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CN1306145C - 从含烃的地下岩层中采收原油的方法和强化采油的表面活性剂 - Google Patents

从含烃的地下岩层中采收原油的方法和强化采油的表面活性剂 Download PDF

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CN1306145C
CN1306145C CNB998159115A CN99815911A CN1306145C CN 1306145 C CN1306145 C CN 1306145C CN B998159115 A CNB998159115 A CN B998159115A CN 99815911 A CN99815911 A CN 99815911A CN 1306145 C CN1306145 C CN 1306145C
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S·周
C·坎普贝尔
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Abstract

本文公开了一种采用特定一类的烷基芳基磺酸盐表面活性剂进行采油的方法。该表面活性剂是由平均碳原子数为12-58的呈宽分布的α-烯烃物流制得的。使烯烃物流与芳族原料(如苯、甲苯、二甲苯或它们的混合物)相反应,以形成烷基化物,然后与SO3相反应形成磺酸。所制得的烷基碳原子数呈宽分布的表面活性剂对原油,特别是含蜡原油具有高的增溶作用并与之形成超低界面张力的界面。

Description

从含烃的地下岩层中采收原油的方法 和强化采油的表面活性剂
                         发明领域
本发明涉及强化采油。本发明尤其涉及采用烷基芳基磺酸盐表面活性剂对含蜡原油进行强化采油。
                         发明背景
已经认识到烷基芳基磺酸盐可作为以活性溶液驱油法(floods)强化采油有希望的表面活性剂。烷基芳基磺酸盐已能大量制造,在适当条件下,与油能形成低的界面张力,见Malmber,E、“大规模磺酸盐的第三代采油实验室研究:制备和有关研究,最后报告(Large scale sulfonatesfor laboratory studies in tertiary oil recovery:preparation andrelated studies,final report)”USDOE report NO.FE2605-20,5月,1979。已对用于轻油的、独特的、单体纯的表面活性剂做了大量的研发工作,见Malmber,E,W等人Al,“对系列合成石油磺酸盐的表征和采油意见(Characterization and oil recorvery observation on a seriesof synthetic petroleum sulfonates)”,SPEJ(4月,1982)226-236;和Comberiati,J,R等人,Al.,“提高一定合成烷基芳基磺酸盐EOR活性(Increasing the EOR activity of certain synthetic alkylarylsulfonates)”,DOE/METC/TRP-83-3,11月,1982。
虽然纯的烷基芳基磺酸盐如十六烷基苯磺酸盐能呈现适当的相态特性,与轻烷烃产生低界面张力,但当处理重质原油特别是蜡含量高的原油时,就不能满足要求。当纯烷基苯磺酸盐与原油和不同盐度的盐水混合时不会出现正常的相态特性。在低盐度时,表面活性剂主要存在于水相中而形成下相微乳液;在高盐度时,表面活性剂主要存在于油相中而形成上相微乳液。正如在“表面活性剂和聚合物驱替提高采油(Improvedoil recovery by Surfactant and Polymer Flooding)”,AcademicPress,1977中所指出的,正常的情况是,具有高采油潜能的表面活性剂-油-盐水体系会随盐度的增加发生从下相微乳液向中相微乳液向上相微乳液的转变。在约中等盐度,通常称为最佳盐度,形成的中相微乳液中有可观量的油和盐水在微乳液相中增溶。然而,如果油中含有相当多的蜡的话,以上所述的相转变常常不会发生,增溶能力很低,结果形成高的界面张力因而采油能力很低。
尤其是为了降低油价,必须考虑表面活性剂的成本效率。先有技术方法采用的窄的碳链长度选择,由于存在大量不适用的副产物和/或需要严格地控制反应器条件或专用催化剂,因而提高了成本。
因此,极其希望有一种适用于采收含蜡原油的方法和组合物。也希望有一种可包含碳链长度分布宽的、因而产物基本上完全适用的组合物。
