US20040223902A1 - Method and device for the continuous production of NaAlCl4 or NaFeCl4 - Google Patents
Method and device for the continuous production of NaAlCl4 or NaFeCl4 Download PDFInfo
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- US20040223902A1 US20040223902A1 US10/787,104 US78710404A US2004223902A1 US 20040223902 A1 US20040223902 A1 US 20040223902A1 US 78710404 A US78710404 A US 78710404A US 2004223902 A1 US2004223902 A1 US 2004223902A1
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- reaction vessel
- sodium chloride
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- chloride
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 229910001538 sodium tetrachloroaluminate Inorganic materials 0.000 title description 5
- 238000010924 continuous production Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 58
- 239000011780 sodium chloride Substances 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- 239000000155 melt Substances 0.000 claims abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 15
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 229910001507 metal halide Inorganic materials 0.000 claims abstract description 13
- 150000005309 metal halides Chemical class 0.000 claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 19
- 229910001510 metal chloride Inorganic materials 0.000 claims description 11
- 239000008187 granular material Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 7
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 4
- 235000002639 sodium chloride Nutrition 0.000 description 44
- 239000004411 aluminium Substances 0.000 description 15
- 229910052783 alkali metal Inorganic materials 0.000 description 14
- -1 for example Chemical class 0.000 description 14
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 229910001508 alkali metal halide Inorganic materials 0.000 description 3
- 150000008045 alkali metal halides Chemical class 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005338 heat storage Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 241000283070 Equus zebra Species 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 239000000274 aluminium melt Substances 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B9/00—General methods of preparing halides
- C01B9/02—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium and two or more other elements, with the exception of oxygen and hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/009—Compounds containing, besides iron, two or more other elements, with the exception of oxygen or hydrogen
Definitions
- the invention relates to a method and a device for the production of NaDCl 4 , in which D is aluminium or iron, where, in a first reaction step, a melt of aluminium or iron is reacted with chlorine gas to give gaseous metal halide, and this is subsequently reacted, in a second reaction step, with solid sodium chloride to give the corresponding compound and is separated off as a melt.
- Salt melts can be employed as storage medium in heat storage systems, as heat transfer media, for example in heating baths, for covering and cleaning molten metals, for the electrocoating of high-melting materials or as melt electrolytes in primary batteries, as described in GB 2046506.
- a further potential application of these salts is in rechargeable sodium batteries.
- the salts are employed in batteries which have operating temperatures of between 130° C. and 200° C. (Abraham. J. Electrochem. Soc., Vol. 137, 1189-1190, (1990)).
- DE 3419279 describes an electrochemical cell in which the cathode matrix is impregnated with a sodium aluminium halide salt melt electrolyte.
- ZEBRA battery This high-temperature cell consists of an electrode of liquid sodium, a beta aluminium electrolyte and an electrode of transition-metal chloride in an NaAlCl 4 melt (Cleaver, J. Electrochem. Soc., Vol. 142, 3409-3413, (1995)).
- DE 3718920 describes the production of salt melts by the addition of a pure metal and an alkali metal halide to the melt.
- the reaction cell is operated at above the melting point of the salt melt.
- the alkali metal halide in the working example is NaCl
- the molten alkali metal is sodium
- the separator is beta-aluminium oxide.
- the object of the invention is to provide a continuous method for the production of pure salt melts which excludes disadvantageous ambient influences, minimises the energy demand and facilitates an optimum space-time yield.
- a further object is to make large quantities of salt melts available in the shortest possible time.
- the object according to the invention is achieved by a method for the production of salt melts, and mixtures thereof, of the general formula
- D is Al or Fe
- the invention furthermore relates to a device for carrying out the method, essentially consisting of a reaction vessel (1) containing the melt of the metal D, with a feed device for chlorine gas (2), a collection device for gaseous metal chloride (4) above the reaction vessel (1), and a further reactor vessel (5) which contains sodium chloride in solid form and is connected to the said collection device.
- the products from the method are suitable for use as melt electrolyte in electrochemical cells, as storage medium in heat storage systems, as heat transfer medium, for example in heating baths, for covering and cleaning molten metals, for the electrocoating of high-melting materials or as melt electrolytes in rechargeable sodium batteries and primary batteries.
