WO2021027237A1 - 一种致密油气藏开采用超临界二氧化碳稠化剂的制备方法 - Google Patents

一种致密油气藏开采用超临界二氧化碳稠化剂的制备方法 Download PDF

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WO2021027237A1
WO2021027237A1 PCT/CN2019/130305 CN2019130305W WO2021027237A1 WO 2021027237 A1 WO2021027237 A1 WO 2021027237A1 CN 2019130305 W CN2019130305 W CN 2019130305W WO 2021027237 A1 WO2021027237 A1 WO 2021027237A1
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carbon dioxide
hours
add
supercritical carbon
propyl ether
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French (fr)
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周明
张劲风
郭肖
凃宏俊
补军成
彭鹏傲
韩宏昌
陈航
李林凯
廖茂
辜银花
易荣军
史永强
夏亮亮
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西南石油大学
成都赛璐石油科技有限公司
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Priority to US16/928,567 priority Critical patent/US11261373B2/en
Publication of WO2021027237A1 publication Critical patent/WO2021027237A1/zh

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    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
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    • C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
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  • the invention relates to a water-free fracturing fluid that does not use water for the development of tight oil and gas reservoirs and a technology for enhancing oil recovery, in particular to a preparation method of a supercritical carbon dioxide thickener containing fluorine, and belongs to the field of oilfield chemicals .
  • Tight oil and gas reservoirs have the characteristics of poor physical properties, low porosity and low permeability, and usually exhibit strong water sensitivity. Therefore, fracturing and later enhanced oil recovery is an effective way to develop tight oil and gas reservoir resources.
  • the use of conventional mining methods is easy to cause the formation of water lock in the reservoir, and the permeability of the reservoir is reduced, which causes damage to the reservoir and affects the effect of fracturing.
  • people have gradually shifted their focus to waterless fracturing, which basically does not require water during the fracturing process. Therefore, the development of waterless fracturing technology that does not use water has important economic and social effects.
  • the invention patents ZL201710416147.2 (a method for preparing supercritical carbon dioxide thickener) and ZL201710480823.2 (a method for preparing supercritical carbon dioxide thickener) can be used as fracturing fluid base fluid in tight oil and gas reservoirs and improve recovery Yield chemical oil-displacing agents are used, but the prepared carbon dioxide thickeners all have ester groups, which can only be used under lower temperature and less water conditions. When working in oil and gas reservoirs with higher temperature and active side and bottom water, the thermal stability of the two thickeners becomes poor and hydrolysis is prone to occur, resulting in a gradual decrease or even disappearance of thickening ability. Based on this, the present invention prepares a four-chain thickening agent containing ether bonds, which can not only ensure the increase of the viscosity of supercritical carbon dioxide, but also improve the thermal stability and hydrolysis stability of the thickener.
  • the purpose of the present invention is to provide a method for preparing tight oil and gas reservoirs using supercritical carbon dioxide thickening agent in view of the situation that conventional mining methods are likely to cause damage to oil and gas reservoirs.
  • the present invention provides a preparation method of a supercritical carbon dioxide thickening agent suitable for tight oil and gas reservoirs.
  • the preparation method includes the following steps:
  • the advantages and beneficial effects of the invention are that the introduction of fluorine-containing segments into the thickening agent can effectively reduce the pressure required for the thickening agent to dissolve in carbon dioxide and improve the dissolution of the thickening agent in carbon dioxide.
  • the hydrogen bonding between the molecules of the thickener and the entanglement between the molecular chains can effectively increase the viscosity of carbon dioxide.
  • the thickener connects the carbon dioxide-philic group and the hydrogen bond cross-linking associative group by an ether bond instead of an ester bond, which effectively improves the thermal stability and hydrolytic stability of the thickener, and can be applied to dense oil and gas with active edge water Vietnamese mining.
  • the testing method of the viscosity of the thickener first add the thickener according to the dosage to the high temperature and high pressure closed system of the rheometer HAAKE MARS, install the supporting devices of the high temperature and high pressure closed system, and use the vacuum pump to remove the air in the closed system. Then, supercritical carbon dioxide is introduced through the sampling valve of the high temperature and high pressure closed system. At the same time, the inner rotor in the system is adjusted to rotate so that the thickening agent carbon dioxide is fully mixed evenly. When the carbon dioxide is introduced to the metering, the system pressure and temperature are adjusted to make the system The carbon dioxide inside reaches the required state, stirs and mixes evenly, that is, the preparation of the mixed system is completed. Finally, the rheometer is turned on and the experimental parameters are set to test the viscosity of the mixed system.
  • the organic layer was dried with anhydrous Na 2 SO 4 , and 1,6 isodicyanate, 1,6-hexamethylene diisocyanate and 1,3-diisocyanate were added.
  • the molar ratio of fluorooctyl ethanol propyl ether-2-carbamic acid tert-butyl propane is 1:2.05, react at 50°C for 2 hours, wash the crude product 4 times with a mixed solvent of ethyl acetate and benzene, and filter, After vacuum drying, the final product [1,6-bis(1,3-diperfluorooctylethanol-2-ureido)]hexane is finally obtained.
  • the measured viscosity values of the mixed system are 4.12mPa ⁇ s, 4.73mPa ⁇ s and 5.24mPa ⁇ s; they are 106.0 times, 118.5 times and 161.0 times of the viscosity of unthickened supercritical carbon dioxide respectively.

