CN1919879B - 作为抑制原油中石蜡沉积的添加剂的丙烯酸聚合物胶乳分散液与含有它们的组合物 - Google Patents

作为抑制原油中石蜡沉积的添加剂的丙烯酸聚合物胶乳分散液与含有它们的组合物 Download PDF

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CN1919879B
CN1919879B CN2006101074027A CN200610107402A CN1919879B CN 1919879 B CN1919879 B CN 1919879B CN 2006101074027 A CN2006101074027 A CN 2006101074027A CN 200610107402 A CN200610107402 A CN 200610107402A CN 1919879 B CN1919879 B CN 1919879B
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dispersion liquid
methyl
acid
weight part
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CN1919879A (zh
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A·巴洛歇
D·朱赫
P·皮卡
T·E·普
C·特鲁斯兹科夫斯基
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Carbonisation et Charbons Actifs CECA SA
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Abstract

本发明涉及以一种或多种(甲基)丙烯酸-n-烷基酯单体，其中n是6-40，任选地一种或多种不太溶于水的(甲基)丙烯酸和/或乙烯类单体，任选地一种或多种选自(甲基)丙烯酰胺及其衍生物的极性单体，和任选地一种或多种选自乙烯不饱和单羧酸和/或二羧酸或乙烯不饱和单羧酸酐和/或二羧酸酐的单体的(共)聚合物为基的胶乳分散液。这些分散液是在水存在下通过乳液自由基聚合得到的。这些分散液原样使用或以很好地稀释在一种或多种溶剂中的溶液使用，抑制石油原油中石蜡的沉积。

Description

作为抑制原油中石蜡沉积的添加剂的丙烯酸聚合物胶乳分散液与含有它们的组合物
技术领域
本发明的技术领域是石油原油和用于改善开采条件的添加剂的技术领域。
石油原油可能含有大量石蜡馏分，石蜡馏分的量与确切性质可随开采的油田(champs d’extraction)改变。在井的温度下这些石蜡是液体的，溶于原油中。当油升到地面时，其温度降低，这些石蜡结晶生成针状和鳞片状的三维网状物。因此导致流动性降低，这会造成在生产、运输、储存，甚至处理这些油时变得非常因难。在管线和处理设备中经常出现堵塞。
现有技术
人们为了解决这个问题提出了许多方法，如机械刮削或加热壁。这些方法的费用高，始终不能实施。
为了改善原油的流变性，SHELL从事了开拓性工作：在FR 1575984中，指出以含烃主链型式构成的“梳状物(peignes)”类大分子化合物能够扰乱重的石蜡结晶，在其含烃主链上接枝了足够长的本身也是含烃的侧链，即至少14个碳原子，至多30个碳原子。其中平均分子量为1000-1000000，优选地4000-100000的大分子可很好地发挥这种性质。
然后，现有技术认为使用添加剂，往往是聚合物，其作用是延缓或改善石蜡结晶，因此改善油的流动性质，并且还阻止生成的晶体在壁上团聚。