- the solids for example NaCl and AlCl 3
- the solids are mixed and warmed to the melting point.
- the amount of heat necessary for this purpose has to be supplied from the outside.
- An essential advantage of the method is the use of cheaper raw materials and the utilisation of the heat of reaction being liberated for controlling the temperature of the method. Method steps, such as the condensation of the metal halide (DCl 3 ), can thereby be saved and the energy demand for carrying out the process reduced.
- reaction vessels which appear suitable to the person skilled in the art can be used for the method.
- a feed device with gas inlet is necessary for the reaction with chlorine gas.
- the reaction vessel is provided with a refractory lining.
- a ceramic lining which is insensitive to the materials employed and the high temperatures is advisable.
- the metal D in powder or granule form is provided for the process via a solids metering unit (3).
- a collection device (4) For collecting the reaction product (DCl 3 ), a collection device (4), provided with a feed line to the downstream reaction vessel (5), is installed above the reaction vessel (1) for the melt.
- the salt melt formed runs off in a downward direction through the alkali metal salt bed (NaCl), which is supported by a support grille or a coarse filter plate.
- NaCl alkali metal salt bed
- a mixture of solid sodium chloride and metal D in powder or granule form is fed continuously, corresponding to the amount of end product formed and separated off, to the reaction vessel ( 5 ) via a solids metering unit ( 6 ).
- a temperature control device is merely necessary for heating up once in the start phase and, where appropriate, for cooling.
- the energy necessary for melting the metal granules (D) is also provided by the heat of reaction.
- the method can be carried out continuously or discontinuously as required.
- FIG. 1 shows a reaction vessel containing metal melt 1 having a feed device for chlorine gas 2 and solids metering device 3 , collection device for gaseous metal chloride DCl 3 4 and reactor vessel 5 containing metal granule or metal powder and alkali metal salt bed, and solids metering device 6 , as well as a downstream reactor vessel 7 .
- the raw materials can be fed to the reaction vessel ( 1 ) in pre-mixed form via the solids metering device ( 3 ).
- the filling can be carried out under inert gas.
- the heatable reaction vessel ( 1 ) contains liquid metal melt. Suitable metals (D) are iron and aluminium. Chlorine gas is fed into the reaction apparatus via the feed device ( 2 ). The volume of the melt and the volume flow of the gas is determined as a function of the requisite residence time and the desired throughput. A temperature above the melting point of the metal (D) is set in the reaction vessel ( 1 ).
- the gaseous metal halide (DCl 3 ) is fed to the reaction vessel ( 5 ) via the collection device ( 4 ) for the reaction product formed.
- the metal halide is fed to the metal granule or metal powder and alkali metal salt bed between the upper and lower quarter of the reactor vessel ( 5 ), preferably between the upper quarter and the centre.
- a mixture of metal granules or powder (D) and alkali metal salt (NaCl) is fed constantly to the reactor vessel via a solids metering device ( 6 ) in accordance with consumption.
- the melt may be contaminated due to contact with water or atmospheric moisture.
- the hydrogen halide formed can react away with the metal granules (D) added to the salt bed in the reactor vessel ( 5 ) to give the metal halide (DCl 3 ).
- the metal halide is passed through the reactor vessel ( 7 ). Flow takes place from bottom to top through the purification unit charged with alkali metal salt NaCl. In the process, the metal halide DCl 3 is reacted with the alkali metal salt NaCl to give the desired salt NaDCl 4 .
- the flow from bottom to top through the reactor vessel ( 7 ) is not absolutely necessary. However, it has the advantage that the particles becoming smaller due to the reaction are not forced onto the sieve plate by the flow, blocking it. Nevertheless, homogeneous through-flow (plug flow) in the column is ensured in this way. Homogeneous through-flow is an essential prerequisite for complete reaction in the purification unit.
- the low-viscosity aluminate formed flows downward out of the reaction vessel and is then advantageously passed through a reactor vessel which contains a bed of pure common salt. Residues of AlCl 3 react therein, likewise to give the desired product.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A method and a device for the production of NaDCl4, in which D is aluminum or iron, is described. The method includes a first reaction step in which a melt of aluminum or iron is reacted with chlorine gas to give gaseous metal halide. This is subsequently reacted, in a second reaction step, with solid sodium chloride to give the corresponding compound and is separated off as a melt.
