WO2022152193A1 - 适用于200℃的酸化用缓蚀剂及应用 - Google Patents

适用于200℃的酸化用缓蚀剂及应用 Download PDF

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WO2022152193A1
WO2022152193A1 PCT/CN2022/071731 CN2022071731W WO2022152193A1 WO 2022152193 A1 WO2022152193 A1 WO 2022152193A1 CN 2022071731 W CN2022071731 W CN 2022071731W WO 2022152193 A1 WO2022152193 A1 WO 2022152193A1
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corrosion inhibitor
parts
component
acidification
quinoline
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French (fr)
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张兴德
原励
张燕
黄晨直
王川
刘爽
吴丽
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Petrochina Co Ltd
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Petrochina Co Ltd
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    • 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
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
    • 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
    • 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
    • C09K8/60—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

Definitions

  • the invention relates to the technical field of oil and gas reservoir stimulation and transformation, in particular to a corrosion inhibitor suitable for acidification at 200° C. and application thereof.
  • Acidizing is an important measure for stimulation and stimulation of oil and gas wells. Acid is injected into the formation through the wellbore, and the chemical reaction between the acid and some minerals in the formation is used to dissolve the connected pores or fracture wall rocks in the reservoir, and increase the communication between pores and fracture conductivity. ability to achieve the purpose of increasing the production of oil and gas wells. During the acidizing process, the acid liquid will corrode the downhole pipe string, so it is necessary to add a corrosion inhibitor to the acid liquid, so as to inhibit or slow down the corrosion of the acid liquid to the downhole pipe string.
  • Corrosion inhibitors for acidification provided by related technologies are mostly used under the condition of well temperature of 160°C. With the gradual development of oil and gas exploration to deep and ultra-deep reservoirs, the well depth exceeds 7000m, and the bottom hole temperature is generally above 160°C. The maximum temperature at the bottom of the oil well and the temperature in the construction section exceeds 200 °C. Corrosion inhibitors for acidification provided by related technologies can no longer meet the needs of deep and ultra-deep reservoirs whose temperature reaches 200°C. Therefore, there is an urgent need to provide a corrosion inhibitor for acidification with high temperature resistance.
  • an object of the present invention is to provide a corrosion inhibitor for acidification suitable for use at 200°C.
  • the corrosion inhibitor for acidification can meet the needs of deep and ultra-deep reservoir stimulation.
  • Another object of the present invention is to provide the application of the corrosion inhibitor for acidification.
  • the present invention provides a corrosion inhibitor for acidification suitable for use at 200° C.
  • the corrosion inhibitor for acidification includes component A, wherein, in parts by weight, the component A includes The following components: aldosterone amine condensate: 30-45 parts; organic acid: 1-17 parts; alkynol derivative: 3-10 parts; organic synergist: 15-40 parts; alcohol solvent: 5-15 parts; dispersant: 5-15 parts.
  • the above-mentioned component A may further include a quinoline quaternary ammonium salt, and the quinoline quaternary ammonium salt can further improve the temperature resistance and corrosion inhibition ability of the corrosion inhibitor.
  • the component A may include the following components: aldolamine condensate: 30 parts-45 parts; quinoline quaternary ammonium salt: 5 parts-8 parts; organic acid: 1 part-17 parts; Alkynyl alcohol derivative: 3 parts to 10 parts; organic synergist: 15 parts to 40 parts; alcohol solvent: 5 parts to 15 parts; dispersant: 5 parts to 15 parts, wherein, the quinoline quaternary ammonium salt can be It is synthesized from the combination of one or more of benzyl chloride, benzyl methanol, benzyl propanol and hexadecyl dimethyl benzyl ammonium chloride and quinoline through quaternization reaction.
  • the above-mentioned component A is generally used in the form of a solution prepared by mixing with water.
  • the component A in percentage by weight (ie, based on the total weight of component A as 100%), includes the following components: aldolamine condensate: 30%-45% ; Quinoline quaternary ammonium salt: 5%-8%; Organic acid: 1%-10%; Alkynol derivatives: 3%-10%; Organic synergist: 15%-40%; Alcohol solvent: 5%- 15%; dispersant: 5%-15%; the balance is water; the quinoline quaternary ammonium salt can be composed of benzyl chloride, benzyl methanol, benzyl propanol and cetyl dimethyl benzyl ammonium chloride.
  • One or more combinations of quinoline and quinoline are synthesized by quaternization reaction.
  • the component A may further include a Mannich base quaternary ammonium salt.
  • the compounding of Mannich base quaternary ammonium salt and quinoline quaternary ammonium salt can slow down the corrosion rate of metal in acid solution and improve the corrosion inhibition effect of corrosion inhibitor.
  • the mass ratio of the Mannich base quaternary ammonium salt to the quinoline quaternary ammonium salt can be controlled to be 25-50:5-10, for example, 30-45:5-10.
  • the aldosterone amine condensate includes a mass ratio of more than 60% of formula (I) or formula (II) polymer shown;
  • R1 is a hydrocarbon group
  • X is a halogen
  • the viscosity average molecular weight of the polymer is 1000 or less.
  • the chelate can be adsorbed on On the metal surface, a dense and stable hydrophobic protective film is formed, which effectively prevents the anodic process of the corrosion reaction in which the corrosion product iron ions diffuse into the solution, and the cathodic process of the corrosion reaction in which the hydrogen ions in the solution migrate to the metal through the covering effect.
  • the aldosterone amine condensate can be obtained by reacting aldehyde compounds, ketone compounds and amine compounds.