后来，许多研究工作都力图通过合成或者通过配方改善这些原始聚合物类添加剂的效率，以便使它们适合于所碰到的不同类型的原油，并且相继地暂时减轻不同生成产物的合成和/或操作困难。例如本申请人的FR 2746400说明了将两类梳状物分布结合的梳状物类大分子化合物在石油原油流动点降低方面带来了出乎意料的协同作用。在GB 2305185和EP 673990中，SHELL指出与该技术领域的技术人员通常使用的(甲基)丙烯酸-n-烷基酯共聚合时，加入少量极性单体的意义。
一般地，在有机溶剂，例如甲苯、二甲苯和烃中，一般质量浓度为10-60％，优选地30-50％时，采用溶液自由基聚合反应可合成出所有这些聚合物。尽管对大多数低比率20-1000ppm，优选地100-500ppm的原油有效，但这些产品的主要缺陷是在30℃以下成为固体。在现场(sur site)使用它们因此需要预先再加热或将它们稀释在溶剂中，例如稀释在它们的合成溶剂中，根据化合物种类和根据使用的温度，可稀释直到其质量浓度低于10％。其结果是增加了这类添加剂的输送和/或经营成本。
为了得到在宽温度范围内都是液体的浓产品，已经提出几种解决办法：
SHELL先在EP 448166中，后在WO 98/51731中，BritishPetroleum在WO 98/33846中说明了借助高压均化器，在一种或多种表面活性剂和/或表面活性聚合物存在下丙烯酸-n-烷基酯共聚物混合物在水中制成悬浮液。这样一种制备方法的缺陷是在工业上不太经济，因为它需要两个制备步骤以及利用特定的乳化材料。
HENKEL的US 5418278或EP 359061提出用乳液可解决这些缺陷中的一部分缺陷，该乳液可以达到30-50％干提取物，这种提取物含有在表面活性剂存在下丙烯酸-n-烷基酯和羧酸或羧酸酐不饱和乙烯衍生物的共聚物。这样一种解决办法的主要缺陷仍在于，为了该乳液稳定，它应该含有大量的酸或酸酐，这样不仅有损于产品的总性能，而且还限制其在特定原油中的应用。
本发明的公开
本发明提出不同组成的丙烯酸共聚物胶乳分散液，它们特别适合于降低石油原油的流动点(point d’écoulement)。
这些分散液的优点是，它在很宽的温度范围内为稳定的浓液体，接近室温尤其如此。使用这些分散液抑制原油中的石蜡沉积时，它们加入原油不需要任何的添加剂。
本发明的胶乳分散液含有至少100重量份下述①-④组分：
①5-70重量份，优选地5-58重量份，有利地5-50重量份的一种或多种(共)聚合物，其结构单元来自于：
A-50-100重量％，优选地70-100重量％的一种或多种(甲基)丙烯酸-n-烷基酯类单体，其中n是6-40，优选地14-30，
B-0-50重量％，优选地0-30重量％的一种或多种不太溶于水(溶解度在20℃低于5％)的(甲基)丙烯酸和/或乙烯类单体，其选自(甲基)丙烯酸-n--烷基酯，其中n小于或等于6，(甲基)丙烯酸-2-乙基己酯、乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、叔碳酸乙烯酯(versatate devinyle)、叔戊酸乙烯酯、月桂酸乙烯酯，乙烯基芳族单体，它们选自苯乙烯及其衍生物，例如α-甲基苯乙烯，
C-0-50重量％，优选地0-30重量％的一种或多种选自如下的极性单体：(甲基)丙烯酰胺及其衍生物，例如N-羟甲基丙烯酰胺、(甲基)丙烯酸二烷基氨基乙酯、磺酸和磷酸单烯烃衍生物，例如丙烯酰胺基甲基丙烷磺酸、N-乙烯基吡咯烷酮、乙烯基吡啶及其衍生物、(甲基)丙烯酸羟基烷基酯，
D-C＝0％时，则0-0.5重量％一种或多种选自乙烯不饱和单羧酸和/或二羧酸或乙烯不饱和单羧酸酐和/或二羧酸酐的单体，
或者C≠0％时，则直到40重量％一种或多种选自选自乙烯不饱和单羧酸和/或二羧酸或乙烯不饱和单羧酸酐和/或二羧酸酐的单体，
②0-30重量份，优选地5-25重量份，有利地5-20重量份助溶剂或助溶剂混合物，其助溶剂选自酮，例如甲乙酮或甲基异丁基酮；芳族溶剂，例如甲苯、二甲苯和芳族烃混合物；醇，例如丁醇或异丙醇；二醇类和聚乙二醇醚类，例如乙二醇或丙二醇、二甘醇或二丙二醇。优选地，选择丙二醇或二丙二醇单甲醚或乙醚，
