WO2021026921A1 - Inhibiteur de corrosion et son procédé de préparation, et procédé d'inhibition de la corrosion de l'acide naphténique dans l'huile - Google Patents

Inhibiteur de corrosion et son procédé de préparation, et procédé d'inhibition de la corrosion de l'acide naphténique dans l'huile Download PDF

Info

Publication number
WO2021026921A1
WO2021026921A1 PCT/CN2019/100874 CN2019100874W WO2021026921A1 WO 2021026921 A1 WO2021026921 A1 WO 2021026921A1 CN 2019100874 W CN2019100874 W CN 2019100874W WO 2021026921 A1 WO2021026921 A1 WO 2021026921A1
Authority
WO
WIPO (PCT)
Prior art keywords
aromatic
corrosion inhibitor
acid
oil
olefin
Prior art date
Application number
PCT/CN2019/100874
Other languages
English (en)
Chinese (zh)
Inventor
刘影
严斌
叶世春
熊靓
Original Assignee
广昌达新材料技术服务（深圳）股份有限公司
深圳市广昌达石油添加剂有限公司
宁波广昌达新材料有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广昌达新材料技术服务（深圳）股份有限公司, 深圳市广昌达石油添加剂有限公司, 宁波广昌达新材料有限公司 filed Critical 广昌达新材料技术服务（深圳）股份有限公司
Priority to PCT/CN2019/100874 priority Critical patent/WO2021026921A1/fr
Publication of WO2021026921A1 publication Critical patent/WO2021026921A1/fr

