CN1182228C - 生物柴油和生物燃料油的添加剂 - Google Patents
生物柴油和生物燃料油的添加剂 Download PDFInfo
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- C10L1/10—Liquid carbonaceous fuels containing additives
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- C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
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Abstract
本发明涉及一种共聚物，由以下单体组分构成：a)48-98wt%的式I化合物，b)2-30wt%一种或多种式II的含氧甲基丙烯酸酯，以及0-30wt%式III甲基丙烯酸酯或苯乙烯，其中a)-c)的量共为100wt%。该共聚物适合作为柴油燃料和生物柴油的添加剂。
Description
很长时间以来，技术热点一方面在于替代性，即非化石来源的能源，另一方面在于所谓的“再生原料”。其中有特别是植物油，即脂肪酸酯，一般情况下是三甘油酯，它们一般归于生物可降解且环境相容性能源。菜籽油/种子油可看作此类油的基本型。追溯至二十年代就提出应用菜籽油作润滑油(参照D.Holde，Chemiker-Zeitung1922(1)，第4页)。
通过环境法规的确立取消了造成农业和普遍生态趋向结构变化而得到的植物油及改性植物油，如菜籽油甲基酯(RME)作为再生原料，从而增加了作为动力燃料和加热油的意义。对实际中使用植物油甲基酯(PME)重要的是它既使在较低温度下仍有的流动性能。与常规的柴油动力燃料相似，生物柴油在低温时也会出现动力燃料组分的结晶，这有损于可过滤性和可流动性。所谓的生物柴油和生物燃料油是指石油化学为基础的柴油和再生原料的混合物，这里，石油化学的动力燃料组分和通过再生原料生产的组分的混合比例可以有变化，并不固定。柴油动力燃料的可过滤性通常由CFPP-值表征(冷滤器堵塞点，按DIN EN116确定)。
根据所基于的植物油的类型和改性或处理的质量，无添加剂的PME的CFPP值典型地在0℃和-15℃之间。所以估计用作生物柴油在低温时会有动力燃料过滤器堵塞的现象。对于冬用柴油，例如规定其CFPP值小于-20℃(DIN EN 590)。传统的柴油燃 料的流动性改善剂，在PME中只显示了有限的有效性，结果经常从根本上CFPP的温度只有微不足道的降低。
DE 196 03 696(Rhm GmbH，1997-08-07)涉及以聚(甲基)丙烯酸烷基酯共齐聚物为基础的抗乳化剂。抗乳化剂的作用是破坏乳液。它们可被应用来例如在液压油中将油和水分开。
FR 2 589 866(Institut Francais Du Petrole，1987-05-15)描述了由短链(C1-Cu)，中等长度链(C8-C14)和长链(C16-C22)的甲基丙烯酸的酯和乙烯基芳香族组分的共聚物。
EP 418 610(Rhm GmbH)描述了适用于改善润滑油的粘度指数的共聚物，它由80-99.5重量份的(甲基)丙烯酸烷基酯(其用长链醇酯化)与0.5-20重量份的官能化(甲基)丙烯酸烷基酯形成，这里甲基丙烯酸通过C2-C6的醇或多重烷氧基化的残基来完成酯化。共聚物具有良好的剪切稳定性和良好的在润滑油中的分散和清洁效果。
EP 543 356(Rhm GmbH)描述了一种工艺，用于生产低温性能改善的组合物，用作动力燃料或作菜籽油甲基酯为基础的润滑油。通过按本发明的工艺可制得一种混合物，它能够使冷过滤器堵塞点降低至-15℃至-20℃。
无添加剂的长链脂肪酸酯上产生的沉淀物被过滤出去。
US-PS 5,578,090(BRI)描述了一种生物柴油添加剂，由脂肪酸烷基酯、甘油酯和三甘油酯组成。此添加剂具有生物可降解性。
EP 691 355(Rhm GmbH)叙述了具有分散作用的以甲基丙烯酸和有一定乙烯氧或丙烯氧单元的烷氧化醇的酯为基础的共齐聚物和共聚物，它用润滑油中的无灰分散剂。有分散作用的共齐聚物和共聚物的分子量在1,000和300,000道尔顿之间。
除了良好的低温性能外，被极性含氧共单体改性的PAMA还预期具有良好的分散性能，也就是能有积极的清洁效果，有助于避免燃料供应系统(例如喷嘴)中的沉淀物。
DE 39 30 142和DE 44 23 358描述了可与之匹敌的含氧分散的PAMA和它作为润滑油添加剂的良好的分散作用，同时与防渗材料有突出的相容性。
这些申请并未考虑到预想不到的作为用于生物柴油和生物燃料油的添加剂的良好效果。
因此，本发明的任务是，提供一种改善一元醇脂肪酸酯，特别是菜籽油甲基酯的低温性能，特别是冷过滤器堵塞点的添加剂。例如在菜籽油甲基酯情况下力争达到CFPP从-15℃降低到-22℃。
由此还存在另一个任务，开发一种高效添加剂，来控制RME的CFPP。特别是在典型的小于等于1wt％的经济的添加剂加入量的条件下应该会达到确保CFPP值调节至小于等于-20℃。其它对于低温流动性重要的性能如倾点(ASTM-D-92)和凝固点(按Herzog MC 852测定)，应当可通过这种添加剂同时受到有利的影响。
