CN103803621A - Method using double salt method to prepare anhydrous aluminum chloride from crystallization aluminum chloride dehydration - Google Patents
Method using double salt method to prepare anhydrous aluminum chloride from crystallization aluminum chloride dehydration Download PDFInfo
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- CN103803621A CN103803621A CN201210436786.2A CN201210436786A CN103803621A CN 103803621 A CN103803621 A CN 103803621A CN 201210436786 A CN201210436786 A CN 201210436786A CN 103803621 A CN103803621 A CN 103803621A
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Abstract
The invention relates to a method using a double salt method to prepare anhydrous aluminum chloride from crystallization aluminum chloride dehydration. The method comprises the steps that an amine substance, imidazole or pyridine is used as a raw material to synthesize organic hydrochloride; mixing reaction is carried out on the synthesized organic hydrochloride, crystallization aluminum chloride and water at the temperature of 80 to 100 DEG C; after reaction, cooling to room temperature is carried out to realize crystal precipitation; drying is carried out for 5 to 10 hours at the temperature of 80 to 100 DEG C, so as to acquire hydration chloride amine aluminum double salt, hydration chloride imidazole aluminum double salt or hydration chloride pyridine aluminum double salt; two-section decomposition is carried out on the formed double salt to remove crystallization water and alchlor; sublimated alchlor gas is trapped, so as to acquire the anhydrous aluminum chloride; and isolated organic hydrochloride can be recycled. The method has the advantages of available raw material of crystallization aluminum chloride, low product cost and low energy consumption, does not produce corrosive gas, and does not pollute the environment. The prepared anhydrous aluminum chloride with the purity more than 98.5% can be used as the raw material of a catalyst of organic synthesis and oil cracking and electrolysis production metallic aluminum.
Description
Technical field
The present invention relates to a kind of preparation method of Aluminum chloride anhydrous, refer more particularly to a kind of by crystal aluminum chloride Dehydration the method for Aluminum chloride anhydrous.
Background technology
Aluminum trichloride (anhydrous) is one of important inorganic chemical product, is mainly used in organic catalyst compound, catalyst of cracking petroleum, is widely used in addition synthetic detergent, agricultural chemicals, dyestuff, spices etc.Except such use, aluminum trichloride (anhydrous) is also used to prepare metallic aluminium, and this is the emerging industry just occurring in the later stage seventies.Make raw material electrolysis processed metallic aluminium than He Er (Hall) method of generally applying in the world at present with aluminum oxide with aluminum trichloride (anhydrous) metallic aluminium processed according to the literature, aluminium per ton can be saved power consumption 3000 degree left and right, there is electric furnace per unit area yield high simultaneously, can air conservation, the advantage such as can extend electrode life, service temperature can reduce, can be continuously produced.Alcoa had once set up the aluminum chloride electrolytic experiment factory of 1.5 ten thousand tons of aluminium of First annual output in 1976, and take aluminum chloride as approximately 7000 tons of raw material electrolysis production metallic aluminiums.Due to high with Preparation of alumina Aluminum chloride anhydrous cost, and in Aluminum chloride anhydrous, require foreign matter content low, thereby the process such as preparation, deposit, transportation requires sternly, cause less economically, the said firm has to stop this production equipment with nineteen eighty-two.Therefore, economically prepare the key that Aluminum chloride anhydrous is aluminum trichloride (anhydrous) electrolysis metallic aluminium processed.
At present, most enterprises generally adopts aluminium ingot method to produce Aluminum chloride anhydrous, its concrete grammar is: the aluminium ingot after preheating drops in airtight chlorination reaction stove, chlorine by top on the way pipe send in stove, at 800-900 ℃, there is chlorination reaction and generate Aluminum chloride anhydrous, enter condenser through sublimation pipe, the crystallize out that is captured, gets product.Need be through washing tower soda lye wash when the deficiency of this technique is exhaust emissions, be that production cost is high in addition.In addition, Ye You minority enterprise produces Aluminum chloride anhydrous by alundum method, as Alcoa, and domestic chemical plant, Jinxi.Producing Aluminum chloride anhydrous cardinal principle by alundum method is take aluminum oxide as main raw material, makes reductive agent with coal, and chlorine is made oxygenant, and under 850-950 ℃ of environment, reaction generates Aluminum chloride anhydrous, mainly contains fixed bed, thermopnore and three kinds of chloridization process of ebullated bed.This technique has the following disadvantages: the one, in tail gas, containing a small amount of chlorine, after needing to process, discharge; The 2nd, the Aluminum chloride anhydrous purity of producing is low, needs sublimation purifying just can obtain highly purified Aluminum chloride anhydrous; The 3rd, technical process complexity, not easy to operate.
