CN110777382A - Neutralizing film-forming corrosion and scale inhibitor and preparation method thereof - Google Patents
Neutralizing film-forming corrosion and scale inhibitor and preparation method thereof Download PDFInfo
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- CN110777382A CN110777382A CN201910993827.XA CN201910993827A CN110777382A CN 110777382 A CN110777382 A CN 110777382A CN 201910993827 A CN201910993827 A CN 201910993827A CN 110777382 A CN110777382 A CN 110777382A
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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
- C23F11/02—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in air or gases by adding vapour phase inhibitors
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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
- C23F11/08—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
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
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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
- C23F15/00—Other methods of preventing corrosion or incrustation
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Abstract
The invention belongs to the technical field of chemical additives, and particularly relates to a neutralization film-forming corrosion and scale inhibitor and a preparation method thereof. The composite material consists of the following raw materials in percentage by mass: 10-15% of neutralizing film-forming amine, 20-40% of salt remover, 5-12% of imidazoline, 2-6% of synergist, 5-14% of vapor phase corrosion inhibitor, 1.5-4% of dispersant, 0.5-1% of water clarifier and 20-50% of solvent. The neutralization film-forming corrosion and scale inhibitor can completely control acid corrosion and under-deposit corrosion of a low-temperature part at the top of a tower, has the function of dissolving and descaling the existing ammonium salt of a system, has the agent consumption lower than that of similar products by more than 20 percent, and has the corrosion inhibition rate of more than or equal to 95 percent; meanwhile, the emulsion inhibitor has good anti-emulsification performance, the condensed water is clear, and the oil content is less than 10 ppm; condensed water Fe
2+Less than 1.5mg/L, the qualification rate is more than 95 percent, and the method has no adverse effect on downstream products, production and environmental protection.
Description
Technical Field
The invention belongs to the technical field of chemical additives, and particularly relates to a neutralization film-forming corrosion and scale inhibitor and a preparation method thereof.
Background
With the increasing amount of high acid and high sulfur crude oil, the corrosion of the refinery equipment is getting worse, which has affected the safety, stability, long period, full load and high quality production of the refinery equipment. The condensing and cooling part at the top of the distillation tower is subjected to HCl + H
2S+H
2The corrosion of O system usually adopts "three-injection" corrosion prevention process, i.e. using neutralizing agent to reduce the acidic material of condensation system, and using film-forming corrosion inhibitor to form a layer of protective film on the metal surface. The traditional method is to inject ammoniaThe acidic substances in the water and the condensate can relieve the corrosion of the system equipment pipeline to a certain extent, but still has a plurality of defects which are mainly expressed in the following two aspects: (1) the hydrochloric acid is neutralized by ammonia water, the pH value jump range is large, and the pH value of a tower top system cannot be controlled to be 6.0-7.5 (the pH value of a general system is more than 9). As ammonia water can not enter the tower return line, NH4Cl can block trays and downcomers to cause under-deposit corrosion; (2) the ammonia water can not effectively neutralize the acidic substances in the condensed water in the initial condensation area of the tower top system, so that the corrosion of the equipment and the pipeline at the position can not be effectively controlled, and the corrosion is serious.
In order to control the pH values of the top of the distillation tower and a condensation cooling system to be 6.0-7.5, 80% of oil refineries in the United states in the early 90 s of the 20 th century changed ammonia water into organic amine, some oil refineries in the 90 s of China changed organic amine, and some oil refineries added with assistants such as corrosion inhibitors and the like. In recent years, with the development of the theory of process corrosion prevention and the technological progress, refineries at home and abroad gradually adopt the technology of injecting a neutralization corrosion inhibitor to control the corrosion of a condensation system at the top of a tower. At present, the aim is to solve the problem of HCl + H
2S+H
2The problem of O corrosion, the neutralization corrosion inhibitor developed in China mainly takes the neutralization effect as the main part, and the solution of HCl + H can be solved only by matching with a film-forming corrosion inhibitor
2S+H
2The corrosion of an O system can not effectively solve the problems of scaling and under-scale corrosion of ammonium salt on the top of the tower, and the prior neutralization corrosion inhibitor and film-forming corrosion inhibitor have very poor emulsification resistance, so that condensed water of an oil-water separator is often oily, COD exceeds the standard, and the phenomenon of scaling of high-boiling-point ammonium salt formed by the reaction of the condensed water and HCl of the system exists. The inventor tries to compound an organic amine neutralizing agent and a water-soluble corrosion inhibitor into a water-soluble neutralizing corrosion inhibitor, and finds that the water-soluble corrosion inhibitor has an applicable pH range, and if the pH range is exceeded, the corrosion inhibition performance is good and the water solubility is not good, otherwise, the water solubility is good but the corrosion inhibition performance is reduced. And the components of the water-soluble neutralization corrosion inhibitor have higher boiling points than water and are easy to form salts in the tower, and the solid salts often have higher melting points and can cause serious scaling of a tower top system.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art and provides a neutralization film-forming corrosion and scale inhibitor. The agent has multiple functions, has the function of neutralizing acidic substances, has the effect of forming a film on the surface of metal, has the functions of preventing and dissolving scale formation and scale secondary corrosion caused by ammonium salt deposition, does not need to be added with an oil-soluble film forming corrosion inhibitor independently, and can thoroughly solve the problems of overall corrosion of a system, scale formation of ammonium salts of the system, corrosion under scale formation and oil carrying of condensed water emulsification.
