态环境研究中心 | Preparation of nanometer type inorganic polymer flocculant and its product |
| CN100460328C (en) * | 2007-04-28 | 2009-02-11 | 王军 | Technical process for producing chloride aluminum |
| CN101734702B (en) * | 2008-11-26 | 2012-07-25 | 天津润沃供水安装工程有限公司 | Device and method for generating liquid high purity nanometer polyaluminium chloride |
| CN103130258A (en) * | 2011-11-28 | 2013-06-05 | 中国科学院生态环境研究中心 | Preparation method of polymeric aluminum with high concentration high alcohol (Alc) content by making use of membrane distillation technology |
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| CN108238621A (en) * | 2018-03-06 | 2018-07-03 | 洪湖源泰科技有限公司 | Utilize the method for the by-product production aluminium polychloride for producing diethyl methyl-phosphonite |
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| CN100460328C (en) * | 2007-04-28 | 2009-02-11 | 王军 | Technical process for producing chloride aluminum |
| CN101734702B (en) * | 2008-11-26 | 2012-07-25 | 天津润沃供水安装工程有限公司 | Device and method for generating liquid high purity nanometer polyaluminium chloride |
| US9463985B2 (en) | 2010-11-02 | 2016-10-11 | Colgate-Palmolive Company | Aluminum salt containing high percentage of Al30 |
| US10118832B2 (en) | 2010-11-02 | 2018-11-06 | Colgate-Palmolive Company | Aluminum salt containing high percentage of Al30 |
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| CN103833059A (en) * | 2014-03-03 | 2014-06-04 | 常州友邦净水材料有限公司 | Method for producing polyaluminum chloride without heating |
| CN104085867B (en) * | 2014-07-18 | 2016-04-13 | 中国人民解放军防化学院 | A kind of aluminium phosphide tablet fumigant draff processing method and device |
| CN104085867A (en) * | 2014-07-18 | 2014-10-08 | 中国人民解放军防化学院 | Method and device for treating residues of aluminum phosphide tablet fumigation agent |
| CN107628631A (en) * | 2017-08-31 | 2018-01-26 | 四川齐力绿源水处理科技有限公司 | A kind of aluminium polychloride preparation method |
| CN107628631B (en) * | 2017-08-31 | 2019-09-13 | 四川齐力绿源水处理科技有限公司 | A kind of aluminium polychloride preparation method |
| CN108238621A (en) * | 2018-03-06 | 2018-07-03 | 洪湖源泰科技有限公司 | Utilize the method for the by-product production aluminium polychloride for producing diethyl methyl-phosphonite |
| CN111747435A (en) * | 2020-07-08 | 2020-10-09 | 宁夏蓝田农业开发有限公司 | Method for preparing flocculant by using oxadiargyl byproduct |
| CN111747435B (en) * | 2020-07-08 | 2022-10-25 | 宁夏蓝田农业开发有限公司 | Method for preparing flocculant by oxadiargyl byproduct |
| CN111977676A (en) * | 2020-07-15 | 2020-11-24 | 中国科学院生态环境研究中心(义乌)长三角中心 | Preparation and purification of Al30Method for morphological polymerization of aluminum |
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