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WO2001025679A1 - Procede et dispositif de recueil et de recuperation de gaz - Google Patents

Procede et dispositif de recueil et de recuperation de gaz Download PDF

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Publication number
WO2001025679A1
WO2001025679A1 PCT/JP2000/006738 JP0006738W WO0125679A1 WO 2001025679 A1 WO2001025679 A1 WO 2001025679A1 JP 0006738 W JP0006738 W JP 0006738W WO 0125679 A1 WO0125679 A1 WO 0125679A1
Authority
WO
WIPO (PCT)
Prior art keywords
gas
exhaust
holders
holder
collecting
Prior art date
Application number
PCT/JP2000/006738
Other languages
English (en)
Japanese (ja)
Inventor
Muneyuki Fukuoka
Yoshihiro Ibaraki
Takako Kimura
Original Assignee
L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude filed Critical L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude
Priority to AU74485/00A priority Critical patent/AU7448500A/en
Publication of WO2001025679A1 publication Critical patent/WO2001025679A1/fr

Links

Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17D—PIPE-LINE SYSTEMS; PIPE-LINES
    • F17D1/00—Pipe-line systems
    • F17D1/02—Pipe-line systems for gases or vapours
    • F17D1/04—Pipe-line systems for gases or vapours for distribution of gas

