CN102275960A - Preparation process and preparation device of anhydrous magnesium chloride - Google Patents

Preparation process and preparation device of anhydrous magnesium chloride Download PDF

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CN102275960A
CN102275960A CN201110180588XA CN201110180588A CN102275960A CN 102275960 A CN102275960 A CN 102275960A CN 201110180588X A CN201110180588X A CN 201110180588XA CN 201110180588 A CN201110180588 A CN 201110180588A CN 102275960 A CN102275960 A CN 102275960A
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magnesium chloride
heating
zone
stationary ring
composite structure
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CN102275960B (en
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仇晓丰
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Nantong Star Graphite Co ltd
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Abstract

The invention provides a preparation process of anhydrous magnesium chloride, and the preparation process comprises the following steps: introducing hydrogen chloride into a rotary kiln with a composite structure, and carrying out three-stage heating dehydration at the following heating ranges, namely, 160-220 DEG C, 180-380 DEG C and 330- 450 DEG C; and absorbing separated water with hydrogen chloride to obtain steam containing hydrogen chloride, introducing the steam containing hydrogen chloride into an integrated absorbing tower to form hydrochloric acid, and desorbing hydrochloric acid to generate hydrogen chloride for recycling. The preparation device of anhydrous magnesium chloride is the rotary kiln with the composite structure, and is composed of alternate three heating regions and four stationary seal rings, wherein the heating regions and the stationary seal rings are combined by a static and dynamic combined form; and the three heating regions can rotate and are in a cylindrical composite structure, the composite structure is composed of a steel plate layer, a flexible graphite layer and a graphite layer, and an electric heating pipe is pre-embedded in the graphite layer. By using hydrogen chloride as a water absorbent in the preparation method, the dehydration efficiency is significantly improved, hydrogen chloride is recycled and the consumption is less; the flexible graphite layer reduces the vibration when the device operates; and the graphite layer has high corrosion resistance.

