CN1954049B - 通过改变重油弹性模量的重油粘弹性改质 - Google Patents
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Abstract
一种通过改变重油弹性模量改质重油粘弹性的方法。使用有效量的一种或多种弹性模量降低剂,其中优选的弹性模量降低剂包括无机和有机酸和碱,优选强碱,比如选自碱金属和碱土金属的金属的氢氧化物。
Description
发明领域
本发明涉及通过改变重油弹性模量,改质升级重油粘弹性的方法。使用有效量的一种或多种弹性模量降低剂,其中优选的弹性模量降低剂包括无机和有机酸,和碱,优选强碱,比如选自碱金属和碱土金属的金属氢氧化物。
发明背景
原油的特性通常取决于油层的地理位置和其地质成因和生物降解的程度。尽管更希望生产轻质,粘性较低,低酸性低硫原油,但这样的原油变得越来越难以发现。许多现在出售的原油是具有高酸性和高粘度的重质含硫原油,并具有差的流动性质使它们难以从地下油层采集,并难以通过管道输送。同样,在炼油厂中,得自于这样原油的渣油也存在同样的流动问题,而且压注性能很差,会堵塞加工设备或者使这样的原油加工不太有效。
常规的原油改质升级的方法集中于减少粘度。在原油生产,运输和精制操作中,减少粘度是重要的。重质原油的运输商和炼油商已经开发了不同的方法以减少重质原油的粘度从而改善其可泵性。通常实施的方法包括用凝析油稀释原油并用苛性碱和水乳化。热处理原油减少其粘度同样是本领域众所周知的。工业上使用热技术用于减粘裂化和氢化减粘裂化(用加氢减粘裂化)。热处理或者添加剂增强的烃减粘裂化的现有技术教导了通过几种不同的方法,改进原油,原油蒸馏物或者渣油的质量或者减少粘度的方法。例如,几篇参考文献教导使用添加剂,比如使用自由基引发剂(US 4,298,455),硫醇化合物和芳香氢供体(EP 175511),自由基受体(US 3,707,459),和氢供体溶剂(US4,592,830)。其它的技术教导使用特定的催化剂,比如低酸性的沸石催化剂(US 4,411,770)和钼催化剂,硫化铵和水(US 4,659,453)。其它的参考文献教导改质升级石油渣油和重油(Murray R.Gray,Marcel Dekker,1994,pp.239-243)和热分解环烷酸(US 5,820,750)。
在美国专利申请20040035749中教导API比重为6-12的原油流动性质,可以在适当的减少粘度添加剂存在下,通过将所述原油加热到35℃-200℃的温度,用足够高的剪切力剪切所述加热的原油以使所述原油粘度减少到250厘泊(cP)-1000厘泊的范围而得以改善。适当的降低粘度的添加剂包括汽油,石脑油,丁醇,石油醚,柴油燃料,基于柑桔油的清洁剂和脱脂剂,和其混合物。
同样,美国专利申请20030132139,其在此引入作为参考,教导通过使用酸和声波处理的组合减少原油和渣油的粘度。每一种单独基本上不能减少粘度,只有当能量,在这种情况下形式为声能,与酸结合使用时,可导致粘度大幅减少。
尽管有许多减少粘度提高原油流动性质的技术,但通常忽视原油同样是粘弹性流体,因此许多的具有高粘度的那些重质原油同样具有相对高的弹性。所述高弹性重油对流动产生有害影响,特别是在处理容器中注入重油期间。最通常使用的改质升级重油的工艺是焦化。粘弹性油在进料注入到炼焦器中时,由于在原料注入期间形成所谓的“颈状物”或者丝状物提出了十分不寻常的难题。通过消除丝状物或者颈状物而改进原料注入从而可以改善重油焦化效率。因此,本领域中仍需要用希望影响原油弹性的试剂处理原油。
发明内容