  • an intermediate product can be formed by reacting an aldehyde compound and a ketone compound first, and then the intermediate product is mixed and reacted with an amine compound to obtain an aldosterone amine condensate.
  • the temperature of the reaction is generally controlled to be 95-115°C, and the time of the reaction is generally controlled to be 240 min.
  • the aldehyde compound may include formaldehyde and the like
  • the ketone compound may include cyclohexanone and the like
  • the amine compound may include aniline and the like.
  • the preparation method of the above-mentioned aldosterone amine condensate can be as follows: in parts by weight, 510 parts of formaldehyde, 600 parts of cyclohexanone, and 65 parts of hydrochloric acid are mixed, kept at a constant temperature of 95° C. for 1.5 hours, and then allowed to stand. Separation to obtain an intermediate product, 750 parts of the intermediate product, 300 parts of aniline and 35 parts of hydrochloric acid were mixed, and the temperature was kept at 115° C. for 1.5 h to obtain an aldosterone amine condensate.
  • the quaternary ammonium salt of quinoline is a chloride-1-benzylquinoline salt obtained by the reaction of benzyl chloride and quinoline.
  • quinoline quaternary ammonium salts can be physically adsorbed in the cathode region of the metal surface, which can effectively prevent H + ions from approaching the metal surface, thereby inhibiting the reduction reaction of H + and inhibiting the cathode reaction.
  • quinoline quaternary ammonium salts contain N elements that do not share electron pairs. These elements can coordinately combine with the metal surface to form a firm chemical adsorption layer, which can improve the activation energy of the anodic reaction of steel in corrosive media, thereby reducing the anodic effect. corrosion rate.
  • the halogen in the quaternary ammonium salt has a certain synergistic effect on the corrosion inhibition of iron, and promotes the adsorption of organic cations on the metal surface to form a stable protective film.
  • the quinoline quaternary ammonium salt contains a condensed ring structure, and the condensed ring has a larger total electron delocalization energy, which can enhance its coordination with metal atoms, so the adsorption film formed on the metal surface is stronger.
  • the organic acid is selected from formic acid or acetic acid.
  • the alkynyl alcohol derivative is selected from the group consisting of propargyl alcohol propoxy compounds (formula IV) or propargyl alcohol ethoxy compounds (formula V);
  • propargyl alcohol derivatives are selected instead of propargyl alcohol is that because propargyl alcohol is a highly toxic substance, it is a controlled drug, and its derivatives are low-toxic substances, which satisfies environmental protection. Require.
  • the organic synergist is selected from one or a combination of two or more of fatty amines, amides and alcohol amines.
  • the organic synergist is selected from one or a combination of two of formamide and N,N-dimethylformamide.
  • the alcohol solvent is selected from any one of ethanol, isobutanol and ethylene glycol.
  • the dispersing agent is selected from one or a combination of two of alkylphenol polyoxyethylene ether and fatty alcohol polyoxyethylene ether.
  • the alkylphenol polyoxyethylene ether is selected from one or a combination of two of OP-10 and NP-10, and the fatty alcohol polyoxyethylene ether is selected from OS-15 and one or a combination of both OS-20.
  • the corrosion inhibitor for acidification further includes component B, and the component B is selected from cuprous chloride, potassium iodide, potassium pyroantimonate, antimony trioxide and sodium molybdate one or a combination of two or more.
  • the mass ratio of the component A and the component B is (4.0-5.0):(0.5-1.5).
  • Alkynyl alcohol derivatives and organic synergists can fill the adsorption void area of aldosterone amine condensate and quinoline quaternary ammonium salt macromolecule corrosion inhibitor.
  • Propynyl alcohol derivatives have relatively longer molecular chains than propynyl alcohol and contain unshared electrons.
  • the oxygen atoms can be adsorbed on the metal surface to form a film, and it has a certain hydrophobic property to form a hydrophobic protective film.
  • the addition of inorganic synergist ie component B) can make the temperature resistance of the corrosion inhibitor reach 200°C.
  • the preparation method of component A may include the following steps: heating the aldosterone amine condensate to 40-50° C., and then heating the organic acid, alkynol derivative, organic synergist A solvent, an alcohol solvent, a dispersant, and the aldehyde-ketone condensate are mixed uniformly to obtain the component A.
  • the preparation method of the component A may include the following steps: heating the aldolamine condensate to 40-50° C., Then, the quinoline quaternary ammonium salt, organic acid, alkynyl alcohol derivative, organic synergist, alcohol solvent, dispersant and the aldehyde-ketone condensate are uniformly mixed to obtain the component A. Further, when the component A further contains a Mannich base quaternary ammonium salt, the Mannich base quaternary ammonium salt and the quinoline corrosion inhibitor can be added at the same time.
  • the present invention also provides the application of the above-mentioned corrosion inhibitor for acidification in deep oil and gas reservoirs.
  • the application includes the following steps: directly adding component A into hydrochloric acid with a concentration of 31% or more, adding component B after dissolving and dispersing, stirring evenly, and after component B is completely dissolved Dilute the acid to the desired concentration.
  • the corrosion inhibitor for acidification provided in the embodiment of the present invention can be applied to high temperatures of 200° C. and below, and the mass concentration of the corrosion inhibitor for acidification in HCl is 15%-25% concentrated hydrochloric acid (the acid concentration in the following refers to the concentration of HCl). It has good dispersibility in mass percentage), and the corrosion rate meets the first-class index requirements of the oil and gas industry.
  • the application of the corrosion inhibitor for acidizing can reduce the corrosion risk of downhole pipe strings in the process of acidizing and reforming ultra-deep and ultra-high temperature carbonate rocks.