Links

Classifications

    • 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

Definitions

  • the invention relates to the field of crude oil refining, in particular to a corrosion inhibitor, a preparation method thereof, and a method for inhibiting naphthenic acid corrosion in oil products.
  • the methods for solving naphthenic acid corrosion can be divided into the following three types: First, use corrosion-resistant materials in oil refining equipment and equipment, and upgrade anti-corrosion materials; second, control the flow rate and flow state of crude oil processing, and improve oil refining The equipment structure is optimized and designed; third, process measures are adopted for anti-corrosion, such as crude oil mixing, crude oil deacidification, and adding corrosion inhibitors to easily corrosive parts. At present, adding corrosion inhibitors is the simplest and most effective solution to high-temperature naphthenic acid corrosion during the processing of high-acid crude oil.
  • high-temperature corrosion inhibitors can be divided into phosphorus-containing corrosion inhibitors and non-phosphorus corrosion inhibitors. Phosphorus-containing high-temperature corrosion inhibitors are mainly composed of phosphate compounds.
  • a corrosion inhibitor in terms of mass percentage, the raw materials for preparing the corrosion inhibitor include:
  • the aromatic polyester is selected from at least one of aromatic polybasic acid esters and aromatic polyphenol esters
  • the corrosion inhibitor is selected from at least one of olefin-maleic anhydride copolymers and oil-soluble magnesium compounds.
  • the oil-soluble magnesium compound is selected from at least one of oil-soluble nano-magnesium oxide and oil-soluble nano-magnesium hydroxide.
  • a preparation method of a corrosion inhibitor includes the following steps:
  • aromatic polyester 25%-65% In terms of mass percentage, weigh the following raw materials: aromatic polyester 25%-65%, corrosion inhibitor 1%-40%, and organic solvent 20%-60%, wherein the aromatic polyester is selected from aromatics At least one of polybasic acid esters and aromatic polyphenol esters, the corrosion inhibitor is selected from at least one of olefin-maleic anhydride copolymers and oil-soluble magnesium compounds, and the oil-soluble magnesium compounds are selected from oils At least one of soluble nano-magnesium oxide and oil-soluble nano-magnesium hydroxide; and
  • the aromatic polyester, the corrosion inhibitor and the organic solvent are mixed to obtain a corrosion inhibitor.
  • a method for inhibiting the corrosion of naphthenic acid in an oil product comprising: adding a corrosion inhibitor to the oil product, and the raw materials for preparing the corrosion inhibitor include: 25%-65% of aromatic polyesters, by mass percentage, Corrosion inhibitor 1%-40%; and organic solvent 20%-60%; wherein, the aromatic polyester is selected from at least one of aromatic polybasic acid esters and aromatic polyphenol esters, and the corrosion inhibitor
  • the auxiliary agent is selected from at least one of olefin-maleic anhydride copolymer and oil-soluble magnesium compound, and the oil-soluble magnesium compound is selected from at least one of oil-soluble nano-magnesium oxide and oil-soluble nano-magnesium hydroxide.
  • the raw materials for preparing the corrosion inhibitor include: aromatic polyester 25%-65%, corrosion inhibitor 1%-40% and organic solvent 20%-60%.
  • the aromatic polyester is selected from at least one of aromatic polybasic acid esters and aromatic polyphenol esters
  • the corrosion inhibitor is selected from at least one of olefin-maleic anhydride copolymers and oil-soluble magnesium compounds, oil-soluble
  • the magnesium compound is selected from at least one of oil-soluble nano-magnesium oxide and oil-soluble nano-magnesium hydroxide.
  • the aromatic polyester is an aromatic compound substituted by a monoester group, and there is at least one carboxyl group or hydroxyl group at other substitution positions of the aromatic polyether;
  • the aromatic polyester is an aromatic compound substituted with at least two ester groups.
  • the aromatic polybasic ester is an aromatic compound substituted with at least two ester groups, there are no carboxyl groups or hydroxyl groups at other substitution positions of the aromatic polybasic ester.
  • the aromatic polyester is an aromatic compound substituted with at least two ester groups, at least one carboxyl group or hydroxyl group exists at other substitution positions of the aromatic polyester.
  • the above-mentioned aromatic polyester contains at least two polar groups.
  • the polar group is an ester group, a hydroxyl group, or a carboxyl group.
  • the above-mentioned aromatic polyester contains at least two ester groups.
  • the above-mentioned aromatic polyester contains at least one ester group and at least one carboxyl group.
  • the aromatic polybasic acid ester contains at least one ester group and at least one hydroxyl group.
  • the parent of the aromatic polyester is selected from at least one of benzene, naphthalene, biphenyl, pyrene, anthracene, phenanthrene, and perylene.
  • Aromatic polyesters are aromatic polybasic acid esters.
  • the raw materials for preparing aromatic polybasic acid esters include aromatic polybasic acids and aliphatic compounds.
  • Aromatic polybasic acids are selected from phthalic acid, trimellitic acid, pyromellitic acid and mellitic acid.
  • Aromatic polyesters are aromatic polyphenol esters.
  • the raw materials for preparing aromatic polyphenol esters include aromatic compounds containing multiple hydroxyl groups and fatty acids, or the raw materials for preparing aromatic polyphenol esters include aromatic compounds containing multiple hydroxyl groups And fatty acid anhydrides, the aromatic compound containing multiple hydroxyl groups is selected from at least one of benzenediol, benzenetriol, benzenehexaol, naphthalenediol, naphthalenetriol, bibenzenediol, and bibenzenetriol, fatty acid
  • the carbon chain length is 4-12.
  • Fatty acid anhydrides are derived from fatty acids with a carbon chain length of 4-12.
  • the function of the above-mentioned hydrocarbon groups with a carbon chain length of 4-12 is to provide non-polar groups to improve the solubility of aromatic polybasic esters in oils.
