EP0648865B1 - Procédé et dispositif de génération d'arsine par voie électrolytique - Google Patents
Procédé et dispositif de génération d'arsine par voie électrolytique Download PDFInfo
- Publication number
- EP0648865B1 EP0648865B1 EP94401974A EP94401974A EP0648865B1 EP 0648865 B1 EP0648865 B1 EP 0648865B1 EP 94401974 A EP94401974 A EP 94401974A EP 94401974 A EP94401974 A EP 94401974A EP 0648865 B1 EP0648865 B1 EP 0648865B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cathode
- arsine
- membrane
- hydrogen
- ions
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 title claims description 63
- 238000000034 method Methods 0.000 title claims description 18
- 230000008569 process Effects 0.000 title claims description 14
- 239000012528 membrane Substances 0.000 claims description 47
- 239000000203 mixture Substances 0.000 claims description 41
- 239000007789 gas Substances 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000001257 hydrogen Substances 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- 150000002500 ions Chemical class 0.000 claims description 20
- 239000012466 permeate Substances 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 238000003860 storage Methods 0.000 claims description 12
- GOLCXWYRSKYTSP-UHFFFAOYSA-N Arsenious Acid Chemical compound O1[As]2O[As]1O2 GOLCXWYRSKYTSP-UHFFFAOYSA-N 0.000 claims description 10
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 9
- 229910052785 arsenic Inorganic materials 0.000 claims description 8
- LZYIDMKXGSDQMT-UHFFFAOYSA-N arsenic dioxide Inorganic materials [O][As]=O LZYIDMKXGSDQMT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 238000005868 electrolysis reaction Methods 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052797 bismuth Inorganic materials 0.000 claims description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052716 thallium Inorganic materials 0.000 claims description 4
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 4
- 230000005679 Peltier effect Effects 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 230000001737 promoting effect Effects 0.000 claims description 3
- 238000010981 drying operation Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000011144 upstream manufacturing Methods 0.000 claims description 2
- 229910000070 arsenic hydride Inorganic materials 0.000 claims 2
- 239000003792 electrolyte Substances 0.000 claims 1
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 238000011010 flushing procedure Methods 0.000 claims 1
- 238000005755 formation reaction Methods 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 230000004888 barrier function Effects 0.000 description 7
- 238000009434 installation Methods 0.000 description 6
- 239000003507 refrigerant Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 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 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 125000000223 arsonoyl group Chemical group [H][As](*)(*)=O 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 230000003902 lesion Effects 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- -1 polypropylene Polymers 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007832 Na2SO4 Substances 0.000 description 1
- 229910003328 NaAsO2 Inorganic materials 0.000 description 1
- 241000287107 Passer Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- IKWTVSLWAPBBKU-UHFFFAOYSA-N a1010_sial Chemical compound O=[As]O[As]=O IKWTVSLWAPBBKU-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910000413 arsenic oxide Inorganic materials 0.000 description 1
- 229960002594 arsenic trioxide Drugs 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- WGRULTCAYDOGQK-UHFFFAOYSA-M sodium;sodium;hydroxide Chemical compound [OH-].[Na].[Na+] WGRULTCAYDOGQK-UHFFFAOYSA-M 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
Definitions
- the invention relates to a method and a device for generating arsine (AsH 3 ) electrolytically.
- Gas hydrides are a key point in the semiconductor industry. We may thus cite the example of the silane used as a precursor for the manufacture of silicon or for the production of silica deposits, or even the example of arsine as source of arsenic for doping semiconductors or for growing layers epitaxial from GaAsP.
- arsine is not without posing safety problems linked to the character highly toxic of this gas, justifying its handling under very great conditions precautions (use of hoods, etc.), both in terms of production and storage, or still transported in the form of bottles containing a concentration generally reduced arsine in a carrier gas.
- document US-A-1,375,819 proposes a process for the production of arsine by electrolysis of a solution of an arsenic oxide (such as As 2 O 3 ) in an acid medium (sulfuric acid) in which is also present potassium sulfate (K 2 SO 4 )
- an arsenic oxide such as As 2 O 3
- an acid medium sulfuric acid
- potassium sulfate K 2 SO 4
- the electrolyser used is of the tank type, the cathode is made of carbon covered with mercury, the anode is made of simple carbon.
