WO2013170492A1 - 一种复合型油气田缓蚀剂 - Google Patents

一种复合型油气田缓蚀剂 Download PDF

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WO2013170492A1
WO2013170492A1 PCT/CN2012/075926 CN2012075926W WO2013170492A1 WO 2013170492 A1 WO2013170492 A1 WO 2013170492A1 CN 2012075926 W CN2012075926 W CN 2012075926W WO 2013170492 A1 WO2013170492 A1 WO 2013170492A1
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corrosion inhibitor
corrosion
gas field
oil
acid
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PCT/CN2012/075926
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English (en)
French (fr)
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杜磊
张金钟
上官昌淮
郭成华
汤晓勇
杜通林
施岱艳
姜放
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中国石油集团工程设计有限责任公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids

Definitions

  • the invention relates to an oil and gas field corrosion inhibitor, which is mainly used for oil and gas well production and metal anticorrosion in pipeline transportation process, and belongs to the field of fine chemicals.
  • H 2 S and CO 2 gases can cause downhole oil production, gas equipment perforation corrosion or fracture, and conventional drilling.
  • Methods and anti-corrosion measures have not solved the corrosion problem of equipment. Adding a small amount of corrosion inhibitor to the medium can significantly reduce the corrosion rate of the metal material and maintain the physical and mechanical properties of the metal.
  • the corrosion inhibitor has the characteristics of low cost, simple operation, quick effect, protection of the whole equipment and long-term protection. The use of corrosion inhibitor is undoubtedly one of the best protection measures for oil and gas field equipment.
  • adsorption type corrosion inhibitors such as imidazolines, quaternary ammonium salts and amides. It is generally believed that these corrosion inhibitors have good corrosion inhibition properties.
  • imidazoline and amide corrosion inhibitors are generally poorly water-soluble, and are incompatible with chemical additives in oil and gas fields, which are prone to precipitation and seriously affect the use of various chemicals.
  • the technical problem to be solved by the present invention is to provide a corrosion inhibitor for oil and gas fields with good compatibility.
  • the gist of the present invention is that a combination of benzoic acid dicyclohexanamide and triphenylamine oleate is used as a main agent of the corrosion inhibitor.
  • the specific formula of the oil and gas field corrosion inhibitor of the invention is:
  • the acyl group in the acid dicyclohexanamide increases the electron cloud density of the amino group.
  • the benzene ring in the triphenylamine oleate is conjugated with the amino group, increasing the electron cloud density of the N atom, making them empty with iron atoms.
  • the orbital forms a coordination bond, which is closely adsorbed on the surface of the iron.
  • the long-chain hydrophobic alkyl group at the other end can effectively prevent the entry speed of water and corrosive agents, and the two synergistically greatly retard the metal corrosion rate.
  • the preparation method of the toluene dicyclohexanamide in the above formula may be:
  • the preparation method of the triphenylamine oleate in the above formula may be:
  • the flask was charged with oleic acid and triphenylamine in a molar ratio of 1:1, and stirred well at 70 ° C until completely dissolved, kept at a constant temperature for 3 hours, and recrystallized after cooling to obtain triphenylamine oleate.
  • the oil and gas field corrosion inhibitor of the invention is prepared by first dissolving citric acid in water, separately adding hexane, propynol and nonionic surfactant, and after fully stirring, adding toluene dicyclohexanamide and three The aniline oleate can be stirred evenly.
  • the oil and gas field corrosion inhibitor of the invention is used for oil preservation in oil and gas wells containing CO 2 and H 2 S in oil and gas fields, and in ground gathering pipelines.
  • the corrosion inhibitor of the invention is used for the collection and transportation of acid and high acid oil and gas fields.
  • the oil and gas field corrosion inhibitor of the invention has good dispersibility, and the compatibility with the acid liquid system reaches one level, and the corrosion inhibition efficiency can reach 95%. It has the advantages of good compatibility, wide practicality, etc. In actual use, it can exert good corrosion protection effect and does not affect the performance of other chemical agents.
  • the corrosion inhibitor example formulation is as follows (% by mass):
  • Formulation process first dissolve citric acid in water, then add hexane, propynol and nonionic surfactant separately, stir well, then add toluene dicyclohexanamide and triphenylamine oleate, and finally stir evenly can.
  • the contact angle refers to the angle between the tangential line of the gas-liquid interface made at the intersection of gas, liquid and solid three-phase through the boundary between the liquid and the solid-liquid boundary. , is a measure of the degree of wetting, is an important indicator to measure the tightness of liquid binding on a solid surface.
  • Use Kruss DSA20 contact angle measuring instrument measured the contact angle of the above four corrosion inhibitor formulations with carbon steel surface as shown in Table 2, which indicates that the corrosion inhibitor has good wettability with the steel surface, and the contact is tight, which can effectively prevent the corrosion liquid and Carbon steel contact, good corrosion inhibition .
  • test piece material is N-80 and the size is 50 ⁇ 10 ⁇ 3 mm.
  • Test temperature is 14 0 °C, the pressure is 16 MPa, and the test time is 4 hours.
  • the acid solution is a solution containing 15% hydrochloric acid or 15% earth acid (see SY 5405-1996 "Table 3 of the Test Methods and Evaluation Indicators for Corrosion Inhibitor Performance".
  • the new corrosion inhibitor of Example 1 was added to the acid solution, and the amount of the corrosion inhibitor was 2% to 3% of the acid solution.
  • test pieces were polished one by one with 400 # metallographic sandpaper, and then the surface was cleaned with acetone to remove oil stains.
  • test piece After dry weighing, the test piece was immersed in a constant temperature acid solution added with a corrosion inhibitor for 4 hours (while blanking with an acid solution without a corrosion inhibitor), and then weighed.
  • the corrosion inhibition rate calculation formula is:

