CN1081944C - 珠状产物的水基形成 - Google Patents

珠状产物的水基形成 Download PDF

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Publication number
CN1081944C
CN1081944C CN96109413A CN96109413A CN1081944C CN 1081944 C CN1081944 C CN 1081944C CN 96109413 A CN96109413 A CN 96109413A CN 96109413 A CN96109413 A CN 96109413A CN 1081944 C CN1081944 C CN 1081944C
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product
mixture
temperature
eutectic
water
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CN1151905A (zh
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小威廉·爱德华·梅耶尔斯
弗瑞丹·艾勃德萨肯
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Corteva Agriscience LLC
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Drexel University College of Medicine
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2/00—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic
    • B01J2/02—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops
    • B01J2/06—Processes or devices for granulating materials, e.g. fertilisers in general; Rendering particulate materials free flowing in general, e.g. making them hydrophobic by dividing the liquid material into drops, e.g. by spraying, and solidifying the drops in a liquid medium
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
    • A01N33/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds containing nitrogen-to-oxygen bonds
    • A01N33/18—Nitro compounds
    • A01N33/20—Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group
    • A01N33/22—Nitro compounds containing oxygen or sulfur attached to the carbon skeleton containing the nitro group having at least one oxygen or sulfur atom and at least one nitro group directly attached to the same aromatic ring system
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/22—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof the nitrogen atom being directly attached to an aromatic ring system, e.g. anilides
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Abstract