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Abstract

本发明涉及一种致密油气藏开采用超临界二氧化碳稠化剂的制备方法。它能解决常规开采方式对油气储层造成伤害的问题。其技术方案：将瓶放入冰水浴中，向瓶中加入全氟辛基乙醇，再加入甲苯磺酰氯和吡啶，在0-20℃反应3小时，反应结束后加入滤纸，超声波分散1小时，然后去除滤纸，加入稀盐酸洗涤3-5次得中间产物(1)；然后在另一瓶中加入(N-叔丁氧基羰基)丝氨醇和中间产物(1)，再加入碳酸钾和N-N-二甲基甲酰胺，升温到40℃反应4小时制得中间产物(2)；最后加入三氟乙酸和二氯甲烷和中间产物(2)，在45℃反应2小时，萃取真空干燥后，加入1，6-已二异氰酸酯反应2小时得最终产物。该稠化剂能够增加二氧化碳粘度，可用于压裂改造和化学驱。

Description

一种致密油气藏开采用超临界二氧化碳稠化剂的制备方法 技术领域
本发明涉及一种用于致密油气藏储层开发不使用水的无水压裂液和提高采收率技术，特别涉及含有氟元素的超临界二氧化碳稠化剂的制备方法，属于油田化学品领域。
背景技术
致密油气藏储层具有物性差，低孔低渗等特点，通常还表现出很强的水敏性。因此，压裂改造和后期提高采收率是一种开发致密油气藏资源的有效方式。使用常规的开采方式容易使储层形成水锁，储层的渗透率降低，从而对储层造成伤害，影响到压裂增产的效果。为了解决常规开采方式对油气储层造成的伤害，人们逐渐将重点转向了无水压裂，无水压裂在压裂过程中基本不需要水。因此，开发出不使用水的无水压裂技术具有重要的经济和社会效应。发明专利ZL201710416147.2(一种超临界二氧化碳稠化剂的制备方法)和ZL201710480823.2(一种超临界二氧化碳稠化剂的制备方法)能在致密油气藏中作为压裂液基液和提高采收率化学驱油剂使用，但所制备的二氧化碳稠化剂都存在酯基，只能在较低温度及少水条件下使用。在较高温度和边底水活跃的油气藏作用时，两种稠化剂热稳定性变差，易发生水解，导致增稠能力逐渐下降甚至消失。基于此，本发明制备了一种含醚键的四链稠化剂，既能保证提高超临界二氧化碳粘度，同时能提高稠化剂的热稳定性和水解稳定性。
发明内容
本发明的目的是：针对常规开采方式对油气储层易造成伤害的情 况，特提供一种致密油气藏开采用超临界二氧化碳稠化剂的制备方法。
本发明提供一种适合致密油气藏超临界二氧化碳稠化剂的制备方法，所述制备方法包括以下步骤：
(1)对甲苯全氟辛基磺酸酯的制备：向三颈瓶中加入全氟辛基乙醇与对甲苯磺酰氯，全氟辛基乙醇与对甲苯磺酰氯的摩尔比1:1.1-1.2，最后加入吡啶并充分搅拌。保持温度在0-20℃，充分搅拌，反应3小时，反应结束后加入滤纸，超声波分散1小时，除掉未反应的对甲苯磺酰氯，然后去除滤纸，再用15％的稀盐酸多次洗涤除掉吡啶，得到白色固体，最后用蒸馏水多次洗涤，40℃真空干燥3小时，制得中间产物(1)对甲苯全氟辛基磺酸酯，如Ⅰ式所示；
Figure PCTCN2019130305-appb-000001
(2)(1，3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷的制备
(1，3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷的制备：向三颈瓶中加入(N-叔丁氧基羰基)丝氨醇和对甲苯全氟辛基磺酸酯，(N-叔丁氧基羰基)丝氨醇和对甲苯全氟辛基磺酸酯之比为2.1-2.2:1，再加入碳酸钾和N，N-二甲基甲酰胺，充分搅拌，升温至40℃反应4h，反应结束后，用蒸馏水多次洗涤，真空干燥得中间产物(2)即(1，3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷，其结构如Ⅱ式所示。
Figure PCTCN2019130305-appb-000002
(3)最终产物[1,6-二(1，3-二全氟辛基乙醇丙醚-2-脲基)]己烷的制备：向三颈瓶加入二氯甲烷和三氟乙酸的混合溶液，二氯甲烷与三氟乙酸体积比为2:1；将(1，3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷加入到上述混合溶液中，恒温45℃反应2小时，向其中加入二氯甲烷萃取3次，得到有机层，无水Na 2SO 4干燥有机层，加入1-6异二氰酸酯，1,6-己二异氰酸酯与1，3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷的摩尔比为1:2.05-2.10，在50℃条件下反应2小时，用乙酸乙酯和苯的混合溶剂多次洗涤粗产物，过滤，真空干燥，最后得到最终产物[1,6-二(1，3-二全氟辛基乙醇丙醚-2-脲基)]己烷，其结构如III式所示。
