TW202005713A - 防污垢分散劑組合物和使用方法 - Google Patents
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Abstract
一種防污垢分散劑組合物,其具有一種藉以下通式表示的醇聚氧乙烯(EO)醚(EO數1-14):
Description
下文中一般性描述之本發明技術是提出一種可用以減少烯烴製程和系統中的污垢之防污垢分散劑組合物和方法,且更具體言之,一種減少在甲醇至烯烴(MTO)水洗系統中之污垢的防污垢分散劑組合物及方法,其中該組合物包含醇聚氧乙烯(EO)醚(EO數1-14)。
熟知在烯烴產製系統中,污垢是一種可能明顯限制個別組件的性能的現象,並因此限制了烯烴產製單元(例如,乙烯、丙烯、異戊二烯、氯丁二烯、丁烯(和其異構物)、異丁烯和丁二烯產製)的整體操作。因此,污垢控制和防止是非常重要的,且已經使用提出數種方法來達到此目的。
通常,烯烴係藉範圍廣泛的烴進料的蒸汽或催化性裂解而商業產製。乙烯主要自裂解石油腦、氣體、油和凝結物而得,且同時產製丙烯、C4烯烴和芳族物。
具體言之,在甲醇至烯烴(MTO)水洗系統中,MTO反應器產製輕質烯烴和一些烴副產物,如芳族烴(包括六甲基苯、五甲基苯、四甲基苯等)。但是,這些烴副產物係強疏水性化合物且將會沉降在水洗塔中而造成嚴重的污垢問題。在MTO水洗系統中的有機污垢包括作為主要組份的六甲基苯和一些次要組份(例如,五甲基苯、四甲基苯等)。這些污垢將會造成水洗塔的效能降低,降低其運轉長度且導致對於烯烴產製的負面衝擊。
因此,先前技術需要的是可有效地消除這些烯烴製程更具體言之,MTO水洗塔系統中遭遇之嚴重污垢問題之防污垢分散劑組合物和方法。
下文中一般性描述的本發明技術是提出一種可有效地消除烯烴製程和其系統中之嚴重污垢問題之防污垢分散劑組合物及方法。
其他具體實施例中,提出可有效地消除MTO水洗塔系統中的污垢問題之防污垢分散劑組合物及方法。
一些具體實施例中,該防污垢分散劑另外包含水和/或一或多種有機溶劑。一些具體實施例中,該組合物包含約0-95%的水。一些具體實施例中,該組合物包含約0-95%的有機溶劑。一些具體實施例中,該有機溶劑包含醇、二醇、二醇醚、甘油、或吡咯烷酮。
一些具體實施例中,該有機溶劑包含甲醇、乙醇、異丙醇、乙二醇、丙二醇、乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、乙二醇單丁醚、二乙二醇、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丙醚、二乙二醇單丁醚、甘油、三乙二醇、1-甲基-2-吡咯烷酮、或其組合。
一些具體實施例中,該防污垢分散劑組合物另外包含一或多種藉以下通式表示的烷基酚系樹脂乙氧化物:,
其中,R1
是C3-C18烷基,乙氧基(EO)數m
是在1-50的範圍內,及樹脂聚合度p
是在0-20的範圍內。一些具體實施例中,該組合物包含約0-60%的烷基酚系樹脂乙氧化物。
一些具體實施例中,該組合物包含約0-60%的烷基酚系樹脂乙氧化物。一些具體實施例中,該防污垢分散劑組合物包含約0-95%的水、約0-95%的有機溶劑、和約0-60%的烷基酚系樹脂乙氧化物。一些具體實施例中,該組合物具有低於約-25℃的凝固點。
本發明技術的又另一方面中,提出一種減少烯烴產製系統中之污垢的方法。該方法包含在烯烴產製系統中添加防污垢分散劑組合物,該防污垢分散劑組合物包含一種藉以下通式表示的醇聚氧乙烯(EO)醚(EO數1-14):,
其中R是具有約3-20個碳原子的烷基;及n是1-14。
一些具體實施例中,該烯烴產製系統包含乙烯、丙烯、異戊二烯、氯丁二烯、丁烯(及其異構物)、異丁烯和丁二烯、或甲醇至烯烴(MTO)水洗系統。一些具體實施例中,約1-1000 ppm的該防污垢分散劑組合物加至甲醇至烯烴(MTO)水洗塔中。一些具體實施例中,該防污垢分散劑組合物係持續或間歇地注入該MTO水洗塔中。一些具體實施例中,該防污垢分散劑組合物另外包含水和/或一或多種有機溶劑。