  • the above-mentioned aromatic polyesters contain multiple polar ester groups (or unreacted carboxyl groups or hydroxyl groups) and planar non-polar aromatic ring structures. These polar groups can interact with the atoms on the metal surface at high temperatures. Chelation forms a stable chelate, which is firmly adsorbed on the metal surface. The planar non-polar aromatic ring structure can evenly cover the metal surface, which can effectively isolate the corrosive substance naphthenic acid from contacting the metal surface. Aromatic rings have better thermal stability than other heterocyclic compounds (such as imidazolines), and are not easily decomposed at high temperatures to cause failure. Therefore, the aromatic polyester has excellent high temperature corrosion inhibition performance.
  • the organic solvent is selected from at least one of aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents. Specifically, the organic solvent is selected from at least one of heavy aromatic hydrocarbons, mixed trimethylbenzene, liquid paraffin, mixed tetramethylbenzene, and coker wax oil.
  • the corrosion inhibitor is an olefin-maleic anhydride copolymer, and among the raw materials for preparing the corrosion inhibitor, the mass percentage of the olefin-maleic anhydride copolymer is 1%-20%.
  • the corrosion inhibitor is an oil-soluble magnesium compound, and the mass percentage of the oil-soluble magnesium compound in the raw materials for preparing the corrosion inhibitor does not exceed 20%.
  • the corrosion inhibitor is a mixture of an olefin-maleic anhydride copolymer and an oil-soluble magnesium compound.
  • the mass percentage of the olefin-maleic anhydride copolymer is 1%-20%, which is oil-soluble The mass percentage of magnesium compounds does not exceed 20%.
  • the corrosion inhibitor is a mixture of olefin-maleic anhydride copolymer and oil-soluble magnesium compound, the obtained corrosion inhibitor has better corrosion inhibition effect.
  • the oil-soluble magnesium compound is obtained by modifying the nanometer magnesium compound so that the nanometer magnesium compound can be dissolved in an organic solvent.
  • the oil-soluble magnesium compound is selected from at least one of fatty acid modified nano magnesium oxide, fatty acid modified nano magnesium hydroxide, sulfonic acid modified nano magnesium oxide, and sulfonic acid modified nano magnesium hydroxide, Sulfonic acid is alkyl sulfonic acid or alkyl benzene sulfonic acid.
  • the fatty acid-modified nano-magnesium oxide and the fatty acid-modified nano-magnesium hydroxide are both Supermega E series products produced by Cestoil. Both the sulfonic acid-modified nano-magnesium oxide and sulfonic acid-modified nano-magnesium hydroxide are the Supermega S series products produced by Cestoil.
  • oil-soluble magnesium compounds have ultra-high alkali values, which can effectively neutralize naphthenic acid in corrosive media, reduce the acid value of oil products, and inhibit the corrosion of equipment from high acid value oil products from the source.
  • oil-soluble nano-magnesium compound clusters can be adsorbed on the defects on the metal surface to strengthen the integrity of the protective film and prevent pitting corrosion of the metal.
  • the raw materials for preparing the olefin-maleic anhydride copolymer include maleic anhydride and olefin, and the olefin is selected from at least one of ⁇ -olefins, styrene and styrene derivatives having a carbon chain length of 8 to 32.
  • the olefin-maleic anhydride copolymer is selected from the group consisting of octene-1 olefins, olefin-maleic anhydride copolymers obtained by the reaction of styrene and maleic anhydride, ⁇ -olefins with a carbon chain length of 14-18, and methylbenzene
  • the olefin-maleic anhydride copolymer obtained by the reaction of ethylene and maleic anhydride the olefin-maleic anhydride copolymer obtained by the reaction of ⁇ -olefins with a carbon chain length of 18-22 and maleic anhydride, and those with a carbon chain length of 24-32
  • the olefin-maleic anhydride copolymer skeleton has alternating non-polar aliphatic carbon chain segments and polar anhydride groups, which can also form a stable chelate with metal atoms.
  • olefin-maleic acid The acid anhydride skeleton has more polar groups, has a stronger chelating effect, and can withstand higher temperatures, which expands the temperature range of the corrosion inhibitor of this embodiment, especially when extremely high temperature corrosion inhibition is required.
  • the aliphatic skeleton of olefin-maleic anhydride copolymers is softer, and can be deformed to fill the irregular voids left by the aromatic polyester film on the metal surface to minimize metal exposure Area, forming a denser protective film, further improving the corrosion inhibition effect.
  • the aromatic polybasic acid ester contains a plurality of polar ester groups (or unreacted carboxyl groups or hydroxyl groups) and a planar non-polar aromatic ring structure, which can pass through these polar
  • the group chelate with the metal surface atoms at high temperature to form a stable chelate, which is firmly adsorbed on the metal surface.
  • the planar non-polar aromatic ring structure can evenly cover the metal surface, which can effectively isolate the corrosive substance ring.
  • the contact between alkanoic acid and the metal surface, and the aromatic ring has better thermal stability than other heterocyclic compounds (such as imidazoline), and it is not easy to decompose at high temperature to cause failure. Therefore, the aromatic polyester has excellent high temperature corrosion inhibition performance .
  • the olefin-maleic anhydride copolymer skeleton has alternating non-polar aliphatic carbon chain segments and polar anhydride groups, which can also form stable chelate with metal atoms.
  • the olefin-maleic anhydride skeleton has more polar groups, has stronger chelating effect, and can withstand higher temperatures, which expands the temperature range of the corrosion inhibitor of this embodiment. Especially for occasions that require extremely high temperature corrosion inhibition.
  • the aliphatic skeleton of olefin-maleic anhydride is softer, and can be deformed to fill the irregular gaps left by the aromatic polyester film on the metal surface to minimize the exposed area of the metal.
  • a denser protective film is formed to further improve the corrosion inhibition effect.