Summary of the invention
the technical problem to be solved in the present invention: a kind of method of preparing Aluminum chloride anhydrous is provided, and the method raw material sources are extensive, and technique is simple, and cost is low, non-exhaust emission, and the Aluminum chloride anhydrous purity making is high.
technical scheme of the present invention: a kind of double salt method is the method for Aluminum chloride anhydrous by crystal aluminum chloride Dehydration, it is characterized in that: take crystal aluminum chloride as raw material, generate double salt take organic salt hydrochlorate as reaction medium, decomposing double salt dewaters, trapping aluminum chloride gas obtains Aluminum chloride anhydrous, the organic salt hydrochlorate recycle and reuse that separation obtains, comprises the following steps:
(1) organic salt hydrochlorate is synthetic: amine substance, imidazoles or pyridine are joined in reactive crystallization still, add afterwards hydrochloric acid, at temperature 10-60 ℃, react 1-6 hour after filtering separation, obtain organic salt hydrochlorate crude product; Crude product is further dry in the loft drier of 50 ℃ obtained organic salt hydrochlorate after 6-10 hour;
(2) double salt is synthetic: dried organic salt hydrochlorate joins in reactive crystallization still, then add crystal aluminum chloride and water, in the situation that stirring, material in reactor is warmed up to 80-100 ℃, until be dissolved into homogeneous phase, be cooled to afterwards room temperature crystallize out, after being separated by filtration by obtain crystal at 80-100 ℃ of dry 5-10 hour, obtain hydration ammonia chloride class aluminium double salts, hydration imidazolitm chloride aluminium double salts or hydration pyridinium chloride aluminium double salts;
(3) double salt decomposes: the double salt obtaining is joined in fluidized-bed reactor, and reactor is warmed up to 120-160 ℃, reaction 20-60 minute, obtains not ammonia chloride class aluminium double salts, imidazolitm chloride aluminium double salts or the pyridinium chloride aluminium double salts containing crystal water; Then the double salt that removes crystal water is joined in another fluidized-bed reactor, control 200-240 ℃ of temperature of reactor and react 10-30 minute, thereby the aluminum chloride gas of trapping distillation obtains Aluminum chloride anhydrous, separate the organic salt hydrochlorate obtaining in order to recycle.
In described step (1), amine substance is one or more mixture in aniline, quadrol or trolamine; Hydrochloric acid is that concentration 30%-36% technical pure or reagent are pure; Amine substance, imidazoles or the pyridine adding and the mol ratio of hydrochloric acid are 1:1-1:1.2.
In described step (1), organic salt hydrochlorate crude product is first with being dried after absolute ethanol washing 2-3 time again, and the purity of the organic salt hydrochlorate obtaining is more than 98%.
In described step (2), the crystal aluminum chloride crystal aluminum chloride crystal that the leaching liquid after hydrochloric acid leaching forms after removal of impurities, evaporation, concentrated and crystallization for commercially available prod or coal gangue.
The crystal aluminum chloride adding in described step (2) and the mol ratio of organic salt hydrochlorate are 1:1-1:1.1, and the mol ratio of water and organic salt hydrochlorate is 0.1:1-0.3:1.1.
the invention has the advantages that:
(1) the present invention prepares organic salt hydrochlorate by one-step synthesis, and preparation and purifying process process are simple, and the organic salt hydrochlorate purity of preparing is high;
(2) the material crystal aluminum chloride wide material sources of the synthetic double salt of the present invention, and synthetic double salt can carry out thermolysis at lower temperature (200 ℃-240 ℃), greatly reduce the cost of preparing Aluminum chloride anhydrous, therefore the inventive method save energy, has reduced production cost;
(3) the synthetic double salt of the inventive method has NH
3with the multiple characteristic of the material such as HCl, in decomposition course, can suppress the hydrolysis of Aluminum chloride anhydrous, and in decomposition course, can not produce HCl and NH
3deng corrosive gases, environmentally friendly;
(4) the organic salt hydrochlorate reusable edible that the synthetic double salt of the present invention obtains after decomposing, greatly reduces the cost of producing Aluminum chloride anhydrous;
(5) the Aluminum chloride anhydrous purity that prepared by the inventive method, more than 98.5%, can be used as the catalyzer of organic synthesis and petroleum cracking and the raw material of electrolytic process production metallic aluminium.
Accompanying drawing explanation
Fig. 1 double salt method of the present invention is the process flow sheet for Aluminum chloride anhydrous by crystal aluminum chloride Dehydration.