根据本发明,提供一种通过降低重油弹性模量改质升级重油的方法,因此改进重油的流动性质,所述的方法包括:
用有效量弹性模量降低剂处理所述原料,所述的弹性模量降低剂选自有机和无机酸和碱,和金属卟啉。
在一个优选实施方式中,弹性模量降低剂是酸的混合物,或者一种或多种酸和一种或多种金属卟啉的混合物。
在另外的优选实施方式中,弹性模量降低剂是碱的混合物,一种或多种碱和一种或多种金属卟啉,金属环烷酸盐,金属乙酰丙酮化物,金属羰酸盐,和一种和两种金属酚盐的混合物。
在一个优选实施方式中,弹性模量降低剂是选自硫酸,盐酸和高氯酸的无机酸。
在另外的优选实施方式中,弹性模量降低剂是有机酸,选自乙酸,对甲苯磺酸,烷基甲苯磺酸,单,二和三烷基磷酸,有机单或者二羧酸,甲酸,C3-C16有机羧酸,琥珀酸和低分子量石油环烷酸。
在本发明又一个优选实施方式中,弹性模量降低剂是碱,选自碱金属或者碱土金属氢氧化物,优选选自氢氧化钠和氢氧化钾。
在本发明又一个优选实施方式中,弹性模量降低剂是金属卟啉。
在另外的优选实施方式中,所述原料是减压渣油。
在又一个优选实施方式中,提供一种通过用如上所述的一种或多种弹性模量降低剂处理重油改善重油注入的方法。
在又一个优选实施方式中,提供一种通过用如上所述的一种或多种弹性模量降低剂处理粘弹性流体改善粘弹性流体流动的方法。
在另外的优选实施方式中,弹性模量降低剂与有效量蒸汽一起引入所述重油原料中。
附图简述
本发明的图1是四种代表性的重质原油,Kome,Hoosier,Tulare andCeltic的“颈”长度对喷嘴出口能量的曲线。
本发明的图2是五种代表性的实施例13-17重质原油的伸长模量对弹性模量的关联曲线。
图3显示出侧面对侧面的对比图片,证明相对于未经处理的重质原油(右手边边框),当弹性模量降低剂加入到重质原油(左手边边框)中由于减少弹性获得的出乎意料的结果。
本发明的详细说明
本发明涉及使用各种各样的化学试剂降低重石油,包括原油以及它们相应的残渣的弹性模量。根据本发明可处理的重石油原料是那些具有高粘性模量和高弹性模量的原料。来自不同地区源的原油它们的弹性模量和粘性模量是不同的。例如,来自美国Mexico和Talco的Maya原油的弹性模量在45℃下为0.090Pa或更少,而来自Venezuela的Hamaca原油的弹性模量在同样温度下大于5Pa(帕斯卡)。原油的弹性模量通常范围为3.3-54Pa,对于渣油通常范围为33-540Pa。所述弹性模量可以通过本领域普通技术人员熟知的振动粘度测量确定。如本发明使用的术语“重油”指API比重小于20的烃油,包括石油原油以及从这样的原油常减压蒸馏获得的渣油。
应理解本发明可以针对各种型式的粘弹性流体进行实施,优选重油。例如,如果重油是在地下油层中的原油,那么可以将有效量的弹性模量降低剂泵送进入油层以减少所述原油的流动特性,因此它更容易地流过地层孔隙并进入井眼被运送到表面。所述弹性模量降低剂也可以在地面设施中施加到所述重油中,从而减少油的弹性,因此它可以更容易地通过管道输送。所述弹性模量降低剂也可以利用载流体,比如蒸汽,轻油或者馏出物进行给料。
所述弹性模量降低剂也可以加入到要送到延迟焦化装置的渣油中。所述模量降低剂优选通过利用原料注入而加入到要送到延迟焦化装置的渣油中。通常有三种不同类型具有不同价值,外观和特性的固体延迟焦化装置产品,即针状焦,海绵状石油焦和粒状焦。针状焦是三个品种中性能最高的。针状焦一经进一步热处理就具有高的电导率(和低的热膨胀系数),可用于电弧炼钢中。它的硫和金属相对的低,通常从一些较高性能的焦化装置原料中生产,所述的原料包括更多的芳香原料,比如来自催化裂化器和热裂化焦油的浆料和澄清油。通常,它不是由渣油原料的延迟焦化形成的。
