CN115029143B - A Carbon Dioxide Responsive Viscosification Surfactant and Its Application in Fracturing Fluids - Google Patents
A Carbon Dioxide Responsive Viscosification Surfactant and Its Application in Fracturing Fluids Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 60
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 60
- 239000012530 fluid Substances 0.000 title claims abstract description 32
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 29
- 230000004044 response Effects 0.000 claims abstract description 17
- 239000002562 thickening agent Substances 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 17
- 239000003345 natural gas Substances 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 abstract description 2
- 230000007797 corrosion Effects 0.000 abstract 1
- 238000005260 corrosion Methods 0.000 abstract 1
- 125000001453 quaternary ammonium group Chemical group 0.000 abstract 1
- 239000011435 rock Substances 0.000 abstract 1
- 150000003512 tertiary amines Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 230000000638 stimulation Effects 0.000 description 15
- 230000008719 thickening Effects 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000002378 acidificating effect Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005755 formation reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229920002907 Guar gum Polymers 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000665 guar gum Substances 0.000 description 2
- 229960002154 guar gum Drugs 0.000 description 2
- 235000010417 guar gum Nutrition 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000009919 sequestration Effects 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 125000001302 tertiary amino group Chemical group 0.000 description 2
- 239000013543 active substance Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
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- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/602—Compositions for stimulating production by acting on the underground formation containing surfactants
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/72—Eroding chemicals, e.g. acids
- C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
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Abstract
Description
技术领域technical field
本发明涉及压裂液稠化剂制备技术领域，该压裂液稠化剂为黏弹性表面活性剂，其具有二氧化碳刺激响应增黏特性，用于天然气、煤层气等的水力压裂。具体涉及一种二氧化碳响应增黏表面活性剂及在压裂液中的应用。The invention relates to the technical field of preparation of a fracturing fluid thickener. The fracturing fluid thickener is a viscoelastic surfactant, which has a carbon dioxide stimulation response viscosity-increasing characteristic, and is used for hydraulic fracturing of natural gas, coal bed methane, and the like. In particular, it relates to a carbon dioxide-responsive viscosity-increasing surfactant and its application in fracturing fluid.
背景技术Background technique
在压裂过程中，压裂液作为传递压力、输送支撑剂的载体，它的性能影响着整个压裂施工的效果。聚合物压裂液体系如硼交联的胍胶及其衍生物压裂液是目前应用最为广发的压裂液体系。然而，多年的现场应用及研究发现，大分子吸附堵塞地层渗流通道、破胶液残渣堵塞支撑剂填充层以及滤饼伤害，是以胍胶及其衍生物作为稠化剂的压裂液影响压裂改造效率的三种主要表现形式。近十几年来，人们针对这几方面的问题做了大量的研究工作，但大分子吸附堵塞及碱性流体侵入伤害等问题仍然没有得到很好的解决。以黏弹性表面活性剂为稠化剂的清洁压裂液体系的出现成功解决了上述问题，但现有的常规的黏弹性表面活性剂在天然气、煤层气等气井压裂时无法自动破胶。另外，随着国家对于全球生态环境变化的重视以及积极应对，提出了“碳达峰，碳中和”的规划目标，进行节能减排。对二氧化碳封存等成为新兴的研究。During the fracturing process, the fracturing fluid is used as a carrier for transmitting pressure and proppant, and its performance affects the effect of the entire fracturing operation. Polymer fracturing fluid systems such as boron-crosslinked guar gum and its derivatives are currently the most widely used fracturing fluid systems. However, many years of field application and research have found that macromolecule adsorption blocks formation seepage channels, gel breaker residue blocks proppant packing layers, and filter cake damage is caused by fracturing fluids that use guar gum and its derivatives as thickeners to affect fracturing fluid. Three main manifestations of cracking transformation efficiency. In the past ten years, people have done a lot of research work on these problems, but the problems of macromolecule adsorption blockage and alkaline fluid intrusion damage have not been well resolved. The emergence of clean fracturing fluid systems using viscoelastic surfactants as thickeners has successfully solved the above problems, but the existing conventional viscoelastic surfactants cannot automatically break the gel when fracturing gas wells such as natural gas and coalbed methane. In addition, as the country attaches great importance to and actively responds to changes in the global ecological environment, it puts forward the planning goal of "carbon peak, carbon neutrality" to carry out energy conservation and emission reduction. Sequestration of carbon dioxide has become an emerging research.