③0.1-10重量份，优选地0.1-8重量份，有利地0.5-5重量份一种或多种表面活性剂(离子表面活性剂和/或非离子表面活性剂和/或胶体保护剂，例如聚乙烯醇，和/或两亲聚合物，该聚合物选自硫酸脂肪醇酯或磺酸脂肪醇酯，或硫酸烷基酚酯或磺酸烷基酚酯，烷基苯磺酸酯和磺基丁二酸酯，季铵盐，例如二甲基二烷基氯化铵，和乙氧基化脂肪醇)，
④水(适量至100：①-④组分之和是100重量份)，
以及任选地其它组分，特别是聚合作用添加剂和/或它们的其余添加剂(引发剂、缓冲剂、转移剂等)，低亲水-亲油平衡的表面活性剂。
在含有至少一种或多种液体多元醇作为一种或多种助溶剂的分散液中，优选其水量是固体多元醇的40重量％以上，有利地50重量％以上的分散液。
有利地，优选本发明的分散液，它们含有：
①约30-约35重量份一种或多种(共)聚合物，
②约14-约18重量份助溶剂，主要地以一种或多种液体多元醇为基的助溶剂，
③约1-约4重量份表面活性剂，
④水补充到100重量份，
以及至少一种引发剂、至少一种转移剂、至少一种缓冲剂。
在一种或多种表面活性剂存在下和任选地在一种或多种助溶剂存在下，可采用乳液聚合方法在水中得到本发明的胶乳分散液。
根据间歇方法、半间歇方法或连续方法，在已知的乳液聚合设备中以通常方式进行乳液自由基聚合作用。使用Manton-Gaulin型高压乳化器，或在聚合前为乳化这种混合物而采用超声处理技术(sonification)，以及为了减少有机助溶剂和表面活性剂的量而采用微乳化(mini-émulsion)或微分散(mini-dispersion)方法都没有超出本发明的范围。
可使用产生自由基的引发剂，它们选自通常的过氧化物，例如过硫酸盐，像过硫酸钾或过硫酸铵；有机氢过氧化物和过氧化物，过氧化氢；过酸；重氮化合物，例如4，4′-偶氮双(4-氰基戊酸)或2，2′-偶氮双(2-脒基丙烷)氢氯化物。在某些情况下，为了在更低的温度下进行，可以使用氧化还原系统，例如过硫酸铵与偏亚硫酸钠配合。
根据选择的引发条件，该聚合反应可以在温度20-90℃范围内进行0.5-4小时。
例如像四硼酸钠之类的缓冲剂和例如像烷基硫醇之类的转移剂对聚合反应和最后产物的性质可能都是有效的。后加在前面列举的有机溶剂，还可后加也是列举的表面活性剂，而且是低HLB(亲水-亲油平衡)的表面活性剂，优选地HLB低于或等于5，例如脱水山梨糖醇脂肪酸酯，也可以显著改善本发明产物的性能。
通过根据标准ASTM D97测量的流动点可以知道本发明产物的性能，该标准是往温度升到高于其流动点的原油中添加确定量的抑制石蜡沉积的添加剂，然后按照3℃分步冷却这种原油，流动点表示原油不再流动的起始温度。
在下面实施例中使用了HERZOG MP852设备，该设备用LCD相机保证检测其流动。
根据这种方法测定的Itteville原油流动点为12℃，用这种原油试验了所有抑制石蜡沉积的添加剂。
实施例1
在1升双壁反应器中，该反应器配备了搅拌器、温度计、回流冷却器、氮气入口和50℃恒温槽，加入220克软化水、2克四硼酸钠(硼砂)、80克Dow Chemical以商品名Dowanol DPM销售的二丙二醇一甲醚和10克Cytec以商品名Aérosol TR70销售的双十三烷基磺基丁二酸钠。
一旦介质温度达到50℃，就添加169克Atofina以商品名Norsocryl A18-22销售的丙烯酸山嵛酯和0.5克预先在50℃熔化的n-十二烷基硫醇的混合物，该混合物升温到80℃。
这时在一分钟内加入1克过硫酸钾在20克软化水中的溶液。
在放热峰后，该反应继续进行2小时，然后冷却直到室温。
在用100微米过滤器过滤后，得到约35％干提取物的稳定胶乳分散液。
可以原样使用如此得到的胶乳分散液，该胶乳分散液命名为S1。
对比实施例1