  • the oil-soluble magnesium compound has an ultra-high alkali value, which can effectively neutralize the naphthenic acid in the corrosive medium, reduce the acid value in the oil, and inhibit the high acid from the source Corrosion of oil products to equipment, on the other hand, the oil-soluble magnesium compound clusters can be adsorbed on the defects of the metal surface, strengthen the integrity of the protective film, and prevent pitting corrosion of the metal.
  • the raw materials in the above corrosion inhibitors cooperate with each other and have a synergistic effect, so that the resulting corrosion inhibitor has good thermal stability and corrosion inhibition effect. It can not only form a stable and dense protective film on the metal surface, but also neutralize the oil. Therefore, it has excellent high temperature corrosion inhibition performance, and the corrosion inhibition effect is better than that when any one of the components is used alone in many cases.
  • the raw materials of the above corrosion inhibitors are easily available and low in cost. There are no harmful elements such as P and Cl in the corrosion inhibitor, or S element. On the one hand, it is environmentally friendly and on the other hand, it avoids the subsequent processing process. It is a kind of high temperature corrosion inhibitor with a wide range of applications.
  • the preparation method of the corrosion inhibitor in one embodiment is a preparation method of the above-mentioned corrosion inhibitor, and includes the following steps:
  • Step S110 In terms of mass percentage, weigh the following raw materials: aromatic polyester 25%-65%, corrosion inhibitor 1%-40% and organic solvent 20%-60%, wherein the aromatic polyester is selected from aromatic At least one of polybasic acid esters and aromatic polyphenol esters, the corrosion inhibitor is selected from at least one of olefin-maleic anhydride copolymers and oil-soluble magnesium compounds, and the oil-soluble magnesium compounds are selected from oil-soluble nano-oxidizers At least one of magnesium and oil-soluble nano-magnesium hydroxide.
  • aromatic polyester is selected from aromatic At least one of polybasic acid esters and aromatic polyphenol esters
  • the corrosion inhibitor is selected from at least one of olefin-maleic anhydride copolymers and oil-soluble magnesium compounds
  • the oil-soluble magnesium compounds are selected from oil-soluble nano-oxidizers At least one of magnesium and oil-soluble nano-magnesium hydroxide.
  • the raw materials for preparing the aromatic polybasic acid ester include aromatic polybasic acids and aliphatic compounds.
  • the aromatic polybasic acid is selected from phthalic acid, trimellitic acid, pyromellitic acid, and benzene.
  • the aliphatic compound is a fatty alcohol with a carbon chain length of 4-12
  • the aliphatic compound is an unsaturated olefin with a carbon chain length of 4-12.
  • Fatty alcohols are monohydric alcohols. Specifically, the fatty alcohol is at least one selected from monohydric fatty alcohols having a carbon chain length of 4-12.
  • the unsaturated olefin is at least one selected from alpha olefins having a carbon chain length of 4-12.
  • the preparation process of the aromatic polybasic acid ester includes: under the protection of nitrogen, the molar ratio of the aromatic polybasic acid and the fatty alcohol is at 80°C to 220°C. The next reaction is 3h-12h to obtain aromatic polybasic acid ester.
  • At least one of a heteropoly acid catalyst and a water-carrying agent can also be added to increase the reaction rate.
  • the ratio of the total mass of aromatic polybasic acid and fatty alcohol to the mass of heteropolyacid catalyst and water-carrying agent is 1:(0 ⁇ 0.1):(0 ⁇ 5).
  • the heteropolyacid catalyst is selected from at least one of a supported phosphotungstic acid catalyst and a supported phosphomolybdic acid catalyst.
  • the supported phosphotungstic acid catalyst is a mesoporous silica supported phosphotungstic acid catalyst
  • the supported phosphomolybdic acid catalyst is a mesoporous silica supported phosphomolybdic acid catalyst.
  • the supported phosphotungstic acid catalyst is prepared according to patent CN103586076A.
  • the preparation process of the supported phosphomolybdic acid catalyst is similar to the preparation process of the supported phosphotungstic acid catalyst, except that the phosphotungstic acid solution is replaced with a phosphomolybdic acid solution.
  • the heteropolyacid catalyst can catalyze the esterification reaction between aromatic polybasic acid and fatty alcohol, and increase the reaction rate.
  • the water-carrying agent is selected from at least one of benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, hexane, heptane, octane and decane.
  • the above-mentioned water-carrying agent can discharge the water generated during the esterification reaction in time, thereby improving the conversion rate of the esterification reaction.
  • the preparation process of the aromatic polybasic acid ester includes: taking aromatic polybasic acids and unsaturated olefins in a molar ratio of 1:1 to 1:6 as raw materials, and sulfonic acid type mesoporous molecular sieves as catalysts. Under the protection of nitrogen, the addition reaction is carried out for 6 hours to 24 hours at 80°C to 160°C and the reaction pressure of 0.1MPa to 2MPa to obtain the aromatic polybasic acid ester.
  • the sulfonic acid type porous molecular sieve is prepared according to patent CN102924272A.
  • the organic solvent is selected from at least one of aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents. Specifically, the organic solvent is selected from at least one of heavy aromatic hydrocarbons, mixed trimethylbenzene, liquid paraffin, mixed tetramethylbenzene, and coker wax oil.
  • the raw materials for preparing the aromatic polyphenol ester include aromatic compounds containing multiple hydroxyl groups and fatty acids, or the raw materials for preparing the aromatic polyphenol ester include aromatic compounds containing multiple hydroxyl groups.
  • the aromatic compound containing multiple hydroxyl groups is at least one selected from aromatic polyphenols. Specifically, the aromatic compound containing multiple hydroxyl groups is at least one selected from the group consisting of benzenediol, benzenetriol, benzenehexaol, naphthalenediol, naphthalenetriol, biphenyldiol, and biphenyltriol.
  • Fatty acids are monobasic acids. Specifically, the carbon chain length of fatty acids is 4-12.
  • Fatty acid anhydrides are derived from fatty acids with a carbon chain length of 4-12. Further, fatty acid anhydrides are acid anhydrides formed from fatty acids with the same or different carbon chain lengths of 4-12.
