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WO2014109463A1 - Procédé et dispositif d'obtention de germane de pureté élevée - Google Patents

Procédé et dispositif d'obtention de germane de pureté élevée Download PDF

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Publication number
WO2014109463A1
WO2014109463A1 PCT/KR2013/009464 KR2013009464W WO2014109463A1 WO 2014109463 A1 WO2014109463 A1 WO 2014109463A1 KR 2013009464 W KR2013009464 W KR 2013009464W WO 2014109463 A1 WO2014109463 A1 WO 2014109463A1
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WIPO (PCT)
Prior art keywords
geh
crude
raw material
impurities
germain
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PCT/KR2013/009464
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English (en)
Korean (ko)
Inventor
문흥만
최형철
이준영
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DIG Airgas Co Ltd
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Daesung Industrial Gases Co Ltd
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Publication of WO2014109463A1 publication Critical patent/WO2014109463A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G17/00—Compounds of germanium

Definitions

  • the present invention relates to a high purity low main production method and apparatus, and more particularly, to a low main production method and apparatus for the production of high purity low main through synthesis, purification and filling process.
  • high purity germane is typically needed in the manufacture of semiconductor devices such as transistors, diodes, integrated circuits, sensors, solar cells and the like. In many of these fields, high purity germane is often used for the doping of substrates or substrates for the deposition of silicon-germanium alloys.
  • Another object of the present invention is to provide a high purity low main production method and apparatus including a commercially available process including synthesis, purification and filling.
  • Production method is solid KOH, NaBH in distilled water 4 , And GeO 2 Sequentially dissolved to form a first aqueous solution, 2 SO 4
  • the first aqueous solution is reacted while a predetermined amount is sequentially added while an aqueous solution is added, and the raw material of the gas state containing impurities (crude GeH) 4 Synthesizing to generate; Part of H that is condensed by cooling the raw material germain to a constant temperature 2 O and Ge 2 H 6 Remove impurities including, and residual H using the adsorbent 2 O and CO 2
  • KOH corresponding to a concentration of 0.3 to 0.8 mol (mole) is dissolved in a first mixing tank into which distilled water is added, NaBH 4 is dissolved in an amount corresponding to a concentration of 0.5 to 1.0 mol (mole), and GeO 2 Dissolved in an amount corresponding to 0.1 to 0.3 mole concentration to produce a first aqueous solution containing KGeH 3 , H 2 SO 4 to 2.0 to 4.0 mole (mole) concentration in the second mixing tank with distilled water Adding an H 2 SO 4 aqueous solution;
  • the first aqueous solution generated in the first mixing tank and the H 2 SO 4 aqueous solution generated in the second mixing tank may be reacted in the reactor to produce a raw material (crude GeH 4 ).
  • the first refining step may include pressurizing the crude GeH 4 that has undergone the synthesis step to a pressure of 2 to 5 barg (gauge pressure) using a compressor; Cooling the pressurized raw material Germain (crude GeH 4 ) to a temperature range of 5 to 10 ° C. using a chiller to remove some H 2 O and Ge 2 H 6 that are condensed impurities;
  • the method may include the step of transferring the crude GeH 4 from which some H 2 O and Ge 2 H 6 have been removed from the chiller to an adsorption tower filled with an adsorbent to remove residual H 2 O and CO 2 as impurities. have.
  • the first refining step may include pressurizing the crude GeH 4 that has undergone the synthesis step to a pressure of 2 to 5 barg (gauge pressure) using a compressor; Condensing and removing the pressurized raw gemain (crude GeH 4 ) by using a water-cooled heat exchanger to condense a part of H 2 O as impurities; Transferring the crude GeH 4 from which some H 2 O is removed from the water-cooled heat exchanger to an adsorption tower filled with an adsorbent to remove residual H 2 O and CO 2 as impurities; The adsorbent removes Ge 2 H 6 , which is a condensed impurity, by cooling the raw material Germain 4 from which H 2 O and CO 2 have been removed to a temperature range of -10 to -20 ° C. using a chiller. It may be provided with a step.
  • the first refining step may include pressurizing the crude GeH 4 that has undergone the synthesis step to a pressure of 2 to 5 barg (gauge pressure) using a compressor; Cooling the pressurized raw material Germain (crude GeH 4 ) to a temperature range of 5 to 10 ° C.
  • the adsorbent is zeolite 4A (MS 4A) for the removal of H 2 O and CO 2 , or zeolite 4A (MS 4A) and zeolite 13X (MS 13X for the removal of H 2 O, CO 2 and Ge 2 H 6 ) May be used.
  • the second purification step may include crude GeH 4 that has undergone the first purification step at -80 to -120 ° C. Transferring the temperature to a distillation column; The upper part of the distillation column is maintained at a temperature control of -80 ⁇ -120 °C, the reboiling is carried out at the bottom, H 2 from the raw material (crude GeH 4 ) relatively low boiling point than Ge Main (GeH 4 ) Distilling and separating in a vaporizing manner; The temperature of the distillation column in which the crude GeH 4 having H 2 separated therefrom is in a liquefied state is raised to ⁇ 45 to ⁇ 65 ° C., so that Ge 2 H has a higher boiling point than that of Ge Main 4 . 6 may be liquefied and the low main (GeH 4 ) may be vaporized to generate a low main gas (GeH 4 ) in which impur
  • the pressure of the distillation column may maintain a state of 2 ⁇ 5barg.
  • the second purification step includes a crude GeH 4 that has undergone the first purification step at a temperature of -80 to -120 ° C. Transferring to a distillation column of the; The upper part of the distillation column is maintained at a temperature control of -80 ⁇ -120 °C, the reboiling is carried out at the bottom, H 2 from the raw material (crude GeH 4 ) relatively low boiling point than Ge Main (GeH 4 ) It may be provided by distilling to separate in a vaporizing manner to produce a liquefied germane (GeH 4 ) in which impurities are removed.