  • Figure 1 shows the corrosion rate of the corrosion inhibitor of the present invention at 90-140°C.
  • the chloride-1-benzylquinoline salt in the following examples was purchased from Chengdu Forest Technology Development Co., Ltd.
  • the aldosterone amine condensate used in the following examples is the acidification corrosion inhibitor aldosterone amine condensate CT1-3D
  • the thickener is the acidification gelling agent cationic polyacrylamide CT1-9B
  • the iron ion stabilizer is the acidification iron
  • the clay stabilizer is the clay stabilizer polyquaternary ammonium salt CT5-8 for oil and gas wells
  • the drainage aid is the fluorocarbon CT5-12A, the drainage aid for fracturing and acidizing.
  • the above reagents are all Produced by Chengdu Dute Technology Development Co., Ltd.
  • This embodiment provides a corrosion inhibitor for acidification, and the corrosion inhibitor for acidification includes component A and component B.
  • component A is prepared by the following method:
  • Component B in this embodiment is potassium pyroantimonate, and the mass ratio of component A to component B is 5.0:1.5.
  • This embodiment provides a corrosion inhibitor for acidification, and the corrosion inhibitor for acidification includes component A and component B.
  • Component B in this embodiment is potassium pyroantimonate, and the mass ratio of component A to component B is 5.0:1.5.
  • This embodiment provides a corrosion inhibitor for acidification, and the corrosion inhibitor for acidification includes component A and component B.
  • component A is prepared by the following method:
  • Component B in this embodiment is sodium molybdate, and the mass ratio of component A to component B is 5.0:1.5.
  • This embodiment provides a corrosion inhibitor for acidification, and the corrosion inhibitor for acidification includes component A and component B.
  • component A is prepared by the following method:
  • Component B in this embodiment is sodium molybdate, and the mass ratio of component A to component B is 5.0:1.5.
  • Example 1 the composite corrosion inhibitor prepared in Example 1, Example 2, Example 3 and Example 4 was tested for corrosion inhibition performance in acid solution.
  • the standard "SY/T5405-1996" is carried out, and the specific results are as follows.
  • Acid solution preparation Measure 210 mL of industrial hydrochloric acid with a mass percentage of 31%, add 25.0 g of component A of the corrosion inhibitor and 7.5 g of component B of the corrosion inhibitor, stir evenly, and make up to 500 mL with tap water, and stir evenly.
  • the coupons are made of BG110SS steel, and the coupons are prepared according to the standard requirements, and the weighing records are made.
  • Formula 1-Formula 4 in Table 1 refer to the formula of component A corresponding to Example 1-Example 4.
  • Acid solution preparation Measure 280 mL of industrial hydrochloric acid with a mass percentage of 31%, add 25.0 g of corrosion inhibitor component A and 7.5 g of corrosion inhibitor component B, stir evenly, and use tap water to make up to 500 mL, and stir evenly.
  • the coupons are made of BG110SS steel, and the coupons are prepared according to the standard requirements, and the weighing records are made.
  • Acid corrosion rate In accordance with "SY-T 5405 Performance Test Method and Evaluation Index of Corrosion Inhibitor for Acidizing", the corrosion rate test at 200 °C was carried out in the high temperature and high pressure dynamic corrosion test system. The results are shown in Table 2.
  • Formula 1-Formula 4 in Table 2 refer to the formula of component A corresponding to Example 1-Example 4.
  • Acid solution preparation Measure 210mL of industrial hydrochloric acid with a mass percentage of 31%, add 25.0g of Component A of the corrosion inhibitor and 7.5g of Component B of the corrosion inhibitor, and then add the thickener, Iron ion stabilizer, clay stabilizer and drainage aid, stir evenly, make up to 500mL with tap water, and stir evenly.
  • the coupons are made of BG110SS steel, and the coupons are prepared according to the standard requirements, and the weighing records are made.
  • Acid corrosion rate In accordance with "SY-T 5405 Performance Test Method and Evaluation Index of Corrosion Inhibitor for Acidizing", the corrosion rate test at 200 °C was carried out in the high temperature and high pressure dynamic corrosion test system. The results are shown in Table 3.
  • Formula 1-Formula 4 in Table 3 refer to the formula of component A corresponding to Example 1-Example 4.
  • Test Mannich base quaternary ammonium salt corrosion inhibitor (the ingredient is Mannich base quaternary ammonium salt, the manufacturer is Chengdu Dute Technology Development Co., Ltd.) and quinoline quaternary ammonium salt corrosion inhibitor (the ingredient is quinoline quaternary ammonium salt, Specifically, the solubility of chloride-1-benzyl quinoline salt) in acid. Adding a certain amount of auxiliary agent when the two main agents are compounded helps to accurately evaluate the corrosion inhibition efficiency of the corrosion inhibitor.
  • the adjuvants used were isopropanol, methyl oleate and O-20 surfactant in a mass ratio of 20:7.5:5.
  • the main compound is mainly Mannich base quaternary ammonium salt corrosion inhibitor, and the designed dosage is 25%, 30%, 45%, 50%, compound quinoline quaternary ammonium salt, the designed dosage is 5%, 6%, 8%, 10%.
  • Orthogonal experimental design was used to optimize the ratio of the two main agents. After compounding, the dosage of corrosion inhibitor was 5%, the dosage of synergist was 1.5%, 15% HCl, and the balance was water. Evaluation standard BG110SS test piece corrosion rate. The orthogonal experiment results are shown in Table 4.
