CN109440115B - Phosphoramidate water-soluble corrosion inhibitor and preparation method thereof - Google Patents
Phosphoramidate water-soluble corrosion inhibitor and preparation method thereof Download PDFInfo
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- CN109440115B CN109440115B CN201811291518.XA CN201811291518A CN109440115B CN 109440115 B CN109440115 B CN 109440115B CN 201811291518 A CN201811291518 A CN 201811291518A CN 109440115 B CN109440115 B CN 109440115B
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- 238000005260 corrosion Methods 0.000 title claims abstract description 126
- 230000007797 corrosion Effects 0.000 title claims abstract description 124
- 239000003112 inhibitor Substances 0.000 title claims abstract description 75
- PTMHPRAIXMAOOB-UHFFFAOYSA-L phosphoramidate Chemical compound NP([O-])([O-])=O PTMHPRAIXMAOOB-UHFFFAOYSA-L 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 63
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 26
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 26
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 26
- COARODKCNGNOQZ-UHFFFAOYSA-N 1-(1-methoxyethoxy)hexane Chemical compound CCCCCCOC(C)OC COARODKCNGNOQZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims abstract description 13
- VUIWJRYTWUGOOF-UHFFFAOYSA-N 2-ethenoxyethanol Chemical compound OCCOC=C VUIWJRYTWUGOOF-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims abstract description 13
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 claims abstract description 13
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 claims abstract description 13
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims abstract description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 13
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims abstract description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 27
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 26
- 239000002253 acid Substances 0.000 claims description 18
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 17
- 239000003784 tall oil Substances 0.000 claims description 17
- 238000007112 amidation reaction Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 230000002862 amidating effect Effects 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910000975 Carbon steel Inorganic materials 0.000 abstract description 6
- 239000010962 carbon steel Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 239000012153 distilled water Substances 0.000 description 10
- 230000005764 inhibitory process Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 230000009435 amidation Effects 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 6
- 238000010998 test method Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000004088 simulation Methods 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005536 corrosion prevention Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 231100000053 low toxicity Toxicity 0.000 description 3
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
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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
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- 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)
- Lubricants (AREA)
Abstract
The invention discloses phosphoramidate waterThe corrosion inhibitor comprises the following components: 30-45 parts of phosphoramidate mixed solution, 4-6 parts of N-methyl thiourea, 5-10 parts of ethylene glycol monomethyl ether, 5-8 parts of formamide, 5-9 parts of p-hydroxybenzoic acid, 1-5 parts of nonylphenol polyoxyethylene ether, 1-2 parts of octylphenol polyoxyethylene ether, 6-23.5 parts of water, 8-15 parts of vinyl glycol ether, 0.5-2.5 parts of 3-methyl-2-pentene-4-alkynol and 2-6.5 parts of acetaldehyde methyl hexyl acetal. The phosphoramidate corrosion inhibitor provided by the invention has high CO content2(partial pressure 0 to 5MPa) and H2And the S coexists (with the partial pressure of 0-1 MPa) in the oil and gas field gathering and transportation system, and has a good anti-corrosion effect on carbon steel.
Description
Technical Field
The invention relates to an aminophosphate water-soluble corrosion inhibitor and a preparation method thereof, belonging to the technical field of metal anti-corrosion materials.
Background
CO2、H2S is often used as natural gas or petroleum associated gasThe components of (A) are present in oil gas, have very strong corrosivity to carbon steel, cause important equipment such as oil gas well tubular columns, gathering pipeline steel products and the like to generate serious general corrosion and local corrosion, and cause huge economic loss and potential safety hazard.
In CO2、H2In corrosion protection of S oil and gas fields, corrosion inhibitors are used as an important corrosion prevention means, most of common corrosion inhibitors are imidazoline corrosion inhibitors, and atoms such as N, O, P are mainly adsorbed on the surface of a steel sheet to form a film so as to prevent a corrosive medium from contacting the surface of a metal material, thereby achieving the purpose of relieving corrosion. Common imidazoline corrosion inhibitors mainly contain N, O groups, have the characteristics of convenient use, no need of modifying equipment pipelines, better corrosion prevention effect in acid media and the like, and have developed mature products at home at present, are applied to various oil and gas fields and achieve certain effect. But at a high CO content2Co-existence of H2Under the condition of S, the corrosion inhibition effect of the existing corrosion inhibitor product is limited, and how to develop a new corrosion inhibitor aiming at the corrosion environments becomes a problem to be solved.