  • the gaseous germane (GeH 4 ) in which the impurities are removed is liquefied and stored in a liquefied state by temperature control in a storage tank, and compressed and filled into the gaseous low mains in a filling cylinder. It may further comprise a step.
  • Production equipment is distilled water (H 2 O) to solid KOH, NaBH 4 , And GeO 2 Sequentially dissolved to form a first aqueous solution, 2 SO 4
  • the first aqueous solution is reacted while a predetermined amount is sequentially added while an aqueous solution is added, and the raw material of the gas state containing impurities (crude GeH) 4
  • a synthesis unit generating a);
  • Partial H which is an impurity condensed by pressurizing the raw material germain and cooling to a predetermined temperature 2 O and Ge 2 H 6 Is removed and residual H 2 O and CO 2
  • a first purification unit for removing impurities including a; H as an impurity by performing a distillation process according to the difference in boiling point of the raw material Jemain after the first purification step 2 To remove impurities to remove germane (GeH 4 And a second refining unit for generating).
  • the synthesis unit distilled water (H 2 O) to KOH, NaBH 4 , And GeO 2
  • a first mixing tank for dissolving sequentially to produce a first aqueous solution
  • a second mixing tank for producing an aqueous solution
  • Crude GeH as a raw material by reacting an aqueous solution 4 May be provided with a reactor for producing ().
  • the reactor may be provided with a temperature control unit for controlling the temperature of the reactor to maintain a constant temperature in the temperature range of 30 ⁇ 50 °C.
  • the first purification unit and a compressor for pressurizing the raw material (crude GeH 4 ) generated in the synthesis unit to a pressure of 2 ⁇ 5 barg (gauge pressure);
  • a chiller (chiller) for removing some H 2 O and Ge 2 H 6 , which are impurities condensed by cooling the raw material Germain (crude GeH 4 ) pressurized by the compressor to a temperature range of 5 to 10 ° C .;
  • An adsorption tower may be provided to remove residual H 2 O and CO 2 using an adsorbent from the crude GeH 4 from which some H 2 O and Ge 2 H 6 are removed from the chiller.
  • the first purification unit and a compressor for pressurizing the raw material (crude GeH 4 ) generated in the synthesis unit to a pressure of 2 ⁇ 5 barg (gauge pressure);
  • a water-cooled heat exchanger for condensing and removing part of H 2 O as an impurity through heat exchange of the crude GeH 4 pressurized through the compressor;
  • An adsorption tower for removing residual H 2 O and CO 2 using an adsorbent from the crude GeH 4 in which some H 2 O is removed from the water-cooled heat exchanger; Chiller to remove Ge 2 H 6 , which is an impurity that is condensed by cooling the raw material Germain 4 (crude GeH 4 ) from which H 2 O and CO 2 are removed through the adsorbent to a temperature range of ⁇ 10 to ⁇ 20 ° C. It may be provided.
  • An adsorption tower for removing residual H 2 O and CO 2 using an adsorbent in the crude geH 4 from which some H 2 O and some Ge 2 H 6 are removed from the first chiller;
  • a second chiller for removing residual Ge 2 H 6 , which is a condensed impurity, by cooling the raw material Gemain (crude GeH 4 ) from which H 2 O and CO 2 are removed through the adsorbent to a temperature range of ⁇ 10 to ⁇ 20 ° C. (Chiller) can be provided.
  • the adsorbent of the adsorption tower is zeolite 4A (MS 4A) is used for the removal of H 2 O and CO 2 , or zeolite 4A (MS 4A) and zeolite 13X (for the removal of H 2 O, CO 2 and Ge 2 H 6 MS 13X) can be used.
  • the second refining unit includes a random packing, a lower side performs reboiling, and an upper side performs condensation using liquid nitrogen to remove H 2 O, CO 2 and Ge 2 H 6 .
  • a distillation column for performing distillation and separation on the raw material jemain;
  • a vaporizer for said reboiling; It may be provided with a temperature sensor for sensing the temperature of the distillation column.
  • the germain production apparatus further includes a storage and charging unit, and the storage and charging unit includes a germain storage tank for storing germain (GeH 4 ) from which impurities are removed through the second purification unit in a liquefied state; A charging cylinder for charging the low main (GeH 4 ) from which the impurities are removed; A compressor for pressurizing the germain (GeH 4 ) stored in the germain storage tank to fill the filling cylinder; It may be provided with a vacuum pump for forming a vacuum of the filling cylinder.
  • a storage and charging unit includes a germain storage tank for storing germain (GeH 4 ) from which impurities are removed through the second purification unit in a liquefied state; A charging cylinder for charging the low main (GeH 4 ) from which the impurities are removed; A compressor for pressurizing the germain (GeH 4 ) stored in the germain storage tank to fill the filling cylinder; It
  • the first purification unit may further include a heater for heating GN 2 (gas nitrogen) for regeneration of the adsorbent provided in the adsorption tower.
  • GN 2 gas nitrogen
  • FIG. 1 is a block diagram illustrating a high purity low main (GeH 4 ) production apparatus and a production method according to the present invention
  • FIG. 2 is a detailed block diagram of FIG. 1 according to a first embodiment of the present invention
  • FIG. 3 is a detailed block diagram of FIG. 1 according to a second embodiment of the present invention.
  • FIG. 4 is a detailed block diagram of FIG. 1 according to a third embodiment of the present invention.
  • FIG. 1 is a block diagram illustrating a high purity low main (GeH 4 ) production apparatus and a production method according to the present invention
  • Figure 2 is a specific block diagram of Figure 1 according to a first embodiment of the present invention.