  • the preparation process of the aromatic polyphenol ester includes: under the protection of nitrogen, the molar ratio of the aromatic compound containing polyhydroxyl group and the fatty acid is at 80°C to 220°C. React for 3h-12h to obtain aromatic polyphenol ester.
  • the preparation process of the aromatic polyphenol ester includes: under the protection of nitrogen, the molar ratio of the aromatic compound containing the polyhydroxyl group and the fatty acid anhydride is reacted at 80°C ⁇ 220°C for 3h ⁇ 12h. , To obtain aromatic polyphenol esters.
  • a heteropoly acid catalyst and a water-carrying agent can also be added to increase the reaction rate.
  • the ratio of the total mass of the polyhydroxy-containing aromatic compound and fatty acid to the mass of the heteropolyacid catalyst and the water-carrying agent is 1:(0 ⁇ 0.1):(0 ⁇ 5).
  • the ratio of the total mass of the polyhydroxy-containing aromatic compound and fatty acid anhydride to the mass of the heteropolyacid catalyst and the water-carrying agent is 1:(0 ⁇ 0.1):(0 ⁇ 5).
  • the heteropolyacid catalyst is the same as the heteropolyacid catalyst used in the preparation process of the above-mentioned aromatic polybasic acid ester.
  • the above heteropolyacid catalyst can catalyze the esterification reaction of aromatic compounds containing multiple hydroxyl groups with fatty acids or fatty acid anhydrides, thereby increasing the reaction rate.
  • the water-carrying agent is the same as the water-carrying agent used in the preparation process of the above-mentioned aromatic polybasic acid ester.
  • the above-mentioned water-carrying agent can discharge the water generated during the esterification reaction in time, thereby improving the conversion rate of the esterification reaction.
  • the oil-soluble magnesium compound is selected from at least one of fatty acid modified nano magnesium oxide, fatty acid modified nano magnesium hydroxide, sulfonic acid modified nano magnesium hydroxide and sulfonic acid modified nano magnesium oxide, Among them, sulfonic acid is alkyl sulfonic acid or alkyl benzene sulfonic acid.
  • the raw materials for preparing the olefin-maleic anhydride copolymer include maleic anhydride and olefin, and the olefin is selected from at least one of ⁇ -olefins, styrene and styrene derivatives having a carbon chain length of 8 to 32.
  • the olefin-maleic anhydride copolymer is selected from the group consisting of octene-1 olefins, olefin-maleic anhydride copolymers obtained by the reaction of styrene and maleic anhydride, ⁇ -olefins with a carbon chain length of 14-18, and methylbenzene
  • the olefin-maleic anhydride copolymer obtained by the reaction of ethylene and maleic anhydride the olefin-maleic anhydride copolymer obtained by the reaction of ⁇ -olefins with a carbon chain length of 18-22 and maleic anhydride, and those with a carbon chain length of 24-32
  • Step S120 mixing the aromatic polyester, the corrosion inhibitor and the organic solvent to obtain the corrosion inhibitor.
  • the temperature is 20° C. to 80° C.
  • the time is 0.5 h to 5 h.
  • the production process of the above corrosion inhibitor is simple, the raw materials are cheap and easy to obtain, and it is easy for industrial production.
  • the method for inhibiting the corrosion of naphthenic acid in an oil product includes: adding a corrosion inhibitor to the oil product.
  • the corrosion inhibitor is the above-mentioned corrosion inhibitor or the corrosion inhibitor obtained by the above-mentioned preparation method of the corrosion inhibitor.
  • the addition amount of the corrosion inhibitor is 5 ppm to 1000 ppm of the oil quality. Further, the added amount of the corrosion inhibitor is 7 ppm-30 ppm of the oil quality.
  • the processing temperature of the oil product is 240°C to 480°C.
  • the above-mentioned corrosion inhibitor has high temperature corrosion inhibition effect and low toxicity, and can be used to inhibit the corrosion of naphthenic acid in oil.
  • naphthalenedicarboxylic acid anhydride 0.05mol
  • naphthalenedicarboxylic acid 0.1mol
  • decanol 0.3mol
  • water-carrying agent tetramethylbenzene 78.9g
  • Example 1 The parameters in the preparation process of the aromatic polybasic acid esters in -1 to Examples 1-7 are listed in Table 1.
  • trimellitic acid (0.05mol), trimellitic anhydride (0.05mol), pentene (0.05mol), hexene (0.1mol) and sulfonic acid type mesoporous molecular sieve catalyst (4.80g) into the reaction vessel, the reaction pressure is 0.1 MPa, the temperature is gradually raised to 120°C with stirring, and the temperature is kept for 15 hours. After the product is separated, the catalyst is removed to obtain the aromatic polybasic acid ester J.
  • M2 is the molar ratio of aromatic polybasic acid to unsaturated olefin
  • m2 is the ratio of the total mass of aromatic polybasic acid and unsaturated olefin to the amount of catalyst
  • T2 is the reaction temperature
  • t2 is the reaction time
  • P1 is the reaction pressure.
  • M3 represents the molar ratio of the aromatic compound containing multiple hydroxyl groups to the fatty acid (or fatty acid anhydride), and m3 represents the total mass of the aromatic compound containing multiple hydroxyl groups and the fatty acid (or fatty acid anhydride) and the mass of the catalyst and water-carrying agent.
  • Ratio, T3 represents the reaction temperature, t3 represents the reaction time, the various parameters in the preparation process of the aromatic polyphenol esters in Examples 1-13 to 1-17 are listed in Table 3.
  • oil-soluble magnesium compound I is fatty acid-modified nano-magnesium oxide
  • oil-soluble magnesium compound II is sulfonic acid-modified nano-magnesium oxide
  • oil-soluble magnesium compound III is fatty acid-modified nano-magnesium hydroxide
  • an oil-soluble magnesium compound IV is sulfonic acid modified nanometer magnesium hydroxide.
  • Olefin-maleic anhydride copolymer a is an olefin-maleic anhydride copolymer obtained by the reaction of octene-1 olefin, styrene and maleic anhydride; olefin-maleic anhydride copolymer b is an ⁇ with a carbon chain length of 14-18 -Olefin-maleic anhydride copolymer obtained by reacting olefin, methyl styrene and maleic anhydride; olefin-maleic anhydride copolymer c is an olefin obtained by reacting an ⁇ -olefin with a carbon chain length of 18-22 and maleic anhydride -Maleic anhydride copolymer; the olefin-maleic anhydride copolymer d is an olefin-maleic anhydride copolymer obtained by reacting an ⁇ -olefin with a carbon chain length of 24-
