CN1839106A - 改进尿素抗碎强度、抗冲击性与可压缩性的方法和尿素组合物 - Google Patents
改进尿素抗碎强度、抗冲击性与可压缩性的方法和尿素组合物 Download PDFInfo
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Abstract
一种通过向熔融的尿素中添加化合物改进尿素颗粒的抗碎强度、抗冲击性和可压缩性的方法,其中所述化合物包括聚乙烯类化合物和由1-10个碳原子和1-10个极性有机基团组成的有机分子。
Description
本发明涉及一种通过在尿素内添加组合物而改进尿素颗粒的抗碎强度、抗冲击性和可压缩性的方法。
通常已知尿素颗粒易在生产、存储和运输期间粉碎。如果尿素肥料在较高温度例如超过40℃被移入储罐或储料船,则高达25wt%的尿素颗粒可被压碎。即使尿素颗粒本身几乎不吸收任何水分,并且实际上不易结块,但高百分比的被压碎颗粒确实导致粉尘问题并具有很强的结块趋向。
还已知许多化学品组合物能被用作添加剂以改进抗碎强度、结块趋向和耐潮性。甲醛、六亚甲基四胺和甲醛/尿素冷凝产品被用作抗碎强度改进剂,同时使用聚(乙酸乙烯酯)/表面活性剂组合(US4812158)来减少结块趋向。所有这些添加剂必须或者以相对大的量添加,或者其毒性特征使它们难于处理。而且,当将尿素用于例如树脂生产的工业应用时,如在聚(乙酸乙烯酯)/表面活性剂中使用表面活性组分导致泡沫增加,同时甲醛衍生物在生产三聚氰胺时是不适合的。相对于使用添加剂还存在一个较大的差异。甲醛衍生物和根据本发明的组合物被掺合到尿素熔体中。然而,聚乙酸乙烯酯/表面活性剂组合被喷洒到预先形成的颗粒上。
GB-A-1217106描述了一种通过使用具有高分子量的聚(乙烯醇)作为防结块添加剂来减少尿素结块的方法。更具体而言,根据这种方法,添加剂的水溶液被掺合到尿素的水溶液中。优选地,基于尿素重量计,0.005到5wt%的添加剂被掺合。根据所提供的实施例,最初尿素水溶液的浓度是80%;在掺合添加剂溶液后,高温下浓度高达95%,其后,尿素可通过冷却结晶。
专利WO02/20471公开了一种把聚乙烯类化合物和无机盐的组合与尿素熔体掺合的方法。与未经处理的尿素相比,所得颗粒的抗碎强度和抗冲击性都出现改进。另外,发现尿素的可压缩性显著减小。后一观测结果可以是很大的优点,因为尿素颗粒在存储时将更不易变形。然而,在尿素中引入无机盐,例如硫酸铝,导致在水中溶解尿素时,pH值的较大降低。这可成为在工业应用中,例如树脂生产中使用尿素的重要的不利情况。
因此,本发明的目的是提供一种方法,通过该方法获得抗碎强度和抗冲击性得到改进的以及低可压缩性的尿素,并且通过该方法克服上述的缺点。
已经发现将包括聚乙烯类化合物和由1-10个碳原子和1-10个极性有机基团组成的有机分子的组合物添加到尿素熔体中使得所形成的尿素颗粒的硬度和可压缩性都得到改进。有机组分可单独地添加到熔融的尿素中或者与聚乙烯类化合物的水溶液一起添加到熔融的尿素中。根据优选的实施方案,小的有机分子的添加总量为至多10wt%,基于尿素总量计。本申请涉及尿素、聚乙烯类化合物和含羟基的小分子的的紧密混合物,与未经处理的尿素相比,其导致组合物的硬度增加和可压缩性降低。优选地,聚乙烯类化合物为聚乙烯醇,而发现优选的小的极性有机分子是季戊四醇。
为了证明本发明的效果,进行了大量实验,使用的方法对生产和检验所生产的尿素颗粒质量有代表性。
通过混合尿素熔体和添加剂的水溶液(浓度在实验中说明)制备尿素丸。通过使熔融的尿素滴落在脂族油(在80℃粘度为10-50厘泊)中而形成尿素丸。在结晶后,将这些丸从油中取走并用三氯甲烷洗涤以除去油。筛分这些丸以获得特定尺寸。这些丸在流化床中在约40℃干燥1小时。把它们收集并保存在密封的烧瓶中直到测量抗碎强度和抗冲击性。
通过掺合添加剂的水溶液(浓度在实验中说明)和由99.7w/w%尿素和0.3w/w%水组成的尿素熔体生产尿素小球。其后,通过使熔融的尿素滴分别地从1厘米的高度落到玻璃板上形成尿素小球。在固化后,将这些小球从玻璃板上刮下,用筛子除去细屑。收集这些小球并保存在密封的瓶子中直到测量可压缩性。
抗碎强度通过IFDC S-115方法测定。抗冲击性通过IFDC S-118方法测量。
可压缩性的测定如下。在室温,用40g尿素小球装满内直径为3厘米的透明圆管。在圆管上带有柱塞,通过该柱塞将约600kPa的压力施加到样品上。在施加过压后立即测量尿素柱的高度,并在24小时之后再次测量尿素柱的高度。由这两个值计算高度的相对差(高度(%)),其为可压缩性的量度。
实验1
按照上述的方法,将大量小的极性有机分子与聚乙烯醇混合并加到尿素熔体中。
添加剂 | 抗碎强度(N) | 抗冲击性(破碎%) | 可压缩性(Δ高度,%) |
空白尿素 | 13 | 75 | 16 |
1000ppm 12wt%的PVA(>99%水解的)水溶液 | 18 | 30 | 11 |
1000ppm 12wt%的PVA和1m/m%的乙二醇水溶液 | 21 | 35 | 9 |
1000ppm 12wt%的PVA和1m/m%的甘油水溶液 | 21 | 32 | 9 |
1000ppm 12wt%的PVA和1m/m%的1,4-丁二醇水溶液 | 18 | 36 | 10 |
1000ppm 12wt%的PVA和1m/m%的二羟甲基脲水溶液 | 21 | 29 | 8 |
1000ppm 12wt%的PVA和1m/m%的季戊四醇水溶液 | 20 | 19 | 3 |
1000ppm 12wt%的PVA和1m/m%的双羟基甲基丙酸水溶液 | 19 | 32 | 4 |
