EP0426127B1 - Apparatus zur Behandlung viskoser Flüssigkeiten - Google Patents

Apparatus zur Behandlung viskoser Flüssigkeiten Download PDF

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Publication number
EP0426127B1
EP0426127B1 EP90120831A EP90120831A EP0426127B1 EP 0426127 B1 EP0426127 B1 EP 0426127B1 EP 90120831 A EP90120831 A EP 90120831A EP 90120831 A EP90120831 A EP 90120831A EP 0426127 B1 EP0426127 B1 EP 0426127B1
Authority
EP
European Patent Office
Prior art keywords
blade
shafts
agitator
blade members
viscous liquid
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.)
Expired - Lifetime
Application number
EP90120831A
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English (en)
French (fr)
Other versions
EP0426127A1 (de
Inventor
Haruyuki Nishimi
Mamoru Mishima
Shoji Morinaga
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.)
Sumitomo Heavy Industries Ltd
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Sumitomo Heavy Industries Ltd
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Filing date
Publication date
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Publication of EP0426127A1 publication Critical patent/EP0426127A1/de
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Publication of EP0426127B1 publication Critical patent/EP0426127B1/de
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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/05Stirrers
    • B01F27/11Stirrers characterised by the configuration of the stirrers
    • B01F27/115Stirrers characterised by the configuration of the stirrers comprising discs or disc-like elements essentially perpendicular to the stirrer shaft axis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/60Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/60Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis
    • B01F27/70Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/60Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis
    • B01F27/70Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms
    • B01F27/701Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms comprising two or more shafts, e.g. in consecutive mixing chambers
    • B01F27/702Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with paddles, blades or arms comprising two or more shafts, e.g. in consecutive mixing chambers with intermeshing paddles
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01FMIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
    • B01F27/00Mixers with rotary stirring devices in fixed receptacles; Kneaders
    • B01F27/60Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis
    • B01F27/73Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with rotary discs
    • B01F27/731Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a horizontal or inclined axis with rotary discs with two or more parallel shafts provided with perpendicularly mounted discs, e.g. lens shaped, one against the other on each shaft and in circumferential contact with the discs on the other shafts, e.g. for cleaning