Description
- The invention relates to a method and a device for the production of NaDCl4, in which D is aluminium or iron, where, in a first reaction step, a melt of aluminium or iron is reacted with chlorine gas to give gaseous metal halide, and this is subsequently reacted, in a second reaction step, with solid sodium chloride to give the corresponding compound and is separated off as a melt.
- Melts of salts, such as, for example, NaAlCl4 have various areas of application. Salt melts can be employed as storage medium in heat storage systems, as heat transfer media, for example in heating baths, for covering and cleaning molten metals, for the electrocoating of high-melting materials or as melt electrolytes in primary batteries, as described in GB 2046506. A further potential application of these salts is in rechargeable sodium batteries. The salts are employed in batteries which have operating temperatures of between 130° C. and 200° C. (Abraham. J. Electrochem. Soc., Vol. 137, 1189-1190, (1990)).
- DE 3419279 describes an electrochemical cell in which the cathode matrix is impregnated with a sodium aluminium halide salt melt electrolyte.
- A relatively new area of application is the “ZEBRA battery”. This high-temperature cell consists of an electrode of liquid sodium, a beta aluminium electrolyte and an electrode of transition-metal chloride in an NaAlCl4 melt (Cleaver, J. Electrochem. Soc., Vol. 142, 3409-3413, (1995)).
- DE 3718920 describes the production of salt melts by the addition of a pure metal and an alkali metal halide to the melt. The reaction cell is operated at above the melting point of the salt melt. The alkali metal halide in the working example is NaCl, the molten alkali metal is sodium, and the separator is beta-aluminium oxide. Owing to the use of pure sodium, special safety precautions, such as working under a protective-gas atmosphere, have to be taken. The reactions must take place in separate cells, since poisoning of the separator by the by-product AlHaI3 formed must be prevented.
- All the methods known hitherto for the production of salt melts work batchwise. A batch procedure has some severe disadvantages compared with a continuous production method. In the case of a batch change, the apparatus has to be opened. The product may then be contaminated by the oxygen from the ambient air, water and dust. The batch change results in down times of the plant and thus in a reduced space-time yield. For an effective discontinuous method, large apparatuses have to be used. The start-up process requires correspondingly more energy and time. It has been found that impurities are entrained into the process, in particular during start-up of plants. FR 2168912 describes a complex purification method for alkali metal aluminium halides. The two-step purification process is composed of an oxygen treatment for degradation of the organic impurities and an aluminium treatment for precipitation of iron and heavy metals. The aluminium treatment must be carried out under a nitrogen or argon atmosphere.
- For the production of the alkali metal aluminium halides, the reaction of corresponding aluminium halides and alkali metal halides in a closed tube is described (Friedmann, J. Am. Chem. Soc., 72, 2236-2243, (1950)). A pressure increase to 6-7 atmospheres has been observed in this method, which results in problems (FR 2168912). The apparatuses have to be fitted with the appropriate safety pre-cautions.
- The object of the invention is to provide a continuous method for the production of pure salt melts which excludes disadvantageous ambient influences, minimises the energy demand and facilitates an optimum space-time yield.
- A further object is to make large quantities of salt melts available in the shortest possible time.
- The object according to the invention is achieved by a method for the production of salt melts, and mixtures thereof, of the general formula
- NaDCl4 (I)
- in which
- D is Al or Fe,
- which, in a first reaction step (i), a melt of aluminium or iron is reacted with chlorine gas to give gaseous metal halide (DCl3), and this is subsequently, in a second reaction step (ii), reacted with solid sodium chloride to give the corresponding compound of the formula (I) and is separated off as a melt.
- The invention furthermore relates to a device for carrying out the method, essentially consisting of a reaction vessel (1) containing the melt of the metal D, with a feed device for chlorine gas (2), a collection device for gaseous metal chloride (4) above the reaction vessel (1), and a further reactor vessel (5) which contains sodium chloride in solid form and is connected to the said collection device.