The neutralization film-forming corrosion and scale inhibitor comprises the following raw materials in percentage by mass:
wherein:
the neutralization film-forming amine is a mixture of ethylenediamine and dimethylamine, and the mass ratio of the ethylenediamine to the dimethylamine is 3:0.5 to 1.5.
The salt remover is a mixture of dimethylethanolamine, ethanolamine and 3-methoxypropylamine; the mass ratio of the dimethylethanolamine to the ethanolamine to the 3-methoxypropylamine is 0.4-1.2: 4: 0.4 to 1.3.
Imidazoline is imidazoline polyoxyethylene ether.
The preparation method of the imidazoline polyoxyethylene ether comprises the following steps:
performing addition dehydration reaction on oleic acid and triethylene tetramine for 4-5 hours under the condition that the reaction temperature is controlled to be 130-150 ℃ under the protection of nitrogen according to the molar ratio of 1: 1.15-1.25, then quickly heating to 190-200 ℃ for cyclodehydration for 4-6 hours, finally cooling under the protection of nitrogen, and performing reduced pressure distillation to obtain an unreacted product to obtain oil-soluble imidazoline; and finally, reacting the oil-soluble imidazoline with ethylene oxide for 3-5 hours at the temperature of 90-100 ℃ according to the molar ratio of 1: 4-8, and performing ethoxylation reaction modification to finally obtain the water-soluble imidazoline-imidazoline polyoxyethylene ether.
The synergist is one of propiolic alcohol, hexynol or methylpentylynol.
The vapor phase inhibitor is one of benzotriazole or hexamethylenetetramine.
The dispersant is one or a mixture of two of maleic acid-acrylic acid copolymer or polyaspartic acid.
The water clarifier is epichlorohydrin dimethylamine copolymer.
The solvent is water.
The preparation method of the neutralization film-forming corrosion and scale inhibitor comprises the steps of firstly adding a vapor phase corrosion inhibitor into solvent water according to the raw material proportion, stirring and dissolving fully, then continuing stirring, sequentially adding components of neutralization film-forming amine, a salt remover, imidazoline, a synergist, a dispersant and a water purifier, controlling the reaction temperature to be 20-30 ℃, and stirring uniformly for 2-3 hours under the condition that the rotation speed is 100r/min to obtain a final product.
The action mechanism of the neutralization film-forming corrosion and scale inhibitor is as follows:
the neutralized film-forming amine component has the functions of film forming and neutralization, can efficiently neutralize acidic substances in a condensation area at the top of the tower, can form a stable and compact adsorption film on the surface of equipment to prevent corrosion inhibition medium from being corroded, can well control hydrochloric acid dew point corrosion of a low-temperature light oil part at the top of the tower, and can provide an ideal and narrow pH value control range to effectively control corrosion of the equipment and pipelines at the part.
The components of the salt eliminating agent are mainly organic film-forming amine with strong alkalinity, which not only has the effect of neutralizing and film-forming, but also has the very low melting point of salt generated by the reaction with hydrochloric acid, thereby completely avoiding the salt deposition and blockage in a system at the top part of the tower at low temperature, and simultaneously, the components can effectively dissolve the ammonium chloride salt scale formed in the system at the top of the tower through chemical reaction.