Definitions

  • the present invention relates to a gas collecting and collecting apparatus and a gas collecting method for collecting and collecting gas from a plurality of gas collecting paths.
  • the present invention is particularly useful for collecting and recovering exhaust gas from industrial equipment such as semiconductor manufacturing equipment, for post-processing, concentration and reuse.
  • Japanese Patent Application Laid-Open No. 10-1965632 discloses that a gas exhausted from a process chamber of a semiconductor manufacturing apparatus such as an etching apparatus or a chemical vapor deposition (CVD) apparatus is used as a gas.
  • a technique for separating and recovering each component from exhaust gas by heating, vaporizing, and sequentially discharging after hot trapping is disclosed.
  • Japanese Patent Application Laid-Open No. Hei 9-1103363 discloses a technique for concentrating and recovering perfluoro compounds from exhaust gas from various etching apparatuses in a semiconductor manufacturing apparatus by using a gas separation membrane. You. This technology employs a method in which exhaust gases from multiple process chambers are combined and collected, and then concentrated and recovered as a whole.
  • the flow rate and component composition of exhaust gas from individual process chambers fluctuate with time, and the flow rate and component composition of exhaust gas also differ between process chambers.
  • the manner of variation may differ between process chambers. For this reason, when performing post-processing collectively, it is extremely difficult to stably perform the processing under favorable conditions, and even if the processing can be performed, the efficiency is very low.
  • the decomposition and detoxification devices used when decomposing or detoxifying exhaust gas, the decomposition and detoxification devices used often have upper limits on the flow rate and component concentration of operable supply gas, so the decomposition efficiency and detoxification There was a problem that efficiency was easily reduced. Also, when performing concentration using a gas separation membrane or the like, stable operation and setting of conditions became difficult, and the recovery rate and purity were easily reduced.
  • an object of the present invention is to recover gas from a plurality of gas sources at a substantially uniform flow rate, thereby facilitating post-processing of the gas. It is an object of the present invention to provide a collective collection device and a collective collection method.
  • the above-mentioned object is to provide a plurality of variable-volume gas holders for storing gas at a substantially constant pressure due to a change in volume, and to be in fluid communication with each of the gas holders, and to supply gas from the gas source power to each gas holder.
  • the gas recovery path refers to a path connecting a gas source such as an exhaust gas source (for example, a process chamber in a semiconductor manufacturing facility) and a gas holder, and an enrichment device or abatement between the two.
  • Equipment can be provided.
  • the apparatus of the present invention can be provided with a concentrating device that is heated upstream of the gas holder after the target gas component is cold-trapped and then vaporized.
  • the device of the present invention includes a detection unit for detecting a volume of gas stored in the gas holder, and a control device for controlling an exhaust operation of the exhaust device based on a signal from the detection unit. be able to.
  • the present invention also provides a plurality of variable-volume gas holders that store at least a portion of each gas from a plurality of gas recovery paths at a substantially constant pressure due to a change in volume.
  • a method of collecting and collecting gas by collecting and collecting gas by combining and exhausting gas from a plurality of gas holders into a collecting path while temporarily storing the gas.
  • the exhaust is started after storing a predetermined amount or more of gas in the gas holder in advance.
  • the method for collecting and collecting gas of the present invention is particularly suitable for semiconductor manufacturing equipment. It is useful for recovering perfluoro compounds from exhaust gas from multiple chambers.
  • the exhaust gas from the exhaust gas source is temporarily stored in a variable volume gas holder that stores gas at a substantially constant pressure by a volume change via a gas recovery path. Is stored temporarily. Therefore, the concentration of the exhaust gas in the gas holder can be made uniform.
  • the gas holder can discharge gas at a substantially constant flow rate while changing the volume in response to the flow rate fluctuation. Therefore, the fluctuation of the flow rate of the gas from one gas source is absorbed by the gas holder, and the flow rate can be made uniform.
  • the gas holders are connected to the respective gas recovery paths, and the gas recovery paths merge into one collective path, and the gas in the gas holder is discharged through the collective path by the exhaust device. And collected.
  • exhaust gas from a plurality of gas sources can be recovered at a uniform flow rate z concentration, and post-treatment can be performed appropriately.
  • the equipment is equipped with a condensing device that cools and vaporizes the target gas component upstream of the gas holder and then evaporates it by heating, multiple trap parts are provided and switching operation is performed sequentially. Even then, the concentration of the concentrated gas discharged from the concentrator tends to change with time, and the flow rate may fluctuate during switching. In such a case, the above-described gas flow / concentration uniformizing operation of the collecting and collecting apparatus of the present invention is performed. Is particularly effective.
  • the device of the present invention includes: a detection unit that detects a volume of gas stored in the gas holder; and a control device that controls an exhaust operation of the exhaust device based on a signal from the detection unit. If equipped, the detection unit detects the volume of gas in the gas holder, and depending on whether or not the gas volume is appropriate, the control device can start and stop the exhaust device, etc. . As a result, it is possible to suitably prevent a change in the flow rate and concentration of the collected gas that occurs when the gas volume in the gas holder is extremely large or small. On the other hand, since it is possible to start evacuation after storing a predetermined amount or more of gas in the gas holder in advance, it is possible to stably exhaust (collect) gas with a uniform flow rate and concentration for a long time. it can.