  • Example 2-1 to Example 2-18 The corrosion inhibitors prepared in Example 2-1 to Example 2-18, Comparative Example 2-1 to Comparative Example 2-6 and the commercial corrosion inhibitors were tested for their corrosion inhibition performance. The results are shown in Table 5, respectively. Table 6 shows.
  • the decompression simulated static metal test piece weight loss method is used to test the corrosion inhibition performance.
  • a 500mL three-necked flask add 250g of refined naphthenic acid to reduce the line oil corrosive medium (acid value 11.3mg KOH/g).
  • the vertical condenser tube of the aforementioned vacuum distillation device was changed to a vacuum simulation test device. Soak the 20# carbon steel test piece that has been cleaned and accurately weighed in the corrosive medium. Adjust the relative vacuum pressure to -0.08MPa, keep it at different temperatures (240°C, 360°C, 480°C) for 6 hours and then cool it down to below 100°C, stop the test. Take out the test piece to observe the surface condition, and calculate the corrosion rate V and the corrosion inhibition rate I according to the weight loss of the test piece. Calculated as follows:
  • V 0 is the corrosion rate of metal without corrosion inhibitor, mm/a
  • V is the corrosion rate of metal when corrosion inhibitor is added, mm/a.
  • V (87600* ⁇ W)/(S*t* ⁇ )
  • ⁇ W is the poor quality of the test piece before and after the test, g;
  • S is the effective surface area of the test piece, cm 2 ;
  • t is the corrosion test time, h
  • ⁇ is the density of the corrosion test piece, and carbon steel is calculated at 7.86g/cm 3 .
  • Example 2-18 78.2 89.1 94.7 95.0 Comparative example 2-1 20.8 35.9 59.7 67.
  • Comparative example 2-4 25.6 48.3 49.2 49.1 Comparative example 2-5 34.2 56.8 57.7 58.3 Comparative example 2-6 19.4 31.8 54.3 66.2
  • the commercially available phosphorus-containing corrosion inhibitor is MN-HSIII type high temperature corrosion inhibitor produced by Weifang Mien Chemical Co., Ltd.
  • the commercially available non-phosphorus corrosion inhibitor is BXH-103 type phosphorus-free high temperature corrosion inhibitor produced by Hubei Benxin Technology Agent.
  • the corrosion inhibition performance of the high temperature corrosion inhibitor prepared in Example 2-1 is slightly lower than that of commercially available phosphorus-containing corrosion inhibitors at low dosages, because the high temperature corrosion inhibitor prepared in Example 2-1 is effective
  • the component content is relatively low, and its corrosion inhibition performance is also better than that of commercially available phosphorus-containing corrosion inhibitors at a relatively high dosage.
  • the effect of the high temperature corrosion inhibitor prepared in Comparative Example 2-3 is worse than that of commercially available phosphorus-containing and non-phosphorus corrosion inhibitors, because the aromatic polyester is not added in Comparative Example 2-3, and the aromatic polyester is a corrosion inhibitor It is the most critical component in the high temperature corrosion inhibitor, which directly determines the performance of high temperature corrosion inhibitor.
  • Comparative Example 2-1 and Comparative Example 2-2 The effects of the high-temperature corrosion inhibitors prepared in Comparative Example 2-1 and Comparative Example 2-2 are far lower than those of the high-temperature corrosion inhibitors prepared in Examples 2-6 and 2-9, respectively, and compared with those in Examples 2-6 and 2-6.
  • the difference between Examples 2-9 is that Comparative Example 2-1 and Comparative Example 2-2 do not contain olefin-maleic anhydride copolymer, which shows that olefin-maleic anhydride copolymer also plays a key role in high temperature corrosion inhibitors. Function, even if a small amount of olefin-maleic anhydride copolymer (1wt%) is added to the high temperature corrosion inhibitor, the effect of the high temperature corrosion inhibitor will be qualitatively improved.
  • the high temperature corrosion inhibitor prepared in Comparative Example 2-4 is not as effective as the high temperature corrosion inhibitor prepared in Examples 2-1 to 2-18, because the main corrosion inhibitor used in Comparative Example 2-4 has no carboxyl group or Hydroxyl-substituted aromatic monobasic esters cannot form complexes with metal ions, and are difficult to adsorb on the metal surface to form a stable protective film.
  • the effect of the high-temperature corrosion inhibitor prepared in Comparative Example 2-5 is not as good as the high-temperature corrosion inhibitor prepared in Examples 2-1 to 2-18, because the main corrosion inhibitor used in Comparative Example 2-5 is the aromatic polyester
  • the ester group in the aromatic compound does not directly replace the hydrogen atoms on the aromatic compound. There will be a certain gap during film formation, which reduces the coverage of the metal surface.
  • Comparative example 2-6 uses trioctyl trimellitate as high temperature corrosion inhibitor. Under the condition of this dosage, its corrosion inhibition effect is not much different from that of comparative example 2-1, which is not as good as that of Examples 2-1 to Examples. 2-18 prepared high temperature corrosion inhibitor.
  • the effect of the high temperature corrosion inhibitor prepared in Example 2-8 is obviously inferior to that of the high temperature corrosion inhibitor prepared in Example 2-7, because the high temperature corrosion inhibitor prepared in Example 2-8 does not contain oil-soluble nano-magnesium In this system, the oil-soluble nano-magnesium compound, aromatic polyester and olefin-maleic anhydride copolymer have a certain complementary effect in the high-temperature corrosion inhibitor of the system. The use of the three together can achieve the best corrosion inhibition effect.
  • the corrosion inhibitor prepared in the above-mentioned embodiments has the advantages of low dosage and good effect.
  • the raw materials used in the corrosion inhibitor prepared in the above-mentioned embodiments are simple and easy to obtain, the process is simple, and the cost is low.
  • the corrosion inhibitor does not contain harmful elements such as phosphorus, sulfur, chlorine, and has good chemical stability at high temperatures, and will not adversely affect catalyst poisoning caused by subsequent processing. Therefore, the corrosion inhibitor prepared in the above embodiment has Broad application prospects.