- the configuration adopted gives rise to the production of a gas which is in fact a mixture of oxygen, hydrogen and arsine.
- the electrolytic cell is here also of the tank type, but consists of two concentric compartments playing the role of electrodes. These two electrodes are separated in their upper part by a solid cylindrical barrier (and concentric around the anode) whose objective is the separation of the gases produced at the anode and the cathode, before their evacuation from the top of the cell. .
- This "upper” barrier is supplemented by a “lower” barrier (always cylindrical and concentric around the anode), continuous or not with the preceding barrier, the objective of which is here also to separate the gases produced, at the bubbling stage.
- the invention provides a process for generating arsine electrolytically from an electrochemical cell where a cathode supplied with H + and AsO 2 - ions is arranged, where two competing reactions occur, respectively producing l arsine and hydrogen gas, and an anode, where an H + ion source reaction takes place, in which the ratio of H + / As concentrations to the cathode is controlled and kept constant, so as to produce a mixture H 2 + AsH 3 in proportions of between 50% and 95% of AsH 3 according to the H + / As ratio applied.
- the reaction source of H + ions may for example consist of the electrolysis of water (in the case of a conventional plane anode supplied with acid solution) or also by the oxidation of hydrogen (supply of gaseous hydrogen d '' a gas diffusion electrode).
- This second type of electrode having a very large specific surface generally has catalyst particles (platinum type) at the gas / liquid interface on which the hydrogen will oxidize to H + ions, and on the gas side is treated so as to be made hydrophobic.
- the Applicant has indeed highlighted the key role of the H + / As ratio at the cathode, and its influence on the yield of arsine obtained (concentration of arsine in the gas mixture obtained at the cathode).
- Each cell geometry corresponds to an optimum of the H + / As ratio to be respected and maintained.
- the conversion rate is understood to mean, according to the invention, the ratio: (As e -As s ) / As e , where As e represents the concentration of arsenic in the fluid supplying the cathode compartment, and As s this same concentration in the outlet fluid which is recycled to the storage tank supplying the cathode compartment.
- the reserve of As 2 O 3 (saturator) is located in the circuit between the cathode compartment and the storage of acid solution which comes to sweep the saturator.
- the reserve of As 2 O 3 (saturator) is located in the circuit inside the storage of acid solution, within this solution, thus ensuring close contact between this solution and the walls of the saturator.
- a material such as that sold under the name NAFION R is suitable for the preparation of such a membrane.
- the use of the As 2 O 3 saturator makes it possible to avoid the use of sodium salts, but also constitutes a kind of buffer capacity which ensures a regular and constant concentration of AsO 2 ions - in the medium supplying the cathode.
- the acid medium used in the composition of the mixtures feeding the two compartments may contain phosphoric, perchloric acid, or preferably sulfuric.
- the electrodes used for the implementation of the invention are advantageously made up as follows: at the cathode, a material promoting the formation of arsine to the detriment of the competing reaction of hydrogen formation, advantageously a material such as copper on which a deposit of bismuth, lead, or thallium or cadmium was carried out, with an electrode surface of the order of 70 cm 2 . At the anode, a material such as titanium on which a deposit of ruthenium oxide or iridium was deposited, or an electrode, for example of the felt type, will be used, depending on the case (conventional electrolysis or gas electrode). carbon.
- a step of downstream of the generator is carried out. separation of the hydrogen / arsine mixture produced at the cathode, by treating this mixture on a membrane module, making it possible to obtain a concentration of arsine higher than in the arsine / hydrogen mixture treated at the entrance to the module, but also to obtain a high stability of this concentration.
- this low pressure is compensated for by performing, on the permeate side of the membrane, vacuum drawing or even sweeping using a "tool" gas, so as to lower the partial pressure of hydrogen (which we want to separate from arsine) on the permeate side.
- Low pressure is understood to mean, according to the invention, a pressure lying in the range 10 4 Pa to 5 ⁇ 10 5 Pa absolute.
- a gas other than that which it is desired to separate, and moreover having a low permeation of the permeate towards the interior of the membrane, so as to prevent this gas "tool” does not pollute the interior of the membrane and therefore does not affect the result obtained at the output of the module.