Description

The preparation technology of Magnesium Chloride Anhydrous and preparation facilities thereof
Technical field
The present invention relates to prepare the method and apparatus of Magnesium Chloride Anhydrous by magnesium chloride hexahydrate.
Background technology
In industrial production, magnesium chloride hexahydrate prepares Magnesium Chloride Anhydrous, has multiple preparation method, but the energy consumption height that has, the technical process complexity that has, the inefficiency that has, the high-level efficiency that the shortage large-scale production needs, the maturation method of less energy-consumption.
MgCl26H2O
Number of patent application is that 200410041515.2 file discloses " micro-wave energy is produced the Magnesium Chloride Anhydrous new process of production ", at first in first microwave heater, realize magnesium chloride hexahydrate dewater moisture 1.5-2.0 magnesium chloride, temperature be controlled at 100-120 ℃ by magnesium chloride hexahydrate dewater Four Modernizations magnesium chloride, temperature be controlled at 100-150 ℃ from four aqueous magnesium chlorides dewater moisture 1.5-2.0 magnesium chloride; Realize in second microwave heater that then moisture 1.5-2.0 magnesium chloride gets Magnesium Chloride Anhydrous, temperature is controlled at 150-350 ℃, the dewatering agent of the 1-10% of adding, and the chlorine add-on of protective atmosphere is for covering material surface-area consumption.The microwave heater size of this technology is less, and throughput is lower.
Number of patent application is that 200710179865.9 file discloses " method that is prepared Magnesium Chloride Anhydrous by bischofite ".With the bischofite is the feedstock production Magnesium Chloride Anhydrous, and specific embodiment is as follows: (1) at first sloughs most of crystal water with the bischofite drying; (2) dried magnesium chloride is dissolved in the ethylene glycol solution of preparation magnesium chloride in the ethylene glycol, adopts the vacuum distilling method to slough moisture in the ethylene glycol solution of magnesium chloride; (3) ethylene glycol solution of the magnesium chloride after the dehydration and ammonia react crystallization generate the magnesium chloride hex-ammoniate crystal; (4) washing, filtration, the dry magnesium chloride hex-ammoniate crystal that gets; (5) exsiccant magnesium chloride hex-ammoniate thermal degradation deamination makes Magnesium Chloride Anhydrous.Adopt these raw materials of ethylene glycol and ammonia in this technology, improved production cost, increased environmental pollution.
Summary of the invention
Goal of the invention: overcome the defective that efficient is low, energy consumption is high in traditional Magnesium Chloride Anhydrous preparation, a kind of preparation technology who consumes the Magnesium Chloride Anhydrous low, that dewatering efficiency is high is provided.Technical scheme: for realizing purpose of the present invention, adopt a kind of preparation technology of Magnesium Chloride Anhydrous, hydrogenchloride feed is loaded in the composite structure rotary kiln of magnesium chloride hexahydrate, divide three grades, level Four, Pyatyi or six grades of dehydrations of heating; When dividing three grades, three grades of scopes of heating are respectively 160 ℃-220 ℃, 180 ℃-380 ℃ and 330 ℃-450 ℃, respectively corresponding three are decomposed dehydrations: by magnesium chloride hexahydrate become four aqueous magnesium chlorides process, by four aqueous magnesium chlorides become magnesium chloride dihydrate process, become the process of the Magnesium Chloride Anhydrous finished product of ultimate demand by magnesium chloride dihydrate, thereby realize having magnesium chloride hexahydrate to become the preparation process of Magnesium Chloride Anhydrous; When being divided into level Four, Pyatyi or six grades, the scope of heating is divided into corresponding progression between 160 ℃-480 ℃, and corresponding four, five or six are progressively decomposed dehydration respectively, and each step can be taken off the water of one or more molecules.
Among the present invention, the moisture of deviating from is chlorinated hydrogen and absorbs and become to contain hydrogenchloride steam, or absorbs cooling through quencher earlier, flows into comprehensive absorption tower again and absorbs into hydrochloric acid.
Described three grades of scopes of heating are preferably 190 ℃-220 ℃, 330 ℃-350 ℃ and 400 ℃-450 ℃, and corresponding respectively three are decomposed dehydration.
Described heating is the heating of preferred employing electrothermal tube.
The speed of rotation of described composite structure rotary kiln can be 10-100 rev/min.
Described hydrochloric acid can be again becomes hydrogenchloride through the resolving of persalt resolution system and reclaims, and part hydrogenchloride can recycle for this technological process, and the acid waste water that the hydrochloric acid resolution system produces is discharged outside this process unit.
Another object of the present invention: a kind of preparation facilities that the preparation technology who realizes above-mentioned Magnesium Chloride Anhydrous is provided.
Realize this purpose technical scheme: the preparation facilities of Magnesium Chloride Anhydrous is a kind of composite structure rotary kiln, by three, four, five or six heat zone and four or more stationary rings are alternate forms.
Be divided into three when heating the zone, three zones of heating can both rotate, and are respectively cold zone, middle warm area, high-temperature zone, the length 2m-18m in each zone of heating; Heating from beginning to end regional and heating is connected with stationary ring between the zone, heat and adopt the combining form of dynamic and static ring sealing between zone and the stationary ring; Magnesium chloride hexahydrate inlet is on the 1st stationary ring, and on the 1st stationary ring, the 2nd stationary ring, the 3rd stationary ring, hydrogenchloride enters the mouth on the 4th stationary ring respectively for three outlets that contain hydrogenchloride steam, and Magnesium Chloride Anhydrous exports on the 4th stationary ring; Heat the zone for columned composite structure, be composited for three layers by steel plate layer, soft graphite layer, graphite linings, electric heating tube is embedded in the graphite linings.Three outlets that contain hydrogenchloride steam are common to connect one or connect three comprehensive absorption towers respectively, connects before the comprehensive absorption tower or is connected with quencher earlier.Comprehensive absorption tower or connect the hydrochloric acid resolution system again, the hydrogenchloride that the hydrochloric acid resolution system is emitted or connect the hydrogenchloride inlet of composite structure rotary kiln again by pipeline.
The diameter in described three zones of heating can be 0.5m-3m, and the thickness of graphite linings can be 80mm-200mm, and the thickness of soft graphite layer can be 1.5mm-6mm.The diameter in three zones of heating and length can require design to determine according to production capacity.