Embodiment
below in conjunction with drawings and Examples, the present invention will be described in detail,
embodiment 1
(1) get 400 trolamines and add in reactor, controlling the temperature of reactor is 40 ℃, in stirring, slowly add concentration be 271 grams of 36% technical hydrochloric acids in reactor, stirring reaction, after 4 hours, filters magma, obtains organic salt hydrochlorate crude product; Crude product, with after absolute ethanol washing 2 times, is placed in to the loft drier of 50 ℃ is dry obtained organic salt hydrochlorate after 6 hours, knows that after testing its purity is 98.2%;
(2) in reactive crystallization still, add 241.5 grams of crystal aluminum chlorides, slowly be warming up to 90 ℃, add 3.6 grams of water, stirring makes it abundant dissolving, then getting 185.6 grams of organic salt hydrochlorates that step (2) obtains joins in reactive crystallization still, stirring and dissolving is until become after homogeneous phase to naturally cool to room temperature, and the crystal obtaining is placed in that 100 ℃ of loft drier are dry obtains approximately 402 grams of double salt after 8 hours;
(3) 402 grams of double salt that step (2) obtained are placed in fluidized-bed reactor, and reactor is warming up to 160 ℃, obtain taking off not containing 285 grams of the chlorination trolamine aluminium double salts of crystal water after 30 minutes; Then 285 grams of obtaining are not placed in to another fluidized-bed reactor containing the double salt of crystal water, 220 ℃ of reactions 20 minutes, the aluminum chloride gas of volatilization are trapped simultaneously, obtain 120.5 grams of aluminum trichloride (anhydrous)s, know after testing its purity 98.7%.
embodiment 2
(1) get 136 grams of imidazoles and add in reactor, controlling the temperature of reactor is 10 ℃, in stirring, slowly add concentration be 267.7 grams of 30% technical hydrochloric acids in reactor, stirring reaction, after 1 hour, filters magma, obtains organic salt hydrochlorate crude product.Crude product, with after absolute ethanol washing 2 times, is placed in to the loft drier of 50 ℃ is dry obtained organic salt hydrochlorate after 6 hours, knows that after testing its purity is 98.7%;
(2) in reactive crystallization still, add 241.5 grams of crystal aluminum chlorides, slowly be warming up to 80 ℃, add 1.8 grams of water, stirring makes it abundant dissolving, then getting 105.2 grams of organic salt hydrochlorates that step (2) obtains joins in reactive crystallization still, stirring and dissolving is until become after homogeneous phase to naturally cool to room temperature, and the crystal obtaining is placed in that 80 ℃ of loft drier are dry obtains approximately 322 grams of double salt after 5 hours;
(3) 322 grams of double salt that step (2) obtained are placed in fluidized-bed reactor, and reactor is warming up to 140 ℃, obtain taking off not containing approximately 223 grams of the imidazolitm chloride aluminium double salts of crystal water after 60 minutes; Then 223 grams of obtaining are not placed in to another fluidized-bed reactor containing the double salt of ctystallizing point water, 240 ℃ of reactions 10 minutes, the aluminum chloride gas of volatilization are trapped simultaneously, obtain 126.8 grams of aluminum trichloride (anhydrous)s, know after testing its purity 98.5%.
embodiment 3
(1) get 158 grams of pyridines and add in reactor, controlling the temperature of reactor is 60 ℃, in stirring, slowly add concentration be 214.7 grams of 34% technical hydrochloric acids in reactor, stirring reaction, after 6 hours, filters magma, obtains organic salt hydrochlorate crude product; Crude product, with after absolute ethanol washing 2 times, is placed in to the loft drier of 50 ℃ is dry obtained organic salt hydrochlorate after 6 hours, knows that after testing its purity is 98.1%;
(2) in reactive crystallization still, add 241.5 grams of crystal aluminum chlorides, slowly be warming up to 90 ℃, add 5.4 grams of water, stirring makes it abundant dissolving, then getting 115.6 grams of organic salt hydrochlorates that step (2) obtains joins in reactive crystallization still, stirring and dissolving is until become after homogeneous phase to naturally cool to room temperature, and the crystal obtaining is placed in that 100 ℃ of loft drier are dry obtains approximately 338 grams of double salt after 8 hours;
(3) 338 grams of double salt that step (2) obtained are placed in fluidized-bed reactor, and reactor is warming up to 160 ℃, obtain taking off not containing approximately 237 grams of the pyridinium chloride aluminium double salts of crystal water after 20 minutes; Then 237 grams of obtaining are not placed in to another fluidized-bed reactor containing the double salt of ctystallizing point water, 200 ℃ of reactions 30 minutes, the aluminum chloride gas of volatilization are trapped simultaneously, obtain 128.7 grams of aluminum trichloride (anhydrous)s, know after testing its purity 98.7%.