  • each gas of a plurality of gas recovery paths is temporarily stored in a plurality of gas holders as described above while communicating with the plurality of recovery paths. Merge and exhaust in one collective path. Therefore, by the same operation as described above, the flow rate and the concentration of the recovered gas can be made uniform, and post-processing can be suitably performed.
  • the concentration of the exhaust gas can be made uniform in each gas holder in advance. Since the gas can be exhausted from a state in which the gas is stored in more gas holders, the concentration of the gas can be uniformed more reliably by mixing the gas.
  • the present invention is based on a plurality of chambers in a semiconductor manufacturing facility. It is particularly useful when recovering perfluorinated compounds from flue gas.
  • the flow rate and the component composition of the exhaust gas fluctuate greatly with time, and the flow rate and the component composition differ between the chambers.
  • the flow rate and concentration of the concentrated gas can be made uniform.
  • the post-treatment includes processes such as concentration, detoxification, and powder removal of the collected gas.
  • FIG. 1 is a schematic configuration diagram showing a gas collecting and collecting apparatus according to one embodiment of the present invention
  • FIG. 2 is a schematic configuration diagram illustrating an example of a collecting and collecting apparatus according to another embodiment
  • FIG. 3 is a schematic configuration diagram illustrating an example of a collecting and collecting apparatus according to another embodiment
  • Fig. 5 is a schematic configuration diagram showing the detection unit that detects the gas volume in the gas holder.
  • a perfluoro compound (hereinafter, referred to as PFC) is cold-trapped from exhaust gas from various etching equipment in a semiconductor manufacturing facility, concentrated, collected, collected, and collected. This is an example of filling in.
  • the gas collecting and collecting apparatus of the present invention shown in FIG. 1 has a plurality of (three in the example shown in FIG. 1) variable-volume gas holders 2a to 2 that store gas at a substantially constant pressure due to volume change. 2 c.
  • Gas recovery paths L1a to L1c are connected to each gas holder, respectively.
  • the upstream ends of the gas recovery paths 13 to 1 (; are connected to the etching chambers A to C, respectively. It is connected.
  • the gas holders 2a to 2c are formed in a cylindrical shape using a sheet of base material such as nylon or polyester coated with rubber that is impervious to gas such as It is a variable volume container formed in a spherical or box shape, etc., and various types are commercially available. Above all, those having a bellows shape and thus changing the volume due to expansion and contraction in one direction are preferable because the change in volume is easily detected.
  • the target gas component (PFC) contained in the exhaust gas from each of the chambers A to C is called to the gas recovery path L1a to L1c on the upstream side of the gas holders 2a to 2c.
  • a concentrating device 3a to 3c for heating and vaporizing after dropping, and a removing device 4a to 4c for removing harmful components and the like are provided.
  • Each of the concentrators 3a to 3c includes a pair of trap units T having a cooling function, and each trap unit T reciprocates alternately between an exhaust path and a regeneration path, so that a PFC is provided.
  • the cold trap and caro heat vaporization are alternately performed.
  • Such a concentrating device (trap device) is itself known in the art, and is described in, for example, Japanese Patent Application Laid-Open No. H10-1965332. That is, each of the concentrators 3 a to 3 c has a trap chamber 3 al to 3 cl and a c trap chamber 3 al to 3 cl having a regeneration chamber 3 a2 to 3 c2 below the trap chamber.
  • Each trap portion T can include a plurality of baffle plates that are cooled by a refrigerant such as, for example, liquid nitrogen or cooling air.
  • Each trap portion T is vertically reciprocated between the trap chamber and the regeneration chamber by, for example, an air cylinder (not shown). Trap T Force When placed in the exhaust path in the S trap chamber, the PFC force in the exhaust gas from chambers A to C, etc. It is trapped, and the remainder is discharged out of the system via line Lex.
  • the trap section T is moved to the regeneration chamber 3a2 to 3c2 (regeneration path), and the trap section T is introduced through the line Lin.
  • the PFC is heated and vaporized by a carrier gas (regenerated gas) of extremely high temperature, and sent to the downstream abatement units 4a to 4c in a concentrated state.
  • the abatement devices 4 a to 4 c remove harmful components such as HF, SiF 4 , F 2 , COF 2 and the like, which are vaporized together with the trap T-palla PFC by heating.
  • a dry packed tower filled with an adsorbent such as activated carbon or a metal oxide catalyst, or a wet packed tower such as a scrubber can be used. It is possible.
  • Such an abatement device may be provided also in the exhaust path of the concentrators 3a to 3c.
  • the gas passages L2a to L2 communicate with the gas holders 2a to 2c, respectively, and the gas passages L2a to L2c merge into one collective path Lcon. Downstream from the confluence of the confluence path L con, there is a A fineta is provided.
  • two filters (6a and 6b) are provided, and these two filters 6a and 6b are operated alternately. Can be done.
  • An exhaust device 5 is provided downstream of the filters 6a and 6b.
  • a compressor for performing gas filling can be used as the exhaust device 5, for example.
  • the compressor 5 has pistons 5 p i and 5 p 2.
  • Each of the gas holders 2a to 2c is provided with a detection unit for detecting whether or not the volume of the stored gas is within a certain range.
  • This detection unit can be composed of, for example, a pair of limit switches each including a lever.
  • the gas holder (in FIG. 5, the gas holders 2a to 2c are collectively indicated by reference numeral 2) is mounted on the mounting table 51, and It is surrounded by frame 52.
  • the frame 52 is provided with a pair of limit switches 53a and 53b.
  • a weight 55 is placed on the gas holder 2 via a plate member 54.
  • the plate member 54 is displaced (moves up and down) together with a displacement surface (upper surface of the gas holder) that is displaced based on a change in the volume of the gas holder, and its end is a limit switch 6a or 6b.
  • the volume of the gas holder 2 corresponding to the position of the switch 6a or 6b is detected.