一些具體實施例中,該防污垢分散劑組合物包含約0-95%的水。一些具體實施例中,該防污垢分散劑組合物包含約0-95%的有機溶劑。一些具體實施例中,該有機溶劑包含醇、二醇、二醇醚、甘油、或吡咯烷酮。
下文中一般描述之本發明技術提出一種可有效地消除在烯烴製程和其系統中觀察到之嚴重污垢問題之防污垢分散劑組合物和方法。例如,該乙烯製程和系統包括,但不限於,烴裂解系統、程序氣體壓縮系統、和MTO水洗塔系統。該防污垢分散劑組合物有效地抑制污垢形成並移除此系統中的污垢,以延長運轉長度和確保操作順利。一些具體實施例中,該防污垢分散劑組合物抑制污垢形成並移除MTO水洗塔中的污垢以延長其運轉長度並確保MTO操作順利。
本發明提出一種防污垢分散劑組合物。該防污垢分散劑組合物安定,特別是在MTO程序中沒有任何劣化,此確保持續有效的防污垢性能。該防污垢分散劑組合物可溶於水且在乙烯製程或MTO製程中不會製造任何污染物,此是有利的,因為在程序流中產生最少量的雜質而得以提供良好的系統配伍性,同時因為有效的防污垢控制的結果而得以延長產製運轉長度。因為該防污垢分散劑組合物能夠達到低於約-25℃之極低的凝固點,所以該組合物另外提供廣泛應用。該組合物之極低的凝固點提供MTO設備有利的容易操作優點,尤其是在天冷的日子。MTO設備通常位於遠距區域且該處大多沒有用於分散劑儲存區、槽、用於投料的管線之加熱。目前可以在市場上取得的產品具有較高的凝固點,其將造成產品凝固問題、相分離問題、在天冷時供料之過高的黏度,且後續引發MTO產製問題,例如製造波動、污垢、意料之外的停機等。
一些具體實施例中,本發明之防污垢分散劑組合物包含藉以下通式表示的醇聚氧乙烯(EO)醚(EO數1-14): ,
其中R是具有約3-20個碳原子的烷基;及n是1-14。EO數代表氧乙烯單元數。EO數很重要,因為它提供了抑制污垢以及MTO有機污垢之良好的分散劑效力。
一些具體實施例中,該防污垢分散劑組合物另外包含水和/或一或多種有機溶劑。一些具體實施例中,該組合物包含約0-95%的水,其他具體實施例中,約10-80%的水,其他具體實施例中,約15-70%的水,和其他具體實施例中,約20-60%的水。
一些具體實施例中,該防污垢分散劑組合物包含約0-95%的有機溶劑,一些具體實施例中,約10-80%的有機溶劑,其他具體實施例中,約15-70%的有機溶劑,和其他具體實施例中,約20-60%的有機溶劑。
一些具體實施例中,該有機溶劑包含醇、二醇、二醇醚、甘油、或吡咯烷酮。一些具體實施例中,該有機溶劑包含甲醇、乙醇、異丙醇、乙二醇、丙二醇、乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、乙二醇單丁醚、二乙二醇、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丙醚、二乙二醇單丁醚、甘油、三乙二醇、1-甲基-2-吡咯烷酮、或其組合。
一些具體實施例中,該防污垢分散劑組合物另外包含一或多種藉以下通式表示的烷基酚系樹脂乙氧化物:,
其中,R1
是C3-C18烷基,乙氧基(EO)數m
是在1-50的範圍內,樹脂聚合度p
是在0-20的範圍內。
一些具體實施例中,該防污垢分散劑組合物包含約0-60%的烷基酚系樹脂乙氧化物,其他具體實施例中,約10-50%的烷基酚系樹脂乙氧化物,和其他具體實施例中,約15-45%的烷基酚系樹脂乙氧化物。
一些具體實施例中,該防污垢分散劑組合物包含約0-95%的水、約0-95%的有機溶劑、和0-60%的烷基酚系樹脂乙氧化物。
本發明另外提出一種減少甲醇至烯烴(MTO)水洗系統中的污垢的方法。該方法包含在甲醇至烯烴(MTO)水洗系統中添加防污垢分散劑組合物,該防污垢分散劑組合物包含一種藉以下通式表示的醇聚氧乙烯(EO)醚(EO數1-14),
其中R是具有約3-20個碳原子的烷基;及n是1-14
一些具體實施例中,包含約1-1000 ppm的該防污垢分散劑組合物之防污垢分散劑組合物加至該甲醇至烯烴(MTO)水洗塔。
一些具體實施例中,該防污垢分散劑組合物係持續或間歇地注入該MTO水洗塔中。該防污垢分散劑組合物的連續注入是較佳的,可有效地分散小粒子,防止其聚集成較大尺寸的粒子,並抑制污垢沉積在MTO水洗系統中。其他具體實施例中,該防污垢分散劑組合物間歇地注入MTO水洗塔中。可接受將該防污垢分散劑組合物間歇地注入以抑制MTO水洗塔中的污垢。如果間歇地供入該防污垢分散劑組合物,則建議MTO水洗塔的水循環。