本发明范围内存在着又一个任务是，制备由按本发明的聚合物和共聚物与生物柴油组成的混合物，它们适于低温下使用。
很久以来为了降低润滑油和其它矿物油产品的倾点技术上就应用聚合化合物，所谓的倾点抑制剂”，它们具有共同的结构特征，即具有许多烷基侧链，其中通常有8-40个，特别是10-28个碳原子。特别的一类是长链醇的聚(甲基)丙烯酸酯(PAMA添加剂)。
这一任务可通过按权利要求1的特征的共聚物来解决。
已发现，一定的被含氧极性基团功能化的PAMA具有未预料到的良好的改善CFPP的作用。这里涉及带有含羟基和/或含醚基的共单体的PAMA，共单体例如，甲基丙烯酸-2-羟基乙酯，甲基丙烯酸羟丙酯，甲基丙烯酸-2-[2-(2-乙氧基乙氧基)乙氧基]乙酯，甲基丙烯酸-2-乙氧基乙酯，甲基丙烯酸-2-甲氧基乙酯，乙氧化的十三碳醇(羰基合成醇C13+20C6)的甲基丙烯酸酯，例如MARLIPAL 013/200(Hüls)，甲氧基聚乙二醇的甲基丙烯酸酯，例如Carbowax 350或Carbowax 750(UnionCarbide)，以及相应的丙烯酸酯，例如丙烯酸-2-羟基乙酯，丙烯酸-2-羟基丙酯。
含羟基基团的单体，例如甲基丙烯酸-2-羟基乙酯得到的效果最好。这种添加剂具有除上面所述之外的在倾点和凝固点方面的良好的作用。
按本发明可使用的聚合物的生产可以用所有已熟悉的聚合方法完成。
实施例
下面的实施例描述了本发明的实施。
1.应用的材料：
AMA-I＝Dobanol 25L(Shell)的甲基丙烯酸酯：
含约80％正醇组分的C12至C15醇的异构体混合物
AMA-II＝硬脂肪醇的甲基丙烯酸酯：
由正-C16和正-C18醇的混合物
AMA-III＝甲基丙烯酸异癸酯
HEMA＝甲基丙烯酸-2-羟基乙酯
HPMA＝甲基丙烯酸-2-羟基丙酯
EOMA＝有平均乙氧化度为20的乙氧化异十三碳醇的甲基丙烯酸
酯
ETGMA＝甲基丙烯酸乙基三甘醇酯
IN-1＝过新戊酸叔丁基酯(75％的烃溶液)
IN-2＝过异壬酸叔丁基酯
IN-3＝过辛酸叔丁基酯
DDM＝十二碳烷基硫醇
Shell Fluid 2613＝烃类混合物(动力学粘度40℃时为5.1mm2/s)
DIOA＝Vestinol OA＝己二酸二(2-乙基己基)酯
RME＝菜籽油甲基酯
ALK-1＝C12至C15醇Lial 125＝Enichem Augusta的商品
RME1-3＝不同种的菜籽油，市场上可买到。它们在对生物产品来说
通常的变动范围内的性能上不同。
2.生产70％添加剂的一般规范：
在一个带有油浴加热，弓形搅拌器，回流冷凝管，内温度计和N2导管的2升三口烧瓶中先加入一种反应混合物，包括：
700.00g单体混合物(组成参见表1)
77.78g溶剂A(参见表1)
X g DDM(参见表1)
混合物在加入约10g干冰下进行惰性气覆盖，额外在N2下加热至75℃，接着加入1.4g IN-1和1.4g IN-2的混合物。当超过最高温度即约120℃后，混合料进一步保持在120℃。第一批引发剂加入后4小时和6小时分别再次加入1.4g IN-2，仍再保持在120℃下4小时。之后用222.22g溶剂B加以稀释。(这里也可能是不同溶剂的混合物。
用作溶剂A或溶剂B可以是所有已知的矿物油为基础的油类(烷烃类，环烷烃类，芳香族类)，也可以是合成液体(酯油，PAO，醇)以及天然油，例如菜籽油或PME，也可考虑它们的混合物。得到了透明粘性的添加剂浓缩物。表1给出了制备实施例的组成和表征。
本申请共聚物的混合物中可含有烷烃类矿物油或环烷烃类矿物油或芳香族的矿物油或酯类油或改性或未改性生物油或天然植物或动物油或上述油类的混合物。
表1：
添加剂组成和表征
| 产品实施例号 | 单体混合物组成，wt％ | DDM#)含量，wt％ | 溶剂A | 溶剂B | 粘度KV100[mm2/s] | ηsp/c[ml/g] |
| 1 | AMA1-AMA2-HEMA79.3-14.7-6.0 | 1.5 | DIOA | RME1 | 123 | 12.2 |
| 2 | AMA1-AMA2-HEMA76.8-14.2-9 | 1.5 | DIOA | RME1 | 159 | 12.9 |
| 3 | AMA1-AMA2-EOMA73.8-13.7-12.5 | 1.0 | DIOA | RME1 | 116 | 15.0 |
| 4 | AMA1-AMA2-ETGMA79.3-14.7-6.0 | 1.5 | DIOA | RME1 | 93 | 11.9 |
| 5 | AMA1-AMA2-ETGMA73.8-13.7-12.5 | 1.5 | DIOA | RME1 | 98 | 12.4 |
| 6 | AMA1-AMA-2-ETGMA67.5-12.5-20.0 | 1.1 | DIOA | RME1 | 166 | 16.9 |
#)基于单体混合物计
*)用0.3％IN-3代替IN-1/IN-2混合物制备
MIX1＝Lial 125/Shell Fluid 2613＝50/50
