JPH0488095A - Dispersion stabilizer for aqueous slurry of coal powder - Google Patents
Dispersion stabilizer for aqueous slurry of coal powderInfo
- Publication number
- JPH0488095A JPH0488095A JP2204828A JP20482890A JPH0488095A JP H0488095 A JPH0488095 A JP H0488095A JP 2204828 A JP2204828 A JP 2204828A JP 20482890 A JP20482890 A JP 20482890A JP H0488095 A JPH0488095 A JP H0488095A
- Authority
- JP
- Japan
- Prior art keywords
- phenol
- coal
- coal powder
- dispersion stabilizer
- present
- 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
Links
- 239000003245 coal Substances 0.000 title claims abstract description 20
- 239000000843 powder Substances 0.000 title claims abstract description 9
- 239000006185 dispersion Substances 0.000 title claims description 17
- 239000002002 slurry Substances 0.000 title claims description 17
- 239000003381 stabilizer Substances 0.000 title abstract description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 40
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229940044652 phenolsulfonate Drugs 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000000087 stabilizing effect Effects 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- WHOZNOZYMBRCBL-OUKQBFOZSA-N (2E)-2-Tetradecenal Chemical compound CCCCCCCCCCC\C=C\C=O WHOZNOZYMBRCBL-OUKQBFOZSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229940044654 phenolsulfonic acid Drugs 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical class OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- MGJURKDLIJVDEO-UHFFFAOYSA-N formaldehyde;hydrate Chemical compound O.O=C MGJURKDLIJVDEO-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 description 2
- HIEHAIZHJZLEPQ-UHFFFAOYSA-M sodium;naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 HIEHAIZHJZLEPQ-UHFFFAOYSA-M 0.000 description 2
- -1 sulfomethyl group Chemical group 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical class OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 239000002006 petroleum coke Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229940087596 sodium phenolsulfonate Drugs 0.000 description 1
- BLXAGSNYHSQSRC-UHFFFAOYSA-M sodium;2-hydroxybenzenesulfonate Chemical compound [Na+].OC1=CC=CC=C1S([O-])(=O)=O BLXAGSNYHSQSRC-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Landscapes
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、石炭粉末の水スラリー用分散安定剤に関する
。更に詳しくは石炭粉末を水中に分散させパイプライン
輸送が可能な状態に分散安定化させる分散安定剤に関す
る。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a dispersion stabilizer for a water slurry of coal powder. More specifically, the present invention relates to a dispersion stabilizer for dispersing coal powder in water and stabilizing the dispersion to a state where it can be transported by pipeline.
近年、石油資源の枯渇により埋蔵量が多く且つ、偏在せ
ず世界中に存在する石炭資源の利用が再認識されている
。しかしながら石炭の場合は石油とは異なり固体である
ためパイプラインによる輸送が不可能であり取り扱い上
著しく不利である。このようなことより取り扱い上の欠
点を改善するために石炭を粉末化し、水中に分散させて
スラリー状にして輸送する方法が種々検討されている。In recent years, due to the depletion of petroleum resources, the use of coal resources, which have large reserves and are not unevenly distributed throughout the world, has been reaffirmed. However, unlike petroleum, coal is a solid, so it cannot be transported by pipeline and is extremely disadvantageous in terms of handling. In order to improve the handling disadvantages, various methods have been studied for pulverizing coal, dispersing it in water, and transporting it in the form of a slurry.
しかしながら、この場合も石炭濃度を上げると著しく増
粘し、流動性を失う。また石炭濃度を下げると輸送効率
が低下し、更に脱水工程にも費用がかかることになり実
用的でない。これは、石炭−水スラリー中の石炭粒子同
士が水中で凝集することにより、粘度の増大及び流動性
の減少を起こさせるからである。この対策として界面活
性剤である分散剤を加えることにより石炭粒子に分散剤
が吸着して石炭粒子をバラバラにほぐず作用や石炭粒子
が互いに凝集するのを防ぐ作用が知られており、種々の
分散剤が使用されている。しかし、今日使用されている
、例えばナフタレンスルホン酸ナトリウムホルマリン縮
合物、ポリスチレンスルホン酸ナトリウム等は分散安定
性や流動性に関し、実用上満足すべきものではなかった
。However, in this case as well, when the coal concentration is increased, the viscosity increases significantly and fluidity is lost. Furthermore, lowering the coal concentration lowers the transportation efficiency and also increases the cost of the dewatering process, which is not practical. This is because the coal particles in the coal-water slurry aggregate in water, causing an increase in viscosity and a decrease in fluidity. As a countermeasure to this problem, it is known that by adding a dispersant, which is a surfactant, the dispersant is adsorbed to the coal particles and has the effect of not loosening the coal particles or preventing the coal particles from agglomerating together. A dispersant is used. However, the materials used today, such as sodium naphthalene sulfonate formalin condensate and sodium polystyrene sulfonate, are not practically satisfactory in terms of dispersion stability and fluidity.