The water-soluble imidazoline is an adsorption film-forming corrosion inhibitor, a polar group and a nonpolar group exist in a molecular structure, an unshared lone pair electron exists in a central atom N of the polar group, and when an empty d orbit exists on the surface of the metal, the lone pair electron of the central electron interacts with the empty d orbit in the metal to form a coordination bond, so that the corrosion inhibitor molecule is adsorbed on the surface of the metal, and meanwhile, the molecule structure contains a pi bond which can also form the coordination bond pi bond adsorption with the empty d orbit on the surface of the metal. The nonpolar group is mainly composed of C, H atoms. Therefore, the film-forming corrosion inhibitor forms a stable and compact adsorption film on the surface of equipment by virtue of the physical and chemical adsorption of polar groups in a molecular structure to prevent corrosion inhibition medium from corroding, and non-polar groups are arranged in the medium, so that on one hand, the contact between metal and a corrosion medium is effectively isolated, the diffusion of corrosion reaction products is hindered, on the other hand, the structure of a double electric layer is changed, the activation energy of the corrosion reaction is improved, and finally, hydrochloric acid dew point corrosion and wet hydrogen sulfide corrosion of a low-temperature light oil part at the top of a tower can be well controlled.
The synergist plays a role in adsorbing the film-forming corrosion inhibitor, has a small molecular weight, has a synergistic effect with the imidazoline corrosion inhibitor, makes up for the steric hindrance of imidazoline on the metal surface, and improves the film-forming shielding effect of the metal surface.
The vapor phase corrosion inhibitor is mainly used for forming a dense protective film layer by being adsorbed on the surface of metal at the vapor phase part of the tower top outflow line, thereby playing a role of corrosion prevention.
The dispersing agent prevents ferrous sulfide, calcium hydroxide, magnesium hydroxide and ammonium salt in the low-temperature condensation part at the tower top from precipitating, depositing and forming under-deposit corrosion.
The water clarifier is mainly used for accelerating oil-water separation of condensed water at the top of the tower and ensuring that discharged condensed water is clear and does not contain oil.
Industrial tests show that the components of the formula complement and promote each other, have strong synergistic interaction effect, enable the agent consumption to be lower than that of similar products by more than 20%, the dosage to be within 10-25 ppm, and the corrosion inhibition rate to be more than or equal to 95%, effectively solve the problems of ammonium salt scaling and corrosion under scale generally existing at the low-temperature part at the top of the atmospheric and vacuum distillation tower of the refinery at present, and simultaneously have the advantages of emulsion resistance, clear condensed water, and clear Fe condensed water
2+Less than 1.5mg/L, the percent of pass is more than 95 percent, the paint does not contain harmful elements such as chlorine, phosphorus and the like, is convenient to use on site, is environment-friendly, has no peculiar smell, and has no adverse effect on downstream products, production and environmental protection.
The neutralization film-forming corrosion and scale inhibitor is mainly used for controlling the condition of the low-temperature part of an atmospheric and vacuum distillation unit of an oil refinery, and is a neutralization film-forming corrosion and scale inhibitor for solving the problems of overall corrosion, under-scale corrosion and ammonium salt scaling of a low-temperature system at the top of the atmospheric and vacuum distillation unit of the oil refinery.
Compared with the prior art, the invention has the following beneficial effects:
(1) the neutralization film-forming corrosion and scale inhibitor has the effect of neutralizing acidic substances, has the effect of forming a film on the surface of metal, can prevent and dissolve scale formation and scale under-scale secondary corrosion caused by ammonium salt deposition, does not need to be separately added with an oil-soluble film-forming corrosion inhibitor, and can thoroughly solve the problems of overall corrosion of a system, scale formation of ammonium salts of the system and under-scale corrosion and oil carrying in condensed water emulsification.
(2) The neutralization film-forming corrosion and scale inhibitor can completely control acid corrosion and under-deposit corrosion of a tower top low-temperature part, can control low pH (5.0-8.5), and can balance and control overall corrosion of acid and NH
4The Cl and the FeS are corroded under the scale, the existing ammonium salt of the system has the functions of dissolving and descaling, the agent consumption is lower than that of similar products by more than 20 percent, and the corrosion inhibition rate is more than or equal to 95 percent; meanwhile, the emulsion inhibitor has good anti-emulsification performance, the condensed water is clear, and the oil content is less than 10 ppm; condensed water Fe
2+Less than 1.5mg/L, the qualification rate is more than 95 percent, and the method has no adverse effect on downstream products, production and environmental protection.
