EP2351811B1 - Coke dry type extinguishing facility, and coke dry type extinguishing method - Google Patents

Coke dry type extinguishing facility, and coke dry type extinguishing method Download PDF

Info

Publication number: EP2351811B1
Authority: EP; European Patent Office
Prior art keywords: coke; head; chamber; main head; dry quenching
Prior art date: 2008-10-14
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.): Not-in-force

Application number

EP08877397.3A

Other languages

German (de)

English (en)

French (fr)

Other versions

EP2351811A4 (en

EP2351811A1 (en

Inventor

Takashi Fukuoka

Atsushi Fujikawa

Hiroshi Otani

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Nippon Steel Engineering Co Ltd

Nippon Steel Plant Designing Corp

Original Assignee

NS Plant Designing Corp

Nippon Steel and Sumikin Engineering Co Ltd

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.)

2008-10-14

Filing date

2008-10-14

Publication date

2017-04-05

2008-10-14 Application filed by NS Plant Designing Corp, Nippon Steel and Sumikin Engineering Co Ltd filed Critical NS Plant Designing Corp

2011-08-03 Publication of EP2351811A1 publication Critical patent/EP2351811A1/en

2014-05-21 Publication of EP2351811A4 publication Critical patent/EP2351811A4/en

2017-04-05 Application granted granted Critical

2017-04-05 Publication of EP2351811B1 publication Critical patent/EP2351811B1/en

Status Not-in-force legal-status Critical Current

2028-10-14 Anticipated expiration legal-status Critical

Images

Classifications

- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B39/00—Cooling or quenching coke
- C10B39/02—Dry cooling outside the oven
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D31/00—Other cooling or freezing apparatus