                         发明概述
本发明涉及利用活性溶液驱油法从地下岩层中采收原油和解决前面提到的所希望的特征,以及提供对普通的技术熟练人员来说是显而易见的其它优点。该方法特别适用于蜡含量高的例如含高于20(体积)%蜡的储层油的采收,其中蜡是20个或20个以上碳原子的石蜡。一种从地层岩层中采收原油的方法,该方法包括:(a)将包含有效量的烷基芳基磺酸盐表面活性剂的水溶液注入所述地层中,所述磺酸盐是通过以烯烃碳原子数分布宽的α-烯烃物流对芳族化合物进行烷基化反应,然后使所得烷基化产物经磺化、中和而制成的,和(b)驱替所述溶液使其通过地层,以从采油井采收烃类物质。本发明也涉及烷基芳基磺酸盐组合物,其中烷基的碳链长度的范围是宽的,碳原子数大于10,优选12-58。更优选为12-40或者还更优选为12-32,而芳基为苯、乙苯、甲苯或二甲苯,其中占较大比例的芳基优选为二甲苯。
                      发明的详细说明
在本发明的一个实施方案中,使α-烯烃生产厂生产的C10为下限的烯烃与芳族化合物(如甲苯)反应,以形成烷基化物,接着使烷基化物与SO3进行磺化反应,并经中和成钠盐。此表面活性剂被称为TS12+
在另一个实施方案中,人们可以只利用C10-C24α-烯烃。由此制得的表面活性剂特别适用于轻质油和较高盐度的情况。这一表面活性剂被称为CR1。
在另一个实施方案中,以AlCl3为催化剂,使混合二甲苯与C10为下限的烯烃,即α-烯烃生产厂的碳链大于C10如C12-C30物料进行烷基化,接着进行磺化和中和。其它的和/或可选择的C10为下限的烯烃可以是α-烯烃生产厂的包括NAO的C12+物料流。这类物料流包括C30+至C58,烷基基团中高碳原子数的C30+至C58可占至多约10%。此表面活性剂被称为XS12+。一个实例是C12至C30+烷基链,其中芳基基团为约90%二甲苯和10%的苯、甲苯及乙苯。拥有不同链长烷基的间二甲苯化合物差不多为混合物的50%。一种特别优选的XS12+包括芳基上接有C12-C30烷基基团,芳基中苯约1.6%,甲苯约1.1%,乙苯约6.8%,对二甲苯约13.8%,间二甲苯约48.8%及邻二甲苯约27.9%。最优选的XS12+包括C12-C30+烷基链,其中芳基基团中含高于90%的邻二甲苯和其余10%的间二甲苯与对二甲苯的混合物。其它的和/或可选择的组合物可以是由含约50%邻二甲苯和任选地高达基本上全是邻位的混合二甲苯与C12+为下限的烯烃所构成。
在再一个实施方案中,二甲苯物料流以HF为催化剂、用α-烯烃生产厂的C10为下限的α-烯烃进行烷基化,接着进行磺化和中和。此表面活性剂被称为CR2。
对于重质储油、低盐度和高温情况来说,以二甲苯作为烷基化的芳族化合物是特别优选的。虽然在此不作详细说明,但人们可利用苯、甲苯和各种馏分二甲苯的混合物,以适应特定的油层达到最佳化,或利用芳族化合物市场的有利条件。
不管上述各种变化,本发明的关键因素之一是采用碳原子高于C10-C58或更高的呈宽分布的α-烯烃或者优选的是全部以C10为下限的馏分即高于C10的α-烯烃(AO)的工艺。适用的α-烯烃范围为C12-C40,优选范围如C10-C32;C12-C28和C10-C24。与本发明不同,常规采用的烷基芳基磺酸盐通常是烯烃碳原子数分布窄的α-烯烃磺酸盐,如C12二甲苯磺酸盐(C12XS),C16甲苯磺酸盐(C16TS),C18甲苯磺酸盐(18TS)和C20-24甲苯磺酸盐(C20-24TS)。在反应过程中制得的其它碳原子数的碳链必须加以分离。这就增加了具体所用产品的成本。
虽然常规烷基芳基磺酸盐很适用于处理轻质油或短链烷烃(从辛烷至十六烷),但它们不能处理重质原油,特别是高蜡含量的重质原油。当与这种原油共存时,其相特性是反常的,即当盐度增加时,不会象通常情况那样发生从下相微乳液向中相微乳液向上相微乳液的转变。而是当盐度从约3000ppm增加到30000ppm时,中相微乳液或者以具有很低增溶作用(通常小于5)的液晶相存在,或者从下相微乳液向上相微乳液的转变中,全然不出现中相微乳液。
出乎意料的是,采用本发明公开的表面活性剂,可使与高蜡含量的原油共存时的相态特性成为常态。此外,在最佳盐度附近呈现很高的增溶作用,与约5或5以下的值不同,常超过40。增溶作用越高,相应于油相与表面活性剂溶液之间的界面张力越低,这就是通过活性溶液驱油法实施强化采油的基础。
表面活性剂用量范围为0.5-3.0%,优选0.5-2.0%而最优选为1.0-1.5%。表面活性剂是分子量为320-650的混合物。助表面活性剂用量为0.1%-1.5%,优选0.25%-1.25%,而最优选0.50%-0.75%,其余为水至100%。诸如仲丁醇等的醇是适用的助表面活性剂。所指百分比是体积百分比。所谓有效量是指波及承载烃的岩层的孔隙体积的10%或高于10%,优选高于25%-100%或更高时所需注入的水性组合物总量。