1000ppm 12wt%的PVA和1m/m%的酒石酸水溶液 | 17 | 39 | 5 |
1000ppm 12wt%的PVA和1m/m%的柠檬酸水溶液 | 14 | 46 | 9 |
1000ppm 12wt%的PVA和1m/m%的乳酸水溶液 | 16 | 55 | 7 |
1000ppm 12wt%的PVA和1m/m%的丁二酸水溶液 | 15 | 50 | 6 |
1000ppm 12wt%的PVA和1m/m%的葡糖酸水溶液 | 14 | 49 | 9 |
该实验表明尿素颗粒的硬度和可压缩性都在添加聚乙烯类化合物和小的极性有机分子后得到改进。发现在这些极性组分中季戊四醇的作用最显著。
实验2
为选择性能最佳的聚乙烯类化合物,将不同的聚合物与季戊四醇一起被添加到尿素熔体中。
添加剂 | 抗碎强度(N) | 抗冲击性(破碎%) | 可压缩性(Δ高度,%) |
空白尿素 | 13 | 75 | 16 |
1000ppm 12wt%的PVA(>99%水解的)水溶液 | 18 | 30 | 11 |
1000ppm 12wt%的PVA(>99%水解的)和1wt%的季戊四醇水溶液 | 20 | 19 | 3 |
1000ppm 12wt%的PVA(83%水解的)水溶液 | 19 | 28 | 9 |
1000ppm 12wt%的PVA(83%水解的)和1wt%的季戊四醇水溶液 | 19 | 19 | 4 |
1000ppm 12wt%的聚马来酸水溶液 | 15 | 60 | 14 |
1000ppm 12wt%的聚马来酸和1wt%的季戊四醇水溶液 | 17 | 51 | 9 |
该实验证明向尿素熔体中添加聚乙烯类化合物和季戊四醇的组合使尿素颗粒具有低的可压缩性和良好的强度。当使用聚乙烯醇和季戊四醇的组合时,得到最佳的性能。
实验3
为发现聚乙烯类化合物和小的极性有机化合物之间的最适比率,将季戊四醇与聚乙烯醇以不同比例混合并加到尿素熔体中。
添加剂 | 抗碎强度(N) | 抗冲击性(破碎%) | 可压缩性(Δ高度,%) |
空白尿素 | 13 | 75 | 16 |
1000ppm 12wt%的PVA水溶液 | 18 | 30 | 11 |
1000ppm 12wt%的PVA和0.1m/m%的季戊四醇水溶液 | 20 | 28 | 8 |
1000ppm 12wt%的PVA和0.5m/m%的季戊四醇水溶液 | 21 | 25 | 5 |
1000ppm 12wt%的PVA和1.0m/m%的季戊四醇水溶液 | 20 | 19 | 3 |
1000ppm 12wt%的PVA和1.5m/m%的季戊四醇水溶液 | 19 | 21 | 3 |
1000ppm 12wt%的PVA和2.0m/m%的季戊四醇水溶液 | 20 | 23 | 4 |
1000ppm 12wt%的PVA和3.0m/m%的季戊四醇水溶液 | 18 | 26 | 6 |
1000ppm 12wt%的PVA和5.0m/m%的季戊四醇水溶液 | 18 | 30 | 7 |
当由12m/m%的聚乙烯醇开始时,在0.5-1.5m/m%的季戊四醇存在下获得最佳结果。
实验4
为测定实验3的最佳混合物的最佳剂量水平,将不同量的该混合物被添加到尿素熔体中。
添加剂 | 抗碎强度(N) | 抗冲击性(破碎%) | 可压缩性(Δ高度,%) |
空白尿素 | 13 | 75 | 16 |
500ppm 12wt%PVA和1.0wt%的季戊四醇水溶液 | 12 | 57 | 16 |
750ppm 12wt%PVA和1.0wt%的季戊四醇水溶液 | 15 | 42 | 9 |
1000ppm 12wt%PVA和1.0wt%的季戊四醇水溶液 | 20 | 19 | 3 |
1250ppm 12wt%PVA和1.0wt%的季戊四醇水溶液 | 21 | 24 | 4 |
1500ppm 12wt%PVA和1.0wt%的季戊四醇水溶液 | 20 | 21 | 4 |
2000ppm 12wt%PVA和1.0wt%的季戊四醇水溶液 | 19 | 27 | 5 |
3000ppm 12wt%PVA和1.0wt%的季戊四醇水溶液 | 20 | 32 | 8 |
该实验表明包含聚乙烯醇和季戊四醇的混合物的最优剂量为750-1500ppm,按尿素与尿素熔体的重量比。
Claims (14)
1.一种通过向熔融的尿素中添加化合物改进尿素颗粒的抗碎强度、抗冲击性和可压缩性的方法,其特征在于所述化合物包括聚乙烯类化合物和由1-10个碳原子和1-10个极性有机基团组成的有机分子。
2.根据权利要求1的方法,其特征在于极性有机基团选自羧酸、羟基、胺和/或酰胺基团。
3.根据权利要求1或2的方法,其特征在于极性有机化合物由2-5个碳原子组成。
4.根据权利要求1到3中任一项的方法,其特征在于所述化合物是季戊四醇。
5.根据权利要求1到4中任一项的方法,其特征在于待添加的极性有机化合物的总量是至多1wt%,基于尿素的量计。
6.根据权利要求1到5中任一项的方法,其特征在于待添加的极性有机化合物的总量是5-100ppm,基于尿素的量计。
7.根据权利要求1到6中任一项的方法,其特征在于所用的聚乙烯类添加剂的通式为(CHX-CHY)n,其中n=4-1000,并且X和Y彼此独立地选自氢原子和极性有机基团。
8.根据权利要求1到7中的任一项的方法,其特征在于所用的添加剂具有权利要求7中所定义的通式,其中所述极性有机基团选自羧基、酯基、羟基、胺基和酰胺基。
9.根据权利要求1到8中任一项的方法,其特征在于如权利要求7或8中所述添加尿素添加剂,其中X为氢原子并且Y基本上由羟基组成。