(3) The neutralizing film-forming corrosion and scale inhibitor is added in an amount of 10-25 ppm of the crude oil processing amount when in use, the agent consumption is lower than that of similar products by more than 20%, and the slow release rate is more than or equal to 95%.
Drawings
FIG. 1 is a process flow diagram of the preparation method of the neutralization film-forming corrosion and scale inhibitor.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The neutralization film-forming corrosion and scale inhibitor comprises the following raw materials in percentage by mass:
wherein:
the neutralization film-forming amine is a mixture of ethylenediamine and dimethylamine, and the mass ratio of the ethylenediamine to the dimethylamine is 3: 1.
the salt remover is a mixture of dimethylethanolamine, ethanolamine and 3-methoxypropylamine; the mass ratio of the dimethylethanolamine to the ethanolamine to the methoxypropylamine is 1:4: 1.
imidazoline is imidazoline polyoxyethylene ether.
The preparation method of the imidazoline polyoxyethylene ether comprises the following steps:
oleic acid and triethylene tetramine were mixed according to a ratio of 1:1.2, under the protection of nitrogen, carrying out addition dehydration reaction for 4 hours under the condition that the reaction temperature is controlled at 140 ℃, then quickly heating to 200 ℃ for cyclodehydration for 6 hours, finally cooling under the protection of nitrogen, and carrying out reduced pressure distillation to obtain an unreacted product so as to obtain oil-soluble imidazoline; and finally, reacting the oil-soluble imidazoline with ethylene oxide for 4 hours at the temperature of 100 ℃ according to the molar ratio of 1:6, and performing ethoxylation reaction modification to finally obtain the water-soluble imidazoline-imidazoline polyoxyethylene ether.
The synergist is methyl pentynol.
The vapor phase corrosion inhibitor is benzotriazole.
The dispersant is polyaspartic acid.
The water clarifier is epichlorohydrin dimethylamine copolymer.
The solvent is water.
The preparation method of the neutralization film-forming corrosion and scale inhibitor comprises the steps of firstly adding a vapor phase corrosion inhibitor into solvent water according to the raw material proportion, stirring and dissolving fully, then continuing stirring, adding components of neutralization film-forming amine, a salt remover, imidazoline, a synergist, a dispersant and a water purifier successively, controlling the reaction temperature to be 25 ℃, and stirring for 2.5 hours to be uniform under the condition that the rotation speed is 100r/min, thus obtaining the final product.
TABLE 1 physicochemical indices of the neutralizing, filming, corrosion and scale inhibitor prepared in example 1
Test detection
Examination of the neutralizing, film-forming, corrosion and scale inhibitor prepared in example 1 in HC + H
2S+H
2The corrosion prevention effect of the O system is evaluated by adopting a laboratory static corrosion inhibition rate evaluation method and a static salt elimination test of a salt eliminating agent, and the evaluation result is as follows by referring to a JB/T7901-1999 laboratory uniform corrosion full-immersion test method for metal materials:
the test method comprises the following steps: heating water in porous water bath to 90 + -1 deg.C, and adding 1000mg/LHC1+1000mg/LH
2Pouring 250mL of corrosion medium consisting of S aqueous solution into a 250mL conical flask with a plug, adjusting the pH value to 7.0 +/-0.10 by using ammonia water or a middle and corrosion inhibitor, cleaning and weighing a 20# carbon steel test piece with a specified size, suspending the test piece in the corrosion medium at 90 +/-1 ℃, putting the conical flask containing the corrosion solution and the test piece into a porous water bath, soaking for 6h, taking out the test piece, observing the surface condition, and measuring the corrosion rate according to the weight loss of the test piece.
According to the reaction mechanism of strong base to replace weak base, if strong acid and weak base salt reacts with strong base, strong base with strong alkalinity will replace weak base ion to release weak base ion, generating a new strong acid and strong base salt. Ammonium chloride is a strong acid and weak base salt generated by the reaction of a strong acid (hydrogen chloride) and a weak base (ammonia water). If the ammonium chloride is contacted with other strong base ions, the ammonium ions in the ammonium chloride are replaced by stronger strong base ions, so that the substitution reaction is carried out. Weighing quantitative salt remover component solution in the neutralization film-forming corrosion and scale inhibitor under the condition of 35 ℃ (simulating field cooler data), adding ammonium chloride solid under the condition of keeping stirring, and recording and analyzing the ammonium chloride dissolution condition.
