WO2020082476A1 - 一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法及应用 - Google Patents

一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法及应用 Download PDF

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WO2020082476A1
WO2020082476A1 PCT/CN2018/116451 CN2018116451W WO2020082476A1 WO 2020082476 A1 WO2020082476 A1 WO 2020082476A1 CN 2018116451 W CN2018116451 W CN 2018116451W WO 2020082476 A1 WO2020082476 A1 WO 2020082476A1
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corrosion inhibitor
dibenzylamine
quaternary ammonium
ammonium salt
salt high
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PCT/CN2018/116451
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English (en)
French (fr)
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李勇明
王鼎立
江有适
陈曦宇
朱炬辉
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西南石油大学
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Priority to US16/622,673 priority Critical patent/US10889748B2/en
Publication of WO2020082476A1 publication Critical patent/WO2020082476A1/zh

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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
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C23F11/143—Salts of amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/84—Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
    • C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
    • 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
    • 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
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • E—FIXED CONSTRUCTIONS
    • E21—EARTH DRILLING; MINING
    • E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
    • E21B41/00—Equipment or details not covered by groups E21B15/00 - E21B40/00
    • E21B41/02—Equipment or details not covered by groups E21B15/00 - E21B40/00 in situ inhibition of corrosion in boreholes or wells
    • 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
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/32—Anticorrosion additives

Definitions

  • the invention relates to a preparation method and application of a dibenzylamine quaternary ammonium salt high temperature resistant acidification corrosion inhibitor in the field of corrosion inhibitor materials.
  • the sustained-release agent contains: 30wt% ⁇ 35wt% alkyl acid imidazoline quaternary ammonium salt, 8wt% % -10wt% nitrogen-containing organic polyphosphate, 1wt% -2wt% amphoteric surfactant, 0.5wt% -1wt% dispersant, 1wt% -2wt% co-solvent, the balance is water.
  • the corrosion inhibitor is self-produced under simulated water at 50 °C, the dosage is 50ppm, and the corrosion inhibition rate is greater than 70%. It can be used in oil and gas wells, gathering and transportation systems, and water injection processes in oil fields. Not conducive to environmental protection.
  • the purpose of the present invention is to provide a preparation method and application of dibenzylamine quaternary ammonium salt high temperature resistant acid corrosion inhibitor, the preparation method is simple and feasible, the principle is reliable, and the prepared corrosion inhibitor has good corrosion inhibition at high temperature Performance, it has good solubility in hydrochloric acid aqueous solution, and has obvious inhibitory effect on the acid corrosion of carbon steel in oil and gas wells.
  • the present invention provides the following technical solutions.
  • a method for preparing a dibenzylamine quaternary ammonium salt high temperature resistant acid corrosion inhibitor includes the following steps in sequence:
  • the molar ratio of epichlorohydrin to amine reactant is 1: 1 to 1: 3.
  • the drop rate of epichlorohydrin is 5-10 mL / min.
  • the organic solvent is acetone, ethanol or acetonitrile.
  • the acid binding agent is potassium carbonate, sodium hydroxide or triethylamine.
  • the molar ratio of dibenzylamine to acid binding agent is 1: 1 to 1: 2.
  • the quaternization reagent is benzyl chloride, chloromethylnaphthalene or bromohexane.
  • the molar ratio of quaternization reagent to intermediate II is 1: 1-2: 1.
  • dibenzylamine quaternary ammonium salt high-temperature acid corrosion inhibitor refers to its use as an oil and gas well acid corrosion inhibitor, which has a significant inhibitory effect on the acid corrosion of carbon steel in oil and gas wells.
  • the preparation method of the invention is simple, and the mechanism analysis is as follows: the epichlorohydrin chlorine atom and the nitrogen atom on dibenzylamine have high activity. Under the above reaction conditions, epichlorohydrin first opens the ring with benzylamine and benzene Ethylamine, morpholine or indole is reacted to obtain intermediate I, and then the chlorine atom on intermediate I is reacted with dibenzylamine to obtain tertiary amine. In this process, an acid binding agent must be added to prevent the reaction of hydrogen chloride and dibenzylamine The reaction produces dibenzylamine hydrochloride, so that no tertiary amine product can be obtained to prevent the next quaternization process.
  • the corrosion inhibitor prepared by this method contains multiple benzene rings, and has multiple nitrogen atoms and oxygen atoms.
  • the nitrogen atoms and oxygen atoms have lone pairs of electrons and can form a hybrid orbital with the empty orbital on the iron atom. Strong adsorption, and the six-membered benzene ring has a large ⁇ bond structure, can also hybridize with iron, tightly adsorbed on iron, inhibit its corrosion;
  • the multiple hydroxyl groups in the inhibitor molecule can greatly Improve the dispersibility of the corrosion inhibitor and the solubility in acid solution.
  • the corrosion inhibitor has good corrosion inhibition performance at high temperature. When the corrosion inhibitor is used as an acidification corrosion inhibitor for oil and gas wells, Acid corrosion has obvious inhibitory effect.
  • a preparation method of dibenzylamine quaternary ammonium salt high temperature resistant acid corrosion inhibitor includes the following steps:
  • a preparation method of dibenzylamine quaternary ammonium salt high temperature resistant acid corrosion inhibitor includes the following steps:
  • a preparation method of dibenzylamine quaternary ammonium salt high temperature resistant acid corrosion inhibitor includes the following steps:
  • a preparation method of dibenzylamine quaternary ammonium salt high temperature resistant acid corrosion inhibitor includes the following steps:
  • the water solubility of the corrosion inhibitor prepared in Example 1-4 and the compatibility of the system with iron ion stabilizer, clay stabilizer and drainage aid added at 90 ° C were measured.
  • the specific process is: weigh the corrosion inhibitor of the present invention Each 0.1g of the agent is dissolved in 200mL of 20% hydrochloric acid solution and stirred to observe its dissolution; formulated with iron ion stabilizer citric acid, clay stabilizer potassium chloride and drainage aid OP-10 or fluorocarbon surfactant In the 20% hydrochloric acid acid system, etc., 0.1 g of each corrosion inhibitor of the present invention was weighed and added thereto, and its compatibility was observed. The results are shown in Table 1.
  • the corrosion inhibitor prepared by the present invention is excellent in water solubility, and has good compatibility with various additives in a high-temperature hydrochloric acid system, and the system is uniform and transparent without delamination.
  • Example 1-4 Using 20% hydrochloric acid as a corrosive medium, using P110 carbon steel, the corrosion inhibition performance of Example 1-4 was determined through a 4h corrosion coupon experiment at 90 ° C. The amount of corrosion inhibitor used was 1000 ppm. The results are shown in Table 2.
  • the preparation process of the present invention is simple and feasible.
  • the prepared corrosion inhibitor is ionic, and has good water solubility in acid solution. Under high temperature conditions of 90 °C, it can obviously inhibit the corrosion of carbon steel in oil and gas wells. Function, and the surface of the hanging piece is flat after cleaning, without obvious pitting corrosion, indicating that the corrosion inhibitor prepared by the invention has the characteristics of acid resistance and high temperature resistance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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  • Environmental & Geological Engineering (AREA)
  • Fluid Mechanics (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
  • Indole Compounds (AREA)