Definitions

the present invention relates to coke dry quenching equipment for cooling red-hot coke and to a coke dry quenching method.
Coke dry quenching (CDQ) equipment installed in ironworks and the like is equipment for quenching red-hot coke dry-distilled in a coke oven using a cooling gas such as an inert gas.
the high temperature coke is gradually cooled to improve its quality, so that the operation of an ironmaking blast furnace is stabilized.
Coke dry quenching equipment is characterized in that the cooling gas is circulated in the system to allow coke dust to be prevented from flying out and that the sensible heat of the coke is recovered by a heat recovery apparatus such as a waste heat boiler to save energy.
conventional coke dry quenching equipment 1 has a chamber in which a pre-chamber 2 having a coke charging port 10 formed at its upper portion is vertically connected to a cooling chamber 3 including a coke discharge unit 11 disposed at its lower portion.
the cooling chamber 3 is formed to have a conical lower part (for example, an inverted conical or inverted truncated conical lower part).
a blast head 4 serving as a cooling gas supplying unit for injecting a cooling gas such as an inert gas to make the descending flow of coke uniform is disposed at the center of the conical part.
the blast head 4 includes a substantially conical cap member 41 and is configured such that the cooling gas is circumferentially injected from an injection port (not shown) formed in the cap member 41.
the blast head 4 is supported by a supporting member 42 having a gas flow passage formed thereinside, and the gas flow passage inside the supporting member 42 is in communication with a gas supply chamber 43.
a part of the cooling gas supplied to the gas supply chamber 43 is configured to be supplied to the cooling chamber 3 also from cooling gas supplying units (for example, supply ports 44) disposed circumferentially in an inclined portion of the cooling chamber 3 that is located in the lower part thereof.
a plurality of divided small flues 5 for discharging the cooling gas injected into the cooling chamber 3 are formed so as to circumferentially surround the barrel portion of the pre-chamber 2.
high temperature red-hot coke 6 is charged into the chamber through the coke charging port 10 and continuously discharged from the bottom of the chamber through the coke discharge unit 11.
the coke 6 descending inside the chamber is cooled by heat exchange with the cooling gas from the lower portion of the chamber that includes the blast head 4.
the cooling gas increased in temperature by heat exchange is discharged from the chamber through the small flues 5.
the discharged gas passes through a dust removing unit is then supplied to a heat recovery apparatus such as a waste gas boiler to recover the heat, and is again supplied as the cooling gas to the chamber.
Patent Document 1 describes a method in which the skirt portion at the end of the blast head is driven to extend and contract, so that the width of the passage of coke is changed to control variation in heat exchange.
Patent Document 2 describes a method in which the entire head portion of the blast head is vertically raised and lowered.
the blast head 4 disposed in the lower part of the chamber receives a high pressure from the charged coke 6 (such as the pressure caused by the mass of the coke and the descent thereof). Therefore, to raise and lower the blast head or to extend and contract the end of the blast head as described in Patent Documents 1 and 2, an expensive high-power driving unit is required. In addition, the temperature inside the chamber environment is high, and the chamber contains a large amount of dust. Therefore, the use of a movable blast head as in Patent Documents 1 and 2 can cause troubles in the equipment.
An object of the present invention is to provide coke dry quenching equipment including a blast head that can make the descent of coke uniform in a chamber to contribute to the improvement of the efficiency of cooling the coke and to provide a coke dry quenching method.
Another object of the present invention is to provide coke dry quenching equipment including a blast head that can improve the efficiency of cooling coke to reduce the size of the chamber and to provide a coke dry quenching method.
red-hot coke is charged from an upper portion of a chamber formed to have a lower conical portion, descends inside the chamber while being cooled by a cooling gas injected from a cooling gas supply unit disposed in the lower portion of the chamber, and is then discharged from a coke discharge port disposed in the lower portion of the chamber.
the coke dry quenching equipment is characterized by disposing at least one cap-shaped small head below a cap-shaped main head and having a diameter d smaller than a diameter D of the main head, wherein a blast head is disposed in the lower portion of the chamber and the diameter D of the main head is the diameter of the blast head.
the cap-shaped main head is placed on a supporting member disposed so as to penetrate a side wall of the conical portion in the lower portion of the chamber, a direction of a flow of the coke descending in a central portion of the chamber in the conical portion is changed to a circumferentially outward direction by the main head.
the small head is disposed such that an angle ( ⁇ 1) between a horizontal axis line passing through the lower end plane of the conical portion and a line (T1) connecting an outer peripheral edge of the small head to the center of the coke discharge port is in the range of 60° to 80°.
the small head and the main head are disposed such that angles ( ⁇ 1, ⁇ 2) between a horizontal axis line and lines (T1, T2) connecting the outer peripheral edges of the small head and the main head to the center of the coke discharge port are in the range of 60° degrees to 80°.
the angles ⁇ 1 and ⁇ 2 may be the same or different.
an inclination angle ⁇ 3 of the conical portion is in the range of ⁇ 4 to ⁇ 4. - 25°, where ⁇ 4 is a smaller one of the angles ( ⁇ 1, ⁇ 2) between a horizontal axis line and lines (T1, T2) connecting outer peripheral edges of the small head and the main head to the center of the coke discharge port.
a bore Dh of the coke discharge port is one-half or more of the diameter d of the small head (Dh ⁇ 0.5d).
the small head is disposed at a position at which H is 1 to 5 times the bore Dh of the coke discharge port, where H is a distance from a repose angle lower plane of the coke that is formed below the small head to the coke discharge port.
a gas flow passage for the cooling gas is provided in the main head or in each of the main head and the small head to constitute a cooling gas supply unit for injecting the cooling gas into the chamber.