Table 2 example 1 comparison of the corrosion inhibiting effect of the neutralizing corrosion inhibitor with the prior art neutralizing corrosion inhibitors
| Corrosion inhibitor | Corrosion Rate (mm/a) | Inhibition ratio (%) | Corrosion of test piece |
| Traditional neutralizer ammonia water | 1.581 | / | Uniform corrosion and blackening specimen |
| Conventional neutralizing corrosion inhibitors 1 | 0.0781 | 85.32 | Local pitting and brightening of the test piece |
| Conventional neutralizing corrosion inhibitors 2 | 0.0578 | 89.91 | A small amount of pitting corrosion and a bright test piece |
| Example 1 neutralizing, film-forming, corrosion and scale inhibitor | 0.023 | 95.73 | Uniform corrosion and bright test piece |
TABLE 3 static desalting test data table of desalting agent
| Name (R) | Amount of dissolved ammonium chloride | Phenomenon of experiment | Observation time |
| 10g of desalting agent | 1.54g | The solid is dissolved faster | 2 hours |
As can be seen from Table 2, the neutralization film-forming corrosion and scale inhibitor prepared in the embodiment 1 of the invention has better corrosion inhibition effect than the traditional neutralizer ammonia water and the existing neutralization corrosion inhibitor, and the dosage is reduced by more than 20%; as shown in Table 3, the salt remover component in the neutralizing film-forming corrosion and scale inhibitor prepared in the embodiment 1 of the invention has strong dissolving capacity for solid ammonium chloride, and the dissolving rate of the solid ammonium chloride reaches 15.4%, which is the performance that the existing neutralizing corrosion inhibitor in the market does not have.
Example 2
The neutralization film-forming corrosion and scale inhibitor comprises the following raw materials in percentage by mass:
wherein:
the neutralization film-forming amine is a mixture of ethylenediamine and dimethylamine, and the mass ratio of the ethylenediamine to the dimethylamine is 3: 1.
the salt remover is a mixture of dimethylethanolamine, ethanolamine and 3-methoxypropylamine; the mass ratio of the dimethylethanolamine to the ethanolamine to the 3-methoxypropylamine is 1:4: 1.
imidazoline is imidazoline polyoxyethylene ether.
The preparation method of the imidazoline polyoxyethylene ether comprises the following steps:
oleic acid and triethylene tetramine were mixed according to a ratio of 1: 1.25, under the protection of nitrogen, carrying out addition dehydration reaction for 4.5 hours under the condition that the reaction temperature is controlled to be 135 ℃, then quickly heating to 195 ℃ for cyclodehydration for 6 hours, finally cooling under the protection of nitrogen, and carrying out reduced pressure distillation to obtain an unreacted product so as to obtain oil-soluble imidazoline; and finally, reacting the oil-soluble imidazoline with ethylene oxide for 4.5 hours at the temperature of 100 ℃ according to the molar ratio of 1:6.5, and performing ethoxylation reaction modification to finally obtain the water-soluble imidazoline-imidazoline polyoxyethylene ether.
The synergist is hexynol.
The vapor phase corrosion inhibitor is benzotriazole.
The dispersant is a mixture of polyaspartic acid and maleic acid-acrylic acid copolymer.
The water clarifier is epichlorohydrin dimethylamine copolymer.
The solvent is water.
The preparation method of the neutralization film-forming corrosion and scale inhibitor comprises the steps of firstly adding a vapor phase corrosion inhibitor into solvent water according to the raw material proportion, stirring and dissolving fully, then continuing stirring, adding components of neutralization film-forming amine, a salt remover, imidazoline, a synergist, a dispersant and a water purifier successively, controlling the reaction temperature to be 25 ℃, and stirring for 2.5 hours to be uniform under the condition that the rotation speed is 100r/min, thus obtaining the final product.
Report on industrial applications
In order to test the practical application effect, the industrial trial evaluation is carried out on the neutralization film-forming corrosion and scale inhibitor in the II atmospheric and vacuum distillation unit of the Middling petrochemical company in 2019 from 8 month 23 to 9 month 23.