表1：
添加剂组成和表征
| 产品实施例号 | 单体混合物组成，wt％ | DDM#)含量，wt％ | 溶剂A | 溶剂B | 粘度KV100[mm2/s] | ηsp/c[ml/g] |
| 7 | AMA1-AMA2-HPMA79.3-14.7-6.0 | 1.5 | DIOA | RME1 | 117 | 12.2 |
| 8 | AMA1-AMA2-HPMA76.8-14.2-9.0 | 1.5 | DIOA | RME1 | 135 | 12.6 |
| 9 | AMA1-HEMA91-9 | 1.5 | DIOA | RME1 | 174 | 13.3 |
| 10 | AMA1-HEMA91-9 | 0.3*) | DIOA | RME1 | 33.1 | |
| 11 | AMA1-HEMA91-9 | 133 | ShellFluid2613 | ShellFluid2613 | 244 | |
| 12 | AMA1-AMA2-AMA3-MMA-HEMA88-1-1-1-9 | ShellFluid2613 | Mix1 | 149 |
#)基于单体混合物计
*)用0.3％IN-3代替IN-1/IN-2混合物制备
MIX1＝Lial 125/Shell Fluid 2613＝50/50
基于这些添加剂低的实时粘度KV100，它们也有很好的加工性。特性粘度ηsp/c是不同种添加剂分子量的量度。
表2至表4显示了这种新型添加剂在不同种市场上通用的RME类中的效果，分别与可得到的现有技术中的PAMA添加剂VIS COPLEX10310(RohMax GmbH)相比较。用这种新型含氧添加剂可在不同RME质量毫无疑问地使CFPP的值达到-20℃以下。同时可得到较好的倾点和凝固点值。
表2：
含氧添加剂在RME-1中的作用
| 添加剂 | RME中添加剂浓度[％] | RME | 倾点[℃](ASTM-D-97) | FP[℃](Herzog MC852) | CFPP[℃](EN116) |
| - | - | RME-1 | -12 | -16.5 | -15 |
| Viscoplex10-310 | 0.20.51.0 | RME-1 | -30-42-42 | -14-18-19 | |
| 实施例1 | 0.20.51.0 | RME-1 | -39-42-42 | -42.3-42.6-42.7 | -16-18-20 |
| 实施例2 | 0.20.51.0 | RME-1 | -42-42-42 | -44.9-45.4-44.1 | -16-22-25 |
| 实施例3 | 0.20.51.0 | RME-1 | -39-42-42 | -42.7-43.1-42.0 | -15-19-20 |
| 实施例4 | 0.20.51.0 | RME-1 | -36-42-42 | -43.2-45.0-43.5 | -17-19-27 |
表2：
含氧添加剂在RME-1中的作用
| 添加剂 | RME中添加剂浓度[％] | RME | 倾点[℃](ASTM-D-97) | FP[℃](Herzog MC852) | CFPP[℃](EN116) |
| 实施例5 | 0.20.51.0 | RME-1 | -39-39-42 | -44.5-44.1-43.4 | -16-16-23 |
| 实施例6 | 0.20.51.0 | RME-1 | -39-39-39 | -44.8-45.0-45.0 | -15-18-20 |
| 实施例7 | 0.20.51.0 | RME-1 | -39-39-39 | -33.2-40.7-43.7 | -16-21-20 |
| 实施例8 | 0.20.51.0 | RME-1 | -39-39-39 | -44.5-45.1-44.2 | -16-18-21 |
| 实施例9 | 0.20.51.0 | RME-1 | -39-42-45 | -44.0-45.1-47.6 | -19-23-14 |
表3：
含氧添加剂在RME-2中的作用
| 添加剂 | RME中添加剂浓度[％] | RME | 倾点[℃](ASTM-D-97) | FP[℃](Herzog MC852) | CFPP[℃](EN116) |
| - | - | RME-2 | -9 | -13.9 | -10 |
| Viscoplex10-310 | 0.20.51.0 | RME-2 | -24-30-39 | -29.9-40.6-40.9 | -14-13-16 |
| 实施例9 | 0.20.51.0 | RME-2 | -18-39-33 | -25.5-41.5-43.0 | -14-24-25 |
| 实施例10 | 0.20.51.0 | RME-2 | -18-27-36 | -26.5-40.6-41.9 | -12-15-23 |
表4：
含氧添加剂在RME-3中的作用
| 添加剂 | RME中添加剂浓度[％] | RME | 倾点[℃](ASTM-D-97) | FP[℃](Herzog MC852) | CFPP[℃](EN116) |