在1升双壁反应器中，该反应器配备了搅拌器、温度计、回流冷却器、氮气入口和50℃恒温槽，加入435克沸点180-200℃的芳族烃馏分(Solvesso 150)和553克Atofina以商品名Norsocryl A18-22销售的丙烯酸山嵛酯。该介质升温到105℃，这时在一小时内添加3.8克Atofina以商品名Trigonox C销售的过苯甲酸叔丁酯在12克沸点180-200℃的芳族烃馏分(Solvesso 150)中的溶液。
该介质再在105℃下保持2小时，以便保证丙烯酸单体完全转化。
在冷却到50℃后，得到55％丙烯酸均聚物的浓溶液。该产物在低于28℃时是固体。
实施例2
作为对比，制备了5.5％对比实施例1产物在其合成的芳族溶剂中的溶液，该溶液称之S2。考虑其产物的固化点，这种稀释操作对于使用这种产物是很必要的。
溶液S1和S2以不同浓度添加到Itteville原油中，再根据前面描述的方法测定如此添加原油的流动点(PE)。下面表汇集了以℃表示的流动点。
  浓度*(ppm)   0   100   200   500
  PE(S1)   12   -12   -18   -27
  PE(S2)   12   -9   -9   -15
*浓度是以对比实施例1的55％干提取物产物当量表示的。
可以清楚地看出，分散液S1是一种降低Itteville原油流动点的有效添加剂，使用时无须进行任何稀释。
实施例3
按照实施例1的操作方式进行，但省去二丙二醇一甲醚，用25克N-乙烯基吡咯烷酮代替一部分169克丙烯酸山嵛酯。
原样使用如此得到的胶乳分散液(称之S3)，添加到Itteville原油中。下面表汇集了以℃表示的流动点。
  浓度*(ppm)   0   500
  PE(S3)   12   -18
*浓度是以对比实施例1的55％干提取物产物当量表示的。
可以看出，如上表所表明的，添加到Itteville原油的本发明溶液S3特别降低了流动点。
实施例4
在1升双壁反应器中，该反应器配备了搅拌器、温度计、回流冷却器、氮气入口和50℃恒温槽，加入225克软化水、81克Dowanol DPM、18克Sc、4克N-烷基二甲基苄基氯化铵和14克HLB为15的乙氧基化脂肪醇混合物。
一旦介质温度达到50℃，就添加169克Norsocryl A18-22和0.5克预先在50℃熔化的n-十二烷基硫醇的混合物，该混合物升温到70℃。
这时在一分钟内加入1克2，2′-偶氮双(2-脒基丙烷)二盐酸盐在20克软化水中的溶液。
在放热峰后，该反应继续进行2小时，然后冷却直到室温。
在用100微米过滤器过滤后，得到约35％干提取物的稳定胶乳分散液。
可以在Itteville原油中原样使用如此得到的胶乳分散液，该胶乳分散液命名为S4。
  浓度*(ppm)   0   300
  PE(S4)   12   -12
*浓度是以对比实施例1的55％干提取物产物当量表示的。
可以看出，添加到Itteville原油的溶液S4特别降低了流动点。
实施例5
再进行实施例1中描述的合成方法，但在冷却过程中，分别后加1.7克和3.4克乙氧基化脂肪醇类非离子表面活性剂(CECA公司以商品名Remcopal 10销售的)，分别得到溶液S5和S6。以与原油流动点同样的方式测定了这些溶液的凝固点(PF)。下面的表汇集了S5和S6的凝固点以及溶液S1的凝固点。
  产物   S1   S5   S6
  PF(℃)   0   -10   -13
可以看出，后加非离子表面活性剂能够显著地改善本发明产品在低温下的稳定性。

Claims (20)

1.胶乳分散液，它含有：
①5-70重量份一种或多种(共)聚合物，其单元来自于：
A：50-100重量％一种或多种(甲基)丙烯酸-n-烷基酯类单体，其中n是6-40，