  • Table 5 shows the evaluation results of the corrosion inhibition effect after the Mannich base is compounded with other types of corrosion inhibitors.
  • the main agent dosage of Mannich base quaternary ammonium salt is set to 40%, the dosage of other types of corrosion inhibitors is set to 5%, the main agent dosage is 40%, and the auxiliary agent is isopropyl with a mass ratio of 20:7.5:5 Alcohol, Methyl Oleate and O-20 Surfactant.
  • the temperature resistance performance test of the main agent of the quinoline quaternary ammonium salt corrosion inhibitor is also carried out, the corrosion rate of the synthetic quinoline quaternary ammonium salt corrosion inhibitor at 90-140 °C is tested, and the corrosion inhibition performance of the corrosion inhibitor is compared with the temperature
  • the test results are shown in Table 6.

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Abstract

本发明提供了一种适用于200℃的酸化用缓蚀剂及应用。该酸化用缓蚀剂包括组分A，按重量百分比计，该组分A包括醛酮胺缩合物，喹啉季铵盐，有机酸，炔醇衍生物，有机增效剂，醇溶剂，分散剂和水，所述喹啉季铵盐是由氯化苄、苄甲醇、苄丙醇和十六烷基二甲基苄基氯化铵中的至少一种与喹啉通过季铵化反应合成。

Description

适用于200℃的酸化用缓蚀剂及应用 技术领域
本发明涉及油气层增产改造技术领域，具体涉及一种适用于200℃的酸化用缓蚀剂及应用。
背景技术
酸化是油气井增产改造的重要措施，通过井筒向地层注入酸液，利用酸液与地层中部分矿物的化学反应，溶蚀储层中的连通孔隙或裂缝壁面岩石，增加孔隙间联通和裂缝导流能力，达到油气井增产的目的。在酸化过程中，酸液会腐蚀井下管柱，因此需要向酸液中添加缓蚀剂，从而抑制或者减缓酸液对井下管柱的腐蚀。
相关技术查询中能够耐温达到200℃缓蚀剂的专利申请只有2件，其中，专利申请号为201611200455.3的专利申请提供了主要组成为油酰基肌氨酸钠、巯基苯并噻唑、多乙烯多胺的一种酸化用缓蚀剂。该酸化用缓蚀剂虽然最高耐温能做到240℃，但是缓蚀速率只有23g/m 2·h左右，且是在22％HCl和8％HF的条件下达到的效果。专利申请号为201310609361.1的专利申请则提供了以苯乙酮、三聚甲醛、环已胺为主要成分的酸化用缓蚀剂，该专利申请只是说明了缓蚀速率低、成本低等优点，但未给出具体的腐蚀效果评价指标。
在实现本发明的过程中，本发明人发现相关技术中至少存在以下问题：
相关技术提供的酸化用缓蚀剂大多在井温160℃的条件下使用，而随着油气勘探逐步向深层、超深层储层发展，井深超过7000m，井底温度普遍在160℃以上，目前部分油井的井底最高温度和施工段温度超过200℃。相关技术提供的酸化用缓蚀剂已不能满足深层、超深层储层温度达到200℃改造需求。因此，亟需提供一种耐高温的酸化用缓蚀剂。
发明内容
为了解决上述问题，本发明的目的在于提供一种适用于200℃的酸化用缓蚀剂。该酸化用缓蚀剂能够满足深层、超深层储层改造需求。
本发明的另一个目的在于提供所述酸化用缓蚀剂的应用。
为达上述目的，一方面，本发明提供了一种适用于200℃的酸化用缓蚀剂，所述酸化用缓蚀剂包括组分A，其中，按重量份计，所述组分A包括如下组分：醛酮胺缩合物：30份-45份；有机酸：1份-17份；炔醇衍生物：3份-10份；有机增效剂：15份-40份； 醇溶剂：5份-15份；分散剂：5份-15份。