| - | - | RME-3 | -9 | -13.3 | -17 |
| Viscoplex10-310 | 0.20.51.0 | RME-3 | -24-36-39 | -33.8-41.5-41.7 | -12-15-18 |
| 实施例9 | 0.20.51.0 | RME-3 | -24-39-27 | -27.3-41.0-42.2 | -16-21-25 |
| 实施例11 | 0.20.51.0 | RME-3 | -24-39-36 | -27.6-41.0-42.5 | -16-20-25 |
| 实施例12 | 0.20.51.0 | RME-3 | -24-39-39 | -28.8-41.3-42.6 | -16-22-20 |
Claims (9)
1.一种生物柴油，含有由下列单体组分构成的共聚物：
a)48-98wt％的分子式I的化合物
这里，R1-H或CH3
R2＝链长为8-30的烷基，也可能为支化的烷基；
b)2-30wt％的分子式II的一种或多种含氧化合物
这里，R1＝与分子式I中意义相同
R3＝H或CH3
R4＝H或CH3
R5＝为H或一个1-20个碳原子的烷基，这里原子团也可支化，或通过一个或多个芳香基取代的1-20个碳原子的烷基，
n＝在1和30之间以及
c)0～30wt％的分子式III的甲基丙烯酸酯
这里，R5＝C1～C4烷基
或苯乙烯
此处，a)～c)的量总计为100wt％，以及共聚物的含量为0.005-5wt％。
2.权利要求1的生物柴油，其特征为，单体b)是甲基丙烯酸羟乙酯。
3.权利要求1的生物柴油，其特征为，单体b)是甲基丙烯酸羟丙酯。
4.权利要求1的生物柴油，其特征为，共聚物的平均分子量在3,000和1,000,000之间。
5.权利要求1的生物柴油，其特征为，功能共单体1b完全或部分接枝到已制备的PAMA聚合物上。
6.权利要求5的生物柴油，其特征为，分子式I中R2是链长为10～20个碳原子的枝化或未枝化醇。
7.生物柴油，含有由权利要求1～6之一的共聚物和烷烃类矿物油或环烷烃类矿物油或芳香族矿物油或酯类油或改性或未改性生物油或天然植物或动物油或上述油类的混合物所组成的混合物。
8.燃料，由传统的矿物油燃料和按权利要求1-6之一的生物柴油的混合物组成，其中，生物柴油占5wt％到100wt％，混合物中含有共聚物的量为0.005wt％到5wt％。
9.由下列单体组分构成的共聚物用于改善生物柴油与生物燃料的低温流动性能和CFPP值的用途：
a)48-98wt％的分子式I的化合物
这里，R1＝H或CH3
R2＝链长为8-30的烷基，也可能为支化的烷基；
b)2-30wt％的分子式II的一种或多种含氧化合物
这里，R1＝与分子式I中意义相同
R3＝H或CH3
R4＝H或CH3
R5＝为H或一个1-20个碳原子的烷基，这里原子团也可支化，或通过一个或多个芳香基取代的1-20个碳原子的烷基，
n＝在1和30之间以及
c)0～30wt％的分子式III的甲基丙烯酸酯
这里，R5＝C1～C4烷基
或苯乙烯
此处，a)～c)的量总计为100wt％。
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| DE19751501 | 1997-11-21 | ||
| DE19751501.0 | 1997-11-21 | ||
| DE19847423A DE19847423A1 (de) | 1997-11-21 | 1998-10-14 | Additiv für Biodiesel und Biobrennstofföle |
| DE19847423.7 | 1998-10-14 |
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| BE600725A (zh) * | 1960-02-29 | |||
| BE629904A (zh) * | 1962-03-23 | |||
| EP0153176B1 (en) * | 1984-02-21 | 1991-11-27 | Exxon Research And Engineering Company | Middle distillate compositions with improved cold flow properties |
| DE3930142A1 (de) * | 1989-09-09 | 1991-03-21 | Roehm Gmbh | Dispergierwirksame viskositaets-index-verbesserer |
| DE4000753A1 (de) * | 1990-01-12 | 1991-07-18 | Roehm Gmbh | Kraftuebertragungsfluessigkeit auf basis mineraloel |
| DE4040317A1 (de) * | 1990-12-17 | 1992-06-25 | Henkel Kgaa | Mischungen von fettsaeureniedrigalkylestern mit verbesserter kaeltestabilitaet |
