CN100519418C - High purity nano polyaluminum sol industrialized preparation method - Google Patents
High purity nano polyaluminum sol industrialized preparation method Download PDFInfo
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- CN100519418C CN100519418C CNB2006100026384A CN200610002638A CN100519418C CN 100519418 C CN100519418 C CN 100519418C CN B2006100026384 A CNB2006100026384 A CN B2006100026384A CN 200610002638 A CN200610002638 A CN 200610002638A CN 100519418 C CN100519418 C CN 100519418C
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- aluminum
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Abstract
The invention discloses a making method and technique of high-density high-purity and nanometer typed polyaluminium chloride sol, which comprises the following steps: grinding raw material into 20-300 deg.c; proceeding pyrogenic activating reaction for aluminium chloride in the fluid bed under 150-300 deg.c for 0.5-4h; obtaining the product; adopting dilute alcaine, dilute sulfuric acid, deionized water or dilute aluminium chloride to hydrolyze and activate; filtering; obtaining the total aluminium density over 2.0mol/L and Alb poly-shaped content over 70%.
Description
Technical field
The present invention relates to a kind of industrialized process for preparing, particularly high-basicity of novel polymeric aluminium colloidal sol, the polymeric aluminum colloidal sol preparation method of high-purity nm type (high Alb content).Product not only can be used for the flocculation agent of water treatment, also is widely used in fine chemistry industry, papermaking, petrochemical industry catalysis, pharmacy and makeup intermediate or additive, the raw material of nano aluminium oxide simultaneously.In addition, it has more potential using value in inorganic nano composite material, the inorganic nano mould material field of rising in recent years.
Background technology
Polymerize aluminum chloride is the inorganic polymer that makes by manually operated pressure aluminium salt hydrolysis polymerization process, belongs to a series of metastable state kinetics intermediate products that generate in the aluminium salt hydrolysis polymerization process, i.e. the hydroxyl polymeric form.Flocculation agent as purification of water quality is handled has advantages such as purification efficiency height, suitability is wide, consumption is few, clarification is fast.In recent years discover, generate nanometer Al in the polymeric aluminum solution with Keggin structure
b(Al
13) and accumulation shape have high positive charge and nano molecular size with it and receive much attention, not only generally believed it is the best cohesion flocculation form in the polymeric aluminum flocculating agent, and in other industrial circle, has widespread use as catalysis, fine chemistry industry, papermaking, medicine etc.Have more the potential application prospect in inorganic nano composite material, the inorganic nano mould material field of rising in recent years.Therefore, high-purity nm type (high Al
bThe preparation of polymeric aluminum product content) just becomes the highest goal that suitability for industrialized production is pursued.
Have high dense (〉 2mol/L that commercialization is worth round how to improve) Nano type (high Al in the polymeric aluminum
b) content of polymeric species, people have carried out a large amount of various experimental studies.These studies show that, Nano type (high Al
b) the best basicity that generates of polymeric species is about 75～80%, but be limited by raw material, solution total aluminium concentration, temperature of reaction and time, basifier kind and alkalization mode, and the influence of many complicated factors such as preparation technology, especially in the polymeric aluminum solution reaction process of thermal zone pressure, high alkalization and high density, Nano type (high Al
b) polymeric species easily changes into aluminum hydroxide gel (Al
c) form.Therefore, high dense high-purity nm type polymeric aluminum preparation is difficult to realize all the time.At present existing big quantity research report all is in the laboratory, drips alkaline process by low-temperature trace and prepares lower concentration (0.2mol/L), high nanometer polymerization form (Al
bMore than 80%) polymeric aluminum solution, but this preparation method does not possess commercial value and suitability for industrialized production.
Polymeric aluminum preparation method and technology all are to adopt to be prepared into polymeric aluminum chlorides solution earlier both at home and abroad at present, are cured and are prepared into the solid polyaluminium chloride product.General main bauxitic clay (or the aluminium scrap resource) high-temperature acid that adopts of the suitability for industrialized production of domestic polymeric aluminum flocculating agent is molten, add the liquid preparation technology that calcium aluminate powder alkali is adjusted again, and then adopt cheap roller drying curing process, technology falls behind, contaminate environment, and goods are low, impurity is a lot of, do not have the nanometer polymerization form in the goods at all, mostly be aluminum hydroxide gel, can only be used for the industrial waste water purifying treating processes.Another kind is that one step of the industrial aluminium hydroxide acid pasting that generally adopts both at home and abroad at present is prepared into total aluminium concentration earlier〉3.0mol/L polymeric aluminum solution, be cured by spray-drying process again and make the pulverous polymerize aluminum chloride product of high purity solid, this preparation technology reacts the control condition harshness, the production cost height, the product basicity can only reach 45～55%, and nanometer polymerization form (Al
b) content only 20～30%.Improve basicity as need, can only adjust, not only influence product purity, and nanometer polymerization form content decreases also in the product by adding basifier.