實例
將在以下實例中進一步描述本發明,應將其視為例示且不應以其窄化本發明之範圍或將其範圍限制於任何特別的本發明之具體實施例。
有系統地進行實驗室工作以評估一些化合物的性能。結果證實相較於市面上使用的產品,該防污垢分散劑和組合物有效分散污垢物質之性能獲得提升。
[程序]
製備含3.125%(wt%)HMB之六甲基苯(HMB)/丙酮溶液。市面使用的分散劑樣品或分散劑候選品及本發明技術之組合物在去離子水中稀釋成1%濃度的分散劑原液。約0.22g上述的HMB/丙酮加至20g的去離子水中以製備HMB的模擬規格液。此HMB的模擬規格液含有約340 ppm HMB和10532 ppm丙酮於水中,並充分混合。將此溶液標示為“空白組”。約0.41g的1%上述市面使用的分散劑溶液加至20g的去離子水中並充分混合,計算得到~200 ppm的分散劑產品。之後,添加約0.225g上述的HMB/丙酮液,並充分混合。將此溶液標記為“對照組”。將經計算重量之分散劑候選品之1%濃度的溶液和上述本發明技術之組合物加至20g的去離子水中並充分混合。添加約0.225g 上述的HMB/丙酮溶液,並充分混合。這些溶液被標記為“化合物X”或“調合物X”。觀察HMB分散液安定性,並以Turbiscan塔檢測該溶液(測試溫度50℃)。Turbiscan試驗有助於迅速且敏感地辨視分散液/乳液的去安定性機理(絮凝、聚集、沉積、乳化等)。Turiscan單元的控溫測定槽得以偵測於特定儲存溫度的分散液/乳液安定性或加速分散液/乳液的去安定化程序。TSI(Turbiscan安定性指數)顯示分散液/乳液的去安定化趨勢。TSI值越低,分散液/乳液的安定性越佳。
實例 1
化合物A是脂肪醇(C14-C20)聚氧乙烯醚(EO8~12)。化合物B是脂肪醇(C3-C8)聚氧乙烯醚(EO10~14)。化合物C是脂肪醇(C10-C16)聚氧乙烯醚(EO3~7)。
如圖1中所示,結果顯示本發明之的抗污垢分散劑化合物(A, B, C)能夠有效地分散污垢物質HMB。結果顯示,相較於對照組(比較例2),本發明的抗污垢分散劑化合物(A, B, C)展現出以較低的分散劑劑量有效地分散污垢物質HMB之更佳的性能。
實例 2
調合物1是20%脂肪醇(C10-C16)聚氧乙烯醚(EO3~7)、35%水和45%乙二醇之組合物。調合物2是15%脂肪醇(C14-C20)聚氧乙烯(EO8~12)醚、10%壬基酚系樹脂乙氧化物(m
=12,p
=8)、15%水、20%乙二醇和40%乙二醇單丁醚之組合物。
如圖2中所示,本發明之防污垢分散劑組合物(調合物1和2)有效地分散污垢物質HMB。相較於200 ppm的對照組(比較例2),本發明之防污垢分散劑組合物(50 ppm,100 ppm)展現更佳之有效地分散污垢物質HMB的性能。
實例 3
如圖3中所示,結果顯示,相較於其他較高EO的脂肪醇乙氧化物化合物,本發明技術提出的抗污垢分散劑化合物展現更佳之有效地分散污垢物質HMB的性能。這些結果指出,與先前技術中提及作為分散劑之其他較高EO的脂肪醇乙氧化物化合物相比,本發明抗污垢分散劑化合物展現明顯較佳之分散MTO水洗系統的污垢物質的性能。
在已描述本發明技術的具體實施例的同時,應理解本揭示不因此受限且可以在不背離本發明技術的情況下作出修飾。本發明技術的範圍由所附申請專利範圍界定,且旨在將在申請專利範圍意義內的所有的裝置、程序、和方法,無論是字意上或等同者,納入其中。
對照附圖,例如,本發明技術的這些和其他特點和優點具體示於現將描述的具體實施例中,附圖中:
圖1是提供本發明技術的例示具體實施例之結果的圖;
圖2是提供本發明技術的例示具體實施例之結果的圖;和
圖3是提供本發明技術的例示具體實施例之結果的圖;
Claims (19)
- 如請求項1之防污垢分散劑組合物,其另外包含水和/或一或多種有機溶劑。
- 如請求項2之防污垢分散劑組合物,其中該組合物包含約0-95%的水。
- 如請求項2之防污垢分散劑組合物,其中該組合物包含約0-95%的有機溶劑。