| DE4137269A1 (de) * | 1991-11-13 | 1993-05-19 | Roehm Gmbh | Motorenoele mit hohem dispergiervermoegen |
| DE4138429A1 (de) * | 1991-11-22 | 1993-05-27 | Roehm Gmbh | Verfahren zur herstellung von kompositionen mit verbessertem tieftemperaturverhalten |
| CA2090200C (en) * | 1992-03-20 | 2005-04-26 | Chung Y. Lai | Ashless dispersant polymethacrylate polymers |
| AU674052B2 (en) * | 1993-05-24 | 1996-12-05 | Lubrizol Corporation, The | Pour point depressant treated fatty acid esters as biodegradable, combustion engine fuels |
| FR2726828A1 (fr) * | 1994-11-10 | 1996-05-15 | Rohm & Haas France | Additifs dispersants ameliorant l'indice de viscosite pour huiles lubrifiantes |
| US5578090A (en) * | 1995-06-07 | 1996-11-26 | Bri | Biodiesel fuel |
-
1998
- 1998-11-18 EP EP98962357A patent/EP1032620B1/de not_active Expired - Lifetime
- 1998-11-18 AU AU17554/99A patent/AU1755499A/en not_active Abandoned
- 1998-11-18 US US09/530,972 patent/US6409778B1/en not_active Expired - Lifetime
- 1998-11-18 JP JP2000522183A patent/JP4056699B2/ja not_active Expired - Fee Related
- 1998-11-18 PL PL98340468A patent/PL340468A1/xx unknown
- 1998-11-18 WO PCT/EP1998/007410 patent/WO1999027037A1/de active IP Right Grant
- 1998-11-18 BR BRPI9814696-3A patent/BR9814696B1/pt not_active IP Right Cessation
- 1998-11-18 CN CNB988113155A patent/CN1182228C/zh not_active Expired - Fee Related
- 1998-11-18 CA CA2311545A patent/CA2311545C/en not_active Expired - Fee Related
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2000
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2001524578A (ja) | 2001-12-04 |
| US6409778B1 (en) | 2002-06-25 |
| CN1279707A (zh) | 2001-01-10 |
| HRP20000324A2 (en) | 2000-12-31 |
| BR9814696B1 (pt) | 2010-02-09 |
| HRP20000324B1 (en) | 2006-04-30 |
| JP4056699B2 (ja) | 2008-03-05 |
| WO1999027037A1 (de) | 1999-06-03 |
| EP1032620B1 (de) | 2004-03-03 |
| EP1032620A1 (de) | 2000-09-06 |
| CA2311545A1 (en) | 1999-06-03 |
| CA2311545C (en) | 2010-04-13 |
| BR9814696A (pt) | 2000-10-03 |
| PL340468A1 (en) | 2001-02-12 |
| AU1755499A (en) | 1999-06-15 |
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