Definitions

  • the present invention relates to a viscous liquid processor and, more particularly, to a viscous liquid processor which includes two horizontal shafts.
  • viscous liquid processors of this kind are roughly classified into a continuous type and a batch type.
  • a horizontal viscous liquid processor of the continuous type is structured in such a manner that a material to be processed is supplied from an-inlet provided on one longitudinal end of a casing, moves toward an outlet provided on the other longitudinal end (making so-called piston flows) while the degree of reaction or the like is increased, and is discharged from the outlet after a desired process has been completed (see Japanese Patent Examined Publication No. 47-27179, Japanese Utility Model Examined Publication Nos. 51-45559 and 54-5805, Japanese Patent Examined Publication Nos. 61-59173 and 62-50179). Consequently, the viscous liquid processor of this continuous type has a characteristic that the degree of reaction varies in accordance with the position of the flowing material in the course from the inlet to the outlet.
  • a horizontal viscous liquid processor of the batch type is structured in such a manner that one dose of a material to be processed, which has been calculated previously, is fed into a casing, and discharged to the outside after a desired process has been completed, another dose of the material being fed into the casing anew (see Japanese Patent Unexamined Publication No. 49-73759 and the like). Therefore, the viscous liquid processor of this batch type has a characteristic that the degree of reaction varies in accordance with the length of processing time, so that it will be preferred that the material at any position in the casing can be simultaneously reacted uniformly in a certain length of processing time.
  • a viscous liquid processor requires such functions as uniform shearing and agitation of viscous liquid, circulation or delivery of the liquid in one direction, cooperative scraping of the liquid by agitator blades (self-cleaning), replacement of the liquid surface.
  • these functions especially the shearing/agitation function and the liquid delivering function can be simultaneously effected by means of disk-like agitator blades having a structure as simple as possible.
  • a viscous liquid processor comprising a horizontal casing which includes side walls on both longitudinal ends thereof, two shafts extending in parallel within the casing along its longitudinal direction and rotatably supported between the side walls, whereby one of said shafts is a low-speed shaft and the other shaft is a high-speed shaft and the two shafts are rotated in opposite directions, and a plurality of agitator blades fixed on each of the shafts and spaced along its longitudinal direction so that the blades on one shaft enter the spaces between the blades on the other shaft, the casing having a bottom portion corresponding to the tracks of the outer peripheral ends of the agitator blades, wherein each of the agitator blades is generally formed in a thick disk-like configuration having a plurality of thick radially sectorial blade members which are made by machining the intermediate portions cut away from a thick disk at the same intervals, such a thick blade member having a parallelogrammic cross section so that
  • This embodiment is a batch-type viscous liquid processor including two horizontal shafts for agitating viscous liquid of high-molecular polymer or the like for the purpose of a process such as polycondensation, bulk polymerization, solution polymerization, gas-liquid reaction and monomer degradation.
  • reference numeral 1 denotes a casing which has a bottom portion corresponding to the tracks of outer peripheral ends of agitator blades which will be explained later. At the center of this bottom portion, a rib 1a is formed along the longitudinal direction of the casing 1.
  • a low-speed shaft 2 and a high-speed shaft 3 extending in parallel are provided horizontally between and through side walls 1b on both longitudinal ends of the casing 1, and the shafts 2 and 3 are rotated in opposite directions to each other, as indicated by arrows p and q, to agitate the liquid to be processed between these shafts from the upper side.
  • the shafts 2, 3 are provided with the agitator blades.
  • the casing 1 can be sealed with a lid (not shown) in order to perform a reaction process in a vacuum condition or a pressurized condition of reaction gas.
  • a low-speed agitator blade 4 is of a shape as shown in Fig. 4. An odd-number (e.g., five) of such blades at different phases are securely fixed on the low-speed shaft 2 so as to form a tandem pattern.
  • Each of the low-speed agitator blades 4 is constituted of a plurality of (e.g., four) radially sectorial blade members 5 which are made by machining the intermediate portions cut away from a thick disk at the same intervals.
  • a jacket through which a thermal medium flows is formed on the inside of each of the sectorial blade members 5 if necessary. As illustrated in Fig.
  • the cross section of the sectorial blade member 5 is formed to be a parallelogram so that the leading end of the blade member as viewed in a direction of rotation of the low-speed agitator blade 4 defines an acute angle, and that the opposite end of the same end surface as the leading end defines an obtuse angle.
  • the acute-angled end serves as a shearing edge 5a, and its inclined surface has a liquid delivering function to an, extent of a thickness (h) thereof.
  • the low-speed agitator blades 4 are each securely fixed on the low-speed shaft 2 through a boss 6.
  • scraper rod 7 is fastened on the trailing outer peripheral end of each sectorial blade member 5 of the low-speed agitator blade 4 as viewed in the direction of rotation, and the other end of the scraper rod 7 is fastened on the leading outer peripheral end of each sectorial blade member 5 of the adjacent agitator blade 4.
  • scraper rods 7 are located in a continuous spiral pattern.
  • each of the high-speed agitator blades 8 is constituted of a plurality of (e.g., two) wide sectorial blade members 10 (Fig. 5), which are substantially the same as the above-mentioned sectorial blade members 5, formed by machining the intermediate portions cut away from a thick disk, and each of the high-speed agitator blades 9 is constituted a plurality of (e.g., two) small blade members 11 (Fig. 6) having a substantially rectangular shape which are formed by further machining the sectorial blade members.
  • the agitator blades 8, 9 are each securely fixed on the high-speed shaft 3 through a boss 13a in such a manner that the blade members 10, 11 are located at phases which are deviated from each other at an angle of 90°C.
  • a jacket through which a thermal medium flows is formed on the inside of each of the blade members 10, 11 if necessary.
  • the cross section of the blade member 10, 11 is formed to be a parallelogram so that the leading end of the blade member as viewed in a direction of rotation of the high-speed agitator blade 8, 9 defines an acute angle, and that the opposite end of the same end surface as the leading end defines an obtuse angle in the same manner as the above-described sectorial blade member 5 for low-speed agitation.
