CN102174332B - 用于烃中固体的沉降助剂 - Google Patents
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Abstract
一种用于加速烃流体中的细颗粒固体沉降的处理方法，包括向烃中加入足够的沉降量的以下组合：(a)聚丙烯酸加成的烷基苯酚-甲醛树脂烷氧基化合物和(b)分子量为约500～约5,000的烷基苯酚-甲醛树脂烷氧基化物。
Description
本发明申请是基于申请日为2004年01月08日，申请号为200480005945.7(国际申请号为PCT/US2004/000369)，发明名称为“用于烃中固体的沉降助剂”的专利申请的分案申请。
发明领域
本发明涉及用于加速烃流体中的固体沉降的处理方法。本发明的处理方法对于加速FCC催化剂细粒子在油浆(oil slurry)中的沉降尤其有效。
未精制的烃如原油、渣油和塔底流出物常常含有细颗粒固体物质，它们在进一步使用或处理之前常常必须被除去。这些固体可以包括有类似土壤性质的固体、细颗粒硅石、粘土、泥沙和焦炭，以及金属氧化物和硫化物腐蚀固体。这些固体还可以包括痕量的金属颗粒如铅、镍、铬等等，以及它们的盐。
例如，流化床催化裂化器(FCC)单元使用沸石型硅铝酸盐粘土颗粒的流化床在高温下将重质石油馏分裂解为较轻的馏分。催化剂由于中毒或焦化而最终失活。这些用过的(spent)细粒子必须从基于连续运行的FCC中除去以便能够加入含有新鲜催化剂的浆料。
一些含有用过的细粒子的淤浆油(slurry oil)通常在储罐中沉降，而旋液分离器有时用来加速这一分离过程。淤浆油中的天然成分和合成成分具有分散剂的作用，能阻止细粒子的沉降。
本发明的发明人发现，特定化学试剂的组合，在加入到淤浆油中时具有抗分散剂(anti-dipersant)或絮凝剂的作用，能够加速沉降过程。这使得在更短的时间内产生较为清洁的澄清油(decant oil)(通常灰份＜0.05wt％)，并可作为碳黑原料或残渣燃料油出售。
发明内容
本发明涉及加速烃流体中的细颗粒固体沉降的组合物和方法，所述方法包括向所述烃中加入有效沉降量的以下组合：(a)聚丙烯酸和烷基苯酚-甲醛树脂烷氧基化物(alkoxylate)的加成物，及(b)烷基苯酚-甲醛树脂烷氧基化物。
对于该组合的第一组分，沉降助剂是低分子量(Mw＝1000～2000)的聚丙烯酸和烷基苯酚-甲醛树脂烷氧基化物的加成物。优选的加成物是壬基苯酚-甲醛树脂丙氧基乙氧基化物(propoxyethoxylate)加成物，例如可以商品名AB-455购自Arjay和可以商品名DRI-9037购自Witco的物质。
聚丙烯酸加成的烷基苯酚-甲醛树脂烷氧基化物被证明在多种烃流体中是有效的。这些烃流体通常是倾向于含有细颗粒固体的未精制的烃。所述烃流体包括但不限于原油、渣油、塔底流出物、减压塔底渣油(vacuum bottoms)、重质尾部馏分(heavy ends)等等。有关本发明这一组分的其他细节可在美国专利No.5,481,059中找到，在此通过引入该专利将其并入本文。
对于本发明的烷基苯酚-甲醛树脂烷氧基化物组分，该物质的分子量通常为约500～约5,000，优选为约1,000～约2,500。所述烷基可以是直链的或支化的，并具有约1～约24个碳原子，优选具有约4～约9个碳原子。烷氧基具有约2～约4个碳原子，优选具有2个碳原子；烷氧基化部分占分子重量的约20～80％，优选约50％。有关本发明该组分的其他细节可在美国专利No.5,681,451中找到，在此通过引入该专利将其并入本文。
由此，本申请包括：
项1.一种用于加速烃流体中的不溶于油和水的细颗粒固体沉降的方法，包括在所述烃流体中加入有效沉降量的以下组合：
(a)聚丙烯酸和烷基苯酚-甲醛树脂烷氧基化物的加成物，和
(b)烷基苯酚-甲醛树脂烷氧基化物。
项2.项1所述的方法，其中所述聚丙烯酸加成物是壬基苯酚-甲醛树脂丙氧基乙氧基化物。
项3.项1所述的方法，其中所述细颗粒固体是流化床催化裂化器的催化剂细粒子。
项4.项1所述的方法，其中所述烃是流化床催化裂化器的淤浆。
项5.项1所述的方法，其中所述烃选自原油和沸点在约400°F以上的原油馏分或残留物。
项6.项1所述的方法，其中所述烷基苯酚-甲醛树脂烷氧基化物的分子量为约500～约5,000。
项7.项1所述的方法，其中所述烷基苯酚-甲醛树脂烷氧基化物的分子量为约1,000～约2,500。
项8.项1所述的方法，其中所述烷基苯酚-甲醛树脂烷氧基化物的烷基具有1～约24个碳原子。
项9.项1所述的方法，其中所述烷基苯酚-甲醛树脂烷氧基化物的烷氧基均具有约2～约4个碳原子。
项10.项1所述的方法，其中所述烷基苯酚-甲醛树脂烷氧基化物的烷氧基化部分占其重量的20～80％。
项11.项1所述的方法，其中所述烷基苯酚-甲醛树脂烷氧基化物是碱催化的壬基苯酚树脂乙氧基化物，其中所述乙氧基化物的乙氧基化部分占其重量的约50重量％。
项12.项1所述的方法，其中将所述组合以每一百万份烃约1～约1000份的量加入到所述烃中。