  • a pair of limit switches 6a and 6b output whether or not the volume of the gas stored in each gas holder 2 is equal to or less than an upper limit value or equal to or more than a lower limit value. Can be performed based on the signal. Then, the controller 55 controls the exhaust operation of the exhaust device 5. The exhaust operation starts, for example, when any one of the gas holders 2 a to 2 c exceeds the upper limit volume value, and all or any one of the gas holders 2 a to 2 c is smaller than the lower limit volume value. It is possible to control to stop the exhaust when it becomes exhausted.
  • each gas recovery route is 1 & to 1.
  • the total flow rate operating time flow rate
  • each gas recovery path L1a to L1c when the total flow rate (operating time flow rate) of each gas recovery path L1a to L1c is different, the flow rate of an orifice having a different diameter in each gas path L2a to L2c.
  • the adjusting device By providing the adjusting device, it is possible to prevent some of the gas holders 2a to 2c from being exhausted first. Even when the gas concentrations stored in the gas holders 2a to 2c are different, the gas is mixed and supplied to the optimum gas concentration when supplying gas to the recovery device using an orifice or the like. It is also possible to do.
  • the bypass path L3 of the compressor includes a corer 8a for removing the gas and a separator 7a. And are provided. Similarly, a core path 8b and a separator 7b are also provided in the downstream path L4 of the compressor 5. Downstream of the A buffer tank 9 is provided, and the recovered gas is charged into the cylinder 11 by the charging device 10 from the nozzle tank 9 via the path L5. You.
  • valve 12 If it is necessary to release the compressed gas when restarting the compressor after stopping the compressor after filling is completed, open the valve 12 and supply the compressed gas to the gas holder 2b via the path L6. Can be returned to
  • the gas collecting and collecting apparatus shown in FIG. 2 includes a plurality of gas holders similar to the gas holders described above, which are connected to the gas collecting paths L 1 d to L 1 e from the plurality of chambers D to E, respectively. 2 d to 2 e.
  • abatement devices 4 d to 4 e similar to the above-mentioned abatement devices are provided.
  • Gas passages L2d to L2e communicate with the gas honorers 2d to 2e, respectively, and the gas passages L2d to 2e merge into one collective route Leon.
  • the downstream side of the junction of the converging path L con is the same as the exhaust system described above.
  • a gas exhaust device 5a is provided to pressurize the gas to a pressure suitable for the membrane separation and concentration device 12.
  • the membrane separation / concentration apparatus 12 includes a membrane 12a having selectivity for a target gas.
  • a membrane 12a a polymer membrane known per se, for example, a polyimid membrane can be used.
  • the pressurized gas is supplied to the membrane separation / concentration device 12, and the PFC is concentrated by the polymer membrane 12a.
  • the concentrated gas (PFC rich gas) concentrated by the membrane separation / concentration device 12 is obtained, for example, as a non-permeate stream, compressed by the compressor 5b, and processed in the same manner as in the first embodiment described above.
  • the cylinder 11 is filled.
  • the permeate logistics is discharged out of the system via line LO.
  • the gas holder 2 d to 2 e When performing the same control as in the first embodiment, after storing a predetermined amount or more of gas in one of the gas holders 1 2 d to 2 e in advance, starting the exhaust, the gas holder 2 d to 2 e When any one of them becomes a certain amount or less, the evacuation is stopped. Since the flow rate and concentration of the raw material gas in 12 are uniform, stable operation and condition setting are easy, and the recovery rate and the concentration of recovered PFC can be maintained higher. You.
  • the PFC was concentrated and then charged and recovered in a cylinder, but as shown in FIG. 3, a membrane provided after the gas collection and recovery apparatus of the present invention was provided as shown in FIG.
  • the PFC enriched by the separation and concentration device may be recycled as it is to the semiconductor manufacturing facility.
  • a plurality of chambers FG A plurality of gas holders 2 f to 2 g are connected to the gas recovery paths L 1 f to L 1 g, respectively, and abatement devices 4 f to 4 g are installed downstream of the gas holders. If no gas is contained or if the gas holders 2f to 2g are made of a corrosion-resistant material, it is effective to arrange them in this order. Many of the abatement systems 4 f to 4 g have an upper limit of the supply gas amount (processing capacity), and the above arrangement can make the supply gas amount and supply pressure uniform. You can do it.
  • the gas holder 1, the gas recovery path Ll, and the gas passage L 2 (the gas recovery paths are collectively indicated by L 1, and the gas paths are collectively indicated by L 2)
  • the connection forms shown in FIG. 1 are used, the connection form shown in FIG. 4A or 4B may be used, for example.
  • connection configuration shown in Fig. 4A the introduction of gas from the gas recovery path L1 to the gas holder 12 and the gas discharge through the gas passage L2 are performed at the bottom of the gas holder 12 through one line 41. It is done. According to this configuration, the structure of the gas holder 2 itself is simplified.
  • both the gas recovery path L 1 and the gas passage L 2 are independently connected to the bottom of the gas holder 2. According to this configuration, the mixing action of the gas in the gas holder 2 is large, and the non-uniform stagnation of the gas is more unlikely to occur.
  • a pair of trap portions is provided, and each trap portion reciprocates alternately between the exhaust path and the regeneration path.
  • the above shows an example of installing a concentrator that alternates between cold trapping and heat vaporization.However, by switching the gas flow path for multiple traps, A concentrator that alternates between dropping and heating and vaporization may be used.
  • As a cooling method a method that can cool to a cold trap temperature according to the type of target gas is adopted, but for PFC, a helium refrigerator, Pulse refrigerator, liquid nitrogen cooling, etc. are adopted.
  • the present invention is also effective in recovering neon from exhaust gas of an excimer laser irradiation apparatus. is there.
  • the present invention is not limited to these, and is effective in collecting and collecting a plurality of types of exhaust gas from various types of industrial equipment, and performing post-processing and reuse.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Treating Waste Gases (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