a coke dry quenching method of the present invention includes charging red-hot coke from an upper portion of a chamber formed to have a lower conical portion, allowing the red-hot coke to descend inside the chamber and cooling the coke by a cooling gas injected from a cooling gas supply unit disposed in a lower portion of the chamber, and discharging the coke from a coke discharge port disposed in the lower portion of the chamber.
the method is characterized by disposing at least one cap-shaped small head below a cap-shaped main head and having a diameter d smaller than a diameter D of the main head, wherein a blast head is disposed in the lower portion of the chamber and the diameter D of the main head is a diameter of the blast head.
the cap-shaped main head is placed on a supporting member disposed so as to penetrate a side wall of the conical portion in the lower portion of the chamber, a direction of a flow of the coke descending in a central portion of the chamber in the conical portion is changed to a circumferentially outward direction by the main head.
the small head is disposed such that an angle ( ⁇ 1) between a horizontal axis line passing through the lower end plane of the conical portion and a line (T1) connecting an outer peripheral edge of the small head to the center of the coke discharge port is in a range of 60° to 80°.
the cooling gas is injected from the main head or from the main head and the small head to cool the red-hot coke.
a small head is disposed below a main head and has a diameter d smaller than a diameter D of the main head, the blast head being disposed in the lower portion of the chamber and the diameter D of the main head is the diameter of the blast head. Therefore, the variation of the coke that descends inside the chamber is improved, and uniform descent of the coke is thereby achieved. This allows uniform heat exchange between the coke and the cooling gas in the chamber, and the efficiency of cooling the coke is thereby improved.
the efficiency of cooling the coke is improved. Therefore, the size of the chamber can be reduced.
the cooling gas is injected also from the small head, a region below the blast head (main head), which is not utilized as a cooling zone in the conventional structure, can be used as a cooling zone. The cooling efficiency can thereby be further improved, and the size of the chamber can be further reduced.
a chamber of coke dry quenching equipment 1 in the present embodiment is configured to include a pre-chamber 2 having a coke charging port 10 in its upper portion and a cooling chamber 3 having a coke discharge port 12 in its bottom portion, the pre-chamber 2 and the cooling chamber 3 being connected vertically.
These chambers can be formed of, for example, a refractory material such as steel or brick.
High temperature coke 6 generated in a coke oven is charged into the pre-chamber 2 from the coke charging port 10 using a coke transferring unit (not shown) such as a bucket.
the coke 6 charged into the pre-chamber 2 gradually descends and enters the cooling chamber 3.
the coke 6 that enters the cooling chamber 3 continues descending gradually, is cooled by a cooling gas 7, and continuously discharged through a coke discharge unit 11 disposed at the coke discharge port 12.
the coke 6 is continuously discharged through the coke discharge unit 11 and is replenished on a batch basis.
the present invention is not limited thereto.
the cooling chamber 3 is formed to have a cone-shaped (for example, inverted conical or inverted truncated conical) lower portion.
a blast head 4 that is used as a cooling gas supply unit for injecting a cooling gas such as an inert gas and to make the descending flow of the coke 6 uniform is disposed in the central portion of the conical portion (for example, on the center axis thereof). As shown in Fig. 2 , the blast head 4 is supported by a substantially cross-shaped supporting member 42 disposed so as to penetrate the side wall of the conical portion.
a gas supply chamber 43 is formed so as to surround the outer circumference of the conical portion, and the ends of the supporting member 42 that penetrate the side wall of the conical portion extend inside the gas supply chamber 43.
a gas flow passage (not shown) for the cooling gas is formed inside the supporting member 42.
the cooling gas supplied to the gas supply chamber 43 is introduced into the blast head 4 through the gas flow passage and then injected into the chamber through the blast head 4.
Part of the cooling gas supplied to the gas supply chamber 43 is supplied to the cooling chamber 3 also from cooling gas supply units (for example, supply ports 44) disposed circumferentially in an inclined portion of the cooling chamber 3 that is located in the lower part thereof.
the cooling gas may be supplied from any one of the blast head 4 and a supply port 44.
the substantially cross-shaped supporting member 42 shown in Fig. 2 is only an example.
the shape of the supporting member 42 is not limited to the cross shape, so long as the supporting member 42 can support the blast head 4.
the blast head 4 of the present embodiment has a two-stage head structure having a main head 41 disposed in an upper section and a small head 45 disposed in a lower section.
Each of the main head 41 and the small head 45 includes a substantially conical cap member and is configured such that the cooling gas is injected, for example, circumferentially from a gas injection port (not shown) formed in the cap member.
the diameter (bore) d of the small head 45 is smaller than the diameter (bore) D of the main head 41.
the shapes of the heads are not limited to the shapes shown in Fig. 1 , so long as they satisfy the above condition. Preferably, as shown in Fig.
the small head 45 and the main head 41 are disposed such that the angles ( ⁇ 1, ⁇ 2) between a horizontal axis line and lines (T1, T2) connecting the outer peripheral edges of the heads (in this example, the outer peripheral edges of the cap members) to the center of the coke discharge port 12 are in the range of 60° to 80° and particularly preferably 70° (condition (I)).
the coke discharge port" in the condition (I) is defined to mean the end of the inclined section of the conical portion (i.e. , the lower end plane of the conical portion), as exemplified in Fig. 3(a) .
both the angles ( ⁇ 1, ⁇ 2) are in the range of 60° to 80°.
Fig. 3(a) shows one exemplary arrangement in which the angles ⁇ 1 and ⁇ 2 are different. However, the heads may be arranged such that the angles ⁇ 1 and ⁇ 2 are the same.