具体实施方式
本发明涉及沉降液体基质中的固体的化学处理方法。所述液体基质可以是有机物，或者有机物与含水基质的混合物。
用于沉降固体的化学物质是(a)聚丙烯酸与烷基苯酚-甲醛树脂烷氧基化物的加成物(A类)和(b)烷基苯酚-甲醛树脂烷氧基化物(B类)的组合。
在本发明的测试中，固体沉降效率由瓶内测试(bottle testing)测定。在混合前加热处理流体(process fluid)；适当混合使流体均化后，将100ml流体倒入150ml的玻璃瓶中。
处理剂量的初始化学溶液包含存在于高级芳烃油(HAN)中的总共20％的原料。用每种化学物质并且之后用化学物质的混合物对流体进行处理(dose)。每轮中都测试一个空白样和一个对比样。空白样没有加溶剂或添加剂。使用适当量的溶剂对对比样进行处理，以在加入有添加剂的测试流体中模拟溶剂的加入。样品用自动振荡器在高档(3～5次冲程(stroke)/秒，每个冲程5英寸)混合3分钟。混合结束后，将样品置于热浴中。现场条件用温度和停留时间表示。
在热浴中放置预定停留时间后，抽取样品顶部的50％用于测定固体含量。一些测试流体容易过滤，而另一些则不容易。因此，顶部50％和底部50％处理流体中的固体用两种方法中的一种来确定，即过滤法或灰份％法。不容易过滤的流体用ASTM Method D482-87测定。灰份百分比用wt/wt百分数给出。容易过滤的流体用Gelman A/E玻璃纤维过滤器过滤。预先称重过滤器并将其放置在适当地贴有标签的罐中。
过滤顶部50％处理流体，并用适当的溶剂清洗过滤器-滤斗。过滤底部50％处理流体，用溶剂清洗玻璃容器并倒入滤斗以除去底部所有的痕量固体。清洗过滤器-滤斗并移去滤纸。然后将滤纸置于900°F的炉中约9小时。记录顶部50％处理样品中残留的无机固体的百分数，作为测试结果。
下面各表表示本发明组合测试化学物质在不同的烃水混合流体以及烃流体中的效果。
表I.在固体百分含量相对高的混合流体中的固体沉降结果
处理流体：具有相对高的固体含量的烃和水的混合流体
上述结果表明，要达到和用300ppm组合(A类和B类各为150ppm)处理相同的沉降结果需要用600ppm的A类(CatA)进行处理。
在剂量为300和600ppm时，单独使用B类只能将固体含量减少至约2％，而300ppm的组合化学物质(A类和B类各为150ppm)能够将无机物含量减少至约1％。
当A类+B类的组合化学物质为600ppm时发生分散，这是过度处理(overtreatment)的标志。
表II.含有中等量固体的烃流体中的固体沉降结果
处理流体：含有中等量的待沉降固体的烃流体
如上所示，A类化学物质需要明显更多的处理量才能达到与组合相同的结果，即600ppm的A类与300ppm的A类+B类处理的结果相当，而300ppm的A类与50ppm的A类+B类处理的结果相当。
当剂量为50～300ppm时，B类化学物质的处理结果显著低于A类+B类组合仅为50ppm时的结果。
表III在含有相对低的固体总量的混合(轻质和重质)汽油流中的固体沉降结果
Claims (10)
1.一种用于加速烃流体中的不溶于油和水的细颗粒固体沉降的方法，包括在所述烃流体中加入有效沉降量的以下组合：
(a)聚丙烯酸和烷基苯酚-甲醛树脂烷氧基化物的加成物，和
(b)烷基苯酚-甲醛树脂烷氧基化物；
其中将所述组合以每一百万份烃1～300份的量加入到所述烃中；
其中所述细颗粒固体是流化床催化裂化器的催化剂细粒子。
2.权利要求1所述的方法，其中所述聚丙烯酸和烷基苯酚-甲醛树脂烷氧基化物的加成物是聚丙烯酸和壬基苯酚-甲醛树脂丙氧基乙氧基化物的加成物。
3.权利要求1所述的方法，其中所述烃是流化床催化裂化器的淤浆。
4.权利要求1所述的方法，其中所述烃选自原油和沸点在400°F以上的原油馏分或残留物。
5.权利要求1所述的方法，其中所述烷基苯酚-甲醛树脂烷氧基化物的分子量为500～5,000。
6.权利要求1所述的方法，其中所述烷基苯酚-甲醛树脂烷氧基化物的分子量为1,000～2,500。
7.权利要求1所述的方法，其中所述烷基苯酚-甲醛树脂烷氧基化物的烷基具有1～24个碳原子。
8.权利要求1所述的方法，其中所述烷基苯酚-甲醛树脂烷氧基化物的烷氧基均具有2～4个碳原子。
9.权利要求1所述的方法，其中所述烷基苯酚-甲醛树脂烷氧基化物的烷氧基化部分占其重量的20～80%。
10.权利要求1所述的方法，其中所述烷基苯酚-甲醛树脂烷氧基化物是碱催化的壬基苯酚-甲醛树脂乙氧基化物，其中所述壬基苯酚-甲醛树脂乙氧基化物的乙氧基化部分占其重量的50重量％。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US10/357,239 | 2003-02-03 | ||