  • the Jermaine production apparatus 100 includes a synthesis unit 110 and a purification unit 120.
  • the storage and charging unit 130 may be further provided.
  • the synthesis unit 110 is to generate a raw material Germain (crude GeH 4) from a raw material such as GeO 2, KOH, NaBH 4.
  • the synthesis unit 110 includes a first mixing tank 112, a second mixing tank 114, and a reactor 116.
  • GeO 2 , KOH, and NaBH 4 are mixed to generate a first aqueous solution.
  • a basic solution of GeOH 2 , KOH and hydrogen supply NaBH 4 must be added together with H 2 O to generate 2KGeH 3 , which is a preliminary step in the synthesis of GeH 4 .
  • GeO 2 , KOH, and NaBH 4 present in the solid state are dissolved in distilled water (H 2 O) to make an aqueous solution and then proceed with the reaction.
  • distilled water H 2 O
  • KOH corresponding to 0.3 to 0.8 mol (mole) concentration
  • NaBH 4 is completely dissolved by adding an amount corresponding to 0.5 to 1.0 mole concentration.
  • GeO 2 is added to and stirred at an amount corresponding to a concentration of 0.1 to 0.3 mol (mole) to generate the first aqueous solution.
  • the first aqueous solution contains 2KGeH 3 .
  • Reaction related in the first mixing tank 112 is the same as the general formula (1) and (2).
  • H 2 SO 4 aqueous solution is produced.
  • H 2 SO 4 aqueous solution is an approximately 2.0 to 4.0 mol (mole) SO 4 aqueous solution of H 2 by introducing a H 2 SO 4 so that the concentration was charged into distilled water (H 2 O) to the second mixing tank 114 Create
  • the concentration of H 2 SO 4 can affect the production yield of GeH 4 , resulting in an aqueous solution of 2.0 to 4.0 mole concentration.
  • an aqueous solution of H 2 SO 4 is introduced into the reactor 116 through the second mixing tank 114, and then the first aqueous solution stored in the first mixing tank 112 is slowly added thereto. Initiate the reaction. Slowly input may mean that a certain amount is sequentially added instead of all at once.
  • the reaction temperature of the reactor 116 may increase according to the reaction. If the reaction temperature of the reactor 116 continues to rise may lead to a decrease in the production yield of the raw material Gemain (crude GeH 4 ). Thus, the reactor 116 is controlled to maintain a constant temperature in the temperature range of approximately 30 ⁇ 50 °C.
  • the reactor 116 may be provided with a temperature control unit separately for temperature control.
  • the reaction in the reactor 116 continues until the input of the first aqueous solution is stopped.
  • the raw material Germain (Crude GeH 4 ) generated in the reactor 116 contains impurities of H 2 O and Ge 2 H 6 , including about 80 to 90% of H 2 , and also a small amount generated in the manufacturing process. Impurities such as CO 2 are contained. Therefore, in order to produce high purity low main (GeH 4 ), the raw material low main (Crude GeH 4 ) generated in the reactor 116 must be purified through the purification unit 120.
  • the raw material germain (Crude GeH 4 ) in the gas (or gas) state generated in the reactor 116 is transferred to the purification unit 120 to be purified through the purification unit 120, and to the reactor 116.
  • By-products eg, NaB (OH) 4 , K 2 SO 4, etc.
  • By-products for generating the remaining raw material Germain (Crude GeH 4 ) may be disposed of or recycled.
  • the purification unit 120 includes a gas compressor 122, a chiller 124, an adsorption tower 126, and a distillation column 128.
  • the compressor (gas compressor) 122, the chiller (gas chiller) 124 and the adsorption column 126 is a first purification unit for the first purification step for performing the purification at room temperature or similar to room temperature
  • the distillation column 128 constitutes a second purification unit for a second purification step of performing purification at low temperature.
  • the purification unit 120 is purified when the raw material Germain (Crude GeH 4 ) generated in the synthesis unit 110 is transferred.
  • the purification method includes completely removing H 2 O and CO 2 and partially removing Ge 2 H 6 through purification in the gas compressor 122, the gas chiller 124, and the adsorption tower 126. Or remove them all.
  • the compressor 122 pressurizes the raw material Germain (Crude GeH 4 ) generated in the reactor 116 to a pressure of approximately 2 to 5 barg (gauge pressure) to be transferred to the gas chiller 124. do.
  • the chiller 124 serves to lower the temperature of the raw material Germain (Crude GeH 4 ) pressurized through the compressor 122.
  • the raw material Germain (Crude GeH 4 ) contains impurities such as H 2 O and Ge 2 H 6 .
  • H 2 O is also removed through the adsorption tower 126, which will be described later, but can be removed in the form of condensate by lowering the temperature in the previous step.
  • the chiller 124 condenses and removes Ge 2 H 6 .
  • the raw material Germain (Crude GeH 4 ) in the form of gas compressed through the compressor 122 is present in the form of H 2 O vaporized, that is, water vapor, but can be removed in the form of condensate because it is partially condensed when the temperature is lowered. . Therefore, in the chiller 124, the temperature is lowered to about 5 to 10 ° C. to condense and remove H 2 O as an impurity.
  • Ge 2 H 6 has a boiling point (break point) of about 31.5 ° C. at normal pressure, when the temperature is lowered to about 5 to 10 ° C. in the chiller 124, Ge 2 H 6 is condensed and exists in a liquid state.
  • Some H 2 O and Ge 2 H 6 condensed in the chiller 124 are discharged and removed through the discharge pipe 124a provided at the bottom.
  • the adsorption tower 126 removes residual H 2 O and CO 2 from the raw material Germain (Crude GeH 4 ) from which some H 2 O is removed through the chiller 124.