Disclosure of Invention
The invention aims to provide an aminophosphate water-soluble corrosion inhibitor and a preparation method thereof, and mainly aims to solve the problem of high CO content2And with H2And S coexists in the carbon steel in the oil and gas field gathering and transportation system. The specific adsorption group is added in the corrosion inhibitor to increase the adsorption capacity of the corrosion inhibitor, so that the adhesion of the corrosion inhibitor on the surface of carbon steel is enhanced. Simultaneously, the polarity characteristic of the corrosion inhibitor is increased, so that the corrosion inhibitor has good hydrolysis resistance, low toxicity and good stability in a wider pH value range, and is suitable for H-containing2S and CO2In an acidic medium.
On one hand, the invention relates to an aminophosphate water soluble corrosion inhibitor, which comprises the following components in parts by weight: 30-45 parts of an phosphoramidate mixed solution, 4-6 parts of N-methylthiourea, 5-10 parts of ethylene glycol monomethyl ether, 5-8 parts of formamide, 5-9 parts of p-hydroxybenzoic acid, 1-5 parts of nonylphenol polyoxyethylene ether, 1-2 parts of octylphenol polyoxyethylene ether, 6-23.5 parts of water, 8-15 parts of vinyl glycol ether, 0.5-2.5 parts of 3-methyl-2-pentene-4-alkynol and 2-6.5 parts of acetaldehyde methyl hexyl acetal,
the phosphoramidate mixed solution is synthesized by reacting tall oil acid, isophorone diamine, phosphorus pentoxide and formaldehyde, wherein the molar ratio of the tall oil acid to the isophorone diamine is 1: 1.
On the other hand, the invention provides a preparation method of the phosphoramidate water soluble corrosion inhibitor, which comprises the following steps:
(1) amidating tall oil acid and isophorone diamine in a molar ratio of 1:1, adding phosphorus pentoxide, formaldehyde and water in a molar ratio of 1:1:1, and reacting for 3-6 hours to synthesize an aminophosphate mixed solution;
(2) according to the weight parts, 30-45 parts of the phosphoramidate mixed solution, 4-6 parts of N-methyl thiourea, 5-10 parts of ethylene glycol monomethyl ether, 5-8 parts of formamide, 5-9 parts of p-hydroxybenzoic acid, 1-5 parts of nonylphenol polyoxyethylene ether, 1-2 parts of octylphenol polyoxyethylene ether, 6-23.5 parts of water, 8-15 parts of vinyl glycol ether, 0.5-2.5 parts of 3-methyl-2-pentene-4-alkynol and 2-6.5 parts of acetaldehyde methyl hexyl acetal are mixed and stirred uniformly at 50-60 ℃ to obtain the phosphoramidate water soluble corrosion inhibitor.
Description
The invention relates to a harsh high CO content oil-gas field2And H2The oil and gas field gathering and transportation environment with coexisting S' refers to that: CO 22Partial pressure of 0-5 MPa, H2S partial pressure is 0-1 MPa, Cl-content of corrosion medium is 100000-120000 mg/L, HCO3-The content of SO is 300-400 mg/L4 2-Ca in an amount of 300-350 mg/L2+The content of Na is 10000-11000 mg/L++K+The content is 50000-60000 mg/L, and the corrosion environment temperature is 40-60 ℃.
The invention provides an aminophosphate water soluble corrosion inhibitor which comprises the following components in parts by weight: 30-45 parts of an phosphoramidate mixed solution, 4-6 parts of N-methylthiourea, 5-10 parts of ethylene glycol monomethyl ether, 5-8 parts of formamide, 5-9 parts of p-hydroxybenzoic acid, 1-5 parts of nonylphenol polyoxyethylene ether, 1-2 parts of octylphenol polyoxyethylene ether, 6-23.5 parts of water, 8-15 parts of vinyl glycol ether, 0.5-2.5 parts of 3-methyl-2-pentene-4-alkynol and 2-6.5 parts of acetaldehyde methyl hexyl acetal,
the phosphoramidate mixed solution is synthesized by reacting tall oil acid, isophorone diamine, phosphorus pentoxide and formaldehyde, wherein the molar ratio of the tall oil acid to the isophorone diamine is 1: 1.