- nitrogen, or even SF 6 will be used as the "tool" gas.
- the mixture produced at the cathode undergoes at least one drying operation, on a device such than a refrigerant (for example Peltier effect), or a molecular sieve, or a combination of these two means, and where appropriate, at least one filtering operation on a particle filter.
- a refrigerant for example Peltier effect
- a molecular sieve for example a molecular sieve
- Another object of the invention is to propose a device for implementing the method according to the invention.
- the device comprises at least one electrochemical cell where at least one cathode is placed, supplied with H + and AsO 2 - ions, where two competing reactions take place, producing respectively arsine and hydrogen gas, and at least one anode, where an H + ion source reaction takes place; a cathionic membrane separating the electrochemical cell into two compartments, anodic and cathodic; and to supply the cathode compartment with H + and AsO 2 - ions, a saturator constituted by a reserve of As 2 O 3 , which is swept away by an acid solution.
- This device is according to the characteristic of claim 10.
- the reaction source of H + ions at the anode is the electrolysis of water, the anode compartment is then supplied with an acid solution.
- the reaction source of H - ions at the anode is the oxidation of hydrogen and we are then in the presence of a gas diffusion electrode supplied with hydrogen gas.
- the saturator is located between the electrochemical cell and the tank for storing the acid solution supplying the cathode compartment.
- the saturator is located inside the tank. storage of the acid solution supplying the cathode compartment, within this solution acid.
- a material promoting the reaction of the cathode will be used. arsine formation at the expense of the hydrogen formation reaction such as copper on which has been deposited with bismuth, lead, or thallium or cadmium.
- a material such as conventional (conventional electrolysis or gas electrode) will be used titanium on which a deposit of ruthenium oxide or iridium has been carried out, or an electrode for example of the carbon felt type.
- the device comprises, downstream of the cell electrochemical, a membrane module, on which the arsine / hydrogen mixture produced at the cathode undergoes a separation step, so as to obtain, at the module output, a higher arsine concentration than in the initial mixture.
- the membrane module is connected to means for carrying out a vacuum on the permeate side of the membrane, so as to bring the pressure on the permeate side to a value of the order of 1 to 100 Pa (primary vacuum).
- the membrane module is connected to a gas source, making it possible to carry out a scanning of the permeate side of the membrane, using this gas, which advantageously will have according to the invention low permeation of the permeate towards the inside of the membrane, such as nitrogen or SF 6 .
- the device comprises, upstream of the module membrane, at least one device for drying the mixture produced at the cathode, such as a refrigerant for example with Peltier effect, or a molecular sieve, or a combination of these two means, and where appropriate, at least one particle filter.
- a refrigerant for example with Peltier effect
- a molecular sieve or a combination of these two means
- FIG. 2 illustrates the performance obtained using a generator such as that described above, using a current density (relative to the electrode surface) of 500 A / m 2 .
- the observed evolution confirms the existence of an optimum for the H + / As ratio, close to 1 for this cell geometry, giving rise to the production at cathode 7 of an arsine / hydrogen mixture containing 95% of arsine, with a flow rate of 50 l / h / m 2 (m 2 of electrode).
- the performances decrease rapidly around the optimum value.
- FIG. 3 illustrates, under these same cell and electrode conditions, the influence of the current density on the flow of arsine produced at cathode 7, this for an H + / As ratio close to 1. It can be seen, in the range [200 A / m 2 , 1500 A / m 2 ] of current density an increasing flow of arsine, from approximately 25 l / h / m 2 to approximately 225 l / h / m 2 .
- Tray 4 has means for discharging the oxygen produced at the anode to a vent 14, via a valve 15 if required, and a pressure sensor 16.
- the cell compartment 12 is supplied with AsO 2 ions - by the storage tank 10, via line 17 which includes a flow sensor 18.
- the reserve of As 2 O 3 (saturator 8) is included here in storage 10, within the acid liquid 19, continuously swept by it, to allow the continuous dissolution of the compound As 2 O 3 in the solution, leading to its saturation with AsO 2 - ions.
- the cathode container 10 includes means for evacuating gas to a vent 20, via a valve 21 if necessary. This evacuation is used in particular during operations purge system.