Un dispositif de recueil et récupération de gaz, comprenant une pluralité de récipients à gaz volumétriquement variables conservant le gaz à pression sensiblement constante par une modification volumétrique, une pluralité de routes de récupération de gaz communiquant, via un fluide, avec chacun des récipients à gaz de façon à permettre au gaz provenant d'une source de gaz de s'écouler dans chacun des récipients à gaz, une pluralité de routes de sortie de gaz communiquant, via un fluide, avec chacun des récipients à gaz et fusionnant avec une route de recueil sur le côté avant des récipients à gaz, et des moyens d'évacuation des gaz livrant le gaz d'évacuation des récipients à gaz vers la route de recueil.
PCT/JP2000/006738 1999-10-01 2000-09-28 Procede et dispositif de recueil et de recuperation de gaz WO2001025679A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU74485/00A AU7448500A (en) 1999-10-01 2000-09-28 Device and method for collecting and recovering gas

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP28175599A JP2001104702A (ja) 1999-10-01 1999-10-01 ガスの集合回収装置および集合回収方法
JP11/281755 1999-10-01

Publications (1)

Publication Number Publication Date
WO2001025679A1 true WO2001025679A1 (fr) 2001-04-12

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PCT/JP2000/006738 WO2001025679A1 (fr) 1999-10-01 2000-09-28 Procede et dispositif de recueil et de recuperation de gaz

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JP (1) JP2001104702A (fr)
AU (1) AU7448500A (fr)
TW (1) TW436595B (fr)
WO (1) WO2001025679A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2248531A1 (fr) 2004-08-03 2010-11-10 Emisphere Technologies, Inc. Combinaison orale antidiabétique d'insuline-biguanide
WO2012119007A1 (fr) 2011-03-01 2012-09-07 N21 Acquisition Holding, Llc Compositions d'insuline et de chrome pour traitement et prévention du diabète, de l'hypoglycémie et de troubles associés
US9005637B2 (en) 2007-06-26 2015-04-14 Jds Therapeutics, Llc Multiple unit dosage form having a therapeutic agent in combination with a nutritional supplement
US9119835B2 (en) 2007-03-13 2015-09-01 JDS Therapeautics, LLC Methods and compositions for the sustained release of chromium
US11865121B2 (en) 2016-02-11 2024-01-09 Nutrition21, LLC Chromium containing compositions for improving health and fitness