根据本发明的一些具体实施方案，上述组分A还可以包括喹啉季铵盐，所述喹啉季铵盐可以进一步提高缓蚀剂的耐温性能和缓蚀能力。在具体实施方案中，所述组分A可以包括如下组分：醛酮胺缩合物：30份-45份；喹啉季铵盐：5份-8份；有机酸：1份-17份；炔醇衍生物：3份-10份；有机增效剂：15份-40份；醇溶剂：5份-15份；分散剂：5份-15份，其中，所述喹啉季铵盐可以是由氯化苄、苄甲醇、苄丙醇和十六烷基二甲基苄基氯化铵中的一种或两种以上的组合与喹啉通过季铵化反应合成。
本发明的具体实施方案中，上述组分A一般是与水混合制成溶液的形式进行应用。
根据本发明的一些具体实施方案，按重量百分比计(即，以组分A的总重量为100％计)，所述组分A包括如下组分：醛酮胺缩合物：30％-45％；喹啉季铵盐：5％-8％；有机酸：1％-10％；炔醇衍生物：3％-10％；有机增效剂：15％-40％；醇溶剂：5％-15％；分散剂：5％-15％；余量为水；所述喹啉季铵盐可以是由氯化苄、苄甲醇、苄丙醇和十六烷基二甲基苄基氯化铵中的一种或两种以上的组合与喹啉通过季铵化反应合成。
根据本发明的一些具体实施方案，所述组分A还可以进一步包括曼尼希碱季铵盐。曼尼希碱季铵盐与喹啉季铵盐复配可以减缓金属在酸液中的腐蚀速率，提高缓蚀剂的缓蚀效果。所述曼尼希碱季铵盐与喹啉季铵盐的质量比可以控制为25-50：5-10，例如可以是30-45：5-10。
根据本发明的一些具体实施方案，以所述醛酮胺缩合物的质量为100％计，所述醛酮胺缩合物中包括质量比例在60％以上的式(I)或者式(II)所示的聚合物；
Figure PCTCN2022071731-appb-000001
其中，R1为烃基，X为卤素，聚合物的粘均分子量为1000以下。
根据本发明的一些具体实施方案，式(II)是式(I)所示的聚合物的季铵化产物， R1为-CH 2CH＝CH 2，X为氯或溴；与式(I)所示的聚合物相比，季铵化后的式(II)所示的化合物分子能量较低，更加稳定，更有利于在高温下与金属表面稳定的吸附。
本发明的醛酮胺缩合物分子中含有的未共用电子对的氮、氧原子转变成鎓离子后，在酸中形成带正电荷的阳离子，这些阳离子与金属表面接触时，通过静电引力和范德华力吸附在金属表面有过剩的位置形成单分子吸附膜，这样H +离子难接近金属表面，H +离子在金属表而得到电子阴极过程被抑制。分子中有未共用电子对的氮、氧原子，以及含有π键的苯环，因此可以和金属表面的铁原子通过配位键形成吸附膜。而且在氧、氮之间隔着两个非配位原子，所以该缓蚀剂分子是个螯合配位体。它的配位原子的孤对电进入铁原子杂化的dsp轨道，形成配位键，发生络合作用，形成稳定的具有六元环环状结构的螯合物，该螯合物能够吸附在金属表面上，形成致密稳定的疏水保护膜，有效阻止腐蚀产物铁离向溶液中扩散的腐蚀反应的阳极过程，通过覆盖效应又能够抑制溶液中氢离子向金属迁移的腐蚀反应的阴极过程。
根据本发明的一些具体实施方案，所述醛酮胺缩合物可以是由醛类化合物、酮类化合物、胺类化合物反应得到的。具体地，可以是先由醛类化合物与酮类化合物反应形成中间产物，再将中间产物与胺类化合物混合反应得到醛酮胺缩合物。所述反应的温度一般控制为95-115℃，所述反应的时间一般控制为240min。所述醛类化合物可以包括甲醛等，所述酮类化合物可以包括环己酮等，所述胺类化合物可以包括苯胺等。
在一些具体实施方案中，上述醛酮胺缩合物的制备方法可以为：以重量份计，将510份甲醛、600份环己酮、与65份盐酸混合，95℃恒温1.5h，然后静置分离，得到中间产物，将750份中间产物、300份苯胺和35份盐酸混合，115℃恒温1.5h，得到醛酮胺缩合物。
根据本发明的一些具体实施方案，所述喹啉季铵盐是由氯化苄与喹啉反应得到的氯化-1-苄喹啉盐。
上述喹啉季铵盐的阳离子可以在金属表面的阴极区发生物理吸附，可以有效阻止H +离子接近金属表面，从而抑制H +的还原反应，对阴极反应有抑制作用。另外喹啉季铵盐分中有未共用电子对的N元素，这些元素可与金属表面配位结合，形成牢固的化学吸附层，提高钢在腐蚀介质中的阳极反应的活化能，从而降低阳极的腐蚀速率。而季铵盐中的卤素对铁的缓蚀有一定的协同作用，促使有机阳离子吸附在金属表面而形成稳定的保护膜，其疏水的非极性基远离金属表面作定向排列，能够有效阻碍腐蚀产物铁离子向溶液中的扩散和溶液中的氢离子向金属的腐蚀反应过程迁移。另外喹啉季铵盐中含有 稠环结构，稠环上有较大的电子总离域能，能够增强其与金属原子的配位作用，因此在金属表面形成的吸附膜更牢固。
根据本发明的一些具体实施方案，所述有机酸选自甲酸或乙酸。
根据本发明的一些具体实施方案，所述炔醇衍生物选自丙炔醇丙氧基化合物(式IV)或丙炔醇乙氧基化合物(式V)；
Figure PCTCN2022071731-appb-000002
上述炔醇衍生物中，选用丙炔醇衍生物而不采用丙炔醇的原因在于，由于丙炔醇是剧毒类物质，是受管制药品，而其衍生物属于低毒类物质，满足环保要求。
根据本发明的一些具体实施方案，所述有机增效剂选自脂肪胺、酰胺和醇胺中的一种或两种以上的组合。