TABLE 4 physicochemical indices of the neutralizing, filming, corrosion and scale inhibitor prepared in example 2
The industrial application conditions of the neutralization film-forming corrosion and scale inhibitor prepared in the embodiment 2 in an atmospheric and vacuum distillation device of an oil refinery are as follows:
TABLE 5 comparison of the neutralization of the film-forming corrosion and scale inhibitor before and after application
As can be seen from Table 5, the neutralizing, film-forming, corrosion and scale inhibiting agent of the present invention has a superior corrosion inhibiting effect as compared to the conventional neutralizing and corrosion inhibiting agents. Although petrochemical units require condensed water Fe
2+The content is less than 3mg/L, the qualification rate is more than or equal to 90 percent, the neutralization corrosion inhibitors of A and B manufacturers meet the requirements, and the neutralization film-forming corrosion and scale inhibitor in the embodiment 2 of the invention condenses Fe in water in the application process
2+The content is less than 1.5mg/L, the qualification rate is more than or equal to 95 percent, and the conditions that the heat exchanger is blocked by scaling ammonium salt and corrosion under the scaling does not occur in the using process, which are not possessed by other corrosion inhibitors, so the neutralization film-forming corrosion and scale inhibitor has the performances of salt elimination and scale inhibition and under-scale corrosion prevention besides excellent corrosion inhibition performance, and the Fe condensate water under the conditions
2+The content is more authentic and representative.
Example 3
The neutralization film-forming corrosion and scale inhibitor comprises the following raw materials in percentage by mass:
wherein:
the neutralization film-forming amine is a mixture of ethylenediamine and dimethylamine, and the mass ratio of the ethylenediamine to the dimethylamine is 3: 1.
The salt remover is a mixture of dimethylethanolamine, ethanolamine and 3-methoxypropylamine; the mass ratio of the dimethylethanolamine to the ethanolamine to the methoxypropylamine is 1:4: 1.
Imidazoline is imidazoline polyoxyethylene ether.
The preparation method of the imidazoline polyoxyethylene ether comprises the following steps:
according to the molar ratio of 1:1.2, carrying out addition dehydration reaction for 5 hours under the condition of controlling the reaction temperature at 150 ℃ under the protection of nitrogen and then quickly heating to 200 ℃ for cyclodehydration for 6 hours, finally cooling under the protection of nitrogen and distilling out unreacted products under reduced pressure to obtain oil-soluble imidazoline; and finally, reacting the oil-soluble imidazoline with ethylene oxide for 5 hours at the temperature of 100 ℃ according to the molar ratio of 1:7, and performing ethoxylation reaction modification to finally obtain the water-soluble imidazoline-imidazoline polyoxyethylene ether.
The synergist is methyl pentynol.
The vapor phase corrosion inhibitor is hexamethylenetetramine.
The dispersant is a maleic acid-acrylic acid copolymer.
The water clarifier is epichlorohydrin dimethylamine copolymer.
The solvent is water.
The preparation method of the neutralization film-forming corrosion and scale inhibitor comprises the steps of firstly adding a vapor phase corrosion inhibitor into solvent water according to the raw material proportion, stirring and dissolving fully, then continuing stirring, adding components of neutralization film-forming amine, a salt remover, imidazoline, a synergist, a dispersant and a water purifier successively, controlling the reaction temperature to be 25 ℃, and stirring for 2.5 hours to be uniform under the condition that the rotation speed is 100r/min, thus obtaining the final product.
Report on industrial applications
In order to test the practical application effect, the industrial trial evaluation is carried out on the neutralization film-forming corrosion and scale inhibitor in the II atmospheric and vacuum distillation unit of the Middling petrochemical company in 2019 from 8 month 23 to 9 month 23.
TABLE 6 physicochemical indices of the neutralizing film-forming corrosion and scale inhibitor prepared in example 3
Conditions for Industrial evaluation
And II, processing mixed crude oil of Daqing crude oil and Russian crude oil with the production capacity of 600 ten thousand tons/year by using an atmospheric and vacuum distillation unit, wherein the Russian oil proportion is 55-65%. The temperature of the top of the primary tower is controlled between 120 ℃ and 150 ℃, and the pressure is controlled between 0.27MPa and 0.33 MPa; the temperature of the top of the atmospheric tower is controlled to be 100-120 ℃, and the pressure is controlled to be 0.02-0.08 MPa; the temperature at the top of the vacuum tower is controlled to be 40-80 ℃, and the vacuum degree is controlled to be 92-100 kPa.