Figure PCTCN2019130305-appb-000003
本发明的优点和有益效果在于：向稠化剂中引入含氟链段，能够有效降低稠化剂在二氧化碳中溶解所需的压力，改善稠化剂在二氧化碳中的溶解情况。同时，稠化剂分子间存在的氢键作用，以及分子链之间的缠结作用，能够有效的起到增加二氧化碳粘度的作用。稠化剂由醚键而不是酯键连接亲二氧化碳基团和氢键交联缔合基团，有效提高了稠化剂的热稳定性和水解稳定性，可应用于边底水活跃的致密油气藏开采。
稠化剂粘度的测试方法：先将稠化剂按照加量加入到流变仪HAAKE MARS的高温高压的密闭***，安装好高温高压密闭***的 配套装置，利用真空泵将密闭***中空气排除。然后，通过高温高压密闭***的进样阀导入超临界二氧化碳，同时，调整***中内转子转动，使稠化剂二氧化碳充分混合均匀，待二氧化碳通入到计量时，调节***压力、温度，使***内的二氧化碳达到所需的状态，搅拌混合均匀，即完成混合体系的配制，最后，开启流变仪，设定实验参数后，即可测试混合体系的粘度。
具体实施方式
下面通过实例来说明本发明，但本发明的内容不仅仅局限于下面的实施例。
实施例1
(1)对甲苯全氟辛基磺酸酯的制备：向三颈瓶中加入全氟辛基乙醇与对甲苯磺酰氯，全氟辛基乙醇与对甲苯磺酰氯的摩尔比1:1.1，最后加入吡啶并充分搅拌。保持温度在0℃，充分搅拌，反应3小时，反应结束后加入滤纸，超声波分散1小时，除掉未反应的对甲苯磺酰氯，然后去除滤纸，再用15％的稀盐酸洗涤3次除掉吡啶，得到白色固体，最后用蒸馏水洗涤5次，40℃真空干燥3小时，制得中间产物(1)对甲苯全氟辛基磺酸酯。
(2)(1,3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷的制备：向三颈瓶中加入(N-叔丁氧基羰基)丝氨醇和对甲苯全氟辛基磺酸酯，(N-叔丁氧基羰基)丝氨醇和对甲苯全氟辛基磺酸酯之比为2.1:1，再加入碳酸钾和N，N-二甲基甲酰胺，充分搅拌，升温至40℃反应4h，反应结束后，用蒸馏水洗涤5次，真空干燥得中间产物(2)-(1,3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷。
(3)最终产物[1,6-二(1,3-二全氟辛基乙醇丙醚-2-脲基)]己烷的制备：向三颈瓶加入二氯甲烷和三氟乙酸的混合溶液，二氯甲烷与三氟乙酸体积比为2:1；将(1,3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷加入到上述混合溶液中，恒温45℃反应2小时，向其中加入二氯甲烷萃取3次，得到有机层，无水Na 2SO 4干燥有机层，加入1,6异二氰酸酯，1,6-己二异氰酸酯与1，3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷的摩尔比为1:2.05，在50℃条件下反应2小时，用乙酸乙酯和苯的混合溶剂洗涤粗产物4次，过滤，真空干燥，最后得到最终产物[1,6-二(1，3-二全氟辛基乙醇丙醚-2-脲基)]己烷。
分别取上述1wt％、2wt％、3wt％超临界二氧化碳稠化剂加入到安装好配套装置的高温高压密闭***中；通过进样阀向密闭***中分别导入99wt％、98wt％、97wt％超临界二氧化碳。转动转子，调节***压力和温度值，充分搅拌使稠化剂完全溶解，即完成混合体系的配制；再开启流变仪，设定压力值为29MPa，温度为60℃，实验中保持剪切速率为100s -1，测定混合体系的粘度值分别为4.12mPa·s、4.73mPa·s和5.24mPa·s；分别是未增稠超临界二氧化碳粘度的106.0倍、118.5倍和161.0倍。
实施例2
(1)对甲苯全氟辛基磺酸酯的制备：向三颈瓶中加入全氟辛基乙醇与对甲苯磺酰氯，全氟辛基乙醇与对甲苯磺酰氯的摩尔比1:1.2，最后加入吡啶并充分搅拌。保持温度在20℃，充分搅拌，反应3小时，反应结束后加入滤纸，超声波分散1小时，除掉未反应的对甲苯磺酰氯，然后去除滤纸，再用15％的稀盐酸洗涤4次除掉吡啶，得到白色 固体，最后用蒸馏水洗涤4次，40℃真空干燥3小时，制得中间产物(1)对甲苯全氟辛基磺酸酯。