- The products from the method are suitable for use as melt electrolyte in electrochemical cells, as storage medium in heat storage systems, as heat transfer medium, for example in heating baths, for covering and cleaning molten metals, for the electrocoating of high-melting materials or as melt electrolytes in rechargeable sodium batteries and primary batteries.
- In the alternative methods, the solids, for example NaCl and AlCl3, are mixed and warmed to the melting point. The amount of heat necessary for this purpose has to be supplied from the outside.
- Surprisingly, it has been found that the exothermicity of the reaction of aluminium or iron (D) with Cl2 to give aluminium chloride or iron chloride (DCl3) can be utilised for the further process for the production of NaDCl4.
- In the process according to the invention, DCl3 (where D=Al or Fe) is formed at temperatures between 700° C. and 1200° C. In contrast to conventional methods, this DCl3 is fed in gaseous form to an alkali metal salt bed of NaCl.
- It has been found that the accompanying heat of the gas (DCl3) is sufficient to warm the alkali metal salt (NaCl) to the melting point of the salt melt NaDCl4 (I).
- An essential advantage of the method is the use of cheaper raw materials and the utilisation of the heat of reaction being liberated for controlling the temperature of the method. Method steps, such as the condensation of the metal halide (DCl3), can thereby be saved and the energy demand for carrying out the process reduced.
- It has been found that the continuous performance of the method enables interfering environmental influences to be excluded. This enables a constantly high quality of the product to be established after the start-up phase.
- All continuously operating reaction vessels which appear suitable to the person skilled in the art can be used for the method. For the reaction with chlorine gas, a feed device with gas inlet is necessary. The reaction vessel is provided with a refractory lining. A ceramic lining which is insensitive to the materials employed and the high temperatures is advisable.
- The metal D in powder or granule form is provided for the process via a solids metering unit (3).
- For collecting the reaction product (DCl3), a collection device (4), provided with a feed line to the downstream reaction vessel (5), is installed above the reaction vessel (1) for the melt.
- The feed of the reaction product takes place between the upper quarter and the lower quarter of the reactor vessel (5), which contains a mixture of metal D and sodium chloride in solid form. Complete conversion of the reactants into the reaction products can thus be ensured.
- The salt melt formed runs off in a downward direction through the alkali metal salt bed (NaCl), which is supported by a support grille or a coarse filter plate.
- A mixture of solid sodium chloride and metal D in powder or granule form is fed continuously, corresponding to the amount of end product formed and separated off, to the reaction vessel (5) via a solids metering unit (6).
- Due to water entrained by the raw materials, undesired HCl gas forms. This can react away to give the metal halide (DCl3) due to amounts of the corresponding metal granules or powder (D) present in the alkali metal salt bed.
- It is advisable for a further reactor vessel (7) with alkali metal salt bed to be installed downstream of the reactor vessel (5) in the flow direction for purification of the melt in order to allow the metal halide (DCl3) formed in turn to react away to give NaDCl4.
- A temperature control device is merely necessary for heating up once in the start phase and, where appropriate, for cooling. The energy necessary for melting the metal granules (D) is also provided by the heat of reaction.
- The method can be carried out continuously or discontinuously as required.
- A general example of the invention, which is shown in the drawing, is explained in greater detail below. FIG. 1 shows a reaction vessel containing metal melt1 having a feed device for
chlorine gas 2 andsolids metering device 3, collection device for gaseousmetal chloride DCl 3 4 andreactor vessel 5 containing metal granule or metal powder and alkali metal salt bed, andsolids metering device 6, as well as adownstream reactor vessel 7. - Reaction Step i:
- For the production of salts conforming to the formula (I) and mixtures thereof, the raw materials can be fed to the reaction vessel (1) in pre-mixed form via the solids metering device (3). The filling can be carried out under inert gas.
- The heatable reaction vessel (1) contains liquid metal melt. Suitable metals (D) are iron and aluminium. Chlorine gas is fed into the reaction apparatus via the feed device (2). The volume of the melt and the volume flow of the gas is determined as a function of the requisite residence time and the desired throughput. A temperature above the melting point of the metal (D) is set in the reaction vessel (1).
- The gaseous metal halide (DCl3) is fed to the reaction vessel (5) via the collection device (4) for the reaction product formed.