B：0-50重量％一种或多种溶解度在20℃低于5％的(甲基)丙烯酸类和/或乙烯类单体，其选自(甲基)丙烯酸-n-烷基酯，其中n小于或等于6，(甲基)丙烯酸-2-乙基己酯、乙酸乙烯基酯、丙酸乙烯基酯、丁酸乙烯基酯、叔碳酸乙烯基酯、叔戊酸乙烯基酯、月桂酸乙烯基酯，乙烯基芳族单体，它们选自苯乙烯及α-甲基苯乙烯，
C：＞0-50重量％一种或多种选自如下的极性单体：(甲基)丙烯酰胺及其衍生物；(甲基)丙烯酸二烷基氨基乙酯；磺酸和磷酸单烯烃衍生物、N-乙烯基吡咯烷酮、乙烯基吡啶及其衍生物、(甲基)丙烯酸羟基烷基酯，
D：直到40重量％一种或多种选自乙烯不饱和单羧酸和/或二羧酸或乙烯不饱和单羧酸酐和/或二羧酸酐的单体，
②0-30重量份助溶剂或助溶剂混合物，其助溶剂选自酮；芳族溶剂；醇；二醇类和聚乙二醇醚类，
③0.1-10重量份一种或多种表面活性剂，
④水补充到100重量份；
其特征在于，在制备所述胶乳分散液的方法中，所述表面活性剂是后加的。
2.根据权利要求1所述的分散液，其中所述胶乳分散液含有5-58重量份①中所述的一种或多种(共)聚合物。
3.根据权利要求1所述的分散液，其中所述胶乳分散液含有5-50重量份①中所述的一种或多种所述(共)聚合物。
4.根据权利要求1所述的分散液，其中所述(共)聚合物的单元来自于70-100重量％所述一种或多种(甲基)丙烯酸-n-烷基酯类单体。
5.根据权利要求1所述的分散液，其中所述(甲基)丙烯酸-n-烷基酯类单体中，n是14-30。
6.根据权利要求1所述的分散液，其中所述(共)聚合物的单元来自于0-30重量％所述一种或多种溶解度在20℃低于5％的(甲基)丙烯酸类和/或乙烯类单体。
7.根据权利要求1所述的分散液，其中所述(共)聚合物的单元来自于＞0-30重量％的所述一种或多种极性单体。
8.根据权利要求1所述的分散液，其中所述胶乳分散液含有5-25重量份②中所述的助溶剂或助溶剂混合物。
9.根据权利要求1所述的分散液，其中所述胶乳分散液含有5-20重量份②中所述的助溶剂或助溶剂混合物。
10.根据权利要求1所述的分散液，其中所述胶乳分散液含有0.1-8重量份③中所述的一种或多种表面活性剂。
11.根据权利要求1所述的分散液，其中所述胶乳分散液含有0.5-5重量份③中所述的一种或多种表面活性剂。
12.根据权利要求1所述的分散液，它含有一种或多种液体多元醇作为助溶剂，其水量是固体多元醇的40重量％以上。
13.根据权利要求1所述的分散液，它含有一种或多种液体多元醇作为助溶剂，其水量是固体多元醇的50重量％以上。
14.根据权利要求1-13之一所述的分散液，它含有：
①30-35重量份一种或多种(共)聚合物，
②14-18重量份助溶剂，
③1-4重量份表面活性剂，
④水补充到100重量份，
以及至少一种引发剂、至少一种转移剂、至少一种缓冲剂。
15.在表面活性剂存在下和任选地在一种或多种助溶剂存在下，通过在水中乳液自由基聚合反应制备如权利要求1-14中任一权利要求中限定的胶乳分散液的方法；
其特征在于，所述表面活性剂是后加的。
16.根据权利要求15所述的方法，其特征在于自由基引发剂选自过氧化物。
17.根据权利要求15或16中所述的方法，其中该聚合反应在温度20-90℃范围内进行。
18.根据权利要求15或16中所述的方法，其中使用缓冲剂和/或转移剂。
19.根据权利要求15或16中所述的方法，其特征在于后加有机溶剂。
20.如权利要求1-14中任一权利要求中限定的胶乳分散液，或者通过直接加入原油中，或者以稀释组合物形式，在抑制石油原油中石蜡沉积的应用，
其中所述稀释组合物含有所述的分散液和一种或多种溶剂，和/或一种或多种有机溶剂。
CN2006101074027A 2001-08-08 2002-08-02 作为抑制原油中石蜡沉积的添加剂的丙烯酸聚合物胶乳分散液与含有它们的组合物 Expired - Fee Related CN1919879B (zh)

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