- an inlet 22 of inert gas such as nitrogen
- inert gas such as nitrogen
- This nitrogen inlet is particularly used for perform purge cycles of the storage, at the start of the installation, but also to purge the downstream of the installation via a line 48 derived from line 25.
- the tank 10 also includes a pressure sensor 26, and a temperature sensor 28.
- the arsine / hydrogen mixture produced at the cathode of cell 12 is first treated on a refrigerant 27 (the temperature of which is controlled by a sensor 29), so as to purify the mixture in question of much of its moisture.
- the mixture undergoes a second purification of water on a molecular sieve 30, before passing over a particle filter 31.
- the mixture then approaches a semi-permeable membrane module 32 of the type with hollow fibers, the active layer of which is a polyaramide (aromatic polyimide) offering a total exchange surface of the module of approximately 0.25 m 2 .
- the installation allows the permeate side of the membrane to be evacuated by a line 35, at a pressure of the order of 10 Pa absolute (primary vacuum).
- the mixture enriched in arsine, at the outlet (rejection) of the membrane, is then directed via a line 46 comprising a non-return valve 33 to a buffer capacity 34 from which the mixture is directed, via a line 47 comprising a pressure sensor 36, to the reactor 39 using arsine.
- the mixture is filtered through a particle filter 38.
- a vent 40 is planned if necessary at the end of the line 47.
- valves of two types All along the route there are valves of two types, depending on the fluids transported valves for the liquid circuit (such as valves 41, 42 etc.), and for the gas pipe (such as valves 43, 44, 45 etc.).
- the application of this installation made it possible to obtain, at the outlet of the cathode compartment, concentrations of arsine in hydrogen varying from 50% to 95%, according to the H + / As ratio applied (as illustrated in FIG. 2), with a flow rate of the mixture leaving the cell of at least 3 l / h.
- the drying stage consisting of the refrigerant 27 and a molecular sieve 30, makes it possible to obtain a mixture almost free of water, any additional drying which can be carried out on the membrane 30.
- the essential objective of the membrane is to concentrate the arsine in the mixture obtained at the membrane outlet.
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
- d'atteindre des concentrations élevées d'arsine dans le gaz de sortie;
- d'obtenir des débits suffisamment élevés, au moins égaux à 1 litre/heure, sans dégradation du rendement en arsine;
- d'obtenir une bonne stabilité des caractéristiques de concentration du mélange produit;
- d'éviter l'utilisation, comme matière première, de sels de sodium (tel NaAsO2) de façon à éviter la précipitation de sels tels que Na2SO4, et donc le rique d'une présence éventuelle de sodium dans la phase gazeuse, toujours préjudiciable aux utilisations ultérieures dans l'industrie électronique.
- On sépare, par une membrane cationique, la cellule électrochimique en deux compartiments anodique et cathodique, permettant ainsi la maitrise des flux de matière à l'intérieur de la cellule;
- On assure une circulation du fluide alimentant le compartiment cathodique suffisamment élevée pour obtenir un taux de conversion en arsenic à la cathode inférieur à 10 %;
- On alimente le compartiment cathodique en ions H+ et AsO2 - via un saturateur constitué par une réserve de composé solide As2O3 que vient balayer une solution acide.
Au niveau du saturateur :
- de laisser passer les ions H+ produits à l'anode vers la cathode, où ils iront alimenter la réaction de formation d'arsine;
- d'isoler les gaz produits à l'anode de ceux produits à la cathode;
- d'empécher que les ions AsO2 -, en solution du coté compartiment cathode, passent du côté anode et aillent s'oxyder sur l'anode, diminuant d'autant le rendement en arsine.
- grâce à l'utilisation d'électrodes appropriées,
- par l'utilisation d'une membrane cationique disposée entre les deux électrodes permettant une bonne maitrise des flux de matière intervenant d'une électrode à l'autre,
- par un apport régulier et constant en ions AsO2 - à l'aide d'un saturateur As2O3, et
- par l'établissement d'une vitesse de circulation de fluides elevée permettant une bonne maitrise du taux de conversion à la cathode,
- La figure 1 est une représentation schématique d'une cellule électrolytique entrant dans l'élaboration d'un générateur convenant pour la mise en oeuvre du procédé selon l'invention;
- La figure 2 représente une courbe donnant, pour une cellule selon la figure 1, la variation de la concentration d'arsine dans le mélange produit en fonction du rapport H+/As à la cathode, réalisée en plomb, et pour une densité de courant i= 500 A/m2.