  • Side surfaces of these blade members 10, 11 are inclined in a direction reverse to a direction of inclination of the inclined surfaces of the sectorial blade member 5 of the low-speed agitator blade 4.
  • scraper rod 12 is fastened on the trailing outer peripheral end of each small blade member 11 of the high-speed agitator blade 9 as viewed in the direction of rotation, and the other end of the scraper rod 12 is fastened on the trailing outer peripheral end of each sectorial blade member 10 of the adjacent agitator blade 8 as viewed in the direction of rotation, while no scraper rod is provided between a sectorial blade member 10 and a small blade member 11 which are adjacent to each other with the above-mentioned low-speed agitator blade 4 interposed therebetween.
  • scraper rods 12 are located in a discontinuous spiral pattern whose lead has the same direction as the lead of the spiral pattern formed by the scraper rods 7 of the low-speed shaft 2.
  • the sectorial blade members 5 of the low-speed agitator blades 4 are located between such unconnected blade members 10 and 11.
  • gate-like agitators formed of the blade members 10, 11 of the high-speed agitator blades 8, 9 and the scraper rods 12 are relatively rotatably provided between the sectorial blade members 5 of two adjacent low-speed agitator blades 4. The condition of these blade members which are rotated across each other when they are viewed from the side wall 1b is illustrated in an area A of Fig. 2.
  • each agitator blade of the high-speed shaft 3 has two blade members or more, and that each agitator blade of the low-speed shaft 2 has an integer times as many blade members as the agitator blade of the high-speed shaft 3, with the rotational ratio being set to be an inverse number of the number of the blade members.
  • the sectorial blade members 5 of the low-speed agitator blades 4 and the blade members 10, 11 of the high-speed agitator blades 8, 9 together with the scraper rods 7, 12 are relatively rotated, with the blade members on one shaft entering the spaces defined by the blade members on the other shaft in a region between the shafts.
  • the viscous liquid is circulated within the casing 1 in a single direction indicated by arrows a, b′, c, b of Fig. 1 under the influence of the liquid delivering functions of the respective inclined surfaces of the blade members 5, 10, 11 in directions indicasted by the arrows a, c.
  • the viscous liquid since portions of the viscous liquid which are adhered on the inner peripheral surfaces of the casing 1 are affected by the liquid delivering function while they are scraped for self-cleaning by means of the scraper rods 7, 12 which are located in the spiral patterns having the identical lead, the above-described circulation of the liquid is promoted. Further, when these scraper rods 7, 12 leave the viscous liquid and raise some of the liquid, hanging thin films of the liquid are formed, and consequently, the gas-liquid contact face can be enlarged to improve the efficiency of deaeration.
  • Diameter of a disk for an agitator blade 134 mm Size of a casing: 236 mmW x 168 mmH x 612 mmL Liquid quantity: 5.6 l Reaction temperature: 330°C max Viscous liquid: A polyester resin in an intermediate state to be further polymerized and collected as a highly polymerized resin.
  • Figs. 11 and 12 illustrate the second embodiment, and the same component parts as those of the first embodiment are denoted by the same reference numerals in these drawings, explanation of such component parts being omitted except for the differences.
  • an inlet is formed on one of the side walls 1b of the casing 1 (left in Fig. 11), and an outlet is formed on the other (right in Fig. 11), so that highly viscous liquid supplied from the inlet is processed while it is continuously delivered in a direction indicated by arrows a' in the drawing, and is discharged from the outlet.
  • the low-speed shaft 2 is provided with low-speed agitator blades 4A each including sectorial blade members 5A which are substantially the same as the low-speed agitator blades 4 of the first embodiment described above, and the high-speed shaft 3 is provided with high-speed agitator blades 14 in a tandem pattern each including sectorial blade members 10A similar to the sectorial blade members 10 of the first embodiment shown in Fig. 5, with the inclined surfaces of the sectorial blade members 5A of the low-speed agitator blades 4A being inclined in the same direction as the inclined surfaces of the sectorial blade members 10A of the high-speed agitator blades 14.
  • scraper rods 15 are fastened on the outer peripheral ends of the sectorial blade members 5A of the low-speed agitator blades 4A so as to form a continuous spiral pattern in the same manner as the first embodiment.
  • each of the high-speed agitator blades 14 is securely fixed on the high-speed shaft 3 at a phase deviated from a phase of the adjacent agitator blade at an angle of 90°C, and one end of a scraper rod 16 is fastened on the leading outer peripheral end of each sectorial blade member 10A of the high-speed agitator blade 14 as viewed in a direction of rotation, while the other end of the scraper rod 16 is fastened on the leading outer peripheral end of each sectorial blade member 10A of the adjacent agitator blade 14, such scraper rods 12 being located in a discontinuous spiral pattern.
  • the viscous liquid supplied from the inlet will be continuously agitated and stirred, traveling in the direction of the arrows a' toward the outlet.
  • each low-speed agitator blade has four sectorial blade members 5, 5A, and each high-speed agitator blade has two blade members 10, 11, 10A.
  • the invention will not exclude other combinations of the numbers of these blade members if they meet a ratio 2:1.
  • each low-speed agitator blade may have six blade members, and each high-speed agitator blade may have three blade members.
  • the low-speed shaft 2 and the high-speed shaft 3 extending in parallel are rotated in such a manner that the agitator blades on both shafts will agitate the liquid between these shafts from the upper side in the above embodiments.
  • the low-speed shaft 2 and the high-speed shaft 3 may be rotated the other way round to cause the agitator blades to agitate the liquid between these shafts from the lower side.
  • the agitator blades on both shafts are rotated to agitate the viscous liquid between the two shafts from the upper or lower side, the viscous liquid between the shafts is pressed against the casing.
  • Each of the inclined surfaces of the sectorial blade members made of machined disks serves to deliver the liquid to an extent of the thickness thereof, and the opposite inclined surface draws the liquid due to the negative pressure generated thereon.
  • each of the agitator blades is thick, so that a jacket for thermal treatment can be formed within the agitator blade.
  • each of the blade members has a cross section of a parallelogram, the surfaces of the blade member are smooth and flat, thereby preventing the viscous liquid from adhering to the blade surfaces, while enabling effective scraping by the scraper rods.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mixers Of The Rotary Stirring Type (AREA)
  • Polyesters Or Polycarbonates (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)