公开了由低熔物质制备无粉珠状产物的方法。本发明方法特别适用于产物制备最后步骤是水洗的加工方法。

Description

珠状产物的水基形成
本发明涉及由低熔物料制备的珠化的，自由流动，无粉固体产物的方法。更详细地，本发明涉及制备珠粒工业级农业化学产物的方法。
在许多化学产物，特别是低熔点化学产物的制备过程中，产物以玻璃体，通常是粘结块形式形成。由于其很难处理，而使其不易包装运输或在后续加工过程中使用。例如，这些物料在运输容器中可形成单一的固体块，而很难移动进行进一步加工这些低熔点材料。这些缺点时常增加了后续加工过程的费用和所需时间。因此，需一种制备易于处理或可加工形式的低熔点产物的方法
JP 62 132854A中公开了制备颗粒化马来酰亚胺的方法，其中液化的马来酰亚胺在至少低于其熔点10℃的温度下，滴加入表面活性剂溶液中。使熔化的马来酰亚胺固化。颗粒大小由液滴大小决定。然而，本方法必须小心地使熔化的马来酰亚胺以控制的速度(滴加)，费时地进入第二容器中的表面活性剂溶液中。此外，本方法需两个容器，其一用于熔化马来酰亚胺，另一用于表面活性剂溶液。我们已经发现，这种马来酰亚胺进入表面活性剂溶液的受控进料可在单一容器中由低熔点物料和水的后混合搅拌进行替代。
本发明提供了形成珠状产物的方法，包括：在高于低熔点物料熔点的温度下形成含低熔点物料和水的混合物；以低熔点产物在混合物内形成液滴的速度混合上述混合物；将混合物冷至液滴固化成珠粒的温度；从混合物中分离珠状物。我们惊异地发现当混合物冷到液滴固化温度时，液滴不会改型或附集成单一块状。本方法的优点之一是它产出含极小的粒子或粉尘形式的珠状产物。此方法特别适用那些制备产品最后一道步骤是水洗的加工方法。
本发明的方法可以应用于任何在珠状物可以保存的温度下形成固体的低熔点产物。适宜的产物包括药物，农业化学品，生物杀伤剂，染料，和其它有机化学品。这些产物可以是单一组分或是几种组分的复合物。用本发明方法形成珠状物的农业化学品包括：fenbuconazole，腈菌唑(myclobutanil)，乙氧氟草醚(oxyfluorfen)，以及敌稗(propanil)。
在本申请中除非有特别说明，“低熔产物”或“产物”意指在任何操作压力下，具有低于水沸点的熔点的物质或组合物，或含水混合物。所述产物优选具有50°～100℃的熔点；更优选为65°～90℃。使用本发明方法优势的产物的最大水溶性依赖于可接受的回收和所用加工条件。通常，产物的水溶性越低，珠状产物的回收率就越高。具有重量百分比低于1％的水溶性的产物是最优选的。
包含低熔产物和水的混合物根据所用的加工方法，可用设备，以及产物和混合物的物理化学性质，以不同方式形成。混合物中可包含表面活性剂，特别是当需要表面活性剂进行混合时。假如其中的产物本身具有某些表面活性性质，则不必再加其它的表面活性剂。如使用，表面活性剂可以在水加人之前、之后或同时加入到混合物中。也可以在产物熔化前、熔化期间、或熔化后加入。优选地，在水和产物合并之前将表面活性剂溶于水中。
所用的形成混合物加工顺序不是严格的。组分可以用任何顺序、任何低于水或水/表面活性剂溶液沸点以下的温度进行混合。如果组分在低于产物熔点以下的温度下混合，则将混合物加热直至产物熔化。优选地，将水加到熔化的产物中。最优选地，添加水在等于或大于熔化产物的温度下进行。混合物中各组分的比率依赖于组分(包括杂质)的物理/化学性质，产物制造方法，所用设备的能力和容量，以及珠状产物的预想回收情况，可用一个与产物和其制造方法的类似的最小实验确定。
各种搅动方法可以用于混合形成的混合物。可接受的方法包括搅拌，摇动，和鼓转。搅拌搅动是优选的。搅拌速度对由本方法制得的珠状物的最终大小的确定是非常重要的。所述速度应足够高到在混合物中形成产物液滴，但不要高到产生乳化。因此，所述速度将依赖于特定产物，产物和水的比率，以及假如使用的表面活性剂，温度，以及所用的加工设备。本领域技术人员很容易通过最小量的实验获得适宜的速度。通常，当速度增加时，珠状物将变小。甚至，优选的速度是不产生乳化的最高速度，但不能比预想的珠状物小。一旦珠状物固化，搅拌通常减小或一起停止。
所用的冷却混合物成珠的速度不严格要求。为了使加工时间最省，加工设备允许的最快冷却速度是优选的。这种速度最重要的冷却因素通常是设备的冷却容量。
一旦形成珠状物，可以用任何由液体中分离固体的标准技术，从混合物的其它组分中分离出来。过滤，离心或倾滗是优选的技术；最优选的是过滤或离心。也可使用这些技术的组合，这决定于所用的特定加工设备和其容量。
下列实施例详细描述本发明的某些实施方案。实施例1工业品乙氧氟草醚珠状物的制备
将乙氧氟草醚工业品(95％纯，400g，熔点约85℃)熔化，然后与热水(1200ml，温度大于85℃)在顶部搅拌器搅拌下混合。加人Triton×100非离子表面活性剂。停止加热混合物在继续搅拌下用冰浴冷却。用真空过滤分离形成的固体珠。实施例2工业品乙氧氟草醚珠状物的制备
将工业品乙氧氟草醚(95％纯，300g，熔点约85℃)熔化，然后在顶部搅拌器搅拌下与热水(900ml温度大于85℃)混合。加人Triton×100非离子表面活性剂(0.25g)。停止加热，继续搅拌下用冰浴冷却。用真空过滤分离形成的固体珠。实施例3工业品敌稗珠状物的制备
将工业品敌稗(约98％纯，70g，熔点约85-88℃)在顶部搅拌器搅拌下与热水(140ml，温度大于85℃)混合。将混合物加热到88℃，加入Triton×100非离子表面活性剂(1.4g)。停止加热，将混合物在搅拌下冷却。用真空过滤分离形成的固体珠。所得珠状物在真空炉内干燥4小时，得到67.35g的干燥珠状物(96.2％回收率)。

Claims (7)

1.形成珠状产物的方法，包括：
a.在高于低熔产物熔点的温度下形成含低熔物质和水的混合物；
b.以在混合物内形成低熔产物液滴的搅拌速度混合混合物；
c.将混合物冷却到使液滴固化形成珠状物的温度；以及
d.从混合物中分离生成的珠状物。
2.根据权利要求1的方法，其中形成步骤包括：
a.a.熔化低熔产物；
a.b.向熔化产物中加入含水溶液。
3.根据权利要求1的方法，其中混合物中进一步包含表面活性剂。
4.根据权利要求2的方法，其中溶液中进一步包含表面活性剂。
5.根据权利要求2的方法，其中溶液的温度至少是熔化产物的温度。
6.根据权利要求1的方法，其中低熔产物是农业化学品。
7.根据权利要求6的方法，其中低熔产物选自fenbuconazole，腈菌唑，乙氧氟草醚和敌稗。
CN96109413A 1995-08-18 1996-08-16 珠状产物的水基形成 Expired - Fee Related CN1081944C (zh)