- La figure 3 représente une courbe illustrant pour une cellule selon la figure 1, l'influence de la densité de courant (rapportée à la surface d'électrode) sur le débit d'arsine à la cathode.
- La figure 4 est une représentation schématique d'une installation globale comprenant un générateur convenant pour la mise en oeuvre du procédé selon l'invention.
- D'un compartiment anodique 1, relié au pôle positif d'un générateur électrique, comportant une anode 3 où se produit une réaction d'oxydation de l'eau, conduisant à la formation d'oxygène gazeux et d'ions H+. Cette anode est constituée de titane sur lequel a été effectué un dépot d'oxyde de ruthénium. Le compartiment anodique est alimenté en une solution acide 1M d'acide sulfurique contenue dans un bac de stockage anodique 4, via une ligne d'alimentation 5 par l'intermédiaire d'une pompe 6.
- D'un compartiment cathodique 2, relié au pôle négatif d'un générateur électrique, comportant une cathode 7, où se produisent deux réactions concurrentes, la première de formation d'arsine gazeux, la seconde de formation d'hydrogène gazeux. Cette cathode est constituée de plomb, elle présente une surface d'électrode de l'ordre de 70 cm2. Le compartiment cathodique est alimenté en composé HAsO2, donc en ions AsO2 -, par une ligne 17, via un saturateur 8 constitué par une réserve de composé solide As2O3, que vient balayer, par l'intermédiaire d'une pompe 9, une solution acide 1M d'acide sulfurique 19, contenue dans un bac de stockage cathodique 10.
- D'une membrane cationique 11 en NAFIONR séparant les deux compartiments.
Claims (20)
- Procédé de génération d'arsine par voie electrolytique à partir d'une cellule electrochimique (12) où sont disposées une cathode (7) alimentée en ions H+ et AsO2 -, où se produisent deux réactions concurrentes produisant respectivement de l'arsine et de l'hydrogène gazeux, et une anode (3), où se produit une réaction source d'ions H+, caractérisé en ce que le rapport des concentrations H+/As à la cathode (7) est controlé et maintenu constant, de manière à produire un mélange H2 + AsH3 dans des proportions comprises entre 50% et 95% de AsH3 selon le rapport H+/As appliqué.
- Procédé selon la revendication 1, caractérisé en ce que le contrôle du rapport H+/As est obtenu par les étapes suivantes :a) On sépare la cellule électrochimique en deux compartiments, anodique et cathodique, à l'aide d' une membrane cationique (11), permettant ainsi la maitrise des flux de matière à l'intérieur de la cellule ;b) On assure une circulation du fluide alimentant le compartiment cathodique suffisamment élevée pour obtenir un taux de conversion en arsenic à la cathode inférieur à 10 %;c) On alimente le compartiment cathodique en ions H+ et AsO2 - par une réserve de As2O3 (8), que vient balayer une solution acide (19).
- Procédé de génération d'arsine par voie électrolytique selon l'une des revendications 1 ou 2, caractérisé en ce que la cathode (7) est élaborée dans un matériau favorisant la réaction de formation d'arsine au détriment de la réaction de formation d'hydrogène.
- Procédé selon l'une des revendications 1 à 3, caractérisé en ce que la cathode (7) est constituée de plomb, ou de cuivre sur lequel a été effectué un dépot de bismuth, de plomb, de thallium ou encore de cadmium.
- Procédé selon l'une des revendications 1 a 4, caractérisé en ce que le rapport H+/As est maintenu entre 0.7 et 1.5, préférentiellement entre 0.75 et 1.25.
- Procédé selon l'une des revendications 1 à 5, caractérisé en ce que l'on fait subir au mélange d'hydrogène et d'arsine produit à la cathode (7) une étape ultérieure de séparation sur un module membranaire (32), de façon à obtenir en sortie de module, une concentration en arsine plus élevée que dans le dit mélange.
- Procédé selon la revendication 6, caractérisé en ce que l'on effectue une mise sous vide du coté perméat de la membrane.
