JPH08169772A - Baking repairing material - Google Patents

Baking repairing material

Info

Publication number
JPH08169772A
JPH08169772A JP6333977A JP33397794A JPH08169772A JP H08169772 A JPH08169772 A JP H08169772A JP 6333977 A JP6333977 A JP 6333977A JP 33397794 A JP33397794 A JP 33397794A JP H08169772 A JPH08169772 A JP H08169772A
Authority
JP
Japan
Prior art keywords
pitch
diphenyl
binder
baking
repairing material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP6333977A
Other languages
Japanese (ja)
Other versions
JP3222709B2 (en
Inventor
Yasushi Tokuse
康司 徳瀬
Yoshiharu Koga
義春 古賀
Shigemitsu Kaida
茂光 甲斐田
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.)
Taiko Refractories Co Ltd
Original Assignee
Taiko Refractories 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.)
Filing date
Publication date
Application filed by Taiko Refractories Co Ltd filed Critical Taiko Refractories Co Ltd
Priority to JP33397794A priority Critical patent/JP3222709B2/en
Publication of JPH08169772A publication Critical patent/JPH08169772A/en
Application granted granted Critical
Publication of JP3222709B2 publication Critical patent/JP3222709B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

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  • Ceramic Products (AREA)
  • Furnace Housings, Linings, Walls, And Ceilings (AREA)

Abstract

PURPOSE: To obtain a baking repairing material excellent in flow spreadability and adhesiveness in a hot state and excellent also in work efficiency and physical properties by mixing refractory aggregate with a binder forming carbon bonds in a hot state and a specified diphenyl type fluidizing aid. CONSTITUTION: Refractory aggregate (A) such as silica, alumina, chromia, magnesia, calcia or silicon carbide is mixed with a binder (B) made of a substance forming carbon bonds in a hot state, e.g. pitch and a fluidizing aid (C) made of diphenyl and/or diphenylamine to obtain the objective baking repairing material. The component B made of pitch having <=300 deg.C softening point and the component C are added by 5-40 pts.wt. and 0.5-40 pts.wt. per 100 pts.wt. of the component A, respectively. An antioxidant for carbon such as Al powder and a dust generation inhibitor such as liq. paraffin may further be blended. The resultant repairing material is suitable for hot repair of various refining furnaces and vessels.

Description

【発明の詳細な説明】Detailed Description of the Invention

【0001】[0001]

【産業上の利用分野】本発明は各種精錬炉や容器などを
熱間で補修するための焼付け補修材に関するものであ
る。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a bake repair material for hot repairing various refining furnaces and vessels.

【0002】[0002]

【従来の技術】各種窯炉の炉壁耐火物の溶損部位を熱間
で補修する方法の一つとして、熱間投げ込み焼付け補修
方法が広く採用されている。これは耐火材料を結合剤と
して機能するピッチ、タールで混練し、練土状にしたも
のが一般的である。しかし、焼付けに要する時間が長い
といった欠点のほか、使用時の発煙や異臭が激しいとい
った欠点があるため、非タール系結合剤としてクメンヒ
ドロペルオキシドベンゼン等の酸分解により得られる生
成物からフエノール等を蒸溜除去して得られる釜残物を
有機溶媒で溶かしたもので混練するもの(特開昭59−
45975号)や、フリット又はフリット及び粉末樹脂
を添加し多価アルコール液で混練したもの(特開昭63
−31435号)が公示されている。
2. Description of the Related Art As one of the methods for hot repairing a melted portion of a furnace wall refractory of various kilns, a hot-throw baking repair method is widely adopted. This is generally made by kneading a refractory material with pitch and tar that function as a binder to form a kneaded clay. However, in addition to the drawback that it takes a long time to bake, it also has the drawback that smoke and offensive odor are severe during use.Therefore, phenol, etc., is obtained from the product obtained by acid decomposition of cumene hydroperoxide benzene as a non-tar binder. Kneading with a pot residue obtained by distilling off and dissolving it in an organic solvent (JP-A-59-59)
No. 45975), or a mixture in which a frit or a frit and a powder resin are added and kneaded with a polyhydric alcohol solution (JP-A-63-63)
-31435) is publicly announced.