根据本发明的一些具体实施方案，所述有机增效剂选自甲酰胺和N,N-二甲基甲酰胺中的一种或两种的组合。
根据本发明的一些具体实施方案，所述醇溶剂选自乙醇、异丁醇和乙二醇中的任意一种。
根据本发明的一些具体实施方案，所述分散剂选自烷基酚聚氧乙烯醚和脂肪醇聚氧乙烯醚中的一种或两种的组合。
根据本发明的一些具体实施方案，所述烷基酚聚氧乙烯醚选自OP-10和NP-10中的一种或两种的组合，所述脂肪醇聚氧乙烯醚选自OS-15和OS-20中的一种或两种的组合。
根据本发明的一些具体实施方案，所述酸化用缓蚀剂还包括组分B，所述组分B选自氯化亚铜、碘化钾、焦锑酸钾、三氧化二锑和钼酸钠中的一种或两种以上的组合。优选地，所述组分A和组分B的质量比例为(4.0-5.0):(0.5-1.5)。
炔醇衍生物和有机增效剂可以填补醛酮胺缩合物和喹啉季铵盐大分子缓蚀剂吸附空隙区域，丙炔醇衍生物比丙炔醇分子链相对长些，含有未共用电子对氧原子能与金属表面吸附成膜，又具有一定疏水性能形成疏水保护膜。无机增效剂(即组分B)的加入可以使缓蚀剂的耐温达到200℃。
根据本发明的一些具体实施方案，组分A的制备方法可以包括如下步骤：将所述醛酮胺缩合物加热至40-50℃，之后将所述有机酸、炔醇衍生物、有机增效剂、醇溶剂、分散剂与所述醛酮缩合物混合均匀，得到所述组分A。
根据本发明的一些具体实施方案，当所述组分A含有喹啉季铵盐时，该组分A的制备方法可以包括如下步骤：将所述醛酮胺缩合物加热至40-50℃，之后将所述喹啉季铵盐、有机酸、炔醇衍生物、有机增效剂、醇溶剂、分散剂与所述醛酮缩合物混合均匀，得到所述组分A。进一步地，当所述组分A还含有曼尼希碱季铵盐时，可以将曼尼希碱季铵盐与喹啉缓蚀剂同时添加。
另一方面，本发明还提供了上述酸化用缓蚀剂在深层油气储层中的应用。
根据本发明的一些具体实施方案，所述应用包括以下步骤：将组分A直接加入浓度大于等于31％的盐酸中，溶解分散后再加入组分B，搅拌均匀，待组分B溶解完全后再把酸稀释到需要的浓度。
本发明的有益效果：
本发明实施例提供的酸化用缓蚀剂能够适用于200℃及以下的高温，该酸化用缓蚀剂在HCl质量浓度为15％-25％浓盐酸(以下所指酸浓度皆是指HCl的质量百分含量)中具有良好的分散性，腐蚀速率满足石油天然气行业一级指标要求。应用该酸化用缓蚀剂能够降低超深层超高温碳酸盐岩酸化改造过程中井下管柱的腐蚀风险。
附图说明
图1为本发明的缓蚀剂在90-140℃下的腐蚀速率。
具体实施方式
为了对本发明的技术特征、目的和有益效果有更加清楚的理解，现对本发明的技术方案进行以下详细说明，但不能理解为对本发明的可实施范围的限定。
如下实施例中的氯化-1-苄喹啉盐购自成都福瑞斯特科技发展有限公司。
以下实施例所用的醛酮胺缩合物为酸化用缓蚀剂醛酮胺缩合物CT1-3D，稠化剂为酸化用胶凝剂阳离子聚丙烯酰胺CT1-9B，铁离子稳定剂为酸化用铁离子稳定剂有机酸盐CT1-7，粘土稳定剂为油气井用粘土稳定剂聚季铵盐CT5-8，助排剂为压裂酸化用助排剂氟碳类CT5-12A，以上试剂均为成都能特科技发展有限公司生产。
实施例1
本实施例提供一种酸化用缓蚀剂，该酸化用缓蚀剂包括组分A和组分B。
其中，组分A由以下方法制备得到：
以重量份计，向反应釜中加入30份醛酮胺缩合物，并将醛酮胺缩合物加热至40-50℃，之后在搅拌状态下依次加入5份氯化-1-苄喹啉盐、10份丙炔醇丙氧基化合物、17份甲酸、19份甲酰胺、9份乙二醇、以及10份O-20，搅拌均匀后得到本实施例的组分A，记为配方1。
本实施例的组分B为焦锑酸钾，组分A与组分B的质量比为5.0:1.5。
实施例2
本实施例提供一种酸化用缓蚀剂，该酸化用缓蚀剂包括组分A和组分B。
以重量份计，向反应釜中加入35份醛酮胺缩合物，并将醛酮胺缩合物加热至40-50℃，之后在搅拌状态下依次加入10份丙炔醇丙氧基化合物、17份甲酸、19份甲酰胺、9份乙二醇、以及10份O-20，搅拌均匀后得到本实施例的组分A，记为配方2。
本实施例的组分B为焦锑酸钾，组分A与组分B的质量比为5.0:1.5。
实施例3
本实施例提供一种酸化用缓蚀剂，该酸化用缓蚀剂包括组分A和组分B。
其中，组分A由以下方法制备得到：
以重量份计，向反应釜中加入30份醛酮胺缩合物，并将醛酮胺缩合物加热至40-50℃，之后在搅拌状态下依次加入5份氯化-1-苄喹啉盐、10份丙炔醇乙氧基化合物、17份乙酸、19份N,N-二甲基甲酰胺、9份乙醇、以及10份O-20，搅拌均匀后得到本实施例的组分A，记为配方3。
本实施例的组分B为钼酸钠，组分A与组分B的质量比为5.0:1.5。
实施例4
本实施例提供一种酸化用缓蚀剂，该酸化用缓蚀剂包括组分A和组分B。
其中，组分A由以下方法制备得到：
以重量份计，向反应釜中加入35份醛酮胺缩合物，并将醛酮胺缩合物加热至40-50℃，之后在搅拌状态下依次加入10份丙炔醇乙氧基化合物、17份乙酸、19份N,N-二甲基甲酰胺、9份乙醇、以及10份O-20，搅拌均匀后得到本实施例的组分A，记为配方4。