Abstract

一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法及应用。制备步骤如下：(1)将胺类反应物苯甲胺、苯乙胺、吗啉或者吲哚溶于有机溶剂中，缓慢滴加环氧氯丙烷，常温搅拌反应12-14h，然后减压蒸馏、洗涤获得中间体I；(2)将中间体I溶于有机溶剂，将二苄胺加入其中，再加入缚酸剂，升温至60-80℃反应14-16h，冷却至室温后，过滤、萃取、减压蒸馏制得中间体Ⅱ；(3)将中间体Ⅱ溶于有机溶剂，并将季铵化试剂加入其中，升温至80-110℃反应12-15h，冷却至室温后，过滤、萃取、减压蒸馏制得二苄胺季铵盐耐高温酸化缓蚀剂。所述制备方法简单可行，原理可靠，制备的酸化缓蚀剂对油气井碳钢的酸腐蚀有明显的抑制作用。

Description

一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法及应用 技术领域
本发明涉及缓蚀剂材料领域中一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法及其应用。
背景技术
在油气田增产改造过程中，压裂酸化已经成为主流的油气田增产改造方式。在酸压酸洗过程中，酸液可以很大程度上解除油气井筒堵塞，提高基质渗透率，从而提高油气采收率。但是酸液的存在也会给油田带来诸多问题，在酸化施工过程中，酸液的注入会造成油气井管材和井下金属设备的腐蚀，严重时可能导致井下管材突发性破裂事故，存在严重安全隐患，同时被酸液溶蚀的金属铁离子又可能对地层造成伤害。为了防止酸液对油管、套管等设备的腐蚀，在酸液中添加缓蚀剂是必不可少且最为常用、有效的防腐措施。目前大部分市售缓蚀剂存在高温下易结焦、分层、溶解分散性能不稳定、制备复杂等缺点。
“一种复合型咪唑啉季铵盐缓蚀剂及其制备方法”(201410360217.3)，所述的缓释剂按质量百分比计含：30wt％～35wt％的烷基酸咪唑啉季铵盐，8wt％～10wt％的含氮有机多元磷酸盐，1wt％～2wt％的两性表面活性剂，0.5wt％～1wt％的分散剂，1wt％～2wt％的助溶剂，余量为水。该缓蚀剂在50℃的自配模拟水下，加药量50ppm，缓蚀率大于70％，可在油田中油气井、集输系统、注水工艺使用，但配方复杂，成本较高，也不利于环保。
“一种水溶性咪唑啉季铵盐缓蚀剂的合成方法”(201310524689.3)，以有机酸和有机胺为反应原料，先通过酰胺化反应合成酰胺，再通过酰胺环化反应得到咪唑啉，最后用亚磷酸二甲酯等季铵化剂把油溶性的咪唑啉季铵化，合成了水溶性咪唑啉季铵盐缓蚀剂。评价试验表明，所得产品水溶性好、缓蚀率高。 但其制备较为复杂，且反应温度高达200多度。
因此，研制一种配方简单、合成条件温和且能满足目前油气井酸化施工苛刻要求的新型耐高温盐酸酸化缓蚀剂具有重要的意义。
发明内容
本发明的目的在于提供一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法及其应用，该制备方法简单可行，原理可靠，制得的缓蚀剂在高温下具有良好的缓蚀性能，在盐酸水溶液中具有良好的溶解性，对油气井碳钢的酸腐蚀有明显的抑制作用。
为实现上述技术目的，本发明提供以下技术方案。
一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法，依次包括以下步骤：
(1)将胺类反应物苯甲胺、苯乙胺、吗啉或者吲哚溶于有机溶剂中，缓慢滴加环氧氯丙烷，常温搅拌反应12-14h，然后减压蒸馏、洗涤获得中间体I；
(2)将中间体I溶于有机溶剂，将二苄胺以一定比例加入其中，再加入缚酸剂，升温至60-80℃反应14-16h，冷却至室温后，过滤、萃取、减压蒸馏制得中间体Ⅱ；
(3)将中间体Ⅱ溶于有机溶剂，并将季铵化试剂以一定比例加入其中，升温至80-110℃反应12-15h，冷却至室温后，过滤、萃取、减压蒸馏制得二苄胺季铵盐耐高温酸化缓蚀剂。