海绵状焦,一种低品质焦炭,最通常在炼油厂形成。含有大量沥青烯,杂原子化合物和金属的低品质的炼油厂焦化装置原料生产这种低品质的焦炭。如果所述硫和金属含量足够的低,则海绵状焦可以用于制造铝工业用电极。如果所述硫和金属含量过高,那么所述焦炭可以用作燃料。名称“海绵状焦”来自其多孔的海绵状外观。常规的延迟焦化过程,使用本发明优选的减压渣油原料,通常生产作为聚结物的海绵状焦,需要包括钻削和水喷射技术的广泛的去除方法。如所讨论的,这种去除由于增加周期而使所述方法变得相当地复杂。
使用本发明的弹性模量降低剂,当在延迟焦化渣油情况下使用时,能够生产更大量的粒状焦,优选基本上是自由流动的粒状焦。尽管粒状焦是延迟焦化中生产的一种品位最低的焦炭,但尤其是当它基本上自由流动时是有利的,因为它大幅减少了从焦炭塔排空焦炭所需要的时间。加入本发明弹性模量降低剂可改进渣油注入焦化装置加热炉,因此所谓的“长颈瓶”基本上被减少,有时被消除。
实施本发明的弹性模量降低剂用量具有相对宽的范围,取决于特定的粘弹性流体,使用的特定试剂及其使用的条件。通常,使用量范围为0.01-10wt%,优选0.1-5wt%,更优选0.1-1wt%。所述wt.%基于粘弹性流体的重量。
所述弹性模量降低剂使用的温度是促进所述试剂与所述粘弹性流体有效接触的有效温度。所述温度范围通常为10℃到高达然而不包括发生热裂化的温度,370℃。
在又一个实施方式中,所述弹性模量降低剂可用于在焦化之前处理渣油,因此它改善原料注入。
可用于实施本发明的弹性模量降低剂非限制性的例子包括酸,碱和卟啉。所述酸可以是无机酸或者有机酸。如果是无机酸,优选的酸选自硫酸,盐酸和高氯酸,更优选硫酸和盐酸。尽管硝酸同样可以降低重质石油的弹性模量,但应该避免使用,因为它可能形成爆炸混合物。可用于实施本发明的有机酸非限制性的例子包括对甲苯磺酸,烷基甲苯磺酸,单,二和三烷基磷酸,有机的单或者二羧酸,甲酸,C3-C16有机羧酸,琥珀酸和低分子量石油环烷酸。优选的有机酸包括对甲苯磺酸。更优选乙酸。环烷酸含量高的原油(TAN)可以用作石油环烷酸的源。无机酸的混合物,有机酸的混合物,或者无机物和有机酸的组合物可以用于产生相同的效果。如本发明使用,原油渣油定义为来自常压的或者减压蒸馏获得的残余原油。
如果是碱用作弹性模量降低剂,则优选碱是碱金属优选钠或者钾的氢氧化物,碳酸钠和碳酸钾,或者碱土金属优选钙和镁的类似物。更优选氢氧化钠和氢氧化钾。
在本发明中金属卟啉同样适合作为弹性模量降低剂。适合用于本发明的金属卟啉非限制性例子包括选自钒,镍,铬,锰,铁,钴,铜和锌的金属的那些。钒和镍是优选的,钒是更优选的。
参考以下仅用于说明性目的的实施例可以更好地理解本发明。
实施例
实施例1-4
使用Hamaca原油通过进行一组重油试验测试沥青烯,环烷酸和碱性氮化合物对重油粘弹性地影响。在实施例1中,Hamaca原油使用正庚烷进行溶剂脱沥青。得到的脱沥青原油命名为HAMACA-ASPH。在实施例4中,将沥青烯再加入到实施例1产生的脱沥青中命名为HAMACA DAO+ASPH。在实施例2中,从所述原油中除去环烷酸命名为HAMACA-NAP ACID。在实施例3中,实施例2的产品用正庚烷脱沥青命名为HAMACA-NAP ACID-ASPH。测定所有样品的弹性模量和粘性模量,结果列于以下表I中。
表I
实施例 | 样品 | 弹性模量G’(Pa) | 粘性模量G”(Pa) |
HAMACA原油 | 3.33 | 54.69 | |