  • H 2 O and CO 2 may be solidified at around 0 ° C. and ⁇ 56 ° C., respectively. Therefore, H 2 O and CO 2 must be completely removed from the adsorption tower 126 at room temperature before low temperature.
  • the adsorption tower 126 is filled with zeolite 4A (MS 4A) with an adsorbent. Therefore, the residual H 2 O and CO 2 are removed through the zeolite 4A (MS 4A).
  • the adsorption tower 126 may be required to further remove Ge 2 H 6 in addition to the remaining H 2 O and CO 2 from the raw material Germain (Crude GeH 4 ).
  • the adsorption tower 126 may have a structure in which a zeolite 4A (MS 4A) is filled with an adsorbent at a lower portion thereof, and a zeolite 13X (MS 13X) is filled with an adsorbent at an upper portion thereof.
  • the zeolite 4A (MS 4A) and the zeolite 13X (MS 13X) will remove H 2 O, CO 2 and some Ge 2 H 6 .
  • H 2 O and CO 2 may be removed through the zeolite 4A
  • some Ge 2 H 6 included in the raw material Germain may be removed through the zeolite 13X.
  • the regeneration of the adsorbent may be performed by heating GN 2 (gas nitrogen) through a heater 127 provided in the adsorption tower 126 after the production process is completed to regenerate impurities adsorbed on the adsorbent. have.
  • GN 2 gas nitrogen
  • the raw material germain (Crude GeH 4 ) generated in the reactor 116 needs to be driven to the refining unit 120. This may obtain a driving force through the compressor 122 and the distillation column 128. That is, the reactor 116 through the driving force obtained by the pressurization through the compressor 122 directly connected to the reactor 116 and the temperature difference generated while cooling through the LN 2 (liquid nitrogen) in the distillation column 128.
  • the raw material germain (Crude GeH 4 ) generated in the) is transferred to the purification unit 120.
  • the raw material Germain (Crude GeH 4 ) is pressurized to a pressure of approximately 2 ⁇ 5 barg through the compressor 122, the pressurized raw material Germain (Crude GeH 4 ) is a chiller (124) and the adsorption tower (126) After passing through) is transferred to the distillation tower (128).
  • the pressing through, LN 2 (liquid nitrogen), the drive force and the compressor 122 according to the temperature difference with the cooling of the LN 2 (liquid nitrogen) and since the cooling is conducted using, as described later in the distillation tower (128)
  • the raw material Jemain (Crude GeH 4 ) is used together with the driving force due to.
  • the feed method of Crude GeH 4 is about -80 by introducing LN 2 (liquid nitrogen) into the distillation column 128 before synthesizing the H 2 SO 4 aqueous solution and the first aqueous solution in the reactor 116.
  • LN 2 liquid nitrogen
  • the first aqueous solution is added to the reactor 116 to initiate a reaction.
  • the reaction is started, the synthesis gas of crude GeH 4 is generated in the reactor 116, and the synthesis gas of crude GeH 4 is a pressure of about 0 to 0.3 barg slightly higher than normal pressure. .
  • the compressor 122 the pressurized to the syngas said material Germain (Crude GeH4) at a pressure of approximately 2 ⁇ 5 barg and the pressure of the synthesis gas in the compressor 122 is the raw material Germain (Crude GeH 4) It is controlled to maintain a constant pressure by repeating the operation and stopping to maintain the pressure.
  • Crude GeH 4 coarse first raw material for the first refining step (Crude GeH 4 ) is all H 2 and CO 2 is removed, Ge 2 H 6 is not removed all may remain. In this case, the remaining Ge 2 H 6 may be removed through the second purification step in the distillation column 128 constituting the second purification unit. It demonstrates below.
  • the distillation column 128 is connected to the raw material Germain (Crude GeH 4 ) from which H 2 O, CO 2 and a part of Ge 2 H 6 are removed through the compressor 122, the chiller 124, and the adsorption tower 126.
  • the distillation column 128 is connected to the raw material Germain (Crude GeH 4 ) from which H 2 O, CO 2 and a part of Ge 2 H 6 are removed through the compressor 122, the chiller 124, and the adsorption tower 126.
  • boiling point difference difference in boiling point
  • the lower portion of the distillation column 128 is provided with a vaporizer (Vaporizer) 129 that serves as a reboiler, the upper side is provided with a heat exchanger (not shown) as a condenser using a coolant such as LN 2 (liquid nitrogen) It is configured to work.
  • a random packing may be provided in the distillation column 128 for distillation.
  • the distillation column 128 is introduced into the LN 2 (liquid nitrogen) before starting the reaction in the reactor 116 to maintain the temperature of the distillation column 128 at approximately -80 ⁇ -120 °C.
  • the distillation column 128 is provided with a temperature sensor (not shown) for sensing the temperature in the distillation column 128, performs a temperature control using the temperature sensor and enters into the distillation column 128 by the temperature control
  • the inflow and blocking of LN 2 (Liquid Nitrogen) is controlled. Therefore, temperature control of the distillation column 128 is possible.
  • the temperature of the distillation column 128 is maintained at approximately -80 to -120 ° C, when the reaction is started in the reactor 116, the raw material Germain (Crude GeH 4 ) generated through the reaction is as described above. After passing through the first purification step (or the first purification unit), the distillation column 128 is transferred.
  • distillation column 128 performs an operation for removing H 2 contained in the raw material Germain (Crude GeH 4 ).
  • a vaporizer 129 may be a standby vaporizer.
  • the operating pressure of the distillation column 128 is maintained at a state of 2 ⁇ 5barg.
  • the pressure of the distillation column 128 may also be controlled by inflow or blocking of LN 2 (liquid nitrogen), reboiling using the vaporizer 129, and the like.