For overcoming the dense high-purity nm type of above-mentioned high polymeric aluminum solution in thermal zone pressure, the difficult shortcoming of high alkalization high density preparation, we had once invented under condition of normal pressure, adopt easy molten aluminium hydroxide and technical hydrochloric acid to make raw material, be equipped with total aluminium concentration 10%～15% (with Al by two sections reverse chemical stripping legal systems
2O
3Meter), basicity adopts refining calcium aluminate to make to make high density more than the basicity to 75% of basifier regulator solution high-basicity, high Al greater than 50% polymeric aluminum chlorides solution then
13And Al
30The preparation method of high-purity polymeric aluminum colloidal sol of content (Chinese patent application number: 200410101786.2).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%.Still there are some shortcomings in above-mentioned these preparation methods and technology: 1) two sections reverse chemical stripping method technological process of productions are longer, adopt easy molten aluminium hydroxide valency height; 2) method for electrochemical production only is suitable for the small-scale production application, and a large amount of aluminium sheets of anode consumption, the product cost height; 3) above-mentioned preparation method still need be prepared into polymeric aluminum liquor earlier, carrying out spraying drying curing, solidifies the energy consumption height; 4) there is the solid articles cost height that finally makes in above-mentioned preparation method, and market is difficult to accept.
The present invention is just for addressing the above problem a kind of high-purity high Al that further develops
bThe preparation method of the nano poly aluminium colloidal sol of content.Be prepared into the pressed powder of polymeric aluminum by the crystallization aluminum chloride that will pulverize in fluidized bed pyrolysis, and then by activator to the activation that is hydrolyzed of polymeric aluminum pressed powder, can be prepared into high density, high Al
bThe nano poly aluminium colloidal sol of content.Technological operation is easy, be easy to realize extensive continuous industry production, and production cost is low and product purity is high, and purposes is wide.
Summary of the invention
The object of the present invention is to provide a kind of preparation of industrialization high density, high-purity nm type (high Al
bContent) method of polymeric aluminum colloidal sol.
Major technique content of the present invention is: the crystalline A lCl that will be crushed to certain particle diameter
3In the pyrolysis fluidized-bed, carry out the pyrolysis activation, make the polymeric aluminum pressed powder, add the activation that is hydrolyzed of dilute hydrochloric acid solution, dilution heat of sulfuric acid, rare liquor alumini chloridi, dilute sulphuric acid aluminum solutions or deionized water then at a certain temperature, can make high density, high-purity nm type (high Al
bContent) polymeric aluminum colloidal sol.
Crystalline A lCl of the present invention
3Can be industrial goods, also can be the aluminum chloride after recrystallization is purified, and its purity is decided the requirement of product purity with the user.
The crystalline A lCl of pulverizing of the present invention
3Particle diameter is 20～300 orders, and particle diameter is littler, and the pyrolysis required time is shorter, and required pyrolysis temperature is lower, and its optimum grain-diameter is about about 100～200 orders.
Fluidized bed pyrolysis activatory temperature controlling range of the present invention is 150～300 ℃, and pyrolysis activatory optimum temps is about 200 ± 20 ℃.Pyrolysis temperature more high material required residence time in fluidized-bed short more, but temperature is too high, causes AlCl easily
3Excessively pyrolysis and form transformation takes place, thus cause hydrolytic activation to generate being difficult to the dissolved hydrogen alumina gel and lost efficacy.
The pyrolysis activatory time of the present invention is 0.5～4.0hr, and the rising of pyrolysis activatory time with pyrolysis temperature reduces, and its pyrolysis activatory Best Times is 2.0 ± 0.5hr.
The consumption of dilute hydrochloric acid solution of the present invention, dilution heat of sulfuric acid, rare liquor alumini chloridi, dilute sulphuric acid aluminum solutions or deionized water is decided the concentration and the performance requriements of product with the client.The temperature of hydrolytic activation is 70～100 ℃, and optimum temps is 90 ± 5 ℃.
The basicity of the polymeric aluminum colloidal sol product that the present invention is prepared is 70～82%, and pyrolysis temperature is high more, and pyrolysis time is long more, and the basicity of colloidal sol is high more.