因此，本发明，提供了一种在二氧化碳刺激下能够响应增黏的表面活性剂。在提高表面活性剂作稠化剂制备清洁压裂液的黏弹性同时，不仅能够消耗二氧化碳，封存二氧化碳，减少排放，而且形成的清洁压裂液显酸性，可以溶蚀部分地层中的无机堵塞物。此外，该响应型清洁压裂液，在压裂时能通过置换作用置换出地层中的一些CH4，并降低黏度，实现破胶，顺利排出。Therefore, the present invention provides a surfactant capable of responding to thickening under carbon dioxide stimulation. While improving the viscoelasticity of clean fracturing fluid prepared by using surfactant as a thickener, it can not only consume carbon dioxide, sequester carbon dioxide, and reduce emissions, but also the formed clean fracturing fluid is acidic and can dissolve inorganic blockages in some formations. In addition, this responsive clean fracturing fluid can replace some CH 4 in the formation through displacement during fracturing, and reduce the viscosity to achieve gel breaking and smooth discharge.
发明内容Contents of the invention
为了，响应国家“碳达峰，碳中和”规划目标，本发明提供了一种二氧化碳响应增黏表面活性剂及在压裂液中的应用。本发明不仅可以提高表面活性剂溶液黏弹性，还可以消耗二氧化碳，降低二氧化碳排放，有利于“碳达峰，碳中和”规划目标。In order to respond to the national planning goal of "carbon peaking and carbon neutrality", the present invention provides a carbon dioxide-responsive viscosity-increasing surfactant and its application in fracturing fluid. The invention can not only improve the viscoelasticity of the surfactant solution, but also consume carbon dioxide and reduce carbon dioxide emission, which is beneficial to the planned goal of "carbon peak and carbon neutrality".
本发明提供的具有二氧化碳刺激响应增黏特性的表面活性剂的方案如下：The scheme of the surfactant provided by the present invention with carbon dioxide stimulation response viscosity-increasing properties is as follows:
一种具有二氧化碳刺激响应增黏特性的表面活性剂，具有以下结构通式：A surfactant with carbon dioxide stimulation response viscosity-increasing properties has the following general structural formula:
其中，R1为碳原子数为17-21的不饱和烃链。Wherein, R 1 is an unsaturated hydrocarbon chain with 17-21 carbon atoms.
本发明提供的表面活性剂亲水基团中存在一个季胺基团和一个叔胺基团，季胺基团使得制备的该表面活性剂快速的在水溶液中溶解，叔胺基团使得该表面活性剂能在二氧化碳刺激下响应增黏。There is a quaternary amine group and a tertiary amine group in the hydrophilic group of the surfactant provided by the invention, the quaternary amine group makes the prepared surfactant dissolve quickly in aqueous solution, and the tertiary amine group makes the surface The active agent is capable of increasing viscosity in response to carbon dioxide stimulation.
本发明具有以下有益效果：The present invention has the following beneficial effects:
采用本发明提供的具有二氧化碳刺激响应增黏特性的表面活性剂能够通过二氧化碳增黏，形成酸性压裂液。The surface active agent provided by the present invention with carbon dioxide stimulation response viscosity-increasing properties can increase the viscosity through carbon dioxide to form acidic fracturing fluid.
本发明提供的二氧化碳增黏型压裂液可以通过气体置换作用实现破胶，克服了清洁压裂液在气藏压裂中无法自动破胶的问题。The carbon dioxide viscosity-increasing fracturing fluid provided by the invention can realize gel breaking through gas replacement, which overcomes the problem that clean fracturing fluid cannot automatically break gel in gas reservoir fracturing.
本发明形成的酸性压裂液能够溶蚀部分地层中的无机堵塞物，提高储层基质渗透率。The acidic fracturing fluid formed by the invention can dissolve the inorganic blockages in part of the strata and improve the permeability of the reservoir matrix.
本发明形成的二氧化碳增黏型压裂液可以实现二氧化碳的封存，缓解温室效应。The carbon dioxide viscosity-increased fracturing fluid formed in the invention can realize the sequestration of carbon dioxide and alleviate the greenhouse effect.
附图说明Description of drawings
无。none.
具体实施方式Detailed ways
以下对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。The principles and features of the present invention are described below, and the examples given are only used to explain the present invention, and are not intended to limit the scope of the present invention. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all conventional products that could be purchased from the market.
实施例1Example 1
将权利要求1中所述具有二氧化碳刺激响应增黏特性的表面活性剂用作稠化剂，制备清洁压裂液时，将其与水100：(3-5)比例混合并溶解，并对配制的溶液进行黏度测试，其测试黏度小于5mPa·s。其中黏度测试包括，未通入二氧化碳的溶液进行黏度测试，以及对向配制的溶液中通入二氧化碳，其中通入二氧化碳的时间为3分钟，黏度测试结果为30mPa·s。The surfactant with carbon dioxide stimulation response thickening properties described in claim 1 is used as a thickener, when preparing clean fracturing fluid, it is mixed with water in a ratio of 100: (3-5) and dissolved, and the preparation The solution was tested for viscosity, and its test viscosity was less than 5mPa·s. The viscosity test includes the viscosity test of the solution without carbon dioxide, and the introduction of carbon dioxide into the prepared solution, wherein the carbon dioxide is injected for 3 minutes, and the viscosity test result is 30mPa·s.