  • the temperature of the distillation column 128 is maintained at -80 to -120 ° C and the pressure of the distillation column 128 is maintained at a state of 2 to 5 barg, the inside of the distillation column 128 Since some Ge 2 H 6 , including Jemaine (GeH 4 ) except H 2 , are all liquefied, it is possible to remove and remove H 2 through the upper VENT line.
  • the raw material Germain (Crude GeH 4 ) remains GeH 4 and some Ge 2 H 6 in a liquefied state.
  • the temperature of the distillation column 128 is increased to approximately ⁇ 45 to ⁇ 65 ° C.
  • the temperature rise of the distillation column 128 may also be performed by controlling the inflow / blocking of LN 2 (liquid nitrogen) and temperature control using a vaporizer.
  • LN 2 liquid nitrogen
  • the temperature of the distillation column 128 is raised in the range of -45 to -65 ° C, Ge 2 H 6 having a high boiling point remains in a liquid state, but GeH 4 is vaporized.
  • the gaseous germane (GeH 4 ) is transferred to the germane storage tank 132 through the upper line L1 of the distillation column 128 and Ge 2 H 6 is transferred to the distillation column ( 128 is discharged through the discharge valve (V3) provided at the bottom of the removal.
  • the distillation column 128 may only perform the above-described process for removing H 2. Can be. Since the above-described H 2 removal is completed and only the high purity low main (GeH 4 ) is present in the distillation column 128 in the liquefied state, the transfer valve (V4) and the transfer line (L2) provided in the lower portion of the distillation column 128 Through the high purity low main (GeH 4 ) of the liquefied state it is possible to transfer to the low main storage tank (132).
  • the storage and charging unit 130 may include a low main storage tank 132 and a filling cylinder 134 and may further include a vacuum pump 136.
  • the low main storage tank 132 is for storing a high purity low main (GeH 4 ) in a liquefied state, and the filling cylinder 134 to fill a high purity low main (GeH 4 ) stored in the low main storage tank 132. It is for.
  • the high purity germane (GeH 4 ) transferred in the gas state from the distillation column 128 is liquefied and stored in the germane storage tank 132.
  • the low main storage tank 132 is supplied with LN 2 (liquid nitrogen) in order to condense the upper part to liquefy high purity low main (GeH 4 ) flowing into the gas state. At this time, the low main storage tank is temperature controlled according to the inflow of LN 2 (liquid nitrogen) and is controlled to a temperature of approximately -70 ⁇ -90 °C. Liquefied high purity germane (GeH 4 ) is stored in the lower portion of the germane storage tank 132.
  • the high purity low main (GeH 4 ) of the liquefied state is transferred to the low main storage tank 132 through the transfer valve (V4) and the transfer line (L2) provided at the lower portion of the distillation column 128
  • the liquefaction process may not be necessary, and the low main storage tank 132 controls the temperature through the inflow and blocking of LN 2 (liquid nitrogen) to maintain the high purity low main (GeH 4 ) in the liquefied state.
  • the low main storage tank 132 is provided with a vaporizer (Vaporizer) 133, the vaporizer 133 serves as a pressure vaporizer to increase the pressure of the low main storage tank 132.
  • Vaporizer vaporizer
  • a gas compressor in front of the filling cylinder 134 in order to effectively transfer to the filling cylinder 134 to be charged without remaining of the high purity germane (GeH 4 ) inside the low main storage tank 132 ( 138 may be further provided.
  • the driving force at this time is obtained through two methods, one of which is the driving force to increase the pressure of the low main storage tank 132 through the vaporizer 133 located below the low main storage tank 132, and the low main storage
  • the high purity germane (GeH 4 ) is elevated to about 1 barg (gauge pressure) pressure by the vaporizer 133, and is pressurized to a pressure of about 2 to 5 barg through the compressor 138.
  • Pressurized high purity low main (GeH 4 ) is transferred to the filling cylinder 134 at room temperature to be filled at a pressure of about 2 to 5 barg.
  • the filling cylinder 134 In order to charge the high purity low main (GeH 4 ) stored in the low main storage tank 132, the filling cylinder 134 preferentially forms a vacuum by using a vacuum pump 136 provided separately. At this time, the filling line (L3) connecting the low main storage tank 132 and the filling cylinder 134 to form a vacuum is blocked by the valve (V6) and open the valve (V7) connected to the vacuum pump 136 to vacuum Will form.
  • the low main storage tank 132 In order to fill the charging cylinder 134 with high purity germane (GeH 4 ), the low main storage tank 132 circulates the high purity germane (GeH 4 ) using a lower vaporizer 133 and the low main storage tank 132. Pressurizes to increase the pressure, and the filling cylinder 134 is filled with a high purity low main (GeH 4 ) in a gas state through the filling line (L3).
  • the remaining high-purity germain (GeH 4 ) inside the germain storage tank 132 is completely filled in the filling cylinder 134.
  • the high purity low main (GeH 4 ) charged to the filling cylinder 134 is monitored through an electronic balance (not shown) provided at the lower portion of the filling cylinder 134, and when the required filling amount is charged, the valve V5, Shut off V6) to complete charging.
  • Figure 3 is a concrete block diagram of Figure 1 showing a Jermaine production apparatus according to a second embodiment of the present invention.
  • the Jermaine production apparatus 200 includes a synthesis unit 110 and a purification unit 120.
  • the storage and charging unit 130 may be further provided.
  • the synthesis unit 110 and the storage and charging unit 130 is the same as described with reference to FIGS. 1 and 2.
  • the purification unit 120 includes a gas compressor 122, a water-cooled heat exchanger 125, an adsorption tower 126, a chiller 121, and a distillation column 128.
