CN110713864B - 防污分散剂组合物和使用方法 - Google Patents
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- C11D1/66—Non-ionic compounds
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Abstract
本发明公开一种防污分散剂组合物,其具有醇聚氧化乙烯(EO)醚(EO数1‑14),由以下通式表示
Description
技术领域
下文通常描述的公开的技术提供防污分散剂组合物和方法,且更具体地,防污分散剂组合物和减少甲醇至烯烃(MTO)水清洗系统中的污垢的方法,其中所述组合物包含醇聚氧化乙烯(EO)醚(EO数1-14)。
背景技术
通常,MTO(甲醇至烯烃)反应器生产轻烯烃和一些烃副产物例如芳族烃,包括六甲基苯、五甲基苯、四甲基苯等。然而,这些烃副产物是强疏水性化合物且将在水清洗塔中沉降,导致严重的污垢问题。MTO水清洗系统中的有机污垢物由作为主要组分的六甲基苯和一些次要组分例如五甲基苯、四甲基苯等构成。这些污垢物将导致水清洗塔的效率降低,降低其运行时长并导致对烯烃生产的负面影响。因此,本领域需要防污分散剂组合物和有效消除MTO水清洗塔系统中的严重污垢问题的方法。
发明内容
下文通常描述的公开的技术提供组合物和用于防污分散剂组合物的方法以及有效消除MTO水清洗塔系统中的严重污垢问题的方法。根据公开的技术的一方面,提供一种防污分散剂组合物。
防污分散剂组合物包含:醇聚氧化乙烯(EO)醚(EO数1-14),由以下通式表示
(I),
其中R为具有约3-20个碳原子的烷基;且n为1-14。
在一些实施方案中,防污分散剂组合物进一步包含水和/或一种或多种有机溶剂。在一些实施方案中,组合物包含约0-95%水。在一些实施方案中,组合物包含约0-95%有机溶剂。在一些实施方案中,有机溶剂选自醇、二醇、二醇醚、甘油或吡咯烷酮。在一些实施方案中,有机溶剂包含甲醇、乙醇、异丙醇、乙二醇、丙二醇、乙二醇单甲基醚、乙二醇单乙基醚、乙二醇单丙基醚、乙二醇单丁基醚、二甘醇、二甘醇单甲基醚、二甘醇单乙基醚、二甘醇单丙基醚、二甘醇单丁基醚、甘油、三甘醇、1-甲基-2-吡咯烷酮,或其组合。
在一些实施方案中,防污垢物分散剂组合物进一步包含一种或多种烷基苯酚树脂乙氧基化物,由以下通式表示
(II),
其中,R 1 为C3-C18烷基,乙氧基化物基团(EO)数m为1-50范围,且树脂聚合度p为0-20范围。在一些实施方案中,组合物包含约0-60%烷基苯酚树脂乙氧基化物。
在一些实施方案中,防污垢物分散剂组合物进一步包含约0-95%水,约0-95%的有机溶剂,和0-60%的烷基苯酚树脂乙氧基化物。在一些实施方案中,组合物具有小于-25℃的凝固点。
在公开的技术的又一个方面,提供减少甲醇至烯烃(MTO)水清洗系统中的污垢的方法。所述方法包括:将防污分散剂组合物加入到甲醇至烯烃(MTO)水清洗塔,所述防污分散剂组合物包含醇聚氧化乙烯(EO)醚(EO数1-14),由以下通式表示
(I),
其中R为具有约3-20个碳原子的烷基;且n为1-14。
在一些实施方案中,将约1-1000ppm的防污分散剂组合物加入到甲醇至烯烃(MTO)水清洗塔。在一些实施方案中,防污分散剂组合物连续或间歇注射到MTO水清洗塔中。
在一些实施方案中,防污分散剂组合物进一步包含水和/或一种或多种有机溶剂。在一些实施方案中,防污分散剂组合物包含约0-95%水。在一些实施方案中,防污分散剂组合物包含约0-95%有机溶剂。在一些实施方案中,有机溶剂包含醇、二醇、二醇醚、甘油或吡咯烷酮。在一些实施方案中,防污分散剂组合物包含约0-60%的烷基苯酚树脂乙氧基化物,由以下通式(II)表示。
附图说明
参考附图,通过示例,在现在描述的实施方案中具体示出所公开的技术的这些和其它特点,以及优点,其中:
图1为提供公开的技术的示意性实施方案的结果的图表;
图2为提供公开的技术的示意性实施方案的结果的图表;和
图3为提供公开的技术的示意性实施方案的结果的图表。