- Procédé selon la revendication 6, caractérisé en ce que l'on effectue un balayage coté perméat de la membrane, à l'aide d'un gaz présentant une faible perméation du perméat vers l'intérieur de la membrane, tel que l'azote ou SF6.
- Procédé selon l'une des revendications 6,7,8, caractérisé en ce que avant son arrivée sur le module membranaire (32), le mélange produit à la cathode (7) subit au moins une opération de séchage, sur un dispositif tel qu'un réfrigérant à effet Peltier (27) ou un tamis moléculaire (30), ou une combinaison de ces deux moyens, et le cas échéant, au moins une opération de filtrage sur un filtre à particule (31).
- Dispositif de génération d'arsine par voie électrolytique, convenant notamment pour la mise en oeuvre du procédé selon l'une des revendications 1 à 9, comportant :Une cellule électrochimique (12) où sont disposées une cathode (7) au contact d'un electrolyte comportant des ions H+ et AsO2 -, où se produisent deux réactions concurrentes produisant respectivement de l'arsine et de l'hydrogène gazeux, et une anode (3), où se produit une réaction source d'ions H+; le rapport des concentrations H+/As à la cathode étant maintenu constant pour obtenir des concentrations en Arsine dans l'hydrogène, en sortie de compartiment cathodique, variant de 50 à 95% selon le rapport H+/As appliqué etUne membrane cationique (11) séparant la cellule électrochimique en deux compartiments, anodique et cathodique; etDes moyens pour alimenter le compartiment cathodique en ions H+ et AsO2 -, comportant un saturateur (8) constitué par une réserve de As2O3, que vient balayer une solution acide (19).
- Dispositif selon la revendication 10, caractérisé en ce que le saturateur (8) est situé entre la cellule électrochimique (12) et le bac de stockage (10) de la solution acide (19) alimentant le compartiment cathodique.
- Dispositif selon la revendication 10, caractérisé en ce que le saturateur (8) est situé à l'intérieur du bac de stockage (19) de la solution acide alimentant le compartiment cathodique, au sein de la dite solution acide (19).
- Dispositif selon l'une des revendications 10 à 12, caractérisé en ce que la cathode (7) est élaborée dans un matériau favorisant la réaction de formation d'arsine au détriment de la réaction de formation d'hydrogène.
- Dispositif selon la revendication 13, caractérisé en ce que la cathode (7) est constituée de plomb, ou de cuivre sur lequel a été effectué un dépot de bismuth, de plomb, de thallium ou encore de cadmium.
- Dispositif selon l'une des revendications 10 à 14, caractérisé en ce qu'il comporte, en aval de la cellule électrochimique, un module membranaire (32), sur lequel le mélange arsine/hydrogène produit à la cathode (7) subit une étape de séparation, de façon à obtenir en sortie de module, une concentration en arsine plus élevée que dans le dit mélange.
- Dispositif selon la revendication 15, caractérisé en ce que le module membranaire est raccordé à des moyens permettant d'effectuer une mise sous vide du coté perméat de la membrane.
- Dispositif selon la revendication 15, caractérisé en ce que le module membranaire est raccordé à une source de gaz, permettant d'effectuer un balayage coté perméat de la membrane à l'aide de ce gaz, qui présente une faible perméation du perméat vers l'intérieur de la membrane, tel l'azote ou SF6.
- Dispositif selon l'une des revendications 15 à 17, caractérisé en ce qu'il comprend, en amont du module membranaire, au moins un dispositif de séchage du mélange produit à la cathode, et le cas échéant, au moins un filtre à particule (31).
- Dispositif selon l'une des revendications 10 à 18, caractérisé en ce que le compartiment anodique est du type électrode plane alimentée en solution acide, où se produit l'électrolyse de l'eau.