1 | HAMACA-ASPH | 0.72 | 7.62 |
2 | HAMACA-TAN | 0.54 | 11.15 |
3 | HAMACA-TAN-ASPH | 0.17 | 2.07 |
4 | HAMACA DAO+ASPH | 2.94 | 29.05 |
上述数据表明通过除去重油中的沥青烯和环烷酸可以降低弹性模量。
实施例5-12
在以下的实施例中,用以下表II中所示浓度的氢氧化钠,硫酸和对甲苯磺酸处理三个Cold Lake原油样品(a,b和c)。使用以振动模式操作的粘度计测定每一样品的弹性模量(G′)和粘性模量(G″)。结果列于以下表II中。
表II
原油源 | 实施例 | 弹性模量降低剂 | 操作温度℃ | 弹性模量G’(Pa) | 粘性模量G”(Pa) |
a | 5 | 无 | 40 | 2.84 | 40.10 |
a | 6 | 1%氢氧化钠水溶液 | 40 | 1.26 | 40.78 |
a | 7 | 无 | 60 | 0.69 | 8.52 |
a | 8 | 1%硫酸水溶液 | 60 | 0.31 | 14.78 |
b | 9 | 无 | 45 | 3.64 | 51.37 |
b | 10 | 1%对甲苯磺酸 | 45 | 2.00 | 51.30 |
c | 11 | 无 | 60 | 2.70 | 27.06 |
c | 12 | 0.1%氧钒基卟啉 | 60 | 1.48 | 12.90 |
上述表中的数据表明本发明出乎意料的特征在于沥青烯和环烷酸不必从重油中除去以降低其弹性模量。这与如以上表I中所示的本领域的教导,只有通过除去沥青烯和环烷酸降低弹性模量相反。以上表显示出本发明的弹性模量降低剂在不除去沥青烯和环烷酸的情况下可以降低弹性模量。同样显示出也可以使用对于降低弹性模量具有选择性的弹性模量降低剂而基本上不改变粘性模量。例如,如在实施例6和10中,在粘性模量基本上没有变化的情况下,使用本发明的试剂可减少重油的弹性模量。在实施例8中,弹性模量被大幅降低,而其中粘性模量大幅增加。
实施例13-17
以下表III中列出的一组重油经受原料注入试验。原料注入装置包括正排量泵,将重油泵送通过开口直径为0.25cm的阀针。所述阀针位于充满水的圆柱玻璃管中,通过开口的渣油流速可改变。所述圆柱的玻璃管录像以记录重油通过所述开口显现的流动特性。
Cold Lake原油代表性的画面显示于本文的图3中。对于重油当它从所述开口出现时观察到长的“颈”,如在本文中图3右手侧的画面所示。观察到的“成颈”现象起因于粘弹性油的高弹性模量。所述颈长度作为流速或者喷嘴出口能量的函数而变化。对于四种代表性重油的颈长度对喷嘴出口能量的曲线显示于本发明的图1种。从各别曲线的斜率计算伸长模量(E),计算值列于本发明的表III中。所述伸长模量(E)与通过振动粘度测定法确定的弹性模量(G′)关联良好,显示于本发明图2的关联曲线中。
所述关联暗示所述弹性模量的减少将减少“成颈”。因此,在重油原料注入通过焦化装置加热炉的分布器盘之前,通过处理所述重油减少弹性模量实施本发明也可以改善焦化装置的重油原料注入。的确,如在图3左手边的画面中注意到的,当cold lake原油用弹性模量还原剂(1wt%硫酸)处理时,我们注意到所述的颈完全消失了。
表III
实施例 | 原油 | 斜率(E) |
13 | Maya Mexico | 0.49 |
14 | Talco(USA) | 0.52 |
15 | Hoosier(Canada) | 17.6 |
16 | Kome(Chad) | 33.5 |