The contact surface of described dynamic and static ring sealing is minute surface preferably, and the material of contact surface place stationary ring is preferably silicon carbide, the contact surface place heat the zone material be preferably graphite.
Described composite structure rotary kiln can have 5 °-20 ° gradient when installing and using, can drive material when heating the zone rotation and be walked to the high-temperature zone by cold zone automatically.
Described electric heating tube can be connected power supply with brush by slide block, and an end of brush is fixedly connected on the stationary ring, guarantees that the supply lines of power supply with the rotation of this rotary kiln entanglement does not take place.(17) top, described comprehensive absorption tower or be connected with vacuum pick-up system, suction hydrogenchloride steam can quicken the dehydration of magnesium chloride.
Beneficial effect: the present invention adopts the absorption agent of hydrogenchloride as water, and hydrogenchloride finally parses, and does not participate in chemical reaction, is similar to the effect of catalyzer, can significantly improve dewatering efficiency.The classification of dewatering process subregion is carried out, and the dehydration link is clear, and ultimate dehydration is thorough.Vibration when the soft graphite layer of composite structure rotary kiln can reduce the device running, running steadily reduce noise; Graphite linings erosion resistance height, life-span are permanent, and dynamic and static ring sealing is good, and friction resistance is little; Hydrogenchloride recycles, and consumes to lack, and pollutes few.Dimensional change scope of the present invention is wide, and the production that is fit to multiple production capacity is used; This device also is suitable for other multiple dehydration or drying treatment that contain inorganic substance with crystal water matter to be used.
Description of drawings
Accompanying drawing is the structure and the process flow diagram of apparatus of the present invention.
Among the figure, 1, magnesium chloride hexahydrate inlet; 2, the outlet of the 1st hydrogenchloride steam; 3, the outlet of the 2nd hydrogenchloride steam; 4, the outlet of the 3rd hydrogenchloride steam; 5, hydrogenchloride inlet; 6, the 1st stationary ring; 7, cold zone; 8, the 2nd stationary ring; 9, middle warm area; 10, the 3rd stationary ring; 11, high-temperature zone; 12, the 4th stationary ring; 13, Magnesium Chloride Anhydrous outlet; 14, hydrochloric acid tourie; 15, waste liquid tank; 16, hydrochloric acid resolution system; 17, comprehensive absorption tower; 18, quencher.
Embodiment
Below, in conjunction with the accompanying drawings and embodiments the present invention is made more specific description.
As shown in drawings, selecting for use each component to be mounted to preparation facilities is the composite structure rotary kiln, heats zone and four stationary ring alternate compositions by three; Three zones of heating can both rotate, and are respectively cold zone 7, middle warm area 9, high-temperature zone 11, the length 4m-6m in each zone of heating.Heating from beginning to end regional and heating is connected with stationary ring between the zone, heat and adopt the combining form of dynamic and static ring sealing between zone and the stationary ring; Magnesium chloride hexahydrate inlet 1 is on the 1st stationary ring, the outlet of the 1st hydrogenchloride steam is on the 1st stationary ring 6, the outlet 3 of the 2nd hydrogenchloride steam on the 2nd stationary ring 8, the outlet 4 of the 3rd hydrogenchloride steam is on the 3rd stationary ring 10, hydrogenchloride inlet 5 is on the 4th stationary ring 12, and Magnesium Chloride Anhydrous outlet 13 is on the 4th stationary ring 12.
Heat the zone for columned composite structure, be composited for three layers by steel plate layer, soft graphite layer, graphite linings, electric heating tube is embedded in the graphite linings.Three contain one of the common connection of outlet of hydrogenchloride steam or connect three comprehensive absorption towers 17 respectively.
Embodiment 1
Three described diameters of heating the zone are 2m, and the thickness of graphite linings is 150mm, and the thickness of soft graphite layer is 3mm.The contact surface of described dynamic and static ring sealing is a minute surface, and the material of contact surface place stationary ring is a silicon carbide, the contact surface place heat the zone material be graphite.Described electric heating tube is connected power supply by slide block with brush, and an end of brush is fixedly connected on the stationary ring.The speed of rotation of described composite structure rotary kiln is 60 rev/mins.
Embodiment 2
Three described diameters of heating the zone are 1.5m, and the thickness of graphite linings is 100mm, and the thickness of soft graphite layer is 2.5mm.The contact surface of described dynamic and static ring sealing is a minute surface, and the material of contact surface place stationary ring is a silicon carbide.Described composite structure rotary kiln has 10 ° gradient when installing and using, drive material when heating the zone rotation and walked to high-temperature zone 11 by cold zone 7 automatically.Described electric heating tube is connected power supply by slide block with brush, and an end of brush is fixedly connected on the stationary ring.The speed of rotation of described composite structure rotary kiln is 30 rev/mins.
Among the foregoing description 1-2, hydrogenchloride is fed the composite structure rotary kiln that loads magnesium chloride hexahydrate from hydrogenchloride inlet 5, divide three grades of dehydrations of heating, three grades of scopes of heating in the accompanying drawing are 190 ℃-220 ℃, 330 ℃-350 ℃ and 400 ℃-450 ℃, corresponding respectively three are decomposed dehydration, thereby realize having magnesium chloride hexahydrate to become the preparation process of Magnesium Chloride Anhydrous. described heating to adopting the electrothermal tube heating.
The moisture of deviating from is chlorinated hydrogen and absorbs and become to contain hydrogenchloride steam, flows into comprehensive absorption tower 17 again and absorbs into hydrochloric acid.Advance before the comprehensive absorption tower 17 or be connected with quencher 18 earlier; After hydrochloric acid flows out from comprehensive absorption tower 17, or connect hydrochloric acid tourie 14 again, connect hydrochloric acid resolution system 16 again, the hydrogenchloride that hydrochloric acid resolution system 16 is emitted or connect the hydrogenchloride inlet 5 of composite structure rotary kiln again by pipeline, recycle for this technological process, the acid waste water that resolution system produces enters waste liquid tank 15, discharges outside this process unit.