具体实施方式
下文通常描述的公开的技术提供组合物和用于防污分散剂组合物的方法以及有效消除MTO水清洗塔系统中的严重污垢问题的方法。防污分散剂组合物有效抑制污垢形成和除去MTO水清洗塔中的污垢物以延长其运行时长并确保平稳的MTO操作。
本发明的技术提供一种防污分散剂组合物。防污分散剂组合物在MTO过程中非常稳定而不具有任何劣化,确保一致有效的防污性能。防污分散剂组合物在水中可溶且将在MTO生产过程中不生产任何污染物。
防污分散剂组合物另外提供通用适用性,由于该组合物可以达到小于-25℃的极低凝固点。组合物的极低凝固点对于MTO装置,尤其在寒冷天气提供有益的方便操作优点。MTO装置位于遥远区域且对于分散剂储存区域、罐和投料管线几乎没有加热。市场上可得的当前产品指示较高的凝固点,将导致产品凝固问题,相分离问题,太高粘度而不能在寒冷天气进料,且继而导致MTO生产问题例如生产波动、污垢、偶然停机等。
在一些实施方案中,本发明的技术的防污分散剂组合物包含醇聚氧化乙烯(EO)醚(EO数1-14),由以下通式表示
(I),
其中R为具有约3-20个碳原子的烷基;且n为1-14。EO数表示氧化乙烯单元数。EO数是重要的,由于其提供良好的分散剂功效来抑制MTO有机污垢。
在一些实施方案中,防污分散剂组合物进一步包含水和/或一种或多种有机溶剂。在一些实施方案中,组合物包含约0-95%水,在其它实施方案中,约10-80%水,在其它实施方案中,约15-70%水,且在其它实施方案中,约20-60%水。
在一些实施方案中,防污分散剂组合物包含约0-95%有机溶剂,在一些实施方案中,约10-80%有机溶剂,在其它实施方案中,约15-70%有机溶剂,且在其它实施方案中,约20-60%溶剂。
在一些实施方案中,有机溶剂包含醇、二醇、二醇醚、甘油或吡咯烷酮。在一些实施方案中,有机溶剂包含甲醇、乙醇、异丙醇、乙二醇、丙二醇、乙二醇单甲基醚、乙二醇单乙基醚、乙二醇单丙基醚、乙二醇单丁基醚、二甘醇、二甘醇单甲基醚、二甘醇单乙基醚、二甘醇单丙基醚、二甘醇单丁基醚、甘油、三甘醇、1-甲基-2-吡咯烷酮,或其组合。
在一些实施方案中,防污分散剂组合物进一步包含一种或多种烷基苯酚树脂乙氧基化物,由以下通式表示
(II),
其中,R 1 为C3-C18烷基,乙氧基化物基团(EO)数m为1-50范围,且树脂聚合度p为0-20范围。
在一些实施方案中,防污分散剂组合物包含约0-60%烷基苯酚树脂乙氧基化物,在其它实施方案中,约10-50%烷基苯酚树脂乙氧基化物,且在其它实施方案中,约15-45%烷基苯酚树脂乙氧基化物。
在一些实施方案中,防污分散剂组合物包含约0-95%水,约0-95%的有机溶剂,和0-60%的烷基苯酚树脂乙氧基化物。
本发明的技术进一步提供减少甲醇至烯烃(MTO)水清洗系统中的污垢的方法。所述方法包括将防污分散剂组合物加入到甲醇至烯烃(MTO)水清洗塔,所述防污分散剂组合物包含醇聚氧化乙烯(EO)醚(EO数1-14),由以下通式表示
(I),
其中R为具有约3-20个碳原子的烷基;且n为1-14。
在一些实施方案中,防污分散剂组合物包含约1-1000ppm的防污分散剂组合物,将其加入到甲醇至烯烃(MTO)水清洗塔。
在一些实施方案中,将防污分散剂组合物连续注射到MTO水清洗塔中。连续进料防污分散剂组合物对有效分散小颗粒是优选的,避免它们团聚成较大尺寸颗粒并抑制污垢物在MTO水清洗系统中沉降。在其它实施方案中,防污分散剂组合物间歇注射到MTO水清洗塔中。间歇进料防污分散剂组合物对于抑制MTO水清洗系统中的污垢是可接受的。如果防污分散剂组合物间歇进料,推荐MTO水清洗系统的水再循环。
实施例
在以下实施例中将进一步描述本发明,这些实施例应被视为是说明性的,且不应被解释为缩小本发明的范围或将范围限制于任何特定的发明实施方案。
进行系统的实验室工作以评估一些化合物的性能。与市场上使用的产品相比,结果证实防污分散剂和组合物有效分散污垢物质的性能增强。
程序