【0003】一方、粉末状(湿潤しているが取り扱い
上、粉末状としてみなしても差し支えない形態のものを
含む、以下同様)のものとしては、特定範囲内量のピッ
チと顆粒状及び液状フェノール樹脂を結合剤として使用
し、タール、ピッチの環境衛生上の欠点を低減したもの
(特開昭60−235772号)、ピッチを結合剤とす
るものに流動展開性を良好にするため重油やクレオソー
ト油等を添加したもの(特開平1−150790号)、
結晶水を持つ無機化合物を添加し、この結晶水が赤熱状
態の炉中において脱水されるときの水分で泥ショウ状態
になるようにして焼付け材とするもの(特開平2−26
874号)、流動展開性を良好にするため、ピッチやフ
ェノール樹脂を含む材料に流動化助剤としてラクタム類
を添加するもの(特開平6−157149号)等が公示
されている。
On the other hand, the powdery form (including the form which is wet but can be regarded as a powdery form for handling, the same applies hereinafter) includes pitches within a specific range and granular and liquid phenols. Resins used as binders to reduce environmental and hygiene defects of tar and pitch (Japanese Patent Laid-Open No. 60-235772), those containing pitch as binders in order to improve fluidity, heavy oil and creos Those to which sort oil or the like is added (Japanese Patent Laid-Open No. 1-150790),
A baking material is prepared by adding an inorganic compound having water of crystallization so that this water of crystallization is in a mud-showing state due to the water content when dehydrated in a red-hot furnace (JP-A-2-26).
No. 874), in which lactams are added as a fluidization aid to a material containing pitch or a phenol resin in order to improve flow developability (Japanese Patent Laid-Open No. 6-157149) and the like.

【0004】[0004]

【発明が解決しようとする課題】焼付け補修材の使用上
や取り扱い上、練土状の形態のものは小さな破袋部分か
らでも液の流出が起きるなど不便であり、また、製造的
立場から見た場合もかなり繁雑な製造となる。これに対
し、粉末状のものは前記の欠点は全くない。しかし、粉
末状のものは練土状のものに比較して流動展開性が悪
く、また、炉壁との接着性が悪く耐用性においてこれま
で満足するものがなかった。
From the viewpoint of manufacturing, it is inconvenient for the bake repairing material to be used and handled, and the material in the form of a dough is inconvenient because the liquid may flow out even from a small crushed bag portion. It is also a very complicated production. On the other hand, the powder form does not have the above-mentioned drawbacks at all. However, the powdery one has a poorer flow spreadability than the kneaded one, and the adhesiveness to the furnace wall is poor, so that there has been no satisfactory durability up to now.

【0005】この点、流動化助剤を使用することを特徴
とする特開平6−157149号の方法は、これまでの
粉末状焼付け補修材にあった欠点を一歩進める方法では
ある。しかしながら、特開平6−157149号に示さ
れている流動化助剤としてのε−カプロラクタムの使用
は保存性に問題があるといえる。すなわち、ε−カプロ
ラクタムは吸湿性の強い物質であり、ドロマイトやマグ
ネシアの水和を起こしやすく、特に夏場の保存性に問題
がある。また、接着強度も従来のものと比較して十分で
あるとはいえない。
In this respect, the method disclosed in Japanese Patent Laid-Open No. 6-157149, which is characterized by using a fluidization aid, is a method for advancing the drawbacks of the powdery baking repair materials to date. However, it can be said that the use of ε-caprolactam as a fluidization aid disclosed in JP-A-6-157149 has a problem in storage stability. That is, ε-caprolactam is a substance having a strong hygroscopic property, and is likely to cause hydration of dolomite and magnesia, and there is a problem in storage stability especially in summer. Also, the adhesive strength is not sufficient as compared with the conventional one.