- Reaction Step ii:
- The metal halide is fed to the metal granule or metal powder and alkali metal salt bed between the upper and lower quarter of the reactor vessel (5), preferably between the upper quarter and the centre. A mixture of metal granules or powder (D) and alkali metal salt (NaCl) is fed constantly to the reactor vessel via a solids metering device (6) in accordance with consumption.
- The metal halide (DCl3) is reacted with the alkali metal salt in the reactor vessel (5) to give NaDCl4.
- Reaction Step iii:
- The melt may be contaminated due to contact with water or atmospheric moisture. The hydrogen halide formed can react away with the metal granules (D) added to the salt bed in the reactor vessel (5) to give the metal halide (DCl3).
- Reaction Step iv:
- For further processing, the metal halide is passed through the reactor vessel (7). Flow takes place from bottom to top through the purification unit charged with alkali metal salt NaCl. In the process, the metal halide DCl3 is reacted with the alkali metal salt NaCl to give the desired salt NaDCl4.
- The flow from bottom to top through the reactor vessel (7) is not absolutely necessary. However, it has the advantage that the particles becoming smaller due to the reaction are not forced onto the sieve plate by the flow, blocking it. Nevertheless, homogeneous through-flow (plug flow) in the column is ensured in this way. Homogeneous through-flow is an essential prerequisite for complete reaction in the purification unit.
- The example given below is given for better illustration of the present invention, but it is not suitable for restricting the invention to the features disclosed herein.
- Production of NaAlCl4
- For the production of 1 kg/h of NaAlCl4, 453.7 g/h of Cl2 gas are fed from a stock vessel to a reaction vessel containing initially introduced aluminium melt. At the same time, 172.5 g/h of aluminium granules are fed to the reaction vessel via a solids metering device. The AlCl3 forming escapes from the reaction vessel in gas form and is fed via a collection device to a reactor vessel which contains a bed of granular common salt and aluminium. This reaction vessel is supplied with 373.8 g/h of NaCl by a further solids metering device. A certain amount of granular aluminium may be mixed in with this salt if required for reaction with HCl.
- The low-viscosity aluminate formed flows downward out of the reaction vessel and is then advantageously passed through a reactor vessel which contains a bed of pure common salt. Residues of AlCl3 react therein, likewise to give the desired product.
Claims (14)
1.-12. (Canceled)
13. A device for the production of a salt melt, or mixture thereof, of the formula
NaDCl4 (I)
in which
D is Al or Fe,
by a method comprising reacting, in a first reaction step (i), a melt of aluminum and/or iron with chlorine gas to give gaseous metal chloride (DCl3), and, in a second reaction step (ii), reacting the gaseous metal halide with solid sodium chloride to produce the compound of formula (I), which is separated off as a melt, the device comprising:
a first reaction vessel for containing the melt of aluminum and/or iron,
a feed device to the reaction vessel for chlorine gas,
a collection device for the gaseous metal chloride above the reaction vessel,
and a second reaction vessel for containing the sodium chloride in solid form and having a feed device for feeding the gaseous metal chloride from said collection device to the second reaction vessel.
14. A device according to claim 13 , further comprising a solids metering unit in communication with the first reaction vessel for metering a powder or granule form of the metal D into the first reaction vessel.
15. A device according to claim 13 , wherein the feed device for feeding the gaseous metal chloride from said collection device to the second reaction vessel feeds the gas at a height between the upper quarter and the center of the second reaction vessel.
16. A device according to claim 14 , wherein the feed device for feeding the gaseous metal chloride from said collection device to the second reaction vessel feeds the gas at a height between the upper quarter and the center of the second reaction vessel.
17. A device according to claim 13 , further comprising a solids metering unit in communication with the second reaction vessel for metering a mixture of solid sodium chloride and metal D into the second reaction vessel.
18. A device according to claim 14 , further comprising a solids metering unit in communication with the second reaction vessel for metering a mixture of solid sodium chloride and metal D into the second reaction vessel.
19. A device according to claim 15 , further comprising a solids metering unit in communication with the second reaction vessel for metering a mixture of solid sodium chloride and metal D into the second reaction vessel.
20. A device according to claim 13 , further comprising a third reaction vessel containing solid sodium chloride in communication downstream of the second reaction vessel for reacting the sodium chloride with residual metal chloride resulting in further product of formula (I).