制备六甲基苯(HMB)/丙酮溶液作为3.125%(重量%)HMB。在去离子水中稀释市场上使用的分散剂样品或分散剂候选物和本发明的组合物,作为1%浓度的分散剂储备溶液。将0.22g上面的HMB/丙酮加入到20g去离子水中以制备模拟的HMB标度溶液。这种模拟的HMB标度溶液在水中含有340ppm HMB和10532ppm丙酮,且充分混合。这种溶液标记为“空白样”。将0.41g上面的1%市场上使用的分散剂溶液加入到20g去离子水中且充分混合,以~200ppm作为产品的分散剂计算。然后加入0.225g上面的HMB/丙酮溶液,且充分混合。这种溶液标记为“对照物”。将上面的分散剂候选物和本发明的组合物的计算重量的1%浓度溶液加入到20g去离子水中且充分混合。然后加入0.225g上面的HMB/丙酮溶液,且充分混合。这些溶液标记为“化合物X”或“制剂X”。观察HMB分散稳定性且用Turbiscan塔(试验温度50C)扫描溶液。Turbiscan试验使得能够快速和灵敏识别分散体/乳液溶液的失稳机制(絮凝,聚结,沉淀,乳化等)。Turbiscan单元的温度受控的测量槽允许在特定储存温度下监控分散体/乳液稳定性或加速分散体/乳液的失稳过程。TSI (Turbiscan稳定性指数)指示分散体/乳液的失稳趋势。TSI的值越低,分散体/乳液的稳定性越好。
实施例1
表1提供对化学品的比较:
表1
化学品 | 剂量 |
空白样(比较实施例1) | 0ppm作为分散剂 |
对照物(MTO市场上使用的产品)(比较实施例2) | 200ppm作为分散剂产品(40ppm作为分散剂活性物) |
化合物A | 25ppm作为分散剂活性物 |
化合物B | 25ppm作为分散剂活性物 |
化合物C | 25ppm作为分散剂活性物 |
化合物A为脂肪醇(C14-C20)聚氧化乙烯醚(EO 8~12)。化合物B为脂肪醇(C3-C8)聚氧化乙烯醚(EO 10~14)。化合物C为脂肪醇(C10-C16)聚氧化乙烯醚(EO 3~7)。
如图1中显示,结果指示防污分散剂化合物(A,B,C)在本发明中可以有效分散污垢物质HMB。结果指示,与用于水清洗系统的MTO分散剂的市场上使用的产品相比,本发明的防污分散剂化合物(A,B,C)在较低分散剂剂量下有效分散污垢物质HMB的好得多的性能。
实施例2
表2提供对分散剂产品的比较:
表2
化学品 | 剂量 |
空白样(比较实施例1) | 0ppm作为分散剂 |
对照物(市场上使用的产品)(比较实施例2) | 200ppm作为分散剂产品 |
制剂1 | 100ppm作为分散剂产品 |
制剂2 | 50ppm作为分散剂产品 |
制剂1为20%脂肪醇(C10-C16)聚氧化乙烯醚(EO 3~7)、35%水和45%乙二醇的组合物。制剂2为15%脂肪醇(C14-C20)聚氧化乙烯(EO 8~12)醚、10%壬基苯酚树脂乙氧基化物(m=12,p=8)、15%水、20%乙二醇和40%乙二醇单丁基醚的组合物。
如图2中显示,防污分散剂组合物(制剂1和2)在本发明中有效分散污垢物质HMB。与200ppm用于水清洗系统的MTO分散剂的市场上使用的产品相比,本发明的防污分散剂组合物(50ppm,100ppm)表现出有效分散污垢物质HMB的好得多的性能。
实施例3
表3提供对具有不同EO数的化学品的比较:
表3
实施例 | 化学 |
化合物D | 脂肪醇(C12-C16)乙氧基化物(EO=3~7) |
比较实施例3 | 脂肪醇(C10-14)乙氧基化物(EO=20) |
比较实施例4 | 脂肪醇(C10-C16)乙氧基化物(EO=30) |
比较实施例5 | 脂肪醇(C12-16)乙氧基化物(EO=40) |
比较实施例6 | 脂肪醇(C14-18)乙氧基化物(EO=50) |
比较实施例7 | 脂肪醇(C16-18)乙氧基化物(EO=80) |
如图3中显示,结果指示,比起其它较高EO的脂肪醇乙氧基化物化合物,如在所公开的发明中提供的防污分散剂化合物有效分散污垢物质HMB的好得多的性能。这些结果指示,比起其它较高EO的脂肪醇乙氧基化物化合物(称为现有技术分散剂),如本公开的防污分散剂化合物表现出分散MTO水清洗系统的污垢物质的显著更好的性能。