本発明者らはかかる従来の石炭−水スラリーの欠点であ
る分散安定性の改良と流動性の向上をはかるべく鋭意検
討した結果、フェノールスルホン酸塩と該フェノールス
ルホン酸塩に対して特定割合のフェノールとを中性以上
のアルカリ領域でホルムアルデヒドと共縮合させること
により分散安定性と流動性に優れた効果を持つ共縮合物
が得られることを見出し本発明を完成した。The present inventors have conducted intensive studies to improve dispersion stability and fluidity, which are the drawbacks of conventional coal-water slurries. The present invention was completed by discovering that a co-condensate with excellent dispersion stability and fluidity can be obtained by co-condensing phenol with formaldehyde in an alkaline region above neutrality.
すなわち、本発明はフェノールスルホン酸塩と該フェノ
ールスルホン酸塩に対し4〜30モル%のフェノールと
をアルカリ性でホルムアルデヒドと共縮合させた共重縮
合物を含有する石炭粉末の水スラリー用分散安定剤を提
供するものである。That is, the present invention provides a dispersion stabilizer for an aqueous slurry of coal powder containing a copolycondensate obtained by cocondensing a phenol sulfonate and 4 to 30 mol% of phenol with formaldehyde in an alkaline environment. It provides:
本発明ではフェノールスルホン酸塩とフェノールをpH
7以上のアルカリ性領域でホルマリン縮合することによ
り、介在するフェノールにより立体的な分子構造をもつ
重縮合物となり、石炭の分散性に有効な構造と分子量分
布を有する重縮合物となるものと推察され、一般のフェ
ノールスルホン酸ホルマリン縮合物(例えば、特開昭5
8−53988号公報)やナフタレンスルホン酸縮合物
の直線状縮合物とは異なるものである。In the present invention, phenol sulfonate and phenol are adjusted to pH
It is presumed that formalin condensation in an alkaline region of 7 or more forms a polycondensate with a three-dimensional molecular structure due to the intervening phenol, resulting in a polycondensate with a structure and molecular weight distribution effective for dispersibility of coal. , general phenolsulfonic acid formalin condensates (for example, JP-A-5
8-53988) and a linear condensate of naphthalenesulfonic acid condensate.
本発明に使用するフェノールスルホン酸塩としては、フ
ェノールスルホン酸の水酸化ナトリウム、炭酸ナトリウ
ム、炭酸カリウム、アンモニア水、トリエタノールアミ
ン塩等のアルカリとの有機あるいは無機の中和塩が挙げ
られるが、特に溶解度の大きい水酸化ナトリウム、水酸
化カリウムによる塩が好ましい。Examples of the phenolsulfonic acid salts used in the present invention include organic or inorganic neutralized salts of phenolsulfonic acid with alkalis such as sodium hydroxide, sodium carbonate, potassium carbonate, aqueous ammonia, and triethanolamine salts. Particularly preferred are salts of sodium hydroxide and potassium hydroxide, which have high solubility.
また、フェノールスルホン酸塩の他にスルホメチル基を
導入したフェノールの使用も可能である。In addition to phenol sulfonate, it is also possible to use phenol into which a sulfomethyl group has been introduced.
本発明において、共縮合反応に用いるフェノールスルホ
ン酸塩とフェノールのモル比は、フェノールスルホン酸
塩1モルに対してフェノールが4〜30モル%であり、
8〜15モル%が特に好ましい。フェノールのモル比が
4モル%未満では縮合が進まず、分散性に有効な重縮合
物に至らない低縮合物となる。また、フェノールのモル
比が30モル%を超えると高分子量部分の多い分子量分
布幅の広い重縮合物となり、有効な分散性が得られない
。In the present invention, the molar ratio of phenol sulfonate and phenol used in the cocondensation reaction is 4 to 30 mol% of phenol to 1 mol of phenol sulfonate,
Particularly preferred is 8 to 15 mol%. When the molar ratio of phenol is less than 4 mol %, condensation does not proceed, resulting in a low condensate that does not result in a polycondensate that is effective for dispersibility. On the other hand, if the molar ratio of phenol exceeds 30 mol %, a polycondensate containing many high molecular weight portions and a wide molecular weight distribution will result, making it impossible to obtain effective dispersibility.
また、本発明にはフェノールをスルホン化するに際して
、未反応フェノールが残存している反応物をそのまま原
料としても良い。Further, in the present invention, when sulfonating phenol, a reactant in which unreacted phenol remains may be used as a raw material as it is.