TABLE 7 EXAMPLE 3 application of neutralizing, filming, corrosion and scale inhibitor to evaluate the completion of acceptance criteria
Data analysis
(1) The average pH value of dehydration of the reflux tank D-101 at the top of the first distillation tower in this month is 7.43, and the qualified rate of the pH value is 100%; the average amount of the primary top dehydrated iron ions is 1.28mg/L, which is lower than the index of 3mg/L, the qualification rate is 100 percent, which is higher than the index of 90 percent, and the qualification rate of the clear COD of the discharged water is 100 percent.
(2) The average pH value of dehydration of a product tank D-102 at the top of the atmospheric tower is 7.03, and the qualified rate of the pH is 100%; the average of the normal-top dehydrated iron ions is 0.95mg/L, which is lower than the index of 3mg/L, the qualification rate is 100 percent, which is higher than the index of 90 percent, and the qualification rate of the clear COD of the discharged water is 100 percent.
(3) The average pH value of dehydration of the reduced-roof dehydration tank D-108 is 7.35, and the qualified rate of the pH value is 100%; the average of the reduced-top dehydrated iron ions is 1.12mg/L, which is lower than the index of 3mg/L, the qualification rate is 100 percent, which is higher than the index of 90 percent, and the qualification rate of the clear COD of the discharged water is 100 percent.
(4) The average content of dehydrated chloride in the product tank D-102 at the top of the atmospheric tower is increased from 31mg/L to 57mg/L and is finally stabilized at 40mg/L, which indicates that ammonium chloride generated in the system is completely dissolved and discharged and has a dissolving effect on ammonium salt already deposited in the system.
Conclusion of evaluation
During industrial evaluation, the pH values of initial topping, normal topping and topping reduction are all 6.5-8.5, the iron ion content is less than 3mg/L, the qualification rate is 100%, the average iron ion content is less than 1.5mg/L, the using effect is good, and the industrial evaluation is excellent.
Claims (8)
1. A neutralization film-forming corrosion and scale inhibitor is characterized in that: the composite material consists of the following raw materials in percentage by mass:
2. the neutralizing, film-forming, corrosion and scale inhibitor according to claim 1, characterized in that: the neutralizing film-forming amine is a mixture of ethylenediamine and dimethylamine; the mass ratio of the ethylenediamine to the dimethylamine is 3: 0.5-1.5.
3. The neutralizing, film-forming, corrosion and scale inhibitor according to claim 1, characterized in that: the salt eliminating agent is a mixture of dimethylethanolamine, ethanolamine and 3-methoxypropylamine; the mass ratio of the dimethylethanolamine to the ethanolamine to the 3-methoxypropylamine is 0.4-1.2: 4: 0.4 to 1.3.
4. The neutralizing, film-forming, corrosion and scale inhibitor according to claim 1, characterized in that: imidazoline is imidazoline polyoxyethylene ether.
5. The neutralizing, film-forming, corrosion and scale inhibiting agent of claim 4, wherein: the preparation method of the imidazoline polyoxyethylene ether comprises the following steps: performing addition dehydration reaction on oleic acid and triethylene tetramine for 4-5 hours under the condition that the reaction temperature is controlled to be 130-150 ℃ under the protection of nitrogen according to the molar ratio of 1: 1.15-1.25, then quickly heating to 190-200 ℃ for cyclodehydration for 4-6 hours, finally cooling under the protection of nitrogen, and performing reduced pressure distillation to obtain an unreacted product to obtain oil-soluble imidazoline; and finally, reacting the oil-soluble imidazoline with ethylene oxide for 3-5 hours at the temperature of 90-100 ℃ according to the molar ratio of 1: 4-8, and performing ethoxylation reaction modification to finally obtain the water-soluble imidazoline-imidazoline polyoxyethylene ether.
6. The neutralizing, film-forming, corrosion and scale inhibitor according to claim 1, characterized in that: the synergist is one of propiolic alcohol, hexynol or methylpentylynol; the vapor phase inhibitor is one of benzotriazole or hexamethylenetetramine.
7. The neutralizing, film-forming, corrosion and scale inhibitor according to claim 1, characterized in that: the dispersant is one or a mixture of maleic acid-acrylic acid copolymer or polyaspartic acid; the water clarifier is epichlorohydrin dimethylamine copolymer; the solvent is water.