the inclination angle ⁇ 3 of the conical portion is in the range of ⁇ 4 to ⁇ 4 - 25° (condition (II)), where ⁇ 4 is a smaller one of the angles ( ⁇ 1, ⁇ 2) between the horizontal axis line and the lines (T1, T2) connecting the outer peripheral edges of the small head 45 and the main head 41 to the center of the coke discharge port 12.
the bore Dh of the coke discharge port 12 shown in Fig. 3(a) is one-half or more of the diameter d of the small head 45 (Dh ⁇ 0.5d) (condition (III)).
the small head 45 is disposed at a position at which H is 1 to 5 times the bore Dh of the coke discharge port 12 and more preferably 1 to 3 times the bore Dh (condition (IV)), where H is the distance from the lower plane (h1) of a space formed below the small head 45 at the angle of repose of the coke 6 to the coke discharge port 12.
H is the distance from the lower plane (h1) of a space formed below the small head 45 at the angle of repose of the coke 6 to the coke discharge port 12.
the coke discharge port 12 in this condition is defined similarly to that in the condition (I) above.
the angle of repose of coke is 34° to 35°. Therefore, the height position of the lower plane (h1) can be computed or arithmetically calculated using this value.
the present invention is not limited thereto.
the angle of repose may be computed using any other known method. For example, the angle of repose is measured using a sample of coke.
condition (I) is combined with condition (II) and/or condition (III).
a plurality of divided small flues 5 for discharging the cooling gas are formed so as to circumferentially surround the straight tubular barrel portion of the pre-chamber 2.
a flue 51 is connected to the small flues 5.
the flue 51 is connected to a heat recovery apparatus 53 such as a waste heat boiler through a dust catcher 52 used as a first dust removing unit.
the gas cooled in the heat recovery apparatus 53 passes through a second dust removing unit 54, is sent to a preheater 56 by a blowing unit 55 such as a blower, and again supplied as the cooling gas to the cooling chamber 3.
a blowing unit 55 such as a blower
the coke 6 charged into the pre-chamber 2 from the coke charging port 10 gradually descends and enters the cooling chamber 3, while the coke 6 is continuously discharged from the bottom of the cooling chamber 3.
the coke 6 is then cooled in the cooling chamber 3 by heat exchange with the cooling gas 7 injected from the main head 41 and the small head 45 and the cooling gas 7 injected from the supply ports 44 and is discharged through the coke discharge unit 11.
the ratio of the volume of gas per unit time from the main head 41 to that from the small head 45 is, for example, 8:2.
the coke 6 descending inside the chamber generally tends to gradually descend along different paths in different directions due to the influence of the shape and wall surface of the chamber and differences in properties of the coke.
the present inventors have thought that this is the main cause of the variation of the descent and have conducted extensive studies.
the inventors have found that the addition of the small head 45 that is smaller than the main head 41 and is disposed below the main head 41 can significantly improve the nonuniformity of the descent.
the invention has been completed.
the main head 41 and the small head 45 satisfy the above relational condition (I) and/or condition (IV), the above effect is high. Tests were actually performed to confirm that the values in the conditions (I) and (IV) are tightly related to the properties of coke.
the reason that the variation of the descent can be improved is as follows.
the direction of the flow of the coke 6 descending in the central portion of the chamber is changed to a circumferentially outward direction by the main head 41, so that the slow descending flow of the coke near the furnace wall is facilitated.
a flowdirected to the center at the angle of repose is formed below the main head 41.
the direction of the flow is changed to the circumferentially outward direction by the small head 45, so that the flow of the coke near the furnace wall is further facilitated.
the circumferentially outward flows formed by the main head 41 and the small head 45 can more effectively act on regions in which the internal friction angle of the coke causes low fluidity, and the variation of the descent can thereby be improved in a more reliable manner. More specifically, the inventors have focused attention on that the internal friction angle of coke is about 75°, and the angles of the outer peripheral edges of the main head 41 and the small head 45 are set to 60° to 80°. This allows the circumferentially outward flows to more effectively act on the regions in which the internal friction angle of the coke causes low fluidity.
the operational effects of the condition (I) can be more effective when the condition (I) is combined with the condition (II) and/or the condition (III).
the condition (IV) described above allows the height position of the small head 45 to be more preferable. If the condition (IV) is satisfied, the variation of the descent can be improved in a more reliable manner. More specifically, as illustrated in Fig. 5 , when the condition Dh ⁇ distance H ⁇ 5Dh is satisfied, the nonuniformity of descent is smaller than that when the distance H is smaller than the bore Dh and that when the distance H is large than 5 times the bore Dh. This may be because, when the distance H is larger than 5 times the bore Dh ( Fig. 5(b) ), the distance from the small head 45 to the coke discharge port 12 is too long, so that the coke that passes over the small head 45 selectively descends through the central portion.
the small head 45 smaller than the main head 41 in size is added to provide a two-stage head structure in which the small head 45 is disposed below the main head 41.
the variation of the descent of the coke inside the conical portion of the chamber is thereby improved, whereby uniform descent of the coke is achieved over the entire chamber.
uniform descent of the coke is obtained inside the chamber, uniform heat exchange between the coke and the cooling gas is achieved in the chamber, and the efficiency of cooling the coke can thereby be improved.
the conditions (I) to (IV) are satisfied, such an effect can be enhanced.
the size of the chamber can be reduced.
the cooling gas may not be injected from the small head 45, and the cooling gas may be injected only from the main head 41.
the number of small heads 45 disposed below the main head 41 is not necessarily limited to one, and a multi-stage head structure having 3 or more stages may be used. In such a case, it is preferable to reduce the head bore (d) gradually for lower heads.