本实施例的组分B为钼酸钠，组分A与组分B的质量比为5.0:1.5。
实施例5
本实施例对实施例1、实施例2、实施例3和实施例4制得的复合缓蚀剂在酸液中进行了缓蚀性能测试，该缓蚀性能测试是按照中华人民共和国石油天然气行业标准 《SY/T5405-1996》进行，具体结果如下。
具体评价方法为：
向质量浓度为15％的盐酸中，分别加入上述实施例1-4提供的酸化用缓蚀剂，采用标准BG110SS试片，开展腐蚀性能评价。
1、15％盐酸腐蚀评价
室内配制500mL盐酸浓度为15％wt、缓蚀剂的组分A为5％wt、缓蚀剂的组分B为1.5％wt的酸液。
酸液配制：量取210mL质量百分数为31％的工业盐酸，加入25.0g缓蚀剂的组分A和7.5g缓蚀剂的组分B，搅拌均匀，用自来水定容至500mL，搅拌均匀。
挂片采用BG110SS钢片，按照标准要求准备好挂片，做好称重记录。
酸液腐蚀速率：按照《SY-T 5405酸化用缓蚀剂性能试验方法及评价指》在高温高压动态腐蚀测试系统中，进行200℃下的腐蚀速率测试。结果见表1。
从表1中可以看出，200℃温度下的腐蚀速率满足石油天然气行业一级指标要求，腐蚀后试片无点蚀、坑蚀现象。
表1
Figure PCTCN2022071731-appb-000003
注：表1中配方1-配方4指的是实施例1-实施例4相应的组分A的配方。
2、20％盐酸腐蚀评价
室内配制500mL盐酸浓度为20％wt、缓蚀剂的组分A为5％wt、缓蚀剂的组分B为1.5％wt的酸液。
酸液配制：量取280mL质量百分数为31％的工业盐酸，加入25.0g缓蚀剂的组分A和7.5g缓蚀剂的组分B，搅拌均匀，用自来水定容至500mL，搅拌均匀。
挂片采用BG110SS钢片，按照标准要求准备好挂片，做好称重记录。
酸液腐蚀速率：按照《SY-T 5405酸化用缓蚀剂性能试验方法及评价指标》在高温高压动态腐蚀测试系统中，进行200℃下的腐蚀速率测试。结果见表2。
从表2中可以看出，200℃温度下、20％的盐酸浓度腐蚀速率满足石油天然气行业一级指标要求，腐蚀后试片无点蚀、坑蚀现象。
表2
Figure PCTCN2022071731-appb-000004
注：表2中配方1-配方4指的是实施例1-实施例4相应的组分A的配方。
3、15％盐酸酸液体系腐蚀评价
室内配制500mL盐酸浓度为15％wt、缓蚀剂的组分A为5％wt、缓蚀剂的组分B为1.5％wt、稠化剂为0.05％wt、铁离子稳定剂2％wt、粘土稳定剂为1％wt、助排剂为1％wt的酸液体系。
酸液配制：量取210mL质量百分数为31％的工业盐酸，加入25.0g缓蚀剂的组分A和7.5g缓蚀剂的组分B，再加入按照以上含量比例称量的稠化剂、铁离子稳定剂、粘土稳定剂和助排剂，搅拌均匀，用自来水定容至500mL，搅拌均匀。
挂片采用BG110SS钢片，按照标准要求准备好挂片，做好称重记录。
酸液腐蚀速率：按照《SY-T 5405酸化用缓蚀剂性能试验方法及评价指标》在高温高压动态腐蚀测试系统中，进行200℃下的腐蚀速率测试。结果见表3。
从表3中可以看出，200℃温度下、15％的盐酸酸液体系腐蚀速率略有提高，但仍能满足石油天然气行业一级指标要求，腐蚀后试片无点蚀、坑蚀现象。
表3
Figure PCTCN2022071731-appb-000005
注：表3中配方1-配方4指的是实施例1-实施例4相应的组分A的配方。
实施例6
本实施例提供了曼尼希碱季铵盐缓蚀剂与喹啉季铵盐缓蚀剂在酸中的溶解性的对比试验。具体如下：
测试曼尼希碱季铵盐缓蚀剂(成分为曼尼希碱季铵盐，厂家为成都能特科技发展有限公司)与喹啉季铵盐缓蚀剂(成分为喹啉季铵盐，具体为氯化-1-苄喹啉盐)在酸中的溶解性，在两种主剂复配时添加一定量的助剂有助于准确评价缓蚀剂的缓蚀效率，本实施例中所用的助剂为质量比为20:7.5:5的异丙醇，油酸甲酯和O-20表面活性剂。根据曼尼希碱季铵盐缓蚀剂与喹啉季铵盐缓蚀剂的实际功能特性，主剂复配以曼尼希碱季铵盐缓蚀剂为主，设计加量为25％、30％、45％、50％，复配喹啉季铵盐，设计加量为5％、6％、8％、10％。采用正交实验设计优化两种主剂的配比，复配后的缓蚀剂加量为5％，增效剂加量为1.5％，15％HCl，余量为水，在200℃条件下评价标准BG110SS试片腐蚀速率。正交实验结果如表4所示。
表4
Figure PCTCN2022071731-appb-000006
由实验结果可知，曼尼希碱季铵盐加量在30-45％区间缓蚀剂缓蚀性能达到较好的缓蚀效果，加量再增加缓蚀效果反而有所降低。
曼尼希碱与其他种类缓蚀剂复配后缓蚀效果评价结果见表5。曼尼希碱季铵盐主剂加量定为40％，其他类型缓蚀剂加量定为5％，主剂加量为40％，助剂为质量比为20:7.5:5 的异丙醇，油酸甲酯和O-20表面活性剂。
表5