Landscapes

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

Abstract

L'invention concerne un inhibiteur de corrosion. En pourcentage massique, les matières premières destinées à préparer l'inhibiteur de corrosion comprennent : un polyester aromatique : de 25 % à 65 % ; un adjuvant d'inhibition de la corrosion : de 1 % à 40 % ; et un solvant organique : de 20 % à 60 %, le polyester aromatique étant choisi parmi un ester d'acide polybasique aromatique et/ou un ester de polyphénol aromatique, l'adjuvant d'inhibition de la corrosion est choisi parmi un copolymère d'oléfine-anhydride maléique et/ou un composé de magnésium soluble dans l'huile, et le composé de magnésium soluble dans l'huile est choisi parmi l'hydroxyde de nano-magnésium soluble dans l'huile et/ou l'oxyde de nano-magnésium soluble dans l'huile.
PCT/CN2019/100874 2019-08-15 2019-08-15 Inhibiteur de corrosion et son procédé de préparation, et procédé d'inhibition de la corrosion de l'acide naphténique dans l'huile WO2021026921A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PCT/CN2019/100874 WO2021026921A1 (fr) 2019-08-15 2019-08-15 Inhibiteur de corrosion et son procédé de préparation, et procédé d'inhibition de la corrosion de l'acide naphténique dans l'huile