8. A method for preparing the neutralizing film-forming corrosion and scale inhibitor according to claim 1, which is characterized in that: firstly, adding a vapor phase corrosion inhibitor into solvent water according to the raw material proportion, stirring and dissolving fully, then continuing stirring, adding components of neutralization film-forming amine, a salt remover, imidazoline, a synergist, a dispersant and a water purifier successively, controlling the reaction temperature to be 20-30 ℃, and stirring for 2-3 hours to be uniform under the condition that the rotating speed is 100r/min, thus obtaining the final product.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111441057A (en) * | 2020-05-22 | 2020-07-24 | 北京赛福贝特能源技术服务有限公司 | Oil-soluble neutralization corrosion inhibitor for refinery tower top low-temperature system and preparation method thereof |
| CN112047886A (en) * | 2020-09-16 | 2020-12-08 | 山东泰和水处理科技股份有限公司 | Synthetic method of oleic acid imidazoline |
| CN112522710A (en) * | 2020-11-12 | 2021-03-19 | 西安石油大学 | CO2Corrosion inhibitor main agent for corrosion inhibition and scale inhibition of oil displacement injection-production system, preparation method and application |
| CN114481140A (en) * | 2021-12-30 | 2022-05-13 | 上海丰信环保科技有限公司 | Circulating water corrosion inhibitor |
| CN116209737A (en) * | 2020-07-30 | 2023-06-02 | Ifp 新能源公司 | Method for treating plastic pyrolysis oil comprising one-step hydrocracking |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732891A (en) * | 2011-03-31 | 2012-10-17 | 武汉润尔华科技有限公司 | Neutral corrosion inhibitor |
| EP2992066A1 (en) * | 2013-05-02 | 2016-03-09 | Instytut Nafty i Gazu Panstwowy Instytut Badawczy | Water-soluble corrosion inhibitor for protection of lifting casings and natural gas pipelines as well as the method of its production. |
| CN108251848A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of corrosion inhibiter and preparation method thereof |
-
2019
- 2019-10-18 CN CN201910993827.XA patent/CN110777382A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102732891A (en) * | 2011-03-31 | 2012-10-17 | 武汉润尔华科技有限公司 | Neutral corrosion inhibitor |
| EP2992066A1 (en) * | 2013-05-02 | 2016-03-09 | Instytut Nafty i Gazu Panstwowy Instytut Badawczy | Water-soluble corrosion inhibitor for protection of lifting casings and natural gas pipelines as well as the method of its production. |
| CN108251848A (en) * | 2016-12-28 | 2018-07-06 | 中国石油天然气股份有限公司 | A kind of corrosion inhibiter and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 王中华等: "《油田化学品实用手册》", 31 July 2004, 中国石化出版社 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116209737A (en) * | 2020-07-30 | 2023-06-02 | Ifp 新能源公司 | Method for treating plastic pyrolysis oil comprising one-step hydrocracking |
| CN112047886A (en) * | 2020-09-16 | 2020-12-08 | 山东泰和水处理科技股份有限公司 | Synthetic method of oleic acid imidazoline |
| CN112047886B (en) * | 2020-09-16 | 2022-03-15 | 山东泰和水处理科技股份有限公司 | Synthetic method of oleic acid imidazoline |
| CN112522710A (en) * | 2020-11-12 | 2021-03-19 | 西安石油大学 | CO2Corrosion inhibitor main agent for corrosion inhibition and scale inhibition of oil displacement injection-production system, preparation method and application |
| CN112522710B (en) * | 2020-11-12 | 2023-06-20 | 西安石油大学 | CO 2 Corrosion inhibitor main agent for inhibiting corrosion and scale of oil-driving injection and production system, preparation method and application |
| CN114481140A (en) * | 2021-12-30 | 2022-05-13 | 上海丰信环保科技有限公司 | Circulating water corrosion inhibitor |
| CN117363379A (en) * | 2023-10-16 | 2024-01-09 | 山东澳润化工科技有限公司 | Composite corrosion and scale inhibitor and preparation method and application thereof |
| CN117363379B (en) * | 2023-10-16 | 2024-07-02 | 山东澳润化工科技有限公司 | Composite corrosion and scale inhibitor and preparation method and application thereof |
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