实施例2Example 2
将权利要求1中所述具有二氧化碳刺激响应增黏特性的表面活性剂用作稠化剂，制备清洁压裂液时，将其与水100：(3-5)比例混合并溶解，并对配制的溶液进行黏度测试，其测试黏度小于5mPa·s。其中黏度测试包括，未通入二氧化碳的溶液进行黏度测试，以及对向配制的溶液中通入二氧化碳，其中通入二氧化碳的时间为5分钟，黏度测试结果为51mPa·s。The surfactant with carbon dioxide stimulation response thickening properties described in claim 1 is used as a thickener, when preparing clean fracturing fluid, it is mixed with water in a ratio of 100: (3-5) and dissolved, and the preparation The solution was tested for viscosity, and its test viscosity was less than 5mPa·s. The viscosity test includes the viscosity test of the solution without carbon dioxide, and the introduction of carbon dioxide into the prepared solution, wherein the carbon dioxide is injected for 5 minutes, and the viscosity test result is 51mPa·s.
实施例3Example 3
将权利要求1中所述具有二氧化碳刺激响应增黏特性的表面活性剂用作稠化剂，制备清洁压裂液时，将其与水100：(3-5)比例混合并溶解，并对配制的溶液进行黏度测试，其测试黏度小于5mPa·s。其中黏度测试包括，未通入二氧化碳的溶液进行黏度测试，以及对向配制的溶液中通入二氧化碳，其中通入二氧化碳的时间为8分钟，黏度测试结果为84mPa·s。The surfactant with carbon dioxide stimulation response thickening properties described in claim 1 is used as a thickener, when preparing clean fracturing fluid, it is mixed with water in a ratio of 100: (3-5) and dissolved, and the preparation The solution was tested for viscosity, and its test viscosity was less than 5mPa·s. The viscosity test includes the viscosity test of the solution without carbon dioxide, and the introduction of carbon dioxide into the prepared solution. The time of carbon dioxide injection is 8 minutes, and the viscosity test result is 84mPa·s.
实施例4Example 4
将权利要求1中所述具有二氧化碳刺激响应增黏特性的表面活性剂用作稠化剂，制备清洁压裂液时，将其与水100：(3-5)比例混合并溶解，交替通入二氧化碳和CH4。其中，二氧化碳的通入时长为8分钟，然后进行黏度测试，然后再向该溶液中通入CH4后，通入的时长为4分钟，并再对该溶液进行黏度测试。通入二氧化碳的溶液黏度为84mPa·s，通入CH4后的溶液零剪切黏度为27mPa·s。The surfactant with carbon dioxide stimulation response thickening properties described in claim 1 is used as a thickener, and when preparing clean fracturing fluid, it is mixed with water in a ratio of 100: (3-5) and dissolved, and alternately passed into carbon dioxide and CH4 . Wherein, the duration of feeding carbon dioxide was 8 minutes, and then the viscosity test was carried out, and then CH 4 was passed into the solution, and the duration of feeding was 4 minutes, and then the viscosity test was carried out on the solution. The viscosity of the solution injected with carbon dioxide is 84mPa·s, and the zero-shear viscosity of the solution after injected with CH 4 is 27mPa·s.
实施例5Example 5
将权利要求1中所述具有二氧化碳刺激响应增黏特性的表面活性剂用作稠化剂，制备清洁压裂液时，将其与水100：(3-5)比例混合并溶解，交替通入二氧化碳和CH4。其中，二氧化碳的通入时长为8分钟，然后进行黏度测试，然后再向该溶液中通入CH4后，通入的时长为8分钟，黏度测试。通入二氧化碳的溶液黏度为84mPa·s，通入CH4后的溶液零剪切黏度为12mPa·s。The surfactant with carbon dioxide stimulation response thickening properties described in claim 1 is used as a thickener, and when preparing clean fracturing fluid, it is mixed with water in a ratio of 100: (3-5) and dissolved, and alternately passed into carbon dioxide and CH4 . Among them, the duration of feeding carbon dioxide is 8 minutes, and then the viscosity test is carried out, and then CH 4 is passed into the solution, the duration of feeding is 8 minutes, and the viscosity test is carried out. The viscosity of the solution injected with carbon dioxide is 84mPa·s, and the zero-shear viscosity of the solution after injected with CH 4 is 12mPa·s.