本発明による重縮合物の製造に使用するホルムアルデヒ
ドは、濃度が30〜45重量%の水溶液であるホルマリ
ンが好ましい。The formaldehyde used in the production of the polycondensate according to the present invention is preferably formalin, which is an aqueous solution having a concentration of 30 to 45% by weight.
ホルムアルデヒドの反応モル比は、メチロル付加、メチ
レン縮合に必要なモル比で、フェノール骨格に対し、1
〜2モル程度で良く、特に限定するものではない。The reaction molar ratio of formaldehyde is the molar ratio necessary for methylol addition and methylene condensation, and is 1 molar ratio to the phenol skeleton.
It may be about 2 moles or so, and is not particularly limited.
本発明の重縮合体は、重縮合体の平均分子量が500〜
40000の範囲であれば良く、1000〜20000
程度がより好ましい。The polycondensate of the present invention has an average molecular weight of 500 to
Any range between 40,000 and 1,000 to 20,000 is fine.
degree is more preferable.
以下に本発明の分散安定剤の製造法の一例を示すが、こ
れによって本発明は何ら限定されるものではない。An example of the method for producing the dispersion stabilizer of the present invention is shown below, but the present invention is not limited thereto.
反応容器中にフェノールスルホン酸ナトリウム塩、フェ
ノール、ホルマリン(37%ホルムアルデヒド水)、水
を所定量仕込み、pHを8,5に調整し、還流下におい
て5〜30時間攪拌する(第一工程)。次いで30℃に
冷却し、pH10,5に調整する。更に還流下で2〜3
時間攪拌(第二工程)して冷却し、本発明の分散剤を得
る。Predetermined amounts of phenolsulfonic acid sodium salt, phenol, formalin (37% formaldehyde water), and water are charged into a reaction vessel, the pH is adjusted to 8.5, and the mixture is stirred under reflux for 5 to 30 hours (first step). It is then cooled to 30°C and adjusted to pH 10.5. Further under reflux 2-3
The mixture is stirred for a period of time (second step) and cooled to obtain the dispersant of the present invention.
本発明の分散安定剤を添加することで得られる石炭粉末
の水スラリーは高濃度でも粘度の上昇が少なく流動性が
良好で且つ長期分散安定性を保つためパイプライン輸送
、タンク貯蔵、ボイラー直接燃焼が可能である。The water slurry of coal powder obtained by adding the dispersion stabilizer of the present invention has good fluidity with little increase in viscosity even at high concentrations and maintains long-term dispersion stability, so it can be transported by pipeline, stored in tanks, and directly fired in boilers. is possible.
以下、実施例について具体的に説明するが、本発明はこ
れらの実施例に限定されるものではない。Examples will be specifically described below, but the present invention is not limited to these examples.
く石炭−水スラリーの調整〉
第1表に示す石炭粉末に、第2表に示す原料比及び重合
条件にて得られた分散安定剤の水溶液を第3表に示す如
き添加量となるように添加し、ホモミキサー(特殊機化
工業源)で5分間分散攪拌して石炭−水スラリーを調製
した。Preparation of coal-water slurry> An aqueous solution of a dispersion stabilizer obtained under the raw material ratio and polymerization conditions shown in Table 2 was added to the coal powder shown in Table 1 in the amount shown in Table 3. The mixture was added and dispersed and stirred for 5 minutes using a homomixer (Tokushu Kika Kogyo Gen) to prepare a coal-water slurry.
なお、ホルムアルデヒドとしてはホルマリン(37%ホ
ルムアルデヒド水)を用いホルマリンモル比は、ホルム
アルデヒド分としてフェノールスルホン酸ナトリウム塩
に対して2モルとした。また反応時のpHは第一工程が
8.5、第二工程が10.5であった。Note that formalin (37% formaldehyde water) was used as the formaldehyde, and the formalin molar ratio was 2 moles relative to sodium phenol sulfonate as formaldehyde. The pH during the reaction was 8.5 in the first step and 10.5 in the second step.
く流動性の評価〉
上記で得られた石炭−水スラリーについて25℃に於い
て粘度(cps)を測定した。粘度の低いものが流動性
の良い事を示している。Evaluation of fluidity> The viscosity (cps) of the coal-water slurry obtained above was measured at 25°C. Low viscosity indicates good fluidity.
く石炭−水スラリーの安定性の評価〉
スラリーの安定性は該スラリーを調製後30日および6
0日間静置した後、直径5[l]mのステンレス棒(重
量50g)をスラリー中に静かに入れその沈降状態を観
察した。その結果を第3表に示す。Evaluation of stability of coal-water slurry> The stability of the slurry was evaluated after 30 days and 6
After standing still for 0 days, a stainless steel rod (50 g in weight) with a diameter of 5 [l]m was gently placed into the slurry and its sedimentation state was observed. The results are shown in Table 3.