| US10/357,239 US7048847B2 (en) | 2003-02-03 | 2003-02-03 | Settling aids for solids in hydrocarbons |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800059457A Division CN1756830A (zh) | 2003-02-03 | 2004-01-08 | 用于烃中固体的沉降助剂 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102174332A CN102174332A (zh) | 2011-09-07 |
| CN102174332B true CN102174332B (zh) | 2013-11-06 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2004800059457A Pending CN1756830A (zh) | 2003-02-03 | 2004-01-08 | 用于烃中固体的沉降助剂 |
| CN2011100711654A Expired - Lifetime CN102174332B (zh) | 2003-02-03 | 2004-01-08 | 用于烃中固体的沉降助剂 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNA2004800059457A Pending CN1756830A (zh) | 2003-02-03 | 2004-01-08 | 用于烃中固体的沉降助剂 |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US7048847B2 (zh) |
| EP (1) | EP1594941A1 (zh) |
| KR (2) | KR20050107409A (zh) |
| CN (2) | CN1756830A (zh) |
| AU (1) | AU2004209381B2 (zh) |
| CA (1) | CA2514999C (zh) |
| MY (1) | MY139603A (zh) |
| TW (1) | TWI355415B (zh) |
| WO (1) | WO2004069963A1 (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100956275B1 (ko) | 2008-01-23 | 2010-05-10 | (주)켐텍인터내셔날 | 원유 전처리 공정에 금속 제거 및 유수분리기능을 갖는첨가제 조성물의 제조방법 |
| US20130175204A1 (en) * | 2012-01-09 | 2013-07-11 | Baker Hughes Incorporated | Method for reducing catalyst fines in slurry oil from a fluidized catalyst cracking process |
| CA2881292C (en) * | 2012-08-14 | 2021-01-12 | General Electric Company | Demulsifying compositions and methods of use |
| CN106390536B (zh) * | 2016-09-09 | 2018-06-15 | 徐文忠 | 从石油工艺油浆脱除催化剂的沉降剂、其制备及使用方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5481059A (en) * | 1994-10-07 | 1996-01-02 | Betz Laboratories, Inc. | Settling aids for solids in hydrocarbons |
| US5681451A (en) * | 1996-01-31 | 1997-10-28 | Betzdearborn Inc. | Settling aids for solids in hydrocarbons |
| CN1339981A (zh) * | 1999-02-26 | 2002-03-13 | 菲利浦石油公司 | 油水乳液的破乳化 |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5366637A (en) * | 1993-05-24 | 1994-11-22 | Betz Laboratories, Inc. | Method for dewatering municipal solid waste refuse |
| US6030467A (en) * | 1993-08-31 | 2000-02-29 | E. I. Du Pont De Nemours And Company | Surfactant-aided removal of organics |