17 | Tulare(USA) | 11.8 |
Claims (19)
1.一种通过降低重油进料弹性模量改进重油进料流动性的方法,所述的方法包括:
用选自卟啉的有效量的一种或多种弹性模量降低剂处理进料。
2.权利要求1的方法,其中所述卟啉包括至少一种金属卟啉。
3.权利要求2的方法,其中所述金属卟啉选自镍和/或钒卟啉。
4.前述权利要求中任一项所述的方法,其中所述弹性模量降低剂还包括酸或碱。
5.权利要求4的方法,其中所述弹性模量降低剂还包括选自硫酸、盐酸和高氯酸的至少一种酸。
6.权利要求4的方法,其中所述弹性模量降低剂为选自碱金属和/或碱土金属的金属的至少一种氢氧化物。
7.权利要求6的方法,其中所述氢氧化物为选自钠、钾、钙和镁的一种或多种金属的氢氧化物。
8.一种延迟焦化方法,包括:
a)在第一加热区加热在室温下基本上为固体的石油渣油,到低于焦化的温度,使其转化为可用泵送的液体;
b)将所述加热的渣油导入第二加热区,其中所述加热的渣油被加热到有效焦化的温度;
c)将所述加热的渣油从所述第二加热区导入到焦化区中,其中从塔顶馏出物收集蒸气产物,形成焦炭;和
d)向所述渣油或者加热的渣油中引入至少一种有效降低渣油弹性模量的弹性模量降低剂,该弹性模量降低剂选自卟啉,其中所述的至少一种弹性模量降低剂在第一加热区的上游,第二加热区的上游或者两者的上游适当的位置处引入所述的减压渣油中。
9.权利要求8的方法,其中所述卟啉包括至少一种金属卟啉。
10.权利要求9的方法,其中所述金属卟啉选自镍和/或钒卟啉。
11.权利要求8~10中任一项的方法,其中所述的弹性模量降低剂还包括酸或碱。
12.权利要求11的方法,其中所述的弹性模量降低剂是选自硫酸,盐酸和高氯酸的至少一种无机酸。
13.权利要求12的方法,其中所述的酸选自硫酸和盐酸。
14.权利要求11的方法,其中所述的酸是选自对甲苯磺酸,烷基甲苯磺酸,一,二和三烷基磷酸,有机单或者二羧酸,甲酸,C3-C16有机羧酸,琥珀酸,低分子量石油环烷酸和其混合物的有机酸。
15.权利要求11的方法,其中所述的酸是对甲苯磺酸。
16.权利要求11的方法,其中所述的弹性模量降低剂是选自碱金属和/或碱土金属的金属的至少一种氢氧化物。
17.权利要求16的方法,其中所述的氢氧化物是选自钠,钾,钙和镁的一种或多种金属的氢氧化物。
18.权利要求17的方法,其中所述的氢氧化物是选自钠和/或钾的金属的氢氧化物。
19.权利要求8的方法,其中所述的弹性模量降低剂与有效量蒸汽结合使用。
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US20050258075A1 (en) | 2005-11-24 |
CN1954049A (zh) | 2007-04-25 |
WO2005113707A1 (en) | 2005-12-01 |
CA2566117C (en) | 2012-12-04 |
CA2566117A1 (en) | 2005-12-01 |
JP2007537342A (ja) | 2007-12-20 |
EP1773967A1 (en) | 2007-04-18 |
BRPI0510984A (pt) | 2007-12-04 |
MXPA06012602A (es) | 2007-01-31 |
AU2005245862A1 (en) | 2005-12-01 |
US7794586B2 (en) | 2010-09-14 |
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