表面活性剂与常规助表面活性剂一起用于碱性、盐水溶液中以提高原油的采收率。最优选的活性强化采油(EOR)表面活性剂是烷基邻二甲苯磺酸的钠盐。
优选的烷基EOR表面活性剂如二甲苯磺酸盐的优选全合成方法包括三个步骤:烷基化、磺化和中和。
烷基化步骤包括以三氯化铝(AlCl3)为催化剂使最优选的邻二甲苯与正α-烯烃(C12-C30+)混合物进行烷基化形成烷基邻二甲苯烷基化物。该过程是在连续烷基化生产厂进行的,其中邻二甲苯经蒸馏并再循环使用。在再循环过程中也补充新的邻二甲苯。在烷基化条件下,一些邻二甲苯会异构化为间二甲苯,因此最终烷基化产物即烷基化物可能包含1%-5%由间二甲苯烷基化生成的烷基化物。所有制造商如Pilot ChemicalCompany可为烷基化产物提供适用的原料。
磺化步骤包括在连续进行的薄膜反应器中用SO3/空气使烷基化物磺化而形成磺酸产物(SA)。
在小规模磺化中试车间中磺化步骤的工艺参数如下:
  烷基化物供料速率(克/分钟)   SO2速率(升/小时)   空气速率(升/小时)   温度(℃)
  4.5-4.6   14-18   192   60
工业规模磺化车间的工艺参数可相应地按比例放大。
中和步骤包括将SA产物与氢氧化钠水溶液相混合以形成磺酸钠。反应是放热的,混合物的粘度随存在的水量而定。
下表说明本发明烷基芳基磺酸盐比常规烷基芳基磺酸盐有高得多的增溶能力。表中每项都是含1.5%表面活性剂和0.5%作为助表面活性剂的仲丁醇的水溶液与等体积原油相混合并在210下平衡后测得的结果。
表1、对高蜡原油的增溶能力和最佳盐度
  表面活性剂   最佳盐度   增溶作用
  CR1   2.6%NaCl   15
  CR2   1.3%NaCl   40
  TS12+   2.0%NaCl   30
  XS12+   0.7%NaCl   45
  C12XS   1.6%NaCl   2
  C16TS   2.1%NaCl   1
  C18TS   1.9%NaCl   1
  C2024TS   1.6%NaCl   2
上表说明CR1和TS12+,特别是XS12+和CR2+优于窄分布或单一碳链长度的烷基芳基磺酸盐。
虽然不受理论所束缚,但本发明的优点可能是烷基链长度宽分布的烷基芳基磺酸盐的相态特性对原油碳链长度的变化不敏感之故。如下表所示,当原油碳链长度从10增至16时,CR2的最佳盐度只稍有增加,而纯的烷基芳基磺酸盐C12XS的最佳盐度增加到两倍以上。
表2、烷烃原油在75的最佳盐度
  最佳盐度%NaCl
  烷烃碳原子数   C12XS   CR2
  10   1.2   1.4
  12   1.6   1.5
  14   2.1   1.55
  16   2.6   1.6
本发明的另一个优点是表面活性剂水溶液的稳定性提高了。对于常规烷基芳基磺酸盐来说,使表面活性剂溶液在室温下变成不稳定的盐度常常低于与油形成所希望的相态特征的最佳盐度。例如,C18TS在75达0.4%Nacl时就不稳定了,而与原油形成微乳液的最佳盐度为1.9%NaCl。这就不能将C18TS的水溶液用于活性溶液驱油法,即使C18TS在油层条件下能与原油呈现符合要求的相态特性和形成低的界面张力。与此不同,XS12在75在1%NaCl时是稳定的,而与原油形成微乳液的最佳盐度在210时为0.7%NaCl。因此,在室温条件下,在制备和注入表面活性剂水溶液时不会发生操作性问题。于是,精确控制就不那么重要了,专门的培训以及在注入其间的测量和控制可简化或取消。
从经济观点考虑,本发明表面活性剂优于常规烷基芳基磺酸盐。在活性溶液驱油法的工业应用方面,所需表面活性剂量是很大的,常常超过1亿磅。如果仅以窄馏分α-烯烃用于制造表面活性剂,则烯烃生产厂的生产能力要超过几十亿磅,目前这是不现实的。虽然,人们可以建造新的工厂以满足活性溶液驱油法的需求,但未利用的烯烃馏份不易用于其它用途,因此必须考虑用于制造表面活性剂的烯烃原料的成本。因此本发明的烷基芳基磺酸盐组合物及方法可更好地利用A0车间生产的所有不同碳链长度的烯烃。因为目前α-烯烃市场很大程度随C10的需求量和用在塑料生产如聚乙烯和/或聚丙烯中较低碳数原子馏分的需求所带动,在本发明中使用C10为下限(即C12和较高碳原子数馏分)的馏分不会产生矛盾或需折衷选择。这实际上为α-烯烃工厂生产的所有α-烯烃提供了更有效的应用途径。事实上,采取所有C10下限(即C12和C12以上)可免去许多费用高的分馏步骤,从而降低了制造表面活性剂用的α-烯烃原料的成本。
已通过特别优选的实施方案对本发明作了说明。技术熟练人员在本发明范围内所作的改变如采用支化的烷基链和各种芳基特别是邻二甲苯烷基化物的混合物,都属本发明和所附权利要求的范围。