| US5474713A (en) * | 1994-03-23 | 1995-12-12 | Amway Corporation | High actives cleaning compositions and methods of use |
| US5476988A (en) * | 1994-05-25 | 1995-12-19 | Betz Laboratories, Inc. | Settling aids for solids in hydrocarbons |
| US5593572A (en) * | 1994-08-04 | 1997-01-14 | Betzdearborn Inc. | Settling aids for solids in hydrocarbons |
-
2003
- 2003-02-03 US US10/357,239 patent/US7048847B2/en not_active Expired - Lifetime
-
2004
- 2004-01-08 KR KR1020057014306A patent/KR20050107409A/ko not_active IP Right Cessation
- 2004-01-08 WO PCT/US2004/000369 patent/WO2004069963A1/en active Application Filing
- 2004-01-08 KR KR1020117022049A patent/KR20110111326A/ko not_active Application Discontinuation
- 2004-01-08 AU AU2004209381A patent/AU2004209381B2/en not_active Ceased
- 2004-01-08 CA CA2514999A patent/CA2514999C/en not_active Expired - Lifetime
- 2004-01-08 CN CNA2004800059457A patent/CN1756830A/zh active Pending
- 2004-01-08 CN CN2011100711654A patent/CN102174332B/zh not_active Expired - Lifetime
- 2004-01-08 EP EP04700840A patent/EP1594941A1/en not_active Withdrawn
- 2004-01-12 MY MYPI20040069A patent/MY139603A/en unknown
- 2004-01-20 TW TW093101578A patent/TWI355415B/zh not_active IP Right Cessation
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5481059A (en) * | 1994-10-07 | 1996-01-02 | Betz Laboratories, Inc. | Settling aids for solids in hydrocarbons |
| US5681451A (en) * | 1996-01-31 | 1997-10-28 | Betzdearborn Inc. | Settling aids for solids in hydrocarbons |
| CN1339981A (zh) * | 1999-02-26 | 2002-03-13 | 菲利浦石油公司 | 油水乳液的破乳化 |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI355415B (en) | 2012-01-01 |
| KR20050107409A (ko) | 2005-11-11 |
| CA2514999A1 (en) | 2004-08-19 |
| TW200422392A (en) | 2004-11-01 |
| EP1594941A1 (en) | 2005-11-16 |
| CN1756830A (zh) | 2006-04-05 |
| US20040152937A1 (en) | 2004-08-05 |
| WO2004069963A1 (en) | 2004-08-19 |
| US7048847B2 (en) | 2006-05-23 |
| AU2004209381A1 (en) | 2004-08-19 |
| AU2004209381B2 (en) | 2009-05-28 |
| KR20110111326A (ko) | 2011-10-10 |
| CA2514999C (en) | 2012-04-10 |
| CN102174332A (zh) | 2011-09-07 |
| MY139603A (en) | 2009-10-30 |
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