- 如請求項2之防污垢分散劑組合物,其中該有機溶劑包含醇、二醇、二醇醚、甘油、或吡咯烷酮。
- 如請求項2之防污垢分散劑組合物,其中該有機溶劑包含甲醇、乙醇、異丙醇、乙二醇、丙二醇、乙二醇單甲醚、乙二醇單***、乙二醇單丙醚、乙二醇單丁醚、二乙二醇、二乙二醇單甲醚、二乙二醇單***、二乙二醇單丙醚、二乙二醇單丁醚、甘油、三乙二醇、1-甲基-2-吡咯烷酮、或其組合。
- 如請求項7之防污垢分散劑組合物,其中該組合物包含約0-60%的烷基酚系樹脂乙氧化物。
- 如請求項1之防污垢分散劑組合物,其另外包含約0-95%的水、約0-95%的有機溶劑、和約0-60%的烷基酚系樹脂乙氧化物。
- 如請求項1之防污垢分散劑組合物,其中該組合物具有低於約-25℃的凝固點。
- 如請求項11之方法,其中該烯烴產製系統包含乙烯、丙烯、異戊二烯、氯丁二烯、丁烯(及其異構物)、異丁烯和丁二烯、或甲醇至烯烴(MTO)水洗系統。
- 如請求項11之方法,其中約1-1000 ppm的該防污垢分散劑組合物加至甲醇至烯烴(MTO)水洗塔中。
- 如請求項11之方法,其中該防污垢分散劑組合物係持續或間歇地注入該MTO水洗塔中。
- 如請求項11之方法,其中該防污垢分散劑組合物另外包含水和/或一或多種有機溶劑。
- 如請求項15之方法,其中該防污垢分散劑組合物包含約0-95%的水。
- 如請求項15之方法,其中該防污垢分散劑組合物包含約0-95%的有機溶劑。
- 如請求項17之方法,其中該有機溶劑包含醇、二醇、二醇醚、甘油、或吡咯烷酮。
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-
2018
- 2018-07-13 CN CN201810769623.3A patent/CN110713864B/zh active Active
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2019
- 2019-06-24 KR KR1020217004116A patent/KR20210032432A/ko active Search and Examination
- 2019-06-24 US US17/259,082 patent/US20210269343A1/en active Pending
- 2019-06-24 CA CA3106160A patent/CA3106160A1/en active Pending
- 2019-06-24 ES ES19736925T patent/ES2967589T3/es active Active
- 2019-06-24 EP EP19736925.9A patent/EP3820948B1/en active Active
- 2019-06-24 WO PCT/US2019/038680 patent/WO2020013978A1/en unknown
- 2019-07-04 TW TW108123626A patent/TW202005713A/zh unknown
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ES2967589T3 (es) | 2024-05-03 |
EP3820948B1 (en) | 2023-10-11 |
CN110713864B (zh) | 2023-09-26 |
CN110713864A (zh) | 2020-01-21 |
EP3820948A1 (en) | 2021-05-19 |
WO2020013978A1 (en) | 2020-01-16 |
BR112020023945A2 (pt) | 2021-02-23 |
KR20210032432A (ko) | 2021-03-24 |
CA3106160A1 (en) | 2020-01-16 |
US20210269343A1 (en) | 2021-09-02 |
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