Claims (12)

1.一种从含烃的地下岩层中采收原油的方法,该方法包括(a)将包含有效量的烷基芳基磺酸盐表面活性剂的水溶液注入所述地层中,表面活性剂是通过以烯烃碳原子数分布宽的α-烯烃物料流对芳族化合物进行烷基化反应,其中所述烯烃物料流是工业乙烯合成的α-烯烃反应器产生的C10为下限的碳链馏分,所述烯烃物料流包括C10+至C58碳链馏分,芳族烷基化合物选自苯、甲苯、二甲苯或它们的混合物,然后使所得烷基化产物经磺化,中和而制成的,和(b)驱替所述溶液使其通过地层,达到对含蜡原油的增溶作用大于5,以从采油井采收烃类物质。
2.权利要求1的方法,其中所述烯烃物料流是C12-C40的碳链的各个烯烃馏分的混合物。
3.根据权利要求1的方法,其中芳基化合物是邻二甲苯,其中注入井和采油井选自相同的井,不同的井或它们的组合。
4.权利要求1的方法,其中烷基化作用是在AlCl3或HF基催化剂存在下进行的。
5.权利要求1的方法,其中所述表面活性剂与不同的烷烃油有基本相同的相态特性。
6.权利要求1的方法,其中所述表面活性剂在49°-99℃范围内具有基本相同的相态特性。
7.根据权利要求1的方法,其中注入井与采油井是相同的或不相同的。
8.权利要求1的方法,包括采用烷基芳基磺酸盐混合物作为所述表面活性剂,其中烷基链包括C10-C24碳链,所述碳链是直链、支链或它们的混合物,和
芳基基团是二甲苯,并且邻二甲苯含量超过85%。
9.一种烷基芳基磺酸盐强化采油的表面活性剂组合物,该组合物包含C10+至C58碳链分布的烷基与选自乙基苯、二甲苯、甲苯或它们混合物的芳基基团的磺酸盐,超过50%的芳基是邻、间或对二甲苯,该表面活性剂是分子量为320-650的混合物,以及组合物对含蜡原油的增溶作用大于5。
10.根据权利要求9的组合物,其中芳基中85%或85%以上是邻二甲苯,而其余为间和对二甲苯。
11.根据权利要求10的组合物,其中芳基中90%是邻二甲苯。
12.根据权利要求9的组合物,其中芳基中50%是烷基取代的间二甲苯。
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