  • the first purification step in which the gas compressor 122, the water-cooled heat exchanger 125, the adsorption tower 126, and the chiller 121 perform purification at room temperature or similar to room temperature.
  • the first purification unit for, the distillation column 128 constitutes a second purification unit for the second purification step to perform the purification in a low temperature state.
  • the configuration or operation of the second purification unit is the same as described with reference to FIGS. 1 and 2.
  • the purification unit 120 is purified when the raw material Germain (Crude GeH 4 ) generated in the synthesis unit 110 is transferred.
  • the purification method completely purifies H 2 O and CO 2 through purification in the gas compressor 122, the water-cooled heat exchanger 125, the adsorption tower 126, and the gas chiller 121. Remove and remove some or all of Ge 2 H 6 .
  • the compressor 122 pressurizes the raw material Germain (Crude GeH 4 ) generated in the reactor 116 to a pressure of approximately 2 to 5 barg (gauge pressure) and transfers the same to the water-cooled heat exchanger 125.
  • the water-cooled heat exchanger 125 serves to lower the temperature of the raw material Germain (Crude GeH 4 ) pressurized through the compressor 122.
  • the raw material Germain (Crude GeH 4 ) contains impurities such as H 2 O and Ge 2 H 6 .
  • H 2 O is also removed through the adsorption tower 126, which will be described later, but can be removed in the form of condensate by lowering the temperature in the previous step.
  • the raw material Germain (Crude GeH 4 ) in the form of gas compressed through the compressor 122 is present in the form of H 2 O vaporized, that is, water vapor, but can be removed in the form of condensate because it is partially condensed when the temperature is lowered. . Accordingly, the water-cooled heat exchanger 125 maintains a temperature of about 30 to 40 ° C. to remove H 2 O, which is partially condensed, through the discharge pipe 125a provided at the bottom of the water-cooled heat exchanger 125.
  • the water-cooled heat exchanger 125 through a portion, if condensed water is not remove the H 2 O removal of the H 2 O contained in the pressure the raw Germain (Crude GeH 4) are all done in the adsorption tower (126) of the rear end .
  • the more H 2 O to be removed the larger the capacity of the adsorption tower 126 and the adsorption performance at a higher temperature may be lowered, so some H 2 O must be removed through the chiller 124.
  • the adsorption tower 126 removes residual H 2 O and CO 2 from the raw material Germain (Crude GeH 4 ) from which some H 2 O is removed through the water-cooled heat exchanger 125.
  • H 2 O and CO 2 may be solidified near 0 ° C. and ⁇ 56 ° C., respectively, and thus may be difficult to purify. Therefore, H 2 O and CO 2 must be completely removed from the adsorption tower 126 at room temperature before low temperature.
  • the adsorption tower 126 is filled with zeolite 4A (MS 4A) with an adsorbent. Therefore, the residual H 2 O and CO 2 are removed through the zeolite 4A (MS 4A).
  • the adsorption tower 126 may have a structure in which a zeolite 4A (MS 4A) is filled with an adsorbent at a lower portion thereof, and a zeolite 13X (MS 13X) is filled with an adsorbent at an upper portion thereof.
  • the zeolite 4A (MS 4A) and the zeolite 13X (MS 13X) will remove H 2 O, CO 2 and some Ge 2 H 6 .
  • H 2 O and CO 2 may be removed through the zeolite 4A
  • some Ge 2 H 6 included in the raw material Germain may be removed through the zeolite 13X.
  • the regeneration of the adsorbent may be performed by heating GN 2 (gas nitrogen) through a heater 127 provided in the adsorption tower 126 after the production process is completed to regenerate impurities adsorbed on the adsorbent. have.
  • GN 2 gas nitrogen
  • the temperature is lowered to approximately ⁇ 10 to ⁇ 20 ° C. with respect to the raw material Germain (Crude GeH 4 ) passing through the adsorption tower 126 to remove some or all of the impurities Ge 2 H 6 .
  • Ge 2 H 6 has a boiling point (boiling point) of approximately 31.5 ° C. at normal pressure, it is possible to condense and remove Ge 2 H 6 from the raw material Germain (Crude GeH 4 ).
  • Ge 2 H 6 condensed in the chiller 121 is discharged and removed through the discharge pipe (121a) provided in the lower portion.
  • the raw material germain (Crude GeH 4 ) generated in the reactor 116 needs to be driven to the refining unit 120. This may obtain a driving force through the compressor 122 and the distillation column 128. That is, the reactor 116 through the driving force obtained by the pressurization through the compressor 122 directly connected to the reactor 116 and the temperature difference generated while cooling through the LN 2 (liquid nitrogen) in the distillation column 128.
  • the raw material germain (Crude GeH 4 ) generated in the) is transferred to the purification unit 120.
  • the raw material Germain (Crude GeH 4 ) is pressurized to a pressure of approximately 2 ⁇ 5 barg through the compressor 122, the pressurized raw material Germain (Crude GeH 4 ) is the water-cooled heat exchanger 125, the adsorption tower 126 And, it passes through the chiller 121 is to be transferred to the distillation column (128).
  • the distillation column 128 in Figure 1 and as also described with reference to 2 LN 2 (liquid nitrogen) to the drive force and the compressor according to the temperature difference with the cooling of the LN 2 (liquid nitrogen), since the cooling is conducted using the
  • the raw material jemain (Crude GeH 4 ) is transferred using a driving force due to the pressure through the 122.
  • the feed method of Crude GeH 4 is about -80 by introducing LN 2 (liquid nitrogen) into the distillation column 128 before synthesizing the H 2 SO 4 aqueous solution and the first aqueous solution in the reactor 116.
  • LN 2 liquid nitrogen
  • the first aqueous solution is added to the reactor 116 to initiate a reaction.