10.根据权利要求1到9中任一项的方法,其特征在于至少70%,优选至少95%的Y由羟基组成。
11.根据权利要求1到10中任一项的方法,其特征在于使用浓度为0.5到25wt%的尿素添加剂水溶液。
12.根据权利要求1到11中任一项的方法,其特征在于使用浓度为1到20wt%的尿素添加剂水溶液。
13.根据权利要求1到12中任一项的方法,其特征在于使用浓度为100到10000ppm,优选500到3000ppm的尿素添加剂水溶液。
14.作为尿素添加剂用于根据前述权利要求中任一项的方法中的组合物。
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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PCT/EP2003/011070 WO2005040069A1 (en) | 2003-10-06 | 2003-10-06 | Method of improving the crushing strength, impact resistance and compressibility of urea, and urea composition |
Publications (2)
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CN1839106A true CN1839106A (zh) | 2006-09-27 |
CN100391905C CN100391905C (zh) | 2008-06-04 |
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CNB2003801104900A Expired - Lifetime CN100391905C (zh) | 2003-10-06 | 2003-10-06 | 改进尿素抗碎强度、抗冲击性与可压缩性的方法和尿素组合物 |
Country Status (10)
Country | Link |
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US (1) | US8084642B2 (zh) |
EP (1) | EP1670735B1 (zh) |
CN (1) | CN100391905C (zh) |
AU (1) | AU2003268922A1 (zh) |
BR (1) | BR0318532A (zh) |
CA (1) | CA2541089C (zh) |
EG (1) | EG26745A (zh) |
ES (1) | ES2391089T3 (zh) |
PL (1) | PL206119B1 (zh) |
WO (1) | WO2005040069A1 (zh) |
Families Citing this family (5)
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NO321761B1 (no) | 2004-06-30 | 2006-07-03 | Yara Int Asa | Fremgangsmate for a forbedre knusestyrke og redusere stovdannelse og tendens til kaking av urea, partikler, og anvendelse av karbohydrater og eventuelt polyvinylforbindelser som additiv til smeltet urea |
US20060025079A1 (en) * | 2004-08-02 | 2006-02-02 | Ilan Sutskover | Channel estimation for a wireless communication system |
EP1843992B1 (en) * | 2005-01-14 | 2013-08-14 | YARA International ASA | Urea composition having reduced compressibility, caking and dust formation, and process for its preparation |
WO2014080352A1 (en) * | 2012-11-21 | 2014-05-30 | Ballance Agri-Nutrients Limited | Fertiliser composition |
EP4015492A1 (en) * | 2020-12-21 | 2022-06-22 | Yara International ASA | Method for the manufacture of a urea-based composition comprising the addition of an additive in an aqueous form |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
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US3195999A (en) * | 1963-07-24 | 1965-07-20 | Grace W R & Co | Composition consisting essentially of crystalline urea coated with sugar |