Claims (5)
- A double salt method by crystal aluminum chloride Dehydration the method for Aluminum chloride anhydrous, it is characterized in that: take crystal aluminum chloride as raw material, generate double salt take organic salt hydrochlorate as reaction medium, decomposing double salt dewaters, trapping aluminum chloride gas obtains Aluminum chloride anhydrous, the organic salt hydrochlorate recycle and reuse that separation obtains, comprises the following steps:(1) organic salt hydrochlorate is synthetic: amine substance, imidazoles or pyridine are joined in reactive crystallization still, add afterwards hydrochloric acid, at temperature 10-60 ℃, react 1-6 hour after filtering separation, obtain organic salt hydrochlorate crude product; Crude product is further dry in the loft drier of 50 ℃ obtained organic salt hydrochlorate after 6-10 hour;(2) double salt is synthetic: dried organic salt hydrochlorate joins in reactive crystallization still, then add crystal aluminum chloride and water, in the situation that stirring, material in reactor is warmed up to 80-100 ℃, until be dissolved into homogeneous phase, be cooled to afterwards room temperature crystallize out, after being separated by filtration by obtain crystal at 80-100 ℃ of dry 5-10 hour, obtain hydration ammonia chloride class aluminium double salts, hydration imidazolitm chloride aluminium double salts or hydration pyridinium chloride aluminium double salts;(3) double salt decomposes: the double salt obtaining is joined in fluidized-bed reactor, and reactor is warmed up to 120-160 ℃, reaction 20-60 minute, obtains not ammonia chloride class aluminium double salts, imidazolitm chloride aluminium double salts or the pyridinium chloride aluminium double salts containing crystal water; Then the double salt that removes crystal water is joined in another fluidized-bed reactor, control 200-240 ℃ of temperature of reactor and react 10-30 minute, thereby the aluminum chloride gas of trapping distillation obtains Aluminum chloride anhydrous, separate the organic salt hydrochlorate obtaining in order to recycle.
- A kind of double salt method according to claim 1 by crystal aluminum chloride Dehydration the method for Aluminum chloride anhydrous, it is characterized in that: in step (1), amine substance is one or more mixture in aniline, quadrol or trolamine; Hydrochloric acid is that concentration 30%-36% technical pure or reagent are pure; Amine substance, imidazoles or the pyridine adding and the mol ratio of hydrochloric acid are 1:1-1:1.2.
- A kind of double salt method according to claim 1 by crystal aluminum chloride Dehydration the method for Aluminum chloride anhydrous, it is characterized in that: in step (1), organic salt hydrochlorate crude product is first with being dried after absolute ethanol washing 2-3 time again, and the purity of the organic salt hydrochlorate obtaining is more than 98%.
- A kind of double salt method according to claim 1 by crystal aluminum chloride Dehydration the method for Aluminum chloride anhydrous, it is characterized in that: in step (2), the crystal aluminum chloride crystal aluminum chloride crystal that the leaching liquid after hydrochloric acid leaching forms after removal of impurities, evaporation, concentrated and crystallization for commercially available prod or coal gangue.
- A kind of double salt method according to claim 1 by crystal aluminum chloride Dehydration the method for Aluminum chloride anhydrous, it is characterized in that: the crystal aluminum chloride adding in step (2) and the mol ratio of organic salt hydrochlorate are 1:1-1:1.1, and the mol ratio of water and organic salt hydrochlorate is 0.1:1-0.3:1.1.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4264569A (en) * | 1978-09-26 | 1981-04-28 | Commonwealth Scientific & Industrial Research Organization | Production of anhydrous aluminium chloride |
| CN1482064A (en) * | 2002-09-10 | 2004-03-17 | 章浩龙 | Method of preparing anhydrous aluminium chloride |
| CN1944261A (en) * | 2006-11-06 | 2007-04-11 | 清华大学 | Process for preparing anhydrous magnesium chloride by dewatering bischofite |
| CN101155759A (en) * | 2005-04-04 | 2008-04-02 | 日本轻金属株式会社 | High-purity anhydrous aluminum chloride and process for production thereof |
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2012
- 2012-11-06 CN CN201210436786.2A patent/CN103803621A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4264569A (en) * | 1978-09-26 | 1981-04-28 | Commonwealth Scientific & Industrial Research Organization | Production of anhydrous aluminium chloride |
| CN1482064A (en) * | 2002-09-10 | 2004-03-17 | 章浩龙 | Method of preparing anhydrous aluminium chloride |
| CN101155759A (en) * | 2005-04-04 | 2008-04-02 | 日本轻金属株式会社 | High-purity anhydrous aluminum chloride and process for production thereof |
| US20090028766A1 (en) * | 2005-04-04 | 2009-01-29 | Nippon Light Metal Company, Ltd. | High Purity Anhydrous Aluminium Chloride and Process for Production Thereof |
| CN1944261A (en) * | 2006-11-06 | 2007-04-11 | 清华大学 | Process for preparing anhydrous magnesium chloride by dewatering bischofite |
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Application publication date: 20140521 |