*200メツシュ以下(%)
〈結果〉
第3表実施例の結果から明らかなように、本発明の分散
剤を用いて調整した石炭−水スラリーは粘度低下による
流動性が顕著であり、且つ分散安定性においても30日
、60日経過後も原審のない優れたスラリーであること
を示している。*200 mesh or less (%) <Results> As is clear from the results of the examples in Table 3, the coal-water slurry prepared using the dispersant of the present invention has remarkable fluidity due to a decrease in viscosity, and has a high dispersion property. In terms of stability, it was also shown that the slurry was excellent with no defects even after 30 and 60 days.
本発明によれば、従来のナフタレンスルホン酸ナトリウ
ムホルマリン縮合物やポリスチレンスルホン酸ナトリウ
ム等に比べより高い分散安定性及び流動性を石炭−水ス
ラリーに付与し得る分散安定剤が得られる。According to the present invention, a dispersion stabilizer capable of imparting higher dispersion stability and fluidity to a coal-water slurry than conventional sodium naphthalene sulfonate formalin condensate, sodium polystyrene sulfonate, etc. can be obtained.
また、本発明の分散安定剤は石炭に限定するものではな
く固体燃料類、例えば石油コークス等にも使用が可能で
ある。Further, the dispersion stabilizer of the present invention is not limited to coal, but can also be used for solid fuels such as petroleum coke.
出願人代理人 古 谷 馨(外3名) ■Applicant's agent: Kaoru Furutani (3 others) ■
Claims (1)
対して4〜30モル%のフェノールとをアルカリ性でホ
ルムアルデヒドと共縮合させた共重縮合物を含有するこ
とを特徴とする石炭粉末の水スラリー用分散安定剤。Stable dispersion of coal powder for water slurry, characterized by containing a copolycondensate of a phenol sulfonate and 4 to 30 mol% of phenol based on the phenol sulfonate, co-condensed with formaldehyde in an alkaline environment. agent.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2204828A JP2733126B2 (en) | 1990-07-31 | 1990-07-31 | Dispersion stabilizer for water slurry of coal powder |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2204828A JP2733126B2 (en) | 1990-07-31 | 1990-07-31 | Dispersion stabilizer for water slurry of coal powder |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0488095A true JPH0488095A (en) | 1992-03-19 |
JP2733126B2 JP2733126B2 (en) | 1998-03-30 |
Family
ID=16497059
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2204828A Expired - Lifetime JP2733126B2 (en) | 1990-07-31 | 1990-07-31 | Dispersion stabilizer for water slurry of coal powder |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2733126B2 (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0984031A1 (en) * | 1998-02-20 | 2000-03-08 | Nagoya Oilchemical Co., Ltd. | Molding material, inner material using the same, and method for producing the same |
JP2013079472A (en) * | 2011-10-05 | 2013-05-02 | Nicca Chemical Co Ltd | Flame retardant agent for polyester-based fiber, flame-retardant processing method for polyester-based fiber, and flame-retardant polyester-based fiber |
CN110194823A (en) * | 2019-05-24 | 2019-09-03 | 中国矿业大学 | A kind of graft copolymer coal water slurry dispersant and preparation method thereof |
CN115490822A (en) * | 2022-08-22 | 2022-12-20 | 上海抚佳精细化工有限公司 | Anionic condensation polymer and preparation method and application thereof |
-
1990
- 1990-07-31 JP JP2204828A patent/JP2733126B2/en not_active Expired - Lifetime
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0984031A1 (en) * | 1998-02-20 | 2000-03-08 | Nagoya Oilchemical Co., Ltd. | Molding material, inner material using the same, and method for producing the same |
EP0984031A4 (en) * | 1998-02-20 | 2000-12-13 | Nagoya Oilchemical | Molding material, inner material using the same, and method for producing the same |
JP2013079472A (en) * | 2011-10-05 | 2013-05-02 | Nicca Chemical Co Ltd | Flame retardant agent for polyester-based fiber, flame-retardant processing method for polyester-based fiber, and flame-retardant polyester-based fiber |
CN110194823A (en) * | 2019-05-24 | 2019-09-03 | 中国矿业大学 | A kind of graft copolymer coal water slurry dispersant and preparation method thereof |
CN115490822A (en) * | 2022-08-22 | 2022-12-20 | 上海抚佳精细化工有限公司 | Anionic condensation polymer and preparation method and application thereof |
CN115490822B (en) * | 2022-08-22 | 2024-03-12 | 上海抚佳精细化工有限公司 | Anionic polycondensate and preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
JP2733126B2 (en) | 1998-03-30 |
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