进一步地，环氧氯丙烷与胺类反应物的摩尔比为1:1-1:3。
进一步地，环氧氯丙烷的滴加速度为5-10mL/min。
进一步地，所述有机溶剂为丙酮、乙醇或乙腈。
进一步地，所述缚酸剂为碳酸钾、氢氧化钠或三乙胺。
进一步地，二苄胺与缚酸剂的摩尔比为1:1-1:2。
进一步地，二苄胺与中间体I的摩尔比为1:1-1:4。
进一步地，所述季铵化试剂为氯化苄、氯甲基萘或溴己烷。
进一步地，季铵化试剂与中间体Ⅱ的摩尔比为1:1-2:1。
所述二苄胺季铵盐耐高温酸化缓蚀剂的应用，是指将其作为油气井酸化缓蚀剂，对油气井碳钢的酸腐蚀有明显的抑制作用。
本发明制备方法简单，其机理分析如下：环氧氯丙烷氯原子以及二苄胺上的氮原子具有较高的活性，在上述反应条件下，环氧氯丙烷首先开环与苯甲胺、苯乙胺、吗啉或吲哚反应得到中间体I，然后中间体I上的氯原子与二苄胺反应得到叔胺，在该过程中必须加入缚酸剂，防止反应生成的氯化氢和二苄胺反应生成二苄胺盐酸盐，从而无法得到叔胺产物阻止下一步季铵化过程。在得到叔胺后加入季铵化试剂得到二苄胺季铵盐缓蚀剂。该方法制得的缓蚀剂包含多个苯环，且具有多个氮原子、氧原子，氮原子、氧原子具有孤对电子，能与铁原子上的空轨道形成杂化轨道，二者具有较强的吸附性，而六元苯环具有大π键的结构，也能与铁杂化，紧紧吸附在铁上，抑制其腐蚀；此外，该缓蚀剂分子中的多个羟基可以大大提高缓蚀剂的分散性和在酸液中的溶解性，该缓蚀剂在高温下具有良好的缓蚀性能，使用该缓蚀剂作为油气井酸化缓蚀剂时，对油气井碳钢的酸腐蚀有明显的抑制作用。
具体实施方式
下面通过实施例进一步说明本发明。
实施例1
一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法，包括以下步骤：
(1)将8.71g吗啉加入到250mL三颈烧瓶中，同时加入80mL无水乙醇作为溶剂并搅拌均匀；
(2)称取9.25g环氧氯丙烷溶于30mL无水乙醇中搅拌均匀，缓慢滴加于吗啉溶液中，常温下搅拌反应14h，减压蒸馏后得到中间体I；
(3)称取1.79g中间体I加入到250mL三颈烧瓶中，同时加入90mL无水乙醇作为溶剂并搅拌均匀，称取1.97g二苄胺溶于30mL无水乙醇中搅拌均匀， 缓慢滴加于中间体I溶液中，并加入1.4g碳酸钾，再升温至80℃回流反应14h，反应结束后冷却至室温，过滤、萃取、减压蒸馏制得中间体Ⅱ；
(4)称取3.76g中间体Ⅱ加入到250mL三颈烧瓶中，同时加入100mL无水乙醇作为溶剂并搅拌均匀，称取1.76g氯甲基萘缓慢滴加于中间体Ⅱ溶液中再升温至80℃回流反应13h，反应结束后冷却至室温，过滤、萃取、减压蒸馏制得二苄胺季铵盐酸化缓蚀剂。
上述制备方法的具体反应历程如下：
Figure PCTCN2018116451-appb-000001
实施例2
一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法，包括以下步骤：
(1)将5.59g吲哚加入到250mL三颈烧瓶中，同时加入70mL丙酮作为溶剂并搅拌均匀；
(2)称取4.62g环氧氯丙烷溶于30mL丙酮中搅拌均匀，缓慢滴加于上述吲哚溶液中，常温下搅拌反应12h，减压蒸馏后得到中间体I；
(3)称取2.11g中间体I加入到250mL三颈烧瓶中，同时加入90mL乙腈作为溶剂并搅拌均匀，称取1.97g二苄胺溶于30mL乙腈中搅拌均匀，缓慢滴加于中间体I溶液中，并加入1.2g三乙胺，再升温至57℃回流反应15h，反应结束后冷却至室温，过滤、萃取、减压蒸馏制得中间体Ⅱ；
(4)称取4.08g中间体Ⅱ加入到250mL三颈烧瓶中，同时加入100mL无水乙腈作为溶剂并搅拌均匀，称取1.26g氯化苄缓慢滴加于中间体Ⅱ溶液中再升温至85℃回流反应14h，反应结束后冷却至室温，过滤、萃取、减压蒸馏制得二苄胺季铵盐酸化缓蚀剂。
上述制备方法的具体反应历程如下：