实施例6Example 6
将权利要求1中所述具有二氧化碳刺激响应增黏特性的表面活性剂用作稠化剂，制备清洁压裂液时，将其与水100：(3-5)比例混合并溶解，交替通入二氧化碳和CH4。其中，二氧化碳的通入时长为8分钟，然后进行黏度测试，然后再向该溶液中通入CH4后，通入的时长为12分钟，并再对该溶液进行黏度测试。通入二氧化碳的溶液黏度为84mPa·s，通入CH4后的溶液零剪切黏度为3mPa·s。The surfactant with carbon dioxide stimulation response thickening properties described in claim 1 is used as a thickener, and when preparing clean fracturing fluid, it is mixed with water in a ratio of 100: (3-5) and dissolved, and alternately passed into carbon dioxide and CH4 . Wherein, the carbon dioxide was introduced for 8 minutes, and then the viscosity test was performed, and then CH 4 was introduced into the solution, and the injected time was 12 minutes, and then the solution was subjected to the viscosity test. The viscosity of the solution fed with carbon dioxide is 84mPa·s, and the zero-shear viscosity of the solution after fed with CH 4 is 3mPa·s.
实施例7Example 7
将权利要求1中所述具有二氧化碳刺激响应增黏特性的表面活性剂用作稠化剂，制备清洁压裂液时，将其与水100：(3-5)比例混合并溶解，交替通入二氧化碳和N2。其中，二氧化碳的通入时长为8分钟，然后进行黏度测试，然后再向该溶液中通入CH4后，通入的时长为4分钟，并再对该溶液进行黏度测试。通入二氧化碳的溶液黏度为84mPa·s，通入N2后的溶液零剪切黏度为33mPa·s。The surfactant with carbon dioxide stimulation response thickening properties described in claim 1 is used as a thickener, and when preparing clean fracturing fluid, it is mixed with water in a ratio of 100: (3-5) and dissolved, and alternately passed into carbon dioxide and N2 . Wherein, the duration of feeding carbon dioxide was 8 minutes, and then the viscosity test was carried out, and then CH 4 was passed into the solution, and the duration of feeding was 4 minutes, and then the viscosity test was carried out on the solution. The viscosity of the solution fed with carbon dioxide is 84mPa·s, and the zero-shear viscosity of the solution after fed with N 2 is 33mPa·s.
实施例8Example 8
将权利要求1中所述具有二氧化碳刺激响应增黏特性的表面活性剂用作稠化剂，制备清洁压裂液时，将其与水100：(3-5)比例混合并溶解，交替通入二氧化碳和N2。其中，二氧化碳的通入时长为8分钟，然后进行黏度测试，然后再向该溶液中通入CH4后，通入的时长为8分钟，并再对该溶液进行黏度测试。通入二氧化碳的溶液黏度为84mPa·s，通入N2后的溶液零剪切黏度为15mPa·s。The surfactant with carbon dioxide stimulation response thickening properties described in claim 1 is used as a thickener, and when preparing clean fracturing fluid, it is mixed with water in a ratio of 100: (3-5) and dissolved, and alternately passed into carbon dioxide and N2 . Wherein, the length of feeding carbon dioxide was 8 minutes, and then the viscosity test was carried out, and then CH 4 was passed into the solution, the length of feeding was 8 minutes, and the viscosity test was carried out on the solution. The viscosity of the solution fed with carbon dioxide is 84mPa·s, and the zero-shear viscosity of the solution after fed with N 2 is 15mPa·s.
实施例9Example 9
将权利要求1中所述具有二氧化碳刺激响应增黏特性的表面活性剂用作稠化剂，制备清洁压裂液时，将其与水100：(3-5)比例混合并溶解，交替通入二氧化碳和N2。其中，二氧化碳的通入时长为8分钟，然后进行黏度测试，然后再向该溶液中通入CH4后，通入的时长为4分钟，并再对该溶液进行黏度测试。通入二氧化碳的溶液黏度为84mPa·s，通入N2后的溶液零剪切黏度为4.2mPa·s。The surfactant with carbon dioxide stimulation response thickening properties described in claim 1 is used as a thickener, and when preparing clean fracturing fluid, it is mixed with water in a ratio of 100: (3-5) and dissolved, and alternately passed into carbon dioxide and N2 . Wherein, the duration of feeding carbon dioxide was 8 minutes, and then the viscosity test was carried out, and then CH 4 was passed into the solution, and the duration of feeding was 4 minutes, and then the viscosity test was carried out on the solution. The viscosity of the solution fed with carbon dioxide is 84mPa·s, and the zero-shear viscosity of the solution after fed with N 2 is 4.2mPa·s.
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