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100449781B1 (ko) * 2001-03-21 2004-09-22 삼성전자주식회사 반도체 제조 공정에서 퍼플루오르계 화합물의 배출을감소시키기 위한 방법 및 장치
KR20230132267A (ko) * 2022-03-08 2023-09-15 크라이오에이치앤아이(주) 배기 가스 처리 장치

Citations (2)

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Publication number Priority date Publication date Assignee Title
JPH09103633A (ja) * 1995-07-17 1997-04-22 L'air Liquide パーフルオロ化合物ガスの分離および回収方法および装置
JPH11218318A (ja) * 1998-02-03 1999-08-10 Air Liquide Japan Ltd 排ガス処理設備

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH09103633A (ja) * 1995-07-17 1997-04-22 L'air Liquide パーフルオロ化合物ガスの分離および回収方法および装置
JPH11218318A (ja) * 1998-02-03 1999-08-10 Air Liquide Japan Ltd 排ガス処理設備

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2248531A1 (fr) 2004-08-03 2010-11-10 Emisphere Technologies, Inc. Combinaison orale antidiabétique d'insuline-biguanide
US10245325B2 (en) 2007-03-13 2019-04-02 Jds Therapeutics, Llc Methods and compositions for the sustained release of chromium
US9119835B2 (en) 2007-03-13 2015-09-01 JDS Therapeautics, LLC Methods and compositions for the sustained release of chromium
US9597404B2 (en) 2007-03-13 2017-03-21 Jds Therapeutics, Llc Methods and compositions for sustained release of chromium
US9675702B2 (en) 2007-03-13 2017-06-13 Jds Therapeutics, Llc Methods and compositions for the sustained release of chromium
US11801224B2 (en) 2007-06-26 2023-10-31 Jds Therapeutics, Llc Multiple unit dosage form having a therapeutic agent in combination with a nutritional supplement
US9005637B2 (en) 2007-06-26 2015-04-14 Jds Therapeutics, Llc Multiple unit dosage form having a therapeutic agent in combination with a nutritional supplement
US9421170B2 (en) 2007-06-26 2016-08-23 Jds Therapeutics, Llc Multiple unit dosage form having a therapeutic agent in combination with a nutritional supplement
US12274791B2 (en) 2007-06-26 2025-04-15 Bonafide Health, Llc Multiple unit dosage form having a therapeutic agent in combination with a nutritional supplement
US10363222B2 (en) 2007-06-26 2019-07-30 Jds Therapeutics, Llc Multiple unit dosage form having a therapeutic agent in combination with a nutritional supplement
US11241388B2 (en) 2007-06-26 2022-02-08 Jds Therapeutics, Llc Multiple unit dosage form having a therapeutic agent in combination with a nutritional supplement
US11850308B2 (en) 2007-06-26 2023-12-26 Bonafide Health, Llc Multiple unit dosage form having a therapeutic agent in combination with a nutritional supplement
EP4070801A1 (fr) 2011-03-01 2022-10-12 Nutrition 21, LLC Compositions d'insuline et de chrome pour le traitement et la prévention du diabète, de l'hypoglycémie et de troubles apparentés
WO2012119007A1 (fr) 2011-03-01 2012-09-07 N21 Acquisition Holding, Llc Compositions d'insuline et de chrome pour traitement et prévention du diabète, de l'hypoglycémie et de troubles associés
US8933022B2 (en) 2011-03-01 2015-01-13 Jds Therapeutics, Llc Methods and compositions for the treatment and prevention Hypoglycemia and related disorders
US11865121B2 (en) 2016-02-11 2024-01-09 Nutrition21, LLC Chromium containing compositions for improving health and fitness

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JP2001104702A (ja) 2001-04-17
TW436595B (en) 2001-05-28

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