The Nano type Al of the polymeric aluminum colloidal sol product that the present invention is prepared
bOr Al
13The content of polymeric species is 45～80%, and the product total aluminium concentration is 0.5～4.0mol/L, promptly is equivalent to Al
2O
3Content is 2.5～18%.
Description of drawings
Accompanying drawing 1 is the technological process of production synoptic diagram of high-purity nm polymeric aluminum colloidal sol of the present invention.
Among the figure: the crystallization aluminum chloride is crushed to certain particle diameter through pulverizer earlier, carries out the pyrolysis activation then in the pyrolysis fluidized-bed, and pyrolysis gas is undertaken entering spray absorber recovery salt sour water after the gas solid separation by cyclonic separator; Then pyrolysis activatory aluminum chloride pressed powder is adopted the activation that is hydrolyzed of dilute hydrochloric acid solution, dilution heat of sulfuric acid, rare liquor alumini chloridi, dilute sulphuric acid aluminum solutions or deionized water in the still in activation, filter, filtrate is required high-purity nm polymeric aluminum colloidal sol product.
Embodiment
Preparation method's example below in conjunction with high density of the present invention, high-purity nm type polymeric aluminum colloidal sol illustrates the specific embodiment of the present invention.
Example 1:
It is 150 μ m that 1000kg crystallization aluminum chloride is crushed to median size, in fluidized-bed in carrying out making active aluminum chloride pressed powder behind the pyrolysis activation 2hr under 200 ℃, add 1850L water in 90 ℃ then and be hydrolyzed that promptly to make total aluminium concentration after activation, solution are filtered be 2.0mol/L, basicity is high-purity sol of polyaluminium chloride 2000L of 76% water white transparency shape, by Al-Ferron by the time complexing colorimetric analysis al species that detects in the colloidal sol be distributed as: Al
a=9.47%, Al
b=71.19%, Al
c=19.34%.
Example 2:
1000kg crystallization aluminum chloride is crushed to median size is about 100 μ m, in fluidized-bed, activate 3hr in 210 ℃ of following pyrolysis, add dilute hydrochloric acid solution active dissolution, the filtration that 1850L concentration is 0.5mol/L in 90 ℃ then, making total aluminium concentration is 2.4mol/L, and basicity is high-purity polymeric aluminum chlorides solution 2000L of 74%.Al species when pursuing by Al-Ferron in the complexing colorimetrically analysing colloidal sol is distributed as: Al
a=13.44%, Al
b=75.40%, Al
c=11.16%.
Example 3:
100kg crystallization aluminum chloride is crushed to median size is about 100 μ m, in fluidized-bed, activate 2hr in 220 ℃ of following pyrolysis, add 1850L water active dissolution, filtration in 95 ℃ then, making total aluminium concentration is 0.2mol/L, and basicity is high-purity polymeric aluminum chlorides solution 2000L of 81%.Al species when pursuing by Al-Ferron in the complexing colorimetrically analysing solution is distributed as: Al
a=5.89%, Al
b=81.63%, Al
c=12.48%.
Example 4:
1000kg crystallization aluminum chloride is crushed to median size is about 200 μ m, in fluidized-bed in 190 ℃ of following pyrolysis 3hr, add 1850L water active dissolution, filtration in 100 ℃ then, making total aluminium concentration is 2.0mol/L, and basicity is high-purity polymeric aluminum chlorides solution 2000L of 81%.Al species when pursuing by Al-Ferron in the complexing colorimetrically analysing solution is distributed as: Al
a=13.22%, Al
b=55.42%, Al
c=31.36%.
Example 5:
1000kg crystallization aluminum chloride is crushed to median size is about 180 μ m, in fluidized-bed in 190 ℃ of following pyrolysis 3hr, add 1850L water active dissolution, filtration in 100 ℃ then, making total aluminium concentration is 2.0mol/L, and basicity is high-purity polymeric aluminum chlorides solution 2000L of 79%.Al species when pursuing by Al-Ferron in the complexing colorimetrically analysing solution is distributed as: Al
a=13.22%, Al
b=55.42%, Al
e=31.36%.
Example 6:
1000kg crystallization aluminum chloride is crushed to median size is about 150 μ m, in fluidized-bed in 250 ℃ of following pyrolysis 2.5hr, add 1850L water active dissolution, filtration in 90 ℃ then, making total aluminium concentration is 2.0mol/L, and basicity is high-purity polymeric aluminum chlorides solution 2000L of 76%.Al species when pursuing by Al-Ferron in the complexing colorimetrically analysing solution is distributed as: Al
a=4.74%, Al
b=61.07%, Al
c=34.18%.