(2)(1,3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷的制备：向三颈瓶中加入(N-叔丁氧基羰基)丝氨醇和对甲苯全氟辛基磺酸酯，(N-叔丁氧基羰基)丝氨醇和对甲苯全氟辛基磺酸酯之比为2.2:1，再加入碳酸钾和N，N-二甲基甲酰胺，充分搅拌，升温至40℃反应4h，反应结束后，用蒸馏水洗涤4次，真空干燥得中间产物(2)即(1,3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷。
(3)最终产物[1,6-二(1,3-二全氟辛基乙醇丙醚-2-脲基)]己烷的制备：向三颈瓶加入二氯甲烷和三氟乙酸的混合溶液，二氯甲烷与三氟乙酸体积比为2:1；将(1,3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷加入到上述混合溶液中，恒温45℃反应2小时，向其中加入二氯甲烷萃取3次，得到有机层，无水Na 2SO 4干燥有机层，加入1,6异二氰酸酯，1,6-己二异氰酸酯与1,3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷的摩尔比为1:2.10，在50℃条件下反应2小时，用乙酸乙酯和苯的混合溶剂洗涤粗产物4次，过滤，真空干燥，最后得到最终产物[1,6-二(1,3-二全氟辛基乙醇丙醚-2-脲基)]己烷。
分别取上述1wt％、2wt％、3wt％超临界二氧化碳稠化剂加入到安装好配套装置的高温高压密闭***中；通过进样阀向密闭***中分别导入99wt％、98wt％、97wt％超临界二氧化碳。转动转子，调节***压力和温度值，充分搅拌使稠化剂完全溶解，即完成混合体系的配制；再开启流变仪，设定压力值为29MPa，温度为60℃，，实验中保持剪切速率为100s -1，测定混合体系的粘度值分别为3.85mPa·s、4.16mPa·s 和4.76mPa·s；分别是未增稠超临界二氧化碳粘度的96.3倍、104.3倍和118.0倍。
实施例3
(1)对甲苯全氟辛基磺酸酯的制备：向三颈瓶中加入全氟辛基乙醇与对甲苯磺酰氯，全氟辛基乙醇与对甲苯磺酰氯的摩尔比1:1.15，最后加入吡啶并充分搅拌。保持温度在10℃，充分搅拌，反应3小时，反应结束后加入滤纸，超声波分散1小时，除掉未反应的对甲苯磺酰氯，然后去除滤纸，再用15％的稀盐酸洗涤5次除掉吡啶，得到白色固体，最后用蒸馏水洗涤5次，40℃真空干燥3小时，制得中间产物(1)对甲苯全氟辛基磺酸酯
(2)(1,3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷的制备：向三颈瓶中加入(N-叔丁氧基羰基)丝氨醇和对甲苯全氟辛基磺酸酯，(N-叔丁氧基羰基)丝氨醇和对甲苯全氟辛基磺酸酯之比为2.15:1，再加入碳酸钾和N，N-二甲基甲酰胺，充分搅拌，升温至40℃反应4h，反应结束后，用蒸馏水洗涤4次，真空干燥得中间产物(2)即(1,3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷。
(3)最终产物[1,6-二(1,3-二全氟辛基乙醇丙醚-2-脲基)]己烷的制备：向三颈瓶加入二氯甲烷和三氟乙酸的混合溶液，二氯甲烷与三氟乙酸体积比为2:1；将(1,3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷加入到上述混合溶液中，恒温45℃反应2小时，向其中加入二氯甲烷萃取3次，得到有机层，无水Na 2SO 4干燥有机层，加入1,6异二氰酸酯，1,6-己二异氰酸酯与1,3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷的摩尔比为1:2.1，在50℃条件下反应2小时，用乙酸乙酯 和苯的混合溶剂洗涤粗产物5次，过滤，真空干燥，最后得到最终产物[1,6-二(1,3-二全氟辛基乙醇丙醚-2-脲基)]己烷。
分别取上述1wt％、2wt％、3wt％超临界二氧化碳稠化剂加入到安装好配套装置的高温高压密闭***中；通过进样阀向密闭***中分别导入99wt％、98wt％、97wt％超临界二氧化碳。转动转子，调节***压力和温度值，充分搅拌使稠化剂完全溶解，即完成混合体系的配制；再开启流变仪，设定压力值为29MPa，温度为60℃，，实验中保持剪切速率为100s -1，测定混合体系的粘度值分别为4.25mPa·s、4.77mPa·s和5.36mPa·s；分别是未增稠超临界二氧化碳粘度的106.3倍、114.3倍和134.0倍。