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Chemical & Material Sciences (AREA)
Engineering & Computer Science (AREA)
Materials Engineering (AREA)
Oil, Petroleum & Natural Gas (AREA)
Organic Chemistry (AREA)
Combustion & Propulsion (AREA)
Physics & Mathematics (AREA)
Mechanical Engineering (AREA)
Thermal Sciences (AREA)
General Engineering & Computer Science (AREA)
Coke Industry (AREA)

EP08877397.3A 2008-10-14 2008-10-14 Coke dry type extinguishing facility, and coke dry type extinguishing method Not-in-force EP2351811B1 (en)

Applications Claiming Priority (1)

Application Number	Priority Date	Filing Date	Title
PCT/JP2008/068583 WO2010044138A1 (ja)	2008-10-14	2008-10-14	コークス乾式消火設備およびコークス乾式消火方法

Publications (3)

Publication Number	Publication Date
EP2351811A1 EP2351811A1 (en)	2011-08-03
EP2351811A4 EP2351811A4 (en)	2014-05-21
EP2351811B1 true EP2351811B1 (en)	2017-04-05

Family

ID=42106316

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP08877397.3A Not-in-force EP2351811B1 (en)	2008-10-14	2008-10-14	Coke dry type extinguishing facility, and coke dry type extinguishing method

Country Status (7)

Country	Link
EP (1)	EP2351811B1 (pt)
JP (1)	JP5341905B2 (pt)
KR (1)	KR101316675B1 (pt)
CN (1)	CN102186947B (pt)
BR (1)	BRPI0822803B1 (pt)
TW (1)	TW201014902A (pt)
WO (1)	WO2010044138A1 (pt)