【0006】[0006]

【課題を解決するための手段】本発明者らは、粉末状焼
付け補修材の開発において、ピッチ、フェノール樹脂の
流動化助剤として種々の物質を探索検討した結果、ジフ
ェニル、又はジフェニルアミンが最も優れていることを
発見し、本発明を完成したものである。すなわち、本発
明は、耐火骨材、結合剤として熱間でカーボン結合を形
成する物質、及び流動化助剤としてジフェニル又は(及
び)ジフェニルアミンよりなる焼付け補修材を提供する
ものである。
Means for Solving the Problems In the development of a powdery baking repair material, the present inventors searched various substances as fluidization aids for pitch and phenol resin, and as a result, diphenyl or diphenylamine was the best. That is, the present invention has been completed. That is, the present invention provides a bake repair material comprising a refractory aggregate, a substance that forms a carbon bond during heat as a binder, and diphenyl or (and) diphenylamine as a fluidization aid.

【0007】本発明に使用する耐火骨材は特に限定され
ず、被補修箇所に使用されている母材組成に合った適当
なものが使用できる。すなわち、シリカ、ジルコン、ジ
ルコニア等のいわゆる酸性酸化物、アルミナ、クロミア
等の中性酸化物、マグネシア、カルシア、ドロマイト等
の塩基性酸化物や、炭素材料、炭化珪素、窒化珪素等の
非酸化物等の一種又は二種以上が適宜使用できる。
The refractory aggregate used in the present invention is not particularly limited, and any suitable one can be used which is suitable for the composition of the base material used in the portion to be repaired. That is, so-called acidic oxides such as silica, zircon and zirconia, neutral oxides such as alumina and chromia, basic oxides such as magnesia, calcia and dolomite, and non-oxides such as carbon materials, silicon carbide and silicon nitride. One kind or two or more kinds of the above can be appropriately used.

【0008】次に熱間でカーボン結合を形成する物質と
しては、通常の有機結合剤として使用されているピッチ
類やフェノール樹脂が使用できる。その使用量は補修箇
所に適した必要な流動性を与え、カーボン結合が十分に
形成される量を使用するが、通常使用量としては耐火骨
材100重量部に対して5〜40重量部を必要とする。
この量が5重量部未満では流動展開性が不足し、また強
度、接着性が劣るものとなる。40重量部以上の使用で
は施工体の気孔率が大きくなり、耐用性が悪くなる。本
発明に使用するピッチは石炭系、石油系のいずれでもよ
く、またその軟化点は、炉熱によって速やかに溶融し焼
付け補修材全体を流動状態とする役目をもっているた
め、300℃以下のものに限定されるが、通常、100
〜150℃のものが望ましい。フェノール樹脂として
は、熱可塑性のいわゆるノボラックタイプのものが望ま
しく、固体であれば粉末状、フレーク状等種々のものが
使用可能である。また、溶融点としては120℃以下の
ものが望ましい。
Next, as the substance which forms a carbon bond by heat, pitches and phenol resins which are commonly used as organic binders can be used. The amount used gives the necessary fluidity suitable for the repaired part and is used in such an amount that carbon bonds are sufficiently formed, but the amount used is usually 5 to 40 parts by weight with respect to 100 parts by weight of the refractory aggregate. I need.
If this amount is less than 5 parts by weight, the flow developability will be insufficient, and the strength and adhesiveness will be poor. If it is used in an amount of 40 parts by weight or more, the porosity of the construction body becomes large and the durability becomes poor. The pitch used in the present invention may be coal-based or petroleum-based, and the softening point thereof should be 300 ° C. or less because it has the role of quickly melting by the furnace heat and making the entire baking repair material into a fluid state. Limited but usually 100
A temperature of up to 150 ° C is desirable. As the phenol resin, a so-called novolac type thermoplastic resin is preferable, and various solid resins such as powder and flakes can be used. The melting point is preferably 120 ° C. or lower.