  • the reaction is started, the synthesis gas of crude GeH 4 is generated in the reactor 116, and the synthesis gas of crude GeH 4 is a pressure of about 0 to 0.3 barg slightly higher than normal pressure. .
  • the compressor 122 the pressurized to the syngas said material Germain (Crude GeH4) at a pressure of approximately 2 ⁇ 5 barg and the pressure of the synthesis gas in the compressor 122 is the raw material Germain (Crude GeH 4) It is controlled to maintain a constant pressure by repeating the operation and stopping to maintain the pressure.
  • FIG. 4 is a detailed block diagram of FIG. 1 showing a Jermaine production apparatus according to a third exemplary embodiment of the present invention.
  • the Jermaine production apparatus 300 includes a synthesis unit 110 and a purification unit 120.
  • the storage and charging unit 130 may be further provided.
  • the synthesis unit 110 and the storage and charging unit 130 is the same as described with reference to FIGS. 1 and 2.
  • the purification unit 120 may include a gas compressor 122, a first chiller 1 124, an adsorption tower 126, a second chiller 2 121, and a distillation column 128. Equipped.
  • the gas compressor 122, the first chiller 124, the adsorption tower 126, and the second chiller 121 perform a first purification step of performing purification in a room temperature state or similar to the room temperature.
  • the first purification unit for, the distillation column 128 constitutes a second purification unit for the second purification step to perform the purification in a low temperature state.
  • the configuration or operation of the second purification unit is the same as described with reference to FIGS. 1 and 2.
  • the purification unit 120 is purified when the raw material Germain (Crude GeH 4 ) generated in the synthesis unit 110 is transferred.
  • the purification method completely removes H 2 O and CO 2 through purification in the gas compressor 122, the first chiller 124, the adsorption tower 126, and the second chiller 121. And remove some or all of Ge 2 H 6 .
  • the compressor 122 pressurizes the raw material Germain (Crude GeH 4 ) generated in the reactor 116 to a pressure of about 2 to 5 barg (gauge pressure) and transfers the same to the first chiller 124.
  • the first chiller 124 serves to lower the temperature of the raw material Germain (Crude GeH 4 ) pressurized through the compressor 122.
  • the raw material Germain (Crude GeH 4 ) contains impurities such as H 2 O and Ge 2 H 6 .
  • H 2 O is also removed through the adsorption tower 126, which will be described later, but can be removed in the form of condensate by lowering the temperature in the previous step.
  • Ge 2 H 6 is also condensed and removed.
  • the raw material Germain (Crude GeH 4 ) in the form of gas compressed through the compressor 122 is present in the form of H 2 O vaporized, that is, water vapor, but can be removed in the form of condensate because it is partially condensed when the temperature is lowered. . Therefore, in the chiller 124, the temperature is lowered to about 5 to 10 ° C. to condense and remove H 2 O as an impurity.
  • Ge 2 H 6 has a boiling point (break point) of about 31.5 ° C. at normal pressure, when the temperature is lowered to about 5 to 10 ° C. in the chiller 124, Ge 2 H 6 is condensed and exists in a liquid state.
  • Some H 2 O and Ge 2 H 6 condensed in the first chiller 124 are discharged and removed through the discharge pipe 124a provided at the lower portion.
  • the adsorption tower 126 removes residual H 2 O and CO 2 from the raw material Germain (Crude GeH 4 ) from which some H 2 O and Ge 2 H 6 have been removed through the chiller 124.
  • H 2 O and CO 2 may be solidified at around 0 ° C. and ⁇ 56 ° C., respectively. Therefore, H 2 O and CO 2 must be completely removed from the adsorption tower 126 at room temperature before low temperature.
  • the adsorption tower 126 is filled with a zeolite 4A (MS 4A) in the lower portion of the adsorption. Therefore, the residual H 2 O and CO 2 are removed through the zeolite 4A (MS 4A).
  • MS 4A zeolite 4A
  • the adsorption tower 126 may be required to further remove Ge 2 H 6 in addition to the remaining H 2 O and CO 2 from the raw material Germain (Crude GeH 4 ).
  • the adsorption tower 126 may have a structure in which a zeolite 4A (MS 4A) is filled with an adsorbent at a lower portion thereof, and a zeolite 13X (MS 13X) is filled with an adsorbent at an upper portion thereof.
  • the zeolite 4A (MS 4A) and the zeolite 13X (MS 13X) will remove H 2 O, CO 2 and some Ge 2 H 6 .
  • H 2 O and CO 2 may be removed through the zeolite 4A
  • some Ge 2 H 6 included in the raw material Germain may be removed through the zeolite 13X.
  • the regeneration of the adsorbent may be performed by heating GN 2 (gas nitrogen) through a heater 127 provided in the adsorption tower 126 after the production process is completed to regenerate impurities adsorbed on the adsorbent. have.
  • GN 2 gas nitrogen
  • the second chiller 121 removes some or all of the impurities Ge 2 H 6 by lowering the temperature of the raw material Germain (Crude GeH 4 ) passing through the adsorption tower 126 to approximately -10 ⁇ -20 °C. .
  • Ge 2 H 6 has a boiling point (boiling point) of approximately 31.5 ° C. at normal pressure, it is possible to condense and remove Ge 2 H 6 from the raw material Germain (Crude GeH 4 ).
  • Ge 2 H 6 condensed in the second chiller 121 is discharged and removed through the discharge pipe (121a) provided in the lower portion.
  • the raw material germain (Crude GeH 4 ) generated in the reactor 116 needs to be driven to the refining unit 120. This may obtain a driving force through the compressor 122 and the distillation column 128. That is, the reactor 116 through the driving force obtained by the pressurization through the compressor 122 directly connected to the reactor 116 and the temperature difference generated while cooling through the LN 2 (liquid nitrogen) in the distillation column 128.