Example 7:
1000kg crystallization aluminum chloride is crushed to median size is about 200 μ m, in fluidized-bed in 150 ℃ of following pyrolysis 1hr, add 1850L water active dissolution, filtration in 80 ℃ then, making total aluminium concentration is 2.0mol/L, and basicity is high-purity polymeric aluminum chlorides solution 2000L of 48%.Al species when pursuing by Al-Ferron in the complexing colorimetrically analysing solution is distributed as: Al
a=51.11%, Al
b=32.82%, Al
c=16.07%.
Claims (5)
1, a kind of industrialized process for preparing of high density high-purity nm type polymeric aluminum colloidal sol, it is characterized in that: the crystallization aluminum chloride that will be crushed to certain particle diameter through pulverizer in the pyrolysis fluidized-bed under 150～300 ℃ of temperature pyrolysis activation 0.5～4.0hr, be prepared into active aluminum chloride pressed powder, and then with the activation that is hydrolyzed of dilute hydrochloric acid solution, dilution heat of sulfuric acid, rare aluminum trichloride solution, dilute sulphuric acid aluminum solutions or the deionized water solid aluminum chloride after with pyrolysis, filter, can make high density high-purity nm type polymeric aluminum colloidal sol.
2, industrialized process for preparing according to claim 1 is characterized in that: the total aluminium concentration of polymeric aluminum colloidal sol is 0.5～4.0mol/L, the Nano type Al in the polymeric aluminum colloidal sol
bOr Al
13Polymeric species content is 45%～80%.
3, industrialized process for preparing according to claim 1 is characterized in that: crystallization aluminum chloride particle diameter after crushed is 20～300 orders, and the temperature of described hydrolytic activation is 70～100 ℃.
4, industrialized process for preparing according to claim 1, it is characterized in that: crystallization aluminum chloride particle diameter after crushed is 100～200 orders, pyrolysis activatory temperature is 200 ± 20 ℃, and the pyrolysis activatory time is 2.0 ± 0.5hr, and the temperature of hydrolytic activation is 90 ± 5 ℃.
5, industrialized process for preparing according to claim 1 is characterized in that: the consumption of described dilute hydrochloric acid solution, dilution heat of sulfuric acid, rare aluminum trichloride solution, dilute sulphuric acid aluminum solutions or deionized water according to the user to product concentration and specification of quality and decide.
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| CN100519418C true CN100519418C (en) | 2009-07-29 |
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| CN104743593B (en) * | 2013-12-31 | 2017-10-20 | 重庆蓝洁广顺净水材料有限公司 | Solid polyaluminium chloride process units |
| CN106590475A (en) * | 2016-10-20 | 2017-04-26 | 太仓驰太电子新材料有限公司 | Novel acrylic ester glue and preparation method thereof |
| CN108585229A (en) * | 2018-01-22 | 2018-09-28 | 中国科学院生态环境研究中心 | A kind of drinking water softening composite drug and its application |
| CN110876948B (en) * | 2018-09-05 | 2022-11-15 | 中国石油化工股份有限公司 | Aluminum sol, preparation method and application thereof, and preparation method of catalytic cracking catalyst |
| CN112642472B (en) * | 2019-10-11 | 2023-06-09 | 中国石油化工股份有限公司 | Aluminum sol binder catalyst for producing low-carbon olefin and BTX by hydrocarbon oil conversion and preparation method and application thereof |
| CN111017971A (en) * | 2019-12-26 | 2020-04-17 | 山东鲁阳浩特高技术纤维有限公司 | Alumina sol and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069006A (en) * | 1991-07-30 | 1993-02-17 | 湖南永兴县化学钙塑厂 | A kind of method of producing polymerize aluminum chloride |
| KR20010106873A (en) * | 2000-05-23 | 2001-12-07 | 김명호 | The method of using insoluable precipitate of polyaluminum chloride to a process of making polyaluminum chroride |
| CN1673089A (en) * | 2005-04-22 | 2005-09-28 | 内蒙古大学 | High-Al13 aluminium trichloride polymer crystal and its prepn |
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2006
- 2006-01-26 CN CNB2006100026384A patent/CN100519418C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1069006A (en) * | 1991-07-30 | 1993-02-17 | 湖南永兴县化学钙塑厂 | A kind of method of producing polymerize aluminum chloride |
| KR20010106873A (en) * | 2000-05-23 | 2001-12-07 | 김명호 | The method of using insoluable precipitate of polyaluminum chloride to a process of making polyaluminum chroride |
| CN1673089A (en) * | 2005-04-22 | 2005-09-28 | 内蒙古大学 | High-Al13 aluminium trichloride polymer crystal and its prepn |
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