【0009】流動化助剤としてのジフェニルやジフェニ
ルアミンは、いずれも室温で粉末(固体)であり、ま
た、ε−カプロラクタムにみられるような吸湿性がない
ので保存上全く問題がない上に、耐火骨材との混合が容
易であり、製造上好都合といえる。これらは、流動展開
性において、ε−カプロラクタムに劣るものでなく、炉
壁との接着性においてはε−カプロラクタムより優れる
もので、いずれもそれぞれ単独で流動化助剤として使用
できるが、焼付け温度や窯炉の熱容量等に応じて流動展
開性を調整する目的から併用使用も可能である。使用量
としては耐火材料100重量部に対して0.5〜40重
量部を、必要とする流動展開性に応じて使用するが、4
0重量部以上の使用は施工体の気孔率を上げ、また焼付
け時間が長くなるので望ましくない。また、0.5%以
下の使用量では流動化助剤としての効果がほとんどみら
れない。
Both diphenyl and diphenylamine as fluidization aids are powders (solids) at room temperature and have no hygroscopicity as seen in ε-caprolactam, so there is no problem in storage and fire resistance. It can be said that it is easy to mix with the aggregate and is convenient in manufacturing. These are not inferior to ε-caprolactam in flow developability, and are superior to ε-caprolactam in adhesiveness to the furnace wall, and both can be used alone as a fluidization aid, but the baking temperature and It can also be used in combination for the purpose of adjusting the flow developability according to the heat capacity of the kiln. The amount used is 0.5 to 40 parts by weight based on 100 parts by weight of the refractory material, depending on the required fluidity.
Use of 0 parts by weight or more is not desirable because it increases the porosity of the construction body and prolongs the baking time. Further, when used in an amount of 0.5% or less, almost no effect as a fluidization aid is observed.

【0010】流動化助剤は炉熱により溶融したピッチや
フェノール樹脂の粘性を低下させ流動を促進するもので
なければならないので、これらと相溶性のあるものでな
ければならない。例えば、炉熱により容易に溶融、低粘
性液体となるがピッチやフェノール樹脂とほとんど相溶
性のないポリエチレングリコールを使用しても、むしろ
これらの溶融を遅らせ、焼付け時間を長くするだけで流
動化助剤としては機能しない。そのほか、流動化助剤と
してはそれ自身も炉熱により溶融し、望ましくはピッチ
やフェノール樹脂より低い温度で溶融し、低粘性化する
ものが良い。この点、ジフェニルやジフェニルアミンは
溶融点がそれぞれ約70℃、52℃であるので好都合で
ある。流動化助剤としてジフェニル又は(及び)ジフェ
ニルアミンを使用した焼付け補修材は赤熱した炉中に投
入されると、結合剤、及び流動化剤として配合されたピ
ッチやフェノール樹脂が溶け、これにジフェニル又は
(及び)ジフェニルアミンが相溶することにより全体が
低粘性化した泥ショウ状態となり流動展開し、損傷した
炉壁の細部まで浸透し緻密に充填され、固化した後はカ
ーボン結合により優れた強度、接着性を発現する。
The fluidizing aid must be compatible with the pitch and the phenol resin melted by the heat of the furnace, because it must lower the viscosity and accelerate the flow. For example, even if polyethylene glycol, which is easily melted and becomes a low-viscosity liquid by furnace heat but has little compatibility with pitch or phenolic resin, is used, the melting of these is delayed, and the fluidization aid is increased simply by increasing the baking time. It does not function as an agent. In addition, as the fluidization aid, it is preferable that the fluidization aid itself is melted by furnace heat, and is desirably melted at a temperature lower than that of the pitch or the phenol resin to lower the viscosity. In this respect, the melting points of diphenyl and diphenylamine are about 70 ° C. and 52 ° C., respectively, which is convenient. When a baking repair material using diphenyl or (and) diphenylamine as a fluidization aid is placed in a red-hot furnace, the binder and the pitch or phenol resin blended as a fluidizing agent melts, and diphenyl or (And) Diphenylamine compatibilized makes the whole mud-shown with low viscosity, flow-developed, penetrated even into the details of the damaged furnace wall and packed densely, and after solidification it has excellent strength and adhesion due to carbon bonding. Develop sex.