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

一种油气田缓蚀剂及其制备方法。缓蚀剂成分及质量百分比为：妥儿酸二环己酰胺：5%-20%；三苯胺油酸盐：10%-30%；非离子表面活性剂：1%-3%；已二醇：10%-15%；丙炔醇：5%-10%；柠檬酸：1%-3%；水：余量；其制备方法为：先把柠檬酸溶解于水中，再分别加入已二醇、丙炔醇和非离子表面活性剂，充分搅拌后，加入妥儿酸二环己酰胺和三苯胺油酸盐，搅拌均匀。

Description

一种复合型油气田缓蚀剂 技术领域
本发明涉及一种油气田缓蚀剂，主要用于油、气井生产，管道运输过程中的金属防腐，属于精细化工领域。
背景技术
油气勘探工业的不断发展，钻探深部地层及含有H2S、CO2 、盐水及其混合物的地层逐渐增多，H2S和CO2气体会引起井下采油、气设备穿孔腐蚀或断裂，用常规钻井方法及防腐措施已不能解决设备腐蚀问题。 在介质中加人少量缓蚀剂 , 可显著减少金属材料的腐蚀速度 , 并可保持金属的物理机械性能不变。缓蚀剂具有成本低、操作简单、见效快、能保护整体设备、适合长期保护等特点 , 采用缓蚀剂无疑是油气田设备的最佳防护措施之一。
传统的油气田缓蚀剂为非环保型的有机化合物，部分还带有剧毒，比如嘧啶和胫类等。随着我国石油企业不断提高企业质量、安全、环境管理要求，已经相继被淘汰。
目前国内使用较多的缓蚀剂基本都是吸附型缓蚀剂，如咪唑啉、季铵盐和酰胺等，普遍认为这些缓蚀剂有较好的缓蚀性能。但咪唑啉和酰胺类缓蚀剂通常水溶性较差，与油气田化学添加剂不配伍，极易产生沉淀现象，严重影响各种药剂的使用效果。
发明内容
本发明所要解决的技术问题是提供一种配伍性好的油气田缓蚀剂。
除非另有说明，本文中出现的百分比都为质量百分含量。
本发明的要点是：用妥儿酸二环己酰胺和三苯胺油酸盐联合作为缓蚀剂的主剂。本发明的油气田缓蚀剂具体的配方为：
妥儿酸二环己酰胺 5%-20%
三苯胺油酸盐 10%-30%
非离子表面活性剂 1%-3%
已二醇 10%-15%
丙炔醇 5%-10%
柠檬酸 1%-3%
水 余量
妥儿酸二环己酰胺中的酰基增加了氨基的电子云密度，三苯胺油酸盐中的苯环与氨基共轭，增大了N原子的电子云密度，使得他们与铁原子上的空轨道形成配位键，紧密吸附在铁的表面，另一端的长链疏水烷基可有效阻止水和腐蚀剂的进入速度，二者协同作用，大大延缓金属腐蚀速率。
上述配方中的妥儿酸二环己酰胺的制备方法可以为：
向 干燥好的三口烧瓶中加入 0.1mol 妥儿酸 和 0.15mol 氯化亚砜，氮气保护 , 在水浴中 加热回流半小时，反应体系保持干燥。直到没有烟气产生之后加入 0.12mol 二环己胺 和 20ml 吡啶，加热回流 4～5 小时。用冰浴将反应物冷却并搅拌 。取出沉淀物，用少量冷水冲洗，干燥，利用吡啶溶解进行重结晶得到白色粉末，即为妥儿酸二环己酰胺。
上述配方中的所述的三苯胺油酸盐的制备方法可以为：
用摩尔比为1:1的油酸和三苯胺加入烧瓶，在70℃下充分搅拌，至完全溶解，恒温3小时，冷却后经重结晶得到三苯胺油酸盐。
本发明的油气田缓蚀剂的制备方法为：先把柠檬酸溶解于水中，再分别加入已二醇、丙炔醇和非离子表面活性剂，充分搅拌后，加入妥儿酸二环己酰胺和三苯胺油酸盐，搅拌均匀即可。
本发明的油气田缓蚀剂用于油气田含CO2和H2S的油井、气井，以及地面集输管道中的金属防腐。
本发明的缓蚀剂剂用于酸性和高酸性油气田集输和储运系统。
本发明的油气田缓蚀剂具有良好的分散性，与酸液体系的配伍性能达到一级，缓蚀效率可达到95%。具有配伍性好、实用性广等优点，在实际使用中，更能发挥良好的腐蚀防护作用，同时也不影响其他化学剂的使用性能。