虽然描述公开的技术的实施方案,应当理解本公开不如此限制且可以在不偏离公开的技术的情况下进行修改。公开的技术的范围通过所附权利要求限定,且落入权利要求的含义内的所有设备、过程和方法字面上或等价地旨在包括在其中。
Claims (17)
1.防污分散剂组合物用于减少甲醇至烯烃(MTO)水清洗系统中的污垢的用途,所述组合物包含:
醇聚氧化乙烯(EO)醚(EO数3-7),由以下通式表示
其中R为具有12-16个碳原子的烷基;且n为3-7,和
一种或多种有机溶剂,包含二醇、二醇醚、甘油或吡咯烷酮。
2.权利要求1所述的用途,其中所述组合物进一步包含水。
3.权利要求2所述的用途,其中所述组合物包含约0-95%水。
4.权利要求2所述的用途,其中所述组合物包含约15-95%有机溶剂。
5.权利要求2所述的用途,其中所述有机溶剂包含乙二醇、丙二醇、乙二醇单甲基醚、乙二醇单乙基醚、乙二醇单丙基醚、乙二醇单丁基醚、二甘醇、二甘醇单甲基醚、二甘醇单乙基醚、二甘醇单丙基醚、二甘醇单丁基醚、甘油、三甘醇、1-甲基-2-吡咯烷酮或其组合。
6.权利要求1所述的用途,其中所述组合物进一步包含一种或多种烷基苯酚树脂乙氧基化物,由以下通式表示
其中,R1为C3-C18烷基,乙氧基化物基团(EO)数m为1-50范围,树脂聚合度p为0-20范围。
7.权利要求6所述的用途,其中所述组合物包含约10-60%烷基苯酚树脂乙氧基化物。
8.权利要求1所述的用途,其中所述组合物进一步包含约0-95%水,约15-95%的有机溶剂,和10-60%的烷基苯酚树脂乙氧基化物。
9.权利要求1所述的用途,其中所述组合物具有小于-25℃的凝固点。
10.减少甲醇至烯烃(MTO)水清洗系统中的污垢的方法,所述方法包括:
将防污分散剂组合物加入到甲醇至烯烃(MTO)水清洗塔,所述防污分散剂组合物包含醇聚氧化乙烯(EO)醚(EO数3-7),由以下通式表示
其中R为具有12-16个碳原子的烷基;且n为3-7,和
一种或多种有机溶剂,包含二醇、二醇醚、甘油或吡咯烷酮。
11.权利要求10所述的方法,其中约1-1000ppm的防污分散剂组合物加入到甲醇至烯烃(MTO)水清洗塔。
12.权利要求10所述的方法,其中将所述防污分散剂组合物连续或间歇注射到MTO水清洗塔中。
13.权利要求10所述的方法,其中所述防污分散剂组合物进一步包含水。
14.权利要求13所述的方法,其中所述防污分散剂组合物包含约0-95%水。
15.权利要求13所述的方法,其中所述防污分散剂组合物包含约15-95%有机溶剂。
16.权利要求10所述的方法,进一步包含一种或多种烷基苯酚树脂乙氧基化物,由以下通式表示
其中,R1为C3-C18烷基,乙氧基化物基团(EO)数m为1-50范围,树脂聚合度p为0-20范围。
17.权利要求10所述的方法,其中所述有机溶剂包含乙二醇、丙二醇、乙二醇单甲基醚、乙二醇单乙基醚、乙二醇单丙基醚、乙二醇单丁基醚、二甘醇、二甘醇单甲基醚、二甘醇单乙基醚、二甘醇单丙基醚、二甘醇单丁基醚、甘油、三甘醇、1-甲基-2-吡咯烷酮或其组合。
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WO2020013978A1 (en) | 2020-01-16 |
KR20210032432A (ko) | 2021-03-24 |
EP3820948A1 (en) | 2021-05-19 |
TW202005713A (zh) | 2020-02-01 |
US12129232B2 (en) | 2024-10-29 |
US20210269343A1 (en) | 2021-09-02 |
EP3820948B1 (en) | 2023-10-11 |
BR112020023945A2 (pt) | 2021-02-23 |
ES2967589T3 (es) | 2024-05-03 |
CN110713864A (zh) | 2020-01-21 |
CA3106160A1 (en) | 2020-01-16 |
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