Figure PCTCN2018116451-appb-000002
实施例3
一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法，包括以下步骤：
(1)将10.82g苯甲胺加入到250mL三颈烧瓶中，同时加入100mL无水乙醇作为溶剂并搅拌均匀；
(2)称取9.25g环氧氯丙烷溶于30mL无水乙醇中搅拌均匀，缓慢滴加于 上述苯甲胺溶液中，常温下搅拌反应12h，减压蒸馏后得到中间体I；
(3)称取2.07g中间体I加入到250mL三颈烧瓶中，同时加入90mL丙酮作为溶剂并搅拌均匀，称取1.97g二苄胺溶于30mL丙酮中搅拌均匀，缓慢滴加于中间体I溶液中，并加入0.7g氢氧化钠，再升温至60℃回流反应13h，反应结束后冷却至室温，过滤、萃取、减压蒸馏制得中间体Ⅱ；
(4)称取4.04g中间体Ⅱ加入到250mL三颈烧瓶中，同时加入100mL无水乙醇作为溶剂并搅拌均匀，称取1.65g溴己烷缓慢滴加于中间体Ⅱ溶液中再升温至80℃回流反应15h，反应结束后冷却至室温，过滤、萃取、减压蒸馏制得二苄胺季铵盐酸化缓蚀剂。
上述制备方法的具体反应历程如下：
Figure PCTCN2018116451-appb-000003
实施例4
一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法，包括以下步骤：
(1)将12.1g苯乙胺加入到250mL三颈烧瓶中，同时加入100mL乙腈作为溶剂并搅拌均匀；
(2)称取9.25g环氧氯丙烷溶于30mL无水乙醇中搅拌均匀，缓慢滴加于 上述苯乙胺溶液中，常温下搅拌反应14h，减压蒸馏后得到中间体I；
(3)称取2.13g中间体I加入到250mL三颈烧瓶中，同时加入90mL无水乙醇作为溶剂并搅拌均匀，称取1.97g二苄胺溶于30mL无水乙醇中搅拌均匀，缓慢滴加于中间体I溶液中，并加入1.6g三乙胺，再升温至80℃回流反应14h，反应结束后冷却至室温，过滤、萃取、减压蒸馏制得中间体Ⅱ；
(4)称取4.1g中间体Ⅱ加入到250mL三颈烧瓶中，同时加入100mL无水乙醇作为溶剂并搅拌均匀，称取1.26g氯化苄缓慢滴加于中间体Ⅱ溶液中再升温至90℃回流反应15h，反应结束后冷却至室温，过滤、萃取、减压蒸馏制得二苄胺季铵盐酸化缓蚀剂。
性能测试1 缓蚀剂的水溶性测定
测定实施例1-4制得的缓蚀剂的水溶性以及在90℃下，添加铁离子稳定剂、粘土稳定剂、助排剂等体系的配伍性，具体过程为：称取本发明缓蚀剂各0.1g，分别溶于200mL20％的盐酸溶液中，搅拌，观察其溶解情况；配制添加铁离子稳定剂柠檬酸、粘土稳定剂氯化钾和助排剂OP-10或氟碳表面活性剂等的20％的盐酸酸液体系，分别称取本发明缓蚀剂各0.1g，加入其中，观察其配伍性，结果见表1。
表1不同缓蚀剂的水溶性及配伍性测试
缓蚀剂 水溶性外观 配伍性
实施例1 易溶的无色透明液体 均一透明，无分层
实施例2 易溶的无色透明液体 均一透明，无分层
实施例3 易溶的无色透明液体 均一透明，无分层
实施例4 易溶的无色透明液体 均一透明，无分层
由表1可知，本发明制得的缓蚀剂水溶性优异，且在高温盐酸体系中与各种添加剂配伍性良好，体系均一透明，无分层现象。
性能测试2 缓蚀剂的缓蚀性能测定
以20％盐酸作为为腐蚀介质，采用P110碳钢，于90℃通过4h腐蚀挂片实验测定实施例1-4的缓蚀性能，缓蚀剂用量均为1000ppm，结果见表2。
表2各缓蚀剂的缓蚀性能测定
Figure PCTCN2018116451-appb-000004
由表2可知，通过本发明方法制得的缓蚀剂具有良好的缓蚀效果。
综上所述，本发明制备工艺简单可行，制得的缓蚀剂为离子型，在酸溶液中具有良好的水溶性，在90℃高温条件下，对油气井碳钢的腐蚀有明显的抑制作用，且挂片清洗后表面平整，无明显点蚀，说明本发明制得的缓蚀剂具有耐酸耐高温特性。