具体实施方式
实施例1
缓蚀剂实施例配方如下表（质量百分比%）：
表一 配方试验
试验序号 妥儿酸二环己酰胺 三苯胺油酸盐 非离子表面活性剂 已二醇 丙炔醇 柠檬酸 水
配方1 5% 10% 1% 10% 10% 1% 余量
配方2 10% 15% 2% 15% 5% 2% 余量
配方3 15 20% 3% 10% 10% 3% 余量
配方4 20% 30% 2% 15% 5% 2% 余量
配方工艺：先把柠檬酸溶解于水中，再分别加入已二醇、丙炔醇和非离子表面活性剂，充分搅拌，再加入妥儿酸二环己酰胺和三苯胺油酸盐，最后搅拌均匀即可。
实施例2
接触角测量
接触角是指在气、液、固三相交点处所作的气-液界面的切线穿过液体与固 - 液交界线之间的夹角 ，是润湿程度的量度，是衡量液体在固体表面结合紧密程度的重要指标。 利用Kruss DSA20型接触角测量仪测得上述四种缓蚀剂配方与碳钢表面的接触角如表二，这表明该缓蚀剂与钢表面有良好的浸润性，接触紧密，可有效阻止腐蚀液与碳钢接触，起到良好缓蚀作用 。
表二 接触角测量
试验序号 接触角（度）
配方1 15.5
配方2 15.1
配方3 14.9
配方4 15.4
实施例3
缓蚀效率测量
根据SY 5405-1996《酸化用缓蚀剂性能试验方法及评价指标》，通过试验模拟具体说明本发明复合型油气田缓蚀剂的缓蚀效果，见表三。具体步骤：
(a) 试件材料为N-80，尺寸为50×10×3 mm。试验温度为14 0 ℃，压力为16MPa，试验时间为4小时。
(b) 酸液为含盐酸为15%，或土酸为15%的溶液（参照SY 5405-1996《酸化用缓蚀剂性能试验方法及评价指标》中的表3）。向酸液加入实例1中新型缓蚀剂，缓蚀剂用量为酸液的2%～3%。
(c) 试验前用400#金相砂纸对试片逐一打磨至光亮，再用丙酮清洗表面，除去油污。
(d) 干燥称重后，试片加入恒温的加入缓蚀剂的酸溶液中浸泡4小时（同时与用未加缓蚀剂的酸溶液做空白），再称重。
(e) 计算失重，按以下公式（1）和公式（2）计算腐蚀速率和腐蚀率。
腐蚀速率计算公式:
Figure PCTCN2012075926-appb-I000001
（1）
式中： v……腐蚀速率，g/(m2 • h)；
△t……反应时间，h；
△m……试片腐蚀失重，g；
A ……试片表面积，mm2。
缓蚀率计算公式为：
Figure PCTCN2012075926-appb-I000002
（2）
式中：η……缓蚀率，%；
ν 0 ……未加缓蚀剂的腐蚀速率，g/(m2 • h)；
ν……加有缓蚀剂的腐蚀速率，g/(m2 • h)。
(f) 具体酸液组成和实验数据计算出的缓蚀速率及缓蚀效率如表三。
表三 腐蚀效率
试验编号 酸液浓度及缓蚀剂量 腐蚀速率
g/(m2 • h)		 缓蚀率
%		 等级
空白试验1 15%HCl 726 ．5 ／ ／
试验1 15%HCl+2% 配方1 37.0 94.8 一级
试验2 15%HCl+2% 配方2 33.4 95.4 一级
试验3 15%HCl+2% 配方3 34.1 95.3 一级
试验4 15%HCl+2% 配方4 36.3 95.0 一级
空白试验2 12%HCl+3%HF 492.9 ／ ／
试验5 12%HCl+3%HF+3% 配方1 34.5 93.0 二级
试验6 12%HCl+3%HF+3% 配方2 27.6 94.4 一级
试验7 12%HCl+3%HF+3% 配方3 29.1 94.1 一级
试验8 12%HCl+3%HF+3% 配方4 36.0 92.7 二级