Claims (10)

1. the preparation technology of a Magnesium Chloride Anhydrous is characterized in that: hydrogenchloride is fed in the composite structure rotary kiln that loads magnesium chloride hexahydrate, divide three grades, level Four, Pyatyi or six grades of dehydrations of heating;
When dividing three grades, three grades of scopes of heating are respectively 160 ℃-220 ℃, 180 ℃-380 ℃ and 330 ℃-450 ℃, respectively corresponding three are decomposed dehydrations: by magnesium chloride hexahydrate become four aqueous magnesium chlorides process, by four aqueous magnesium chlorides become magnesium chloride dihydrate process, become the process of the Magnesium Chloride Anhydrous finished product of ultimate demand by magnesium chloride dihydrate, thereby realize having magnesium chloride hexahydrate to become the preparation process of Magnesium Chloride Anhydrous;
When being divided into level Four, Pyatyi or six grades, the scope of heating is divided into corresponding progression between 160 ℃-480 ℃, and corresponding four, five or six are progressively decomposed dehydration respectively, and each step can be taken off the water of one or more molecules;
The moisture of deviating from is chlorinated hydrogen and absorbs and become to contain hydrogenchloride steam, or absorbs cooling through quencher (18) earlier, flows into comprehensive absorption tower (17) again and absorbs into hydrochloric acid.
2. the preparation technology of Magnesium Chloride Anhydrous according to claim 1, it is characterized in that: described three grades of scopes of heating are 190 ℃-220 ℃, 330 ℃-350 ℃ and 400 ℃-450 ℃, corresponding respectively three are decomposed dehydrations.
3. the preparation technology of Magnesium Chloride Anhydrous according to claim 1 and 2 is characterized in that: described heating to adopting the electrothermal tube heating.
4. according to the preparation technology of the described Magnesium Chloride Anhydrous of claim 1, it is characterized in that: the speed of rotation of described composite structure rotary kiln is 10-100 rev/min.
5. the preparation technology of Magnesium Chloride Anhydrous according to claim 1, it is characterized in that: described hydrochloric acid becomes the hydrogenchloride recovery through the resolving of persalt resolution system (16) again, part hydrogenchloride recycles for this technological process, and the acid waste water that hydrochloric acid resolution system (16) produces is discharged outside this process unit.
6. preparation facilities that adopts the preparation technology of the described Magnesium Chloride Anhydrous of claim 1, it is characterized in that: preparation facilities is the composite structure rotary kiln, by three, four, five or six heat zone and four or more stationary rings are alternate forms;
Be divided into three when heating the zone, three zones of heating can both rotate, and are respectively cold zone (7), middle warm area (9), high-temperature zone (11), the length 2m-18m in each zone of heating; Heating from beginning to end regional and heating is connected with stationary ring between the zone, heat and adopt the combining form of dynamic and static ring sealing between zone and the stationary ring; Magnesium chloride hexahydrate inlet (1) is on the 1st stationary ring (6), three outlets that contain hydrogenchloride steam are respectively on the 1st stationary ring (6), the 2nd stationary ring (8), the 3rd stationary ring (10), hydrogenchloride inlet (5) is on the 4th stationary ring (12), and Magnesium Chloride Anhydrous outlet (13) is on the 4th stationary ring (12); Heat the zone for columned composite structure, be composited for three layers by steel plate layer, soft graphite layer, graphite linings, electric heating tube is embedded in the graphite linings; Three outlets that contain hydrogenchloride steam are common to connect one or connect three comprehensive absorption towers (17) respectively, and it is preceding or be connected with quencher (18) earlier to connect comprehensive absorption tower (17); Comprehensive absorption tower (17) or connect hydrochloric acid resolution system (16) again, the hydrogenchloride that hydrochloric acid resolution system (16) is emitted or connect the hydrogenchloride inlet (5) of composite structure rotary kiln again by pipeline.
7. the preparation facilities of Magnesium Chloride Anhydrous according to claim 6 is characterized in that: three described diameters of heating the zone are 0.5m-3m, and the thickness of graphite linings is 80mm-200mm, and the thickness of soft graphite layer is 1.5mm-6mm.
8. the preparation facilities of Magnesium Chloride Anhydrous according to claim 6, it is characterized in that: the contact surface of described dynamic and static ring sealing is a minute surface, and the material of contact surface place stationary ring is a silicon carbide, and the heat material in zone of contact surface place is a graphite.
9. the preparation facilities of Magnesium Chloride Anhydrous according to claim 6, it is characterized in that: described composite structure rotary kiln has 5 °-20 ° gradient when installing and using, and drives material when heating the zone rotation and is walked to high-temperature zone (11) by cold zone (7) automatically.
10. according to the preparation facilities of claim 6 or 8 described Magnesium Chloride Anhydrouss, it is characterized in that: described electric heating tube is connected power supply by slide block with brush, and an end of brush is fixedly connected on the stationary ring; (17) top, described comprehensive absorption tower or be connected with vacuum pick-up system.
CN 201110180588 2011-06-30 2011-06-30 Preparation process and preparation device of anhydrous magnesium chloride Active CN102275960B (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103922371A (en) * 2014-04-30 2014-07-16 中国科学院青海盐湖研究所 Method for preparing anhydrous magnesium chloride
CN107208287A (en) * 2014-12-10 2017-09-26 联盟镁公司 By the way that two hydrated magnesium chlorides to be dehydrated to the method to produce magnesium metal
CN107998825A (en) * 2017-12-07 2018-05-08 青海盐湖工业股份有限公司 The purifier and purification technique of a kind of HCl tail gas
CN111453701A (en) * 2020-05-09 2020-07-28 中国成达工程有限公司 Recycling method and system of protective gas for drying and dehydration
CN115676859A (en) * 2022-09-05 2023-02-03 中国科学院青海盐湖研究所 Method and system for preparing anhydrous magnesium chloride