Claims (2)

  1. 一种致密油气藏开采用超临界二氧化碳稠化剂的制备方法，其特征在于该制备方法包括以下步骤：
    (1)对甲苯全氟辛基磺酸酯的制备：向三颈瓶中加入全氟辛基乙醇与对甲苯磺酰氯，全氟辛基乙醇与对甲苯磺酰氯的摩尔比1∶1.1-1.2，最后加入吡啶并充分搅拌；保持温度在0-20℃，充分搅拌，反应3小时，反应结束后加入滤纸，超声波分散1小时，除掉未反应的对甲苯磺酰氯，然后去除滤纸，再用15％的稀盐酸多次洗涤除掉吡啶，得到白色固体，最后用蒸馏水多次洗涤，40℃真空干燥3小时，制得中间产物(1)对甲苯全氟辛基磺酸酯；
    (2)(1，3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷的制备：向三颈瓶中加入(N-叔丁氧基羰基)丝氨醇和对甲苯全氟辛基磺酸酯，(N-叔丁氧基羰基)丝氨醇和对甲苯全氟辛基磺酸酯摩尔比为2.1-2.2∶1，再加入碳酸钾和N，N-二甲基甲酰胺，充分搅拌，升温至40℃反应4h，反应结束后，用蒸馏水多次洗涤，真空干燥得中间产物(2)即(1，3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷；
    (3)最终产物[1，6-二(1，3-二全氟辛基乙醇丙醚-2-脲基)]己烷的制备：向三颈瓶加入二氯甲烷和三氟乙酸的混合溶液，二氯甲烷与三氟乙酸体积比为2∶1；将(1，3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷加入到上述混合溶液中，恒温45℃反应2小时，向其中加入二氯甲烷萃取3次，得到有机层，用无水Na 2SO 4干燥有机层，加入1-6异二氰酸酯，1，6-己二异氰酸酯与1，3-全氟辛基乙醇丙醚-2-氨基甲酸叔丁酯)丙烷的摩尔比为1∶2.05-2.10，在50℃条件下反应2小时，用乙酸乙酯和苯的混合溶剂多次洗涤粗产物，过滤，真空干燥，最后得到 最终产物[1，6-二(1，3-二全氟辛基乙醇丙醚-2-脲基)]己烷。
  2. 权利要求1中所述致密油气藏开采用超临界二氧化碳增稠剂的应用，其特征在于：分别取上述1wt％、2wt％、3wt％超临界二氧化碳增稠剂加入到安装好配套装置的高温高压密闭***中；通过进样阀向密闭***中分别导入99wt％、98wt％、97wt％超临界二氧化碳；转动转子，调节***压力和温度值，充分搅拌使稠化剂完全溶解，即完成混合体系的配制；开启流变仪，设定压力值为28MPa，温度为60℃，测定混合体系的粘度值与未增稠的超临界二氧化碳的粘度相比，增加96～163倍。
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