Claims (9)

  1. 一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法，依次包括以下步骤：
    (1)将胺类反应物苯甲胺、苯乙胺、吗啉或者吲哚溶于有机溶剂中，缓慢滴加环氧氯丙烷，常温搅拌反应12-14h，然后减压蒸馏、洗涤获得中间体I；
    (2)将中间体I溶于有机溶剂，将二苄胺加入其中，再加入缚酸剂，升温至60-80℃反应14-16h，冷却至室温后，过滤、萃取、减压蒸馏制得中间体Ⅱ；
    (3)将中间体Ⅱ溶于有机溶剂，并将季铵化试剂加入其中，升温至80-110℃反应12-15h，冷却至室温后，过滤、萃取、减压蒸馏制得二苄胺季铵盐耐高温酸化缓蚀剂。
  2. 如权利要求1所述的一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法，其特征在于，环氧氯丙烷与胺类反应物的摩尔比为1:1-1:3。
  3. 如权利要求1所述的一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法，其特征在于，所述有机溶剂为丙酮、乙醇或乙腈。
  4. 如权利要求1所述的一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法，其特征在于，所述缚酸剂为碳酸钾、氢氧化钠或三乙胺。
  5. 如权利要求1所述的一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法，其特征在于，二苄胺与缚酸剂的摩尔比为1:1-1:2。
  6. 如权利要求1所述的一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法，其特征在于，二苄胺与中间体I的摩尔比为1:1-1:4。
  7. 如权利要求1所述的一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法，其特征在于，所述季铵化试剂为氯化苄、氯甲基萘或溴己烷。
  8. 如权利要求1所述的一种二苄胺季铵盐耐高温酸化缓蚀剂的制备方法，其特征在于，所述季铵化试剂与中间体Ⅱ的摩尔比为1:1-2:1。
  9. 如权利要求1、2、3、4、5、6、7或8所述的一种二苄胺季铵盐耐高温酸化缓蚀剂的应用，是指将其作为油气井酸化缓蚀剂，对油气井碳钢的酸腐蚀有明显的抑制作用。
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