Claims (5)

  1. Ein Gerät zur Behandlung viskoser Flüssigkeiten, mit einem horizontalen Gehäuse (1), das Seitenwände (1b) an dessen beiden längsseitigen Enden umfaßt,
       zwei Wellen (2,3), die sich parallel zueinander im Gehäuse (1) entlang dessen Längsrichtung erstrecken und drehbar zwischen den Seitenwänden gelagert sind, wobei eine der Wellen (2,3) eine Welle (2) für niedrige Geschwindigkeit und die andere Welle eine Welle (3) für hohe Geschwindigkeit ist und die beiden Wellen (2,3) in entgegengesetzten Richtungen gedreht werden, und
       einer Anzahl von Agitator-Flügeln oder -Schaufeln (4,8,9), die an jeder der Wellen (2,3) angebracht und entlang deren Längsrichtung beabstandet sind, derart, daß die Flügel (4,8,9) an der einen Welle in die Zwischenräume zwischen den Flügeln (4,8,9) an der anderen Welle eintreten, wobei das Gehäuse (1) einen Bodenabschnitt aufweist, der den Bahnen der Außenumfangsenden der Agitator-Flügel (4,8,9) entspricht und jeder der Agitator-Flügel (4,8,9) allgemein in einer dicken, scheibenartigen Konfiguration mit einer Anzahl dicker radialer abschnittsweiser Flügel- bzw. Schaufelelemente (5,10,11) ausgebildet ist, die durch maschinelle (spanabhebende) Abtragung von Zwischenbereichen in gleichen Intervallen aus einer dicken Scheibe hergestellt sind, wobei ein solches dickes radiales abschnittsweises Flügel- bzw. Schaufelelement (5,10,11) einen parallelogrammartigen Querschnitt besitzt, so daß das Vorderende jedes Flügel- bzw. Schaufelelements (5,10,11) in Richtung dessen Drehung gesehen einen spitzen Winkel festlegt.
  2. Ein Gerät zur Behandlung viskoser Flüssigkeiten gemäß Anspruch 1, wobei die Anzahl der Flügel- bzw. Schaufelelemente (5,10,11) jedes an einem der beiden Wellen (2,3) angebrachten Agitator-Flügels bzw. jeder Agitator-Schaufel (4,8,9) zwei oder mehr beträgt und die Anzahl der Flügel- bzw. Schaufelelemente (5,10,11) jedes an der anderen Welle angebrachten Agitator-Flügels bzw. jeder Agitator-Schaufel (4,8,9) ein ganzzahliges Vielfaches der Anzahl der Flügel- bzw. Schaufelelemente (5,10,11) des an der einen Welle angebrachten Agitator-Flügels bzw. der Agitator-Schaufel ist, wobei ein Verhältnis relativer Drehungen der beiden Wellen (2,3) auf einen inversen Wert eines Verhältnisses der Anzahlen der Flügel- bzw. Schaufelelemente (5,10,11) der Agitator-Flügel bzw. Agitator-Schaufeln (4,8,9) ist.
  3. Ein Gerät zur Behandlung viskoser Flüssigkeiten gemäß Anspruch 1, wobei die schrägen Seiten der jeweiligen parallelogrammartigen Querschnitte der Flügel- bzw. Schaufelelemente (5,10,11) der an den beiden Wellen (2,3) angebrachten Agitator-Flügel bzw. Agitator-Schaufeln (4,8,9) in umgekehrten Richtungen zueinander geneigt sind.
  4. Ein Gerät zur Behandlung viskoser Flüssigkeiten gemäß Anspruch 1, wobei die schrägen Seiten der jeweiligen parallelogrammartigen Querschnitte der Flügel- bzw. Schaufelelemente (5,10,11) der an den beiden Wellen (2,3) angebrachten Agitator-Flügel bzw. Agitator-Schaufeln (4,8,9) in derselben Richtung geneigt sind.
  5. Ein Gerät zur Behandlung viskoser Flüssigkeiten gemäß Anspruch 1, weiterhin umfassend Abstreiferstäbe (7,12), die die Außenränder bzw. -umfänge der Anzahl der an jeder der beiden Wellen (2,3) angebrachten Agitator-Flügel bzw. Agitator-Schaufeln (4,8,9) verbinden, derart, daß ein Spiralmuster gebildet wird.
EP90120831A 1989-11-02 1990-10-30 Apparatus zur Behandlung viskoser Flüssigkeiten Expired - Lifetime EP0426127B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP1287150A JP2925599B2 (ja) 1989-11-02 1989-11-02 高粘度液処理装置
JP287150/89 1989-11-02