21. A device according to claim 14 , further comprising a third reaction vessel containing solid sodium chloride in communication downstream of the second reaction vessel for reacting the sodium chloride with residual metal chloride resulting in further product of formula (I).
22. A device according to claim 15 , further comprising a third reaction vessel containing solid sodium chloride in communication downstream of the second reaction vessel for reacting the sodium chloride with residual metal chloride resulting in further product of formula (I).
23. A device according to claim 17 , further comprising a third reaction vessel containing solid sodium chloride in communication downstream of the second reaction vessel for reacting the sodium chloride with residual metal chloride resulting in further product of formula (I).
24. A device according to claim 13 , further comprising means for utilizing the energy being liberated from the first reaction vessel to heat the second reaction vessel.
25. A device according to claim 13 , wherein the device is a capable of carrying out the method of reaction steps (i) and (ii) continuously.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US10/787,104 US20040223902A1 (en) | 1999-05-28 | 2004-02-27 | Method and device for the continuous production of NaAlCl4 or NaFeCl4 |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19924495.2 | 1999-05-28 | ||
DE19924495A DE19924495A1 (en) | 1999-05-28 | 1999-05-28 | Process and apparatus for the continuous production of NaDCI¶4¶ |
US09/979,921 US6733738B1 (en) | 1999-05-28 | 2000-04-25 | Method and device for the continuous production of NaAlCl4 or NaFeCl4 |
US10/787,104 US20040223902A1 (en) | 1999-05-28 | 2004-02-27 | Method and device for the continuous production of NaAlCl4 or NaFeCl4 |
Related Parent Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/979,921 Division US6733738B1 (en) | 1999-05-28 | 2000-04-25 | Method and device for the continuous production of NaAlCl4 or NaFeCl4 |
PCT/EP2000/003686 Division WO2000073209A1 (en) | 1999-05-28 | 2000-04-25 | METHOD AND DEVICE FOR THE CONTINUOUS PRODUCTION OF NaAlCl4 OR NaFeCl¿4? |
Publications (1)
Publication Number | Publication Date |
---|---|
US20040223902A1 true US20040223902A1 (en) | 2004-11-11 |
Family
ID=7909476
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/979,921 Expired - Fee Related US6733738B1 (en) | 1999-05-28 | 2000-04-25 | Method and device for the continuous production of NaAlCl4 or NaFeCl4 |
US10/787,104 Abandoned US20040223902A1 (en) | 1999-05-28 | 2004-02-27 | Method and device for the continuous production of NaAlCl4 or NaFeCl4 |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/979,921 Expired - Fee Related US6733738B1 (en) | 1999-05-28 | 2000-04-25 | Method and device for the continuous production of NaAlCl4 or NaFeCl4 |
Country Status (7)
Country | Link |
---|---|
US (2) | US6733738B1 (en) |
EP (1) | EP1198417A1 (en) |
JP (1) | JP2003500327A (en) |
AU (1) | AU4751300A (en) |
DE (1) | DE19924495A1 (en) |
WO (1) | WO2000073209A1 (en) |
ZA (1) | ZA200110474B (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20090238748A1 (en) * | 2008-03-24 | 2009-09-24 | Mitsubishi Materials Corporation | Chlorosilanes purifying apparatus and chlorosilanes manufacturing method |
CN104282954A (en) * | 2013-07-09 | 2015-01-14 | 中国科学院上海硅酸盐研究所 | Method for preparing fused electrolyte and device thereof |
CN104282955A (en) * | 2013-07-09 | 2015-01-14 | 中国科学院上海硅酸盐研究所 | Method for preparing fused electrolyte and device thereof |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9567232B1 (en) | 2015-08-20 | 2017-02-14 | General Electric Company | Method for preparing sodium chloro-aluminate |
CN112456462B (en) * | 2019-09-09 | 2022-03-29 | 江苏优士化学有限公司 | Recovery processing method of sodium tetrachloroaluminate catalyst composition |