【0011】その他、本発明品にはカーボンの酸化防止
剤として機能するアルミニウム粉末、シリコン粉末、フ
ェロシリコン粉末等の金属粉末やボロンカーバイト(B
4C)の使用も可能である。また、投入時の発塵防止
等、取り扱い上の便宜のため、流動パラフィン、イソパ
ラフィン、エタノール等の有機溶媒や灯油、重油、水等
によってプレミックスし湿潤化することも可能である。
In addition to the above, in the product of the present invention, metal powder such as aluminum powder, silicon powder, and ferrosilicon powder, which functions as a carbon antioxidant, and boron carbide (B
4 C) can also be used. Further, for convenience of handling such as prevention of dust generation at the time of addition, it is also possible to premix and wet with an organic solvent such as liquid paraffin, isoparaffin, ethanol and the like, kerosene, heavy oil, water and the like.

【0012】[0012]

【実施例】表1に本発明の実施例と比較例が示されてい
る。実施例1〜6は本発明の粉末状焼付け補修材の例で
あり、比較例1〜4は結合剤としてピッチ、又はピッチ
と熱可塑性フェノール樹脂粉末を併用し、流動化助剤を
使用していないものと、結合剤としてピッチ、及び流動
化助剤としてε−カプロラクタムを使用した例である。
EXAMPLES Examples of the present invention and comparative examples are shown in Table 1. Examples 1 to 6 are examples of the powdery baking repair material of the present invention, and Comparative Examples 1 to 4 use pitch, or pitch and thermoplastic phenolic resin powder in combination as a binder, and use a fluidization aid. And the examples using Pitch as a binder and ε-caprolactam as a fluidization aid.

【0013】表1に示す各配合の特性値は、いずれも1
100℃に保持された試験炉で試験した時の値である。
すなわち、広がり面積指数は、試験炉(1100℃に保
持されている、以下同様)にセットしたマグネシア煉瓦
上に試料200gを落とした時の広がり面積を比較例1
を100として指数化したものである。硬化時間は、内
径100mmφ×深さ70mmの大きさの鉄製容器に試
料500gを入れて試験炉に投入し、試料が溶融固化す
るまでの時間である。接着セン断強度は、試験炉にセッ
トしたマグネシア煉瓦上に縦70mm×横80mm×深
さ50mmサイズの鉄枠を置き、この中に試料500g
を投入しマグネシア煉瓦に焼付け接着させた後、炉外に
取り出し冷却後測定したものである。熱間施工後の物性
値は、内径150mmφ×深さ170mmの大きさの鉄
製容器に試料2kgを入れて試験炉に投入し、溶融固化
後、固化物を容器より取り出し測定したものである。
The characteristic value of each composition shown in Table 1 is 1
It is a value when tested in a test furnace maintained at 100 ° C.
That is, as the spread area index, the spread area when 200 g of the sample was dropped on a magnesia brick set in a test furnace (held at 1100 ° C., the same applies hereinafter) was used as Comparative Example 1.
Is indexed to 100. The curing time is the time until 500 g of the sample is placed in an iron container having an inner diameter of 100 mmφ and a depth of 70 mm and placed in a test furnace to melt and solidify the sample. The adhesive shear strength is determined by placing an iron frame measuring 70 mm in length x 80 mm in width x 50 mm in depth on a magnesia brick set in a test furnace, in which 500 g of a sample is placed.
Was put into a magnesia brick by baking to bond it, taken out of the furnace, cooled, and measured. The physical properties after hot working are measured by putting 2 kg of a sample in an iron container having an inner diameter of 150 mmφ and a depth of 170 mm, placing the sample in a test furnace, melting and solidifying, and then removing the solidified product from the container.

【0014】実施例は、比較例に比べて、試料の広がり
面積指数で表される流動展開性、及び接着セン断強度の
いずれにおいても良好な結果を示しており、特に接着セ
ン断強度が優れていることが分かる。
Compared with the comparative examples, the examples show good results in both the flow spreadability represented by the spread area index of the sample and the adhesive shear strength, and the adhesive shear strength is particularly excellent. I understand that.