Publications (2)

Publication Number Publication Date
EP0426127A1 EP0426127A1 (de) 1991-05-08
EP0426127B1 true EP0426127B1 (de) 1994-12-28

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Application Number Title Priority Date Filing Date
EP90120831A Expired - Lifetime EP0426127B1 (de) 1989-11-02 1990-10-30 Apparatus zur Behandlung viskoser Flüssigkeiten

Country Status (7)

Country Link
EP (1) EP0426127B1 (de)
JP (1) JP2925599B2 (de)
KR (1) KR0144482B1 (de)
CN (1) CN1035237C (de)
AU (1) AU640737B2 (de)
CA (1) CA2029082C (de)
DE (1) DE69015577T2 (de)

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CN101837273A (zh) * 2009-03-19 2010-09-22 上海亦晨信息科技发展有限公司 组合式三腔混合反应釜及其方法
KR101066273B1 (ko) * 2009-06-12 2011-09-20 안동철 유체 가열장치
JP6081137B2 (ja) * 2012-10-22 2017-02-15 株式会社新日南 混練装置
JP6083733B2 (ja) * 2012-11-12 2017-02-22 日工株式会社 連続式ミキサ
JP6771908B2 (ja) * 2016-03-14 2020-10-21 株式会社栗本鐵工所 混練撹拌装置用撹拌翼構造
CN108236910B (zh) * 2018-01-31 2020-04-10 浙江大学 一种搅拌装置和一种卧式双轴自清洁反应器
CN111225737B (zh) * 2018-09-05 2022-02-25 田中控股株式会社 液体搅拌装置
JP6870018B2 (ja) * 2019-03-18 2021-05-12 株式会社栗本鐵工所 混練撹拌装置用撹拌翼構造
JP2020044536A (ja) * 2019-12-20 2020-03-26 株式会社栗本鐵工所 混練撹拌装置用撹拌翼構造
CN111185131B (zh) * 2020-02-25 2024-01-26 扬州瑞邦科技发展有限公司 一种异形高粘聚合物熔体连续生产装置
CN113279076B (zh) * 2021-06-30 2022-03-29 邱群子 一种超高分子量聚乙烯纤维预牵热水溶剂收集装置
CN114367222A (zh) * 2022-01-18 2022-04-19 青岛大厨四宝餐料有限公司 一种用于老母鸡粉调味料加工用卧式混合罐

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EP0144092B1 (de) * 1983-12-05 1988-10-12 Dipl.-Ing. H. List Industrielle Verfahrenstechnik Misch- und Knetmaschine
WO1988004198A1 (en) * 1986-12-11 1988-06-16 Heinz Nienhaus Multi-axial mixing drier or reactor
CH680196A5 (de) * 1988-02-16 1992-07-15 List Ag

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KR910009329A (ko) 1991-06-28
AU7027591A (en) 1992-08-20
JP2925599B2 (ja) 1999-07-28
DE69015577T2 (de) 1995-05-11
CN1051682A (zh) 1991-05-29
CN1035237C (zh) 1997-06-25
JPH03151033A (ja) 1991-06-27
KR0144482B1 (ko) 1998-07-15
CA2029082C (en) 1999-12-21
CA2029082A1 (en) 1991-05-03
AU640737B2 (en) 1993-09-02
EP0426127A1 (de) 1991-05-08
DE69015577D1 (de) 1995-02-09

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