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US08/516,841 US5688742A (en) 1995-08-18 1995-08-18 Water based formation of a beaded product
US516,841 1995-08-18
US516841 1995-08-18

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US (1) US5688742A (zh)
EP (1) EP0759324A3 (zh)
JP (1) JPH09124405A (zh)
KR (1) KR970009558A (zh)
CN (1) CN1081944C (zh)
AU (1) AU719931B2 (zh)
BR (1) BR9603407A (zh)
CA (1) CA2183137A1 (zh)
HU (1) HUP9602276A3 (zh)
IL (1) IL119001A (zh)
SG (1) SG52831A1 (zh)
TW (1) TW322409B (zh)
ZA (1) ZA966965B (zh)

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DE19816853A1 (de) * 1998-04-16 1999-10-21 Fraunhofer Ges Forschung Verfahren zur Herstellung von Partikeln schmelzfähiger Treib- und Explosivstoffe
JP5292105B2 (ja) * 2007-01-11 2013-09-18 株式会社カネカ 補酵素ｑ１０粒子の製造方法
WO2015136461A2 (en) * 2014-03-12 2015-09-17 Basf Se Improved catalyzed soot filter

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0106634A1 (en) * 1982-10-08 1984-04-25 THE PROCTER &amp; GAMBLE COMPANY Bodies containing bleach activators
JPS62132854A (ja) * 1985-12-06 1987-06-16 Nippon Oil & Fats Co Ltd 顆粒状マレイミド化合物の製造法
JPH01167850A (ja) * 1987-12-24 1989-07-03 Toyo Ink Mfg Co Ltd カプセルトナー

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DE1229501B (de) * 1962-03-14 1966-12-01 Herbert James Elliott Verfahren zur Aufbereitung von Schwefel oder schwefelhaltigen Produkten
DE1467203B2 (de) * 1964-09-09 1974-03-28 Bundesrepublik Deutschland Vertr. Durch Den Bundesminister Der Verteidigung, 5300 Bonn Verfahren zum Herstellen von kugeligem Ammoniumnitrat
US4024210A (en) * 1973-09-20 1977-05-17 Canadian Occidental Petroleum, Ltd. Sulfur pelletizing
GB1594471A (en) * 1978-04-24 1981-07-30 Mason & Co Ltd Vaughan Production of beads from molten or thermoplastic material
JPS6213285A (ja) * 1985-06-28 1987-01-22 Hitachi Electronics Eng Co Ltd 厚膜モジユ−ル基板用ロ−ダ・アンロ−ダ

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0106634A1 (en) * 1982-10-08 1984-04-25 THE PROCTER &amp; GAMBLE COMPANY Bodies containing bleach activators
JPS62132854A (ja) * 1985-12-06 1987-06-16 Nippon Oil & Fats Co Ltd 顆粒状マレイミド化合物の製造法
JPH01167850A (ja) * 1987-12-24 1989-07-03 Toyo Ink Mfg Co Ltd カプセルトナー

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IL119001A0 (en) 1996-11-14
HUP9602276A3 (en) 2000-03-28
TW322409B (zh) 1997-12-11
ZA966965B (en) 1997-02-19
BR9603407A (pt) 1998-05-12
US5688742A (en) 1997-11-18
KR970009558A (ko) 1997-03-27
JPH09124405A (ja) 1997-05-13
MX9603153A (es) 1997-07-31
CN1151905A (zh) 1997-06-18
AU719931B2 (en) 2000-05-18
CA2183137A1 (en) 1997-02-19
HU9602276D0 (en) 1996-10-28
AU6088796A (en) 1997-02-20
SG52831A1 (en) 1998-09-28
HUP9602276A2 (en) 1997-03-28
EP0759324A3 (en) 1997-12-29
EP0759324A2 (en) 1997-02-26
IL119001A (en) 2000-02-29

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