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Publication number Priority date Publication date Assignee Title
CN1229400A (en) * 1997-06-20 1999-09-22 挪威海德罗公开有限公司 Process for producing anhydrous MgC12
CN1429770A (en) * 2002-01-01 2003-07-16 中国科学院青海盐湖研究所 Method of preparing anhydrous magnesium chloride by dehydration of bischefite
CN101041448A (en) * 2006-03-16 2007-09-26 谷亮 Method for preparation of anhydrous magnesium chloride
CN101121536A (en) * 2007-06-15 2008-02-13 浙江海虹控股有限公司 Combination preparation method for anhydrous magnesium chloride and potassium sulphate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1229400A (en) * 1997-06-20 1999-09-22 挪威海德罗公开有限公司 Process for producing anhydrous MgC12
CN1429770A (en) * 2002-01-01 2003-07-16 中国科学院青海盐湖研究所 Method of preparing anhydrous magnesium chloride by dehydration of bischefite
CN101041448A (en) * 2006-03-16 2007-09-26 谷亮 Method for preparation of anhydrous magnesium chloride
CN101121536A (en) * 2007-06-15 2008-02-13 浙江海虹控股有限公司 Combination preparation method for anhydrous magnesium chloride and potassium sulphate

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103922371A (en) * 2014-04-30 2014-07-16 中国科学院青海盐湖研究所 Method for preparing anhydrous magnesium chloride
CN103922371B (en) * 2014-04-30 2016-05-11 中国科学院青海盐湖研究所 A kind of preparation method of anhydrous magnesium chloride
CN107208287A (en) * 2014-12-10 2017-09-26 联盟镁公司 By the way that two hydrated magnesium chlorides to be dehydrated to the method to produce magnesium metal
US10617995B2 (en) 2014-12-10 2020-04-14 Alliance Magnésium Process for producing magnesium metal by dehydrating dihydrate magnesium chloride
CN107998825A (en) * 2017-12-07 2018-05-08 青海盐湖工业股份有限公司 The purifier and purification technique of a kind of HCl tail gas
CN107998825B (en) * 2017-12-07 2021-05-25 青海盐湖工业股份有限公司 HCl tail gas purification device and HCl tail gas purification process
CN111453701A (en) * 2020-05-09 2020-07-28 中国成达工程有限公司 Recycling method and system of protective gas for drying and dehydration
CN115676859A (en) * 2022-09-05 2023-02-03 中国科学院青海盐湖研究所 Method and system for preparing anhydrous magnesium chloride

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