  • the raw material germain (Crude GeH 4 ) generated in the) is transferred to the purification unit 120.
  • the raw material Germain (Crude GeH 4 ) is pressurized to a pressure of approximately 2 ⁇ 5 barg through the compressor 122, the pressurized raw material Germain (Crude GeH 4 ) is the first chiller 124, the adsorption tower 126 And the second chiller 121 are transferred to the distillation column 128.
  • the distillation column 128 in Figure 1 and as also described with reference to 2 LN 2 (liquid nitrogen) to the drive force and the compressor according to the temperature difference with the cooling of the LN 2 (liquid nitrogen), since the cooling is conducted using the
  • the raw material jemain (Crude GeH 4 ) is transferred using a driving force due to the pressure through the 122.
  • the feed method of Crude GeH 4 is about -80 by introducing LN 2 (liquid nitrogen) into the distillation column 128 before synthesizing the H 2 SO 4 aqueous solution and the first aqueous solution in the reactor 116.
  • LN 2 liquid nitrogen
  • the first aqueous solution is added to the reactor 116 to initiate a reaction.
  • the reaction is started, the synthesis gas of crude GeH 4 is generated in the reactor 116, and the synthesis gas of crude GeH 4 is a pressure of about 0 to 0.3 barg slightly higher than normal pressure. .
  • the compressor 122 the pressurized to the syngas said material Germain (Crude GeH4) at a pressure of approximately 2 ⁇ 5 barg and the pressure of the synthesis gas in the compressor 122 is the raw material Germain (Crude GeH 4) It is controlled to maintain a constant pressure by repeating the operation and stopping to maintain the pressure.
  • the high purity germane (GeH 4 ) produced through this process has a recovery of more than about 70-80% with a purity of about 99.999% (5N) or more.

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  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Of Gases By Adsorption (AREA)

Abstract

La présente invention porte sur un procédé et sur un dispositif qui permettent d'obtenir du germane de pureté élevée. Le procédé d'obtention de germane (GeH4) selon la présente invention comporte les étapes suivantes : la synthèse, afin de générer une première solution aqueuse par dissolution séquentielle de KOH, de NaBH4 et de GeO2 à l'état solide dans de l'eau distillée et de générer du GeH4 brut, à l'état gazeux, dopé par des impuretés, par réaction et introduction séquentielles d'une quantité prédéfinie de la première solution aqueuse dans un réacteur alors qu'une solution aqueuse de H2SO4 est introduite dans le réacteur; un premier raffinage afin d'éliminer des impuretés contenant une partie de l'H2O et du Ge2H6 condensés par refroidissement du GeH4 brut à une température prédéfinie et d'éliminer des impuretés contenant l'H2O et le CO2 résiduels à l'aide d'un adsorbant; un second raffinage, afin de générer du GeH4 dont les impuretés sont éliminées par élimination d'H2, qui est une impureté, du GeH4 brut après le premier raffinage à l'aide d'un processus de distillation fondé sur une différence de points d'ébullition. La présente invention présente l'avantage de pouvoir obtenir du GeH4 de pureté élevée et d'avoir un taux de récupération élevé.
PCT/KR2013/009464 2013-01-14 2013-10-23 Procédé et dispositif d'obtention de germane de pureté élevée Ceased WO2014109463A1 (fr)

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CN110548364A (zh) * 2019-10-17 2019-12-10 清远先导材料有限公司 一种回收分子筛吸附的特种气体的方法和装置
US10777331B2 (en) 2016-11-11 2020-09-15 Curium Us Llc Processes for generating germanium-68 with reduced volatiles
CN113135953A (zh) * 2021-05-06 2021-07-20 广东先导微电子科技有限公司 一种二甲基锗烷的制备方法及装置
CN114524413A (zh) * 2022-03-02 2022-05-24 沧州华宇特种气体科技有限公司 一种制备锗烷的系统及其制备方法
CN114538499A (zh) * 2022-03-02 2022-05-27 沧州华宇特种气体科技有限公司 一种制备单锗烷的系统及其制备方法

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CN113181752B (zh) * 2021-03-26 2021-12-07 博纯材料股份有限公司 一种锗烷收集纯化设备及方法
KR102538855B1 (ko) * 2021-05-21 2023-06-02 주식회사 솔 머티리얼즈 저메인 제조 장치 및 저메인 제조 방법
KR102803318B1 (ko) * 2022-08-01 2025-05-07 주식회사 솔 머티리얼즈 저메인 가스 제조 방법
KR102748595B1 (ko) * 2024-03-11 2025-01-06 (주)에이치케이머티리얼즈 고순도 사수소화게르마늄의 제조방법
KR102748076B1 (ko) 2024-04-18 2024-12-31 이경석 고순도 저메인 생성방법 및 생성장치

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US10777331B2 (en) 2016-11-11 2020-09-15 Curium Us Llc Processes for generating germanium-68 with reduced volatiles
CN110548364A (zh) * 2019-10-17 2019-12-10 清远先导材料有限公司 一种回收分子筛吸附的特种气体的方法和装置
CN113135953A (zh) * 2021-05-06 2021-07-20 广东先导微电子科技有限公司 一种二甲基锗烷的制备方法及装置
CN114524413A (zh) * 2022-03-02 2022-05-24 沧州华宇特种气体科技有限公司 一种制备锗烷的系统及其制备方法
CN114538499A (zh) * 2022-03-02 2022-05-27 沧州华宇特种气体科技有限公司 一种制备单锗烷的系统及其制备方法
CN114538499B (zh) * 2022-03-02 2023-07-11 沧州华宇特种气体科技有限公司 一种制备单锗烷的系统及其制备方法

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