- Dispositif selon l'une des revendications 10 à 18, caractérisé en ce le compartiment anodique est du type électrode à diffusion gazeuse, alimentée en hydrogène, où se produit l'oxydation de l'hydrogène.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9311082A FR2710043B1 (fr) | 1993-09-17 | 1993-09-17 | Procédé et dispositif de génération d'arsine par voie électrolytique. |
FR9311082 | 1993-09-17 |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0648865A1 EP0648865A1 (fr) | 1995-04-19 |
EP0648865B1 true EP0648865B1 (fr) | 1999-12-29 |
Family
ID=9450959
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP94401974A Expired - Lifetime EP0648865B1 (fr) | 1993-09-17 | 1994-09-06 | Procédé et dispositif de génération d'arsine par voie électrolytique |
Country Status (6)
Country | Link |
---|---|
US (1) | US5425857A (fr) |
EP (1) | EP0648865B1 (fr) |
JP (1) | JPH07180076A (fr) |
DE (1) | DE69422367T2 (fr) |
FR (1) | FR2710043B1 (fr) |
TW (1) | TW285780B (fr) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
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US5925232A (en) * | 1995-12-06 | 1999-07-20 | Electron Tranfer Technologies | Method and apparatus for constant composition delivery of hydride gases for semiconductor processing |
US6080297A (en) * | 1996-12-06 | 2000-06-27 | Electron Transfer Technologies, Inc. | Method and apparatus for constant composition delivery of hydride gases for semiconductor processing |
US6277342B1 (en) | 1999-08-23 | 2001-08-21 | Air Products And Chemicals, Inc. | Storage and safe delivery of hazardous specialty gases by acid/base reactions with ionic polymers |
US8021536B2 (en) | 2006-04-13 | 2011-09-20 | Air Products And Chemical, Inc. | Method and apparatus for achieving maximum yield in the electrolytic preparation of group IV and V hydrides |
US20090159454A1 (en) | 2007-12-20 | 2009-06-25 | Air Products And Chemicals, Inc. | Divided electrochemical cell and low cost high purity hydride gas production process |
TWI421601B (zh) | 2008-04-25 | 2014-01-01 | Au Optronics Corp | 適用雷射切割技術之顯示面板及其母板 |
US8361303B2 (en) * | 2010-09-02 | 2013-01-29 | Air Products And Chemicals, Inc. | Electrodes for electrolytic germane process |
GB201015022D0 (en) | 2010-09-09 | 2010-10-20 | Johnson Matthey Plc | Metal passivation |
CN110950382B (zh) * | 2018-09-26 | 2022-03-15 | 紫石能源有限公司 | 砷烷的制备方法 |
CN111103392A (zh) * | 2018-10-29 | 2020-05-05 | 东泰高科装备科技有限公司 | 一种砷烷气体吸收过滤系统 |
CN111378979B (zh) * | 2018-12-29 | 2022-03-15 | 紫石能源有限公司 | 砷纳米颗粒及其制备方法、电解制砷烷的系统和方法 |
CN114438534A (zh) * | 2022-01-05 | 2022-05-06 | 飞马牧场(上海)信息咨询服务有限公司 | 一种高纯气体制备装置及制备方法 |
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US4178224A (en) * | 1978-01-19 | 1979-12-11 | Texas Instruments Incorporated | Apparatus for generation and control of dopant and reactive gases |
SU962335A1 (ru) * | 1980-03-24 | 1982-09-30 | Казахский Ордена Трудового Красного Знамени Государственный Университет Им.С.М.Кирова | Электролизер дл получени летучих гидридов |
US5158656A (en) * | 1991-03-22 | 1992-10-27 | Electron Transfer Technologies, Inc. | Method and apparatus for the electrolytic preparation of group IV and V hydrides |
-
1993
- 1993-09-17 FR FR9311082A patent/FR2710043B1/fr not_active Expired - Fee Related
-
1994
- 1994-09-06 EP EP94401974A patent/EP0648865B1/fr not_active Expired - Lifetime
- 1994-09-06 DE DE69422367T patent/DE69422367T2/de not_active Expired - Fee Related
- 1994-09-07 TW TW083108247A patent/TW285780B/zh active
- 1994-09-13 JP JP6219198A patent/JPH07180076A/ja active Pending
- 1994-09-14 US US08/305,835 patent/US5425857A/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
EP0648865A1 (fr) | 1995-04-19 |
TW285780B (fr) | 1996-09-11 |
FR2710043A1 (fr) | 1995-03-24 |
US5425857A (en) | 1995-06-20 |
JPH07180076A (ja) | 1995-07-18 |
DE69422367D1 (de) | 2000-02-03 |
DE69422367T2 (de) | 2000-08-24 |
FR2710043B1 (fr) | 1995-10-13 |
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