According to the phosphoramidate water-soluble corrosion inhibitor, after the phosphoramidate mixed solution reacts for 3-6 hours, the phosphoramidate mixed solution is a brown viscous liquid at normal temperature and has certain fluidity, and is a main component of the phosphoramidate water-soluble corrosion inhibitor.
On the other hand, the invention also relates to a preparation method of the phosphoramidate water soluble corrosion inhibitor, which comprises the following steps:
(1) amidating tall oil acid and isophorone diamine in a molar ratio of 1:1, adding phosphorus pentoxide, formaldehyde and water in a molar ratio of 1:1:1, and reacting for 3-6 hours to synthesize an aminophosphate mixed solution;
(2) according to the weight parts, 30-45 parts of the phosphoramidate mixed solution, 4-6 parts of N-methyl thiourea, 5-10 parts of ethylene glycol monomethyl ether, 5-8 parts of formamide, 5-9 parts of p-hydroxybenzoic acid, 1-5 parts of nonylphenol polyoxyethylene ether, 1-2 parts of octylphenol polyoxyethylene ether, 6-23.5 parts of water, 8-15 parts of vinyl glycol ether, 0.5-2.5 parts of 3-methyl-2-pentene-4-alkynol and 2-6.5 parts of acetaldehyde methyl hexyl acetal are mixed and stirred uniformly at 50-60 ℃ to obtain the phosphoramidate water soluble corrosion inhibitor.
According to the preparation method of the phosphoramidate water soluble corrosion inhibitor, the reaction process of the phosphoramidate mixed solution is as follows:
according to the preparation method of the phosphoramidate water-soluble corrosion inhibitor, the amidation reaction temperature of tall oil acid and isophorone diamine is 120-160 ℃, the reaction time is 4-8h, and the temperature is reduced to 80-120 ℃ after the reaction is finished. When the corrosion inhibitor is applied at a higher temperature, a higher amidation temperature and a shorter amidation time are preferably adopted, and the temperature is reduced to a higher temperature.
In the process of synthesizing the phosphoramidate mixed solution, the reactant phosphorus pentoxide is added to increase the adsorption capacity of the corrosion inhibitor, so that the adhesion of the corrosion inhibitor on the surface of the carbon steel is enhanced. Meanwhile, the polarity characteristic of the corrosion inhibitor is enhanced, so that the corrosion inhibitor has good hydrolysis resistance, low toxicity and good stability within a wider pH value range.
Compared with the prior art, the phosphoramidate water soluble corrosion inhibitor has the following excellent technical effects:
1. the preparation method of the phosphoramidate water soluble corrosion inhibitor is simple, and the obtained phosphoramidate water soluble corrosion inhibitor is used for a harsh gathering and transportation pipeline corrosion environment (such as high CO)2Content, H2S coexists) has a good corrosion prevention effect.
2. The water-soluble phosphoramidate corrosion inhibitor increases the adsorption capacity of the corrosion inhibitor by adding the P-containing adsorption group in the corrosion inhibitor, so that the adhesion of the corrosion inhibitor on the surface of carbon steel is enhanced. Meanwhile, the polarity characteristic of the corrosion inhibitor is enhanced, so that the corrosion inhibitor has good hydrolysis resistance, low toxicity and good stability within a wider pH value range.
3. The phosphoramidate water soluble corrosion inhibitor can be suitable for 40-60 ℃ and high CO content2And H2S coexists in the gathering and transportation environment of the oil and gas field, has excellent corrosion inhibition performance, the corrosion rate is less than or equal to 0.076mm/a by adding 30ppm of the corrosion inhibitor, the corrosion inhibition efficiency is more than or equal to 95 percent and is far higher than the industrial standard and more than or equal to 70 percent.
Detailed Description
In order to better understand the technical solutions, the technical solutions of the present application are described in detail with specific embodiments below, and it should be understood that the specific features in the embodiments and examples of the present application are detailed descriptions of the technical solutions of the present application, but not limitations of the technical solutions of the present application, and the technical features in the embodiments and examples of the present application may be