【0015】[0015]

【発明の効果】本発明品は、流動化剤としてジフェニル
又は(及び)ジフェニルアミンを使用しているので、熱
間での流動展開性、及び接着性に優れ、従って作業性、
物性に優れた焼付け補修材を得ることができた。また、
本発明品は、その流動化助剤が吸湿性がなく常温で固体
であることから、保存性が良く、輸送を含めた取り扱い
上や製造上の観点からも優れた焼付け補修材を得ること
ができた。
Since the product of the present invention uses diphenyl or (and) diphenylamine as a fluidizing agent, it has excellent fluidity and adhesiveness during hot working, and therefore has good workability.
It was possible to obtain a baked repair material with excellent physical properties. Also,
Since the fluidization aid of the present invention is solid at room temperature without hygroscopicity, it has good storability, and it is possible to obtain a baking repair material excellent in terms of handling including transportation and manufacturing. did it.

【0016】[0016]

【表1】 [Table 1]

Claims (3)

【特許請求の範囲】[Claims] 【請求項1】 耐火骨材、結合剤として熱間でカーボン
結合を形成する物質及び流動化助剤としてジフェニル又
は(及び)ジフェニルアミンよりなることを特徴とする
焼付け補修材。
1. A baking repair material comprising a refractory aggregate, a substance that forms a carbon bond during heating as a binder, and diphenyl or (and) diphenylamine as a fluidization aid.
【請求項2】 流動化助剤として、ジフェニル又は(及
び)ジフェニルアミンを耐火骨材100重量部に対し
0.5〜40重量部配合することを特徴とする請求項1
に記載する焼付け補修材。
2. As a fluidizing aid, diphenyl or (and) diphenylamine is added in an amount of 0.5 to 40 parts by weight per 100 parts by weight of the refractory aggregate.
Bake repair material described in.
【請求項3】 結合剤として耐火骨材100重量部に対
し軟化点300℃以下のピッチを5〜40重量部、及び
ジフェニル又は(及び)ジフェニルアミンを耐火骨材1
00重量部に対し0.5〜40重量部配合することを特
徴とする請求項1に記載する焼付け補修材。
3. As a binder, 5 to 40 parts by weight of a pitch having a softening point of 300 ° C. or less, and diphenyl or (and) diphenylamine are used as the binder to 100 parts by weight of the refractory aggregate.
The baking repair material according to claim 1, wherein 0.5 to 40 parts by weight is blended with respect to 00 parts by weight.
JP33397794A 1994-12-16 1994-12-16 Powder baking repair material Expired - Fee Related JP3222709B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP33397794A JP3222709B2 (en) 1994-12-16 1994-12-16 Powder baking repair material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP33397794A JP3222709B2 (en) 1994-12-16 1994-12-16 Powder baking repair material

Publications (2)

Publication Number Publication Date
JPH08169772A true JPH08169772A (en) 1996-07-02
JP3222709B2 JP3222709B2 (en) 2001-10-29

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Family Applications (1)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998050321A1 (en) * 1997-05-07 1998-11-12 Shinagawa Refractories Co., Ltd. Seizure repairing material
JP6383033B1 (en) * 2017-03-10 2018-08-29 黒崎播磨株式会社 Baking repair material
CN112225542A (en) * 2020-09-30 2021-01-15 鞍钢股份有限公司 Method for prolonging service life of KR stirring paddle

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998050321A1 (en) * 1997-05-07 1998-11-12 Shinagawa Refractories Co., Ltd. Seizure repairing material
EP0936203A1 (en) * 1997-05-07 1999-08-18 Shinagawa Refractories Co., Ltd. Seizure repairing material
US6214081B1 (en) * 1997-05-07 2001-04-10 Shinagawa Refractories Co., Ltd. Hot repair mix comprising bisphenol as a fluidizing agent
EP0936203A4 (en) * 1997-05-07 2003-06-04 Shinagawa Refractories Co Seizure repairing material
JP6383033B1 (en) * 2017-03-10 2018-08-29 黒崎播磨株式会社 Baking repair material
CN112225542A (en) * 2020-09-30 2021-01-15 鞍钢股份有限公司 Method for prolonging service life of KR stirring paddle

Also Published As

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