Figure PCTCN2022071731-appb-000007
曼尼希碱季铵盐与其他类型缓蚀剂评价结果可以看出，只有喹啉类季铵盐与其复配在200℃高温条件下才有较好的缓蚀效果。
实施例7
本发明还进行了喹啉季铵盐缓蚀剂主剂的耐温性能测试，测试合成喹啉季铵盐缓蚀剂在90-140℃下的腐蚀速率，对比温度对缓蚀剂缓蚀性能的影响；测试结果如表6所示。
表6
Figure PCTCN2022071731-appb-000008
通过该表以及图1可以看出，在90℃-140℃范围内，随着温度的上升，季铵盐缓蚀剂的缓蚀性能呈现出比较明显的下降趋势。

Claims (19)

  1. 一种适用于200℃的酸化用缓蚀剂，其中，所述酸化用缓蚀剂包括组分A，其中，按重量份计，所述组分A包括如下组分：醛酮胺缩合物：30份-45份；有机酸：1份-17份；炔醇衍生物：3份-10份；有机增效剂：15份-40份；醇溶剂：5份-15份；分散剂：5份-15份。
  2. 根据权利要求1所述的酸化用缓蚀剂，其中，按重量份计，所述组分A包括如下组分：醛酮胺缩合物：30份-45份；喹啉季铵盐：5份-8份；有机酸：1份-17份；炔醇衍生物：3份-10份；有机增效剂：15份-40份；醇溶剂：5份-15份；分散剂：5份-15份，其中，所述喹啉季铵盐是由氯化苄、苄甲醇、苄丙醇和十六烷基二甲基苄基氯化铵中的一种或两种以上的组合与喹啉通过季铵化反应合成。
  3. 根据权利要求1或2所述的酸化用缓蚀剂，其中，按重量百分比计，所述组分A包括如下组分：醛酮胺缩合物：30％-45％；喹啉季铵盐：5％-8％；有机酸：1％-10％；炔醇衍生物：3％-10％；有机增效剂：15％-40％；醇溶剂：5％-15％；分散剂：5％-15％；余量为水；
    其中，所述喹啉季铵盐是由氯化苄、苄甲醇、苄丙醇和十六烷基二甲基苄基氯化铵中的一种或两种以上的组合与喹啉通过季铵化反应合成。
  4. 根据权利要求2或3所述的酸化用缓蚀剂，其中，所述组分A还包括曼尼希碱季铵盐，所述曼尼希碱季铵盐与喹啉季铵盐的质量比为25-50：5-10。
  5. 根据权利要求1-4任一项所述的酸化用缓蚀剂，其中，以所述醛酮胺缩合物的质量为100％计，所述醛酮胺缩合物中包括质量比例在60％以上的式(I)或者式(II)所示的聚合物；
    Figure PCTCN2022071731-appb-100001
    其中，R1为烃基，X为卤素，聚合物的粘均分子量为1000以下。
  6. 根据权利要求5所述的酸化用缓蚀剂，其中，所述式(II)是式(I)所示的聚合物的季铵化产物，R1为-CH 2CH＝CH 2，X为氯或溴。
  7. 根据权利要求2-4任一项所述的酸化用缓蚀剂，其中，所述喹啉季铵盐是由氯化苄与喹啉反应得到的氯化-1-苄喹啉盐。
  8. 根据权利要求1-4任一项所述的酸化用缓蚀剂，其中，所述有机酸选自甲酸或乙酸。
  9. 根据权利要求1-4任一项所述的酸化用缓蚀剂，其中，所述炔醇衍生物选自丙炔醇丙氧基化合物或丙炔醇乙氧基化合物。
  10. 根据权利要求1-9任一项所述的酸化用缓蚀剂，其中，所述有机增效剂选自脂肪胺、酰胺和醇胺中的一种或两种以上的组合。
  11. 根据权利要求1-4或10任一项所述的酸化用缓蚀剂，其中，所述有机增效剂选自甲酰胺和N,N-二甲基甲酰胺中的一种或两种的组合。
  12. 根据权利要求1-4任一项所述的酸化用缓蚀剂，其中，所述醇溶剂选自乙醇、异丁醇和乙二醇中的任意一种。
  13. 根据权利要求1-4任一项所述的酸化用缓蚀剂，其中，所述分散剂选自烷基酚聚氧乙烯醚和脂肪醇聚氧乙烯醚中的一种或两种的组合。
  14. 根据权利要求13所述的酸化用缓蚀剂，其中，所述烷基酚聚氧乙烯醚选自OP-10和NP-10中的一种或两种的组合，所述脂肪醇聚氧乙烯醚选自OS-15和OS-20中的一种或两种的组合。
  15. 根据权利要求1-14任一项所述的酸化用缓蚀剂，其中，所述酸化用缓蚀剂还包括组分B，所述组分B选自氯化亚铜、碘化钾、焦锑酸钾、三氧化二锑和钼酸钠中的一种或两种以上的组合。
  16. 根据权利要求15所述的酸化用缓蚀剂，其中，所述组分A和组分B的比例为(4.0-5.0):(0.5-1.5)。
  17. 根据权利要求1所述的酸化用缓蚀剂，其中，组分A的制备方法包括如下步骤：
    将所述醛酮胺缩合物加热至40-50℃，之后将所述有机酸、炔醇衍生物、有机增效剂、醇溶剂、分散剂与所述醛酮缩合物混合均匀，得到所述组分A。
  18. 权利要求1-17任一项所述的酸化用缓蚀剂在深层油气储层中的应用。
  19. 根据权利要求18所述的应用，其中，包括以下步骤：
    将组分A直接加入盐酸中，溶解分散后再加入组分B，搅拌均匀。
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