CN110817913A (en) * | 2019-09-29 | 2020-02-21 | 浙江安力能源有限公司 | Preparation method of high-purity sodium tetrachloroaluminate for sodium salt battery |
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US3729543A (en) * | 1971-01-21 | 1973-04-24 | Dunn Inc Wendell E | Process for preparing alkali-metal tetra-chloroferrate |
US3799746A (en) * | 1971-10-29 | 1974-03-26 | H Underwood | Apparatus for manufacturing anhydrous aluminum chloride |
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-
1999
- 1999-05-28 DE DE19924495A patent/DE19924495A1/en not_active Withdrawn
-
2000
- 2000-04-25 US US09/979,921 patent/US6733738B1/en not_active Expired - Fee Related
- 2000-04-25 AU AU47513/00A patent/AU4751300A/en not_active Abandoned
- 2000-04-25 EP EP00929420A patent/EP1198417A1/en not_active Withdrawn
- 2000-04-25 WO PCT/EP2000/003686 patent/WO2000073209A1/en not_active Application Discontinuation
- 2000-04-25 JP JP2000621284A patent/JP2003500327A/en active Pending
-
2001
- 2001-12-20 ZA ZA200110474A patent/ZA200110474B/en unknown
-
2004
- 2004-02-27 US US10/787,104 patent/US20040223902A1/en not_active Abandoned
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US3729543A (en) * | 1971-01-21 | 1973-04-24 | Dunn Inc Wendell E | Process for preparing alkali-metal tetra-chloroferrate |
US3683590A (en) * | 1971-04-29 | 1972-08-15 | Wendell E Dunn Jr | Dual flue condenser |
US3799746A (en) * | 1971-10-29 | 1974-03-26 | H Underwood | Apparatus for manufacturing anhydrous aluminum chloride |
US3870511A (en) * | 1971-12-27 | 1975-03-11 | Union Carbide Corp | Process for refining molten aluminum |
US3944647A (en) * | 1974-04-08 | 1976-03-16 | Scm Corporation | Recovering chlorine from the chlorination of titaniferous material |
US4076794A (en) * | 1974-08-01 | 1978-02-28 | Foote Mineral Company | Process for the production of high purity alkali metal tetrahaloaluminates and products produced thereby |
US4026698A (en) * | 1975-09-18 | 1977-05-31 | Urban Reclamation Technologies, Inc. | Removal of tin from molten iron by chlorination, using oxygen to conserve chlorine and to produce tin oxide |
US4039647A (en) * | 1975-12-24 | 1977-08-02 | Aluminum Company Of America | Production of aluminum chloride |
US4900521A (en) * | 1987-01-21 | 1990-02-13 | Atochem | Process for purifying aluminum chloride |
US5057194A (en) * | 1987-04-20 | 1991-10-15 | Aluminum Company Of America | Salt-based melting process |
US5298233A (en) * | 1990-07-24 | 1994-03-29 | Molten Metal Technology, Inc. | Method and system for oxidizing hydrogen- and carbon-containing feed in a molten bath of immiscible metals |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
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US20090238748A1 (en) * | 2008-03-24 | 2009-09-24 | Mitsubishi Materials Corporation | Chlorosilanes purifying apparatus and chlorosilanes manufacturing method |
EP2105410A1 (en) * | 2008-03-24 | 2009-09-30 | Mitsubishi Materials Corporation | Chlorosilanes purifying apparatus and chlorosilanes purifying method |
US8101131B2 (en) | 2008-03-24 | 2012-01-24 | Mitsubishi Materials Corporation | Chlorosilanes purifying apparatus and chlorosilanes manufacturing method |
CN104282954A (en) * | 2013-07-09 | 2015-01-14 | 中国科学院上海硅酸盐研究所 | Method for preparing fused electrolyte and device thereof |
CN104282955A (en) * | 2013-07-09 | 2015-01-14 | 中国科学院上海硅酸盐研究所 | Method for preparing fused electrolyte and device thereof |
Also Published As
Publication number | Publication date |
---|---|
AU4751300A (en) | 2000-12-18 |
EP1198417A1 (en) | 2002-04-24 |
JP2003500327A (en) | 2003-01-07 |
ZA200110474B (en) | 2003-03-20 |
US6733738B1 (en) | 2004-05-11 |
DE19924495A1 (en) | 2000-11-30 |
WO2000073209A1 (en) | 2000-12-07 |
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