DE1916089A1 (de) | 1968-04-01 | 1969-12-18 | Kurashiki Rayon Company Ltd | Nichtzusammenballende Harnstoff-Zusammensetzung |
US4063919A (en) | 1976-06-17 | 1977-12-20 | Monsanto Company | Fertilizer rods |
JPH0696475B2 (ja) | 1986-05-21 | 1994-11-30 | 花王株式会社 | 肥料の固結防止剤 |
IT1250045B (it) * | 1991-11-07 | 1995-03-30 | Butterfly Srl | Procedimento per la produzione di alcool polivinilico plastificato e suo impiego per la preparazione di composizioni termoplastiche biodegradabili a base di amido. |
US6217630B1 (en) * | 1999-05-03 | 2001-04-17 | Cargill, Incorporated | Conditioned fertilizer product, method for conditioning fertilizer, and method for using conditioned fertilizer product |
EP1315688A2 (en) | 2000-09-07 | 2003-06-04 | Holland Novochem B.V. | Method of improving the crushing strength and the impact resistance of urea, and urea composition |
-
2003
- 2003-10-06 WO PCT/EP2003/011070 patent/WO2005040069A1/en active Application Filing
- 2003-10-06 CA CA2541089A patent/CA2541089C/en not_active Expired - Lifetime
- 2003-10-06 AU AU2003268922A patent/AU2003268922A1/en not_active Abandoned
- 2003-10-06 EP EP03750693A patent/EP1670735B1/en not_active Expired - Lifetime
- 2003-10-06 ES ES03750693T patent/ES2391089T3/es not_active Expired - Lifetime
- 2003-10-06 US US10/574,815 patent/US8084642B2/en active Active
- 2003-10-06 PL PL379866A patent/PL206119B1/pl unknown
- 2003-10-06 BR BRPI0318532-0A patent/BR0318532A/pt active IP Right Grant
- 2003-10-06 CN CNB2003801104900A patent/CN100391905C/zh not_active Expired - Lifetime
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2006
- 2006-04-04 EG EGPCTNA2006000323A patent/EG26745A/en active
Also Published As
Publication number | Publication date |
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US20070131011A1 (en) | 2007-06-14 |
CA2541089C (en) | 2011-12-06 |
PL206119B1 (pl) | 2010-07-30 |
EP1670735B1 (en) | 2012-08-01 |
CN100391905C (zh) | 2008-06-04 |
CA2541089A1 (en) | 2005-05-06 |
WO2005040069A1 (en) | 2005-05-06 |
EG26745A (en) | 2014-07-15 |
BR0318532A (pt) | 2006-09-12 |
AU2003268922A1 (en) | 2005-05-11 |
EP1670735A1 (en) | 2006-06-21 |
PL379866A1 (pl) | 2006-11-27 |
ES2391089T3 (es) | 2012-11-21 |
US8084642B2 (en) | 2011-12-27 |
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