Claims (2)

1、 一种复合型油气田缓蚀剂，其特征在于，其成分及质量百分比为：
妥儿酸二环己酰胺 5%-20%
三苯胺油酸盐 10%-30%
非离子表面活性剂 1%-3%
已二醇 10%-15%
丙炔醇 5%-10%
柠檬酸 1%-3%
水 余量 。
2 、 一种复合型油气田缓蚀剂的制备方法，其特征在于，先把柠檬酸溶解于水中，再分别加入已二醇、丙炔醇和非离子表面活性剂，充分搅拌后，加入妥儿酸二环己酰胺和三苯胺油酸盐，搅拌均匀。
PCT/CN2012/075926 2012-05-17 2012-05-23 一种复合型油气田缓蚀剂 WO2013170492A1 (zh)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103882437A (zh) * 2014-04-01 2014-06-25 马杨洋 油气集输管道缓蚀剂及其制备方法
CN114481138A (zh) * 2022-01-28 2022-05-13 东北石油大学 一种用于油田的金属缓蚀剂及其制备方法

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US6063334A (en) * 1998-03-06 2000-05-16 Champion Technologies, Inc. Sulfur based corrosion inhibitor
US6695897B1 (en) * 2002-12-26 2004-02-24 Cortec Corporation Corrosion resistant system for performance drilling fluids utilizing formate brine
CN1667102A (zh) * 2004-01-07 2005-09-14 雅富顿公司 具有强抗振性的动力传输流体
CN1769529A (zh) * 2004-11-05 2006-05-10 姚凯 一种油井酸化缓蚀剂及制备方法
CN102168272A (zh) * 2011-03-22 2011-08-31 中国石油集团工程设计有限责任公司 一种用于酸性油气田的缓蚀剂

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6063334A (en) * 1998-03-06 2000-05-16 Champion Technologies, Inc. Sulfur based corrosion inhibitor
US6695897B1 (en) * 2002-12-26 2004-02-24 Cortec Corporation Corrosion resistant system for performance drilling fluids utilizing formate brine
CN1667102A (zh) * 2004-01-07 2005-09-14 雅富顿公司 具有强抗振性的动力传输流体
CN1769529A (zh) * 2004-11-05 2006-05-10 姚凯 一种油井酸化缓蚀剂及制备方法
CN102168272A (zh) * 2011-03-22 2011-08-31 中国石油集团工程设计有限责任公司 一种用于酸性油气田的缓蚀剂

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103882437A (zh) * 2014-04-01 2014-06-25 马杨洋 油气集输管道缓蚀剂及其制备方法
CN114481138A (zh) * 2022-01-28 2022-05-13 东北石油大学 一种用于油田的金属缓蚀剂及其制备方法
CN114481138B (zh) * 2022-01-28 2023-12-01 东北石油大学 一种用于油田的金属缓蚀剂及其制备方法

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