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Publication number	Priority date	Publication date	Assignee	Title
JP5438486B2 (ja) *	2009-12-10	2014-03-12	新日鉄住金エンジニアリング株式会社	コークス乾式消火設備
CN102994118A (zh) *	2011-12-21	2013-03-27	山西鑫立能源科技有限公司	煤热解炉的干熄焦装置
CN103131435B (zh) *	2012-04-23	2014-03-26	太原理工大学	气液两相分布器及应用该分布器的熄焦炉
CN103087728B (zh) *	2012-08-06	2014-04-30	山西鑫立能源科技有限公司	一种煤热解炉的连续炼焦装置
CN102786960B (zh) *	2012-08-06	2014-04-30	山西鑫立能源科技有限公司	一种煤热解炉的干熄装置
CN102786961B (zh) *	2012-08-06	2014-04-30	山西鑫立能源科技有限公司	一种煤热解炉的熄焦桥弓
KR101434545B1 (ko) *	2012-11-22	2014-08-27	주식회사 포스코	배출 장치 및 이를 구비하는 코크스 소화 장치
JPWO2019221282A1 (ja) *	2018-05-18	2021-03-11	株式会社Ｉｈｉポールワース	コークス乾式消火設備

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US1462119A (en) *	1922-01-19	1923-07-17	Moetteli Arnold	Arrangement in coke containers or the like
US1496094A (en) *	1923-03-16	1924-06-03	Firm Of Gebruder Sulzer Ag	Container for the dry cooling of coke
DE2952065C2 (de) *	1979-12-22	1984-10-11	Carl Still Gmbh & Co Kg, 4350 Recklinghausen	Verfahren zur Trockenkühlung von Koks und Kokskühleinrichtung zur Durchführung des Verfahrens
JPS5917883Y2 (ja) *	1980-01-23	1984-05-24	日立造船株式会社	乾式コ−クス冷却バンカ
DE3215807A1 (de) *	1982-05-04	1983-11-10	Gosudarstvennyj vsesojuznyj institut po proektirovaniju predprijatij koksochimi&ccaron;eskoj promy&scaron;lennosti GIPROKOKS, Charkov	Vorrichtung zum trockenloeschen von koks
JPS60172752U (ja) *	1984-04-25	1985-11-15	住友金属工業株式会社	コ−クス乾式消火炉における冷風吹込装置
JPH01110592A (ja)	1987-10-22	1989-04-27	Ishikawajima Harima Heavy Ind Co Ltd	コークス乾式消火設備のコークス降下制御装置
JPH0397782A (ja) *	1989-09-09	1991-04-23	Nkk Corp	コークス乾式消火設備におけるガス吹込装置
JPH06310691A (ja)	1993-04-23	1994-11-04	Kawasaki Steel Corp	半導体装置

2008
- 2008-10-14 CN CN200880131562.2A patent/CN102186947B/zh active Active
- 2008-10-14 BR BRPI0822803 patent/BRPI0822803B1/pt active IP Right Grant
- 2008-10-14 WO PCT/JP2008/068583 patent/WO2010044138A1/ja not_active Ceased
- 2008-10-14 KR KR1020117010816A patent/KR101316675B1/ko active Active
- 2008-10-14 EP EP08877397.3A patent/EP2351811B1/en not_active Not-in-force
- 2008-10-14 JP JP2010533738A patent/JP5341905B2/ja active Active
- 2008-11-06 TW TW097142862A patent/TW201014902A/zh unknown

Also Published As

Publication number	Publication date
WO2010044138A1 (ja)	2010-04-22
CN102186947A (zh)	2011-09-14
TW201014902A (en)	2010-04-16
EP2351811A4 (en)	2014-05-21
KR101316675B1 (ko)	2013-10-10
JP5341905B2 (ja)	2013-11-13
KR20110084921A (ko)	2011-07-26
CN102186947B (zh)	2014-09-03
EP2351811A1 (en)	2011-08-03
BRPI0822803B1 (pt)	2019-12-10
JPWO2010044138A1 (ja)	2012-03-08
BRPI0822803A2 (pt)	2019-01-15

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