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2019/100874 WO2021026921A1 (fr) 2019-08-15 2019-08-15 Inhibiteur de corrosion et son procédé de préparation, et procédé d'inhibition de la corrosion de l'acide naphténique dans l'huile

Publications (1)

Publication Number Publication Date
WO2021026921A1 true WO2021026921A1 (fr) 2021-02-18

Family

ID=74570417

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2019/100874 WO2021026921A1 (fr) 2019-08-15 2019-08-15 Inhibiteur de corrosion et son procédé de préparation, et procédé d'inhibition de la corrosion de l'acide naphténique dans l'huile

Country Status (1)

Country Link
WO (1) WO2021026921A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030063999A1 (en) * 2001-09-04 2003-04-03 Tirthankar Ghosh Inhibiting metallic corrosion in aqueous systems
CN105238461A (zh) * 2015-10-21 2016-01-13 深圳市广昌达石油添加剂有限公司 一种多功能纳米MgO抑钒剂及其制备方法和用途
CN107880953A (zh) * 2017-11-03 2018-04-06 深圳市广昌达石油添加剂有限公司 腐蚀抑制剂及其制备方法和应用
CN107892959A (zh) * 2017-10-23 2018-04-10 宁波广昌达新材料有限公司 抑钒剂、抑钒剂的制备方法、抑钒组合物及其应用、抑钒组合物的制备方法
CN108486574A (zh) * 2018-04-18 2018-09-04 山东澳润化工科技有限公司 一种复合型高温缓蚀剂及其制备方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030063999A1 (en) * 2001-09-04 2003-04-03 Tirthankar Ghosh Inhibiting metallic corrosion in aqueous systems
CN105238461A (zh) * 2015-10-21 2016-01-13 深圳市广昌达石油添加剂有限公司 一种多功能纳米MgO抑钒剂及其制备方法和用途
CN107892959A (zh) * 2017-10-23 2018-04-10 宁波广昌达新材料有限公司 抑钒剂、抑钒剂的制备方法、抑钒组合物及其应用、抑钒组合物的制备方法
CN107880953A (zh) * 2017-11-03 2018-04-06 深圳市广昌达石油添加剂有限公司 腐蚀抑制剂及其制备方法和应用
CN108486574A (zh) * 2018-04-18 2018-09-04 山东澳润化工科技有限公司 一种复合型高温缓蚀剂及其制备方法

Similar Documents

Publication Publication Date Title
US10106752B2 (en) Method, apparatus and chemical products for treating petroleum equipment
JP6490084B2 (ja) 燃料混合成分としての混合ブタノールおよびジイソブテンの生成方法
EP3338884B1 (fr) Procede d'oligomerisation d'olefines mettant en oeuvre un dispositif de nettoyage
EP1993980B1 (fr) Diminution de la teneur en bases de lewis azotées pendant l'oligomérisation sur tamis moléculaire
CN103351888A (zh) 一种油浆阻垢剂
CN105753622A (zh) 制备线性α-烯烃的方法
US5994601A (en) Process for preparing butene oligomers from Fischer-Tropsch olefins
JP2014510025A (ja) 混合アルコールを生産する混合ブテンの水和のプロセス
WO2021026921A1 (fr) Inhibiteur de corrosion et son procédé de préparation, et procédé d'inhibition de la corrosion de l'acide naphténique dans l'huile
CN112391632B (zh) 缓蚀剂及其制备方法和抑制油品中环烷酸腐蚀的方法
CN110205161B (zh) 一种耐高温油浆阻垢剂
CN110627662B (zh) 一种清净分散剂及含有该清净分散剂的油浆阻垢剂
EA025207B1 (ru) Способ уменьшения образования отложений при переработке жидких углеводородов
US6368422B1 (en) Process for removing solid asphalt residues produced in the petroleum industry
CN103361109B (zh) 煤焦油脱水剂及其应用
CN113122312A (zh) 一种以环烷烃为共催化剂助催化生产烷基化汽油的方法
US20030079879A1 (en) Maintenance of oil production and refining equipment
BR102015006944A2 (pt) aditivo de fase líquida a ser utilizado em processo de craqueamento térmico para melhorar o rendimento de produtos
CN111304659B (zh) 一种复配聚异丁烯基亚磷酸酯缓蚀剂
JP2013095671A (ja) オレフィンの製造方法
KR100447522B1 (ko) 안정화된 히드록시알킬 아크릴레이트 조성물 또는 히드록시알킬 메타크릴레이트 조성물
US8912379B2 (en) Method of preparing alkene compound
CN115247078B (zh) 一种烷基化汽油及其制备方法
JPS5884897A (ja) Ｎ−メチルピロリドンを使用する石油処理操作で腐食を防止する方法
JP2013060400A (ja) オレフィンの製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19941601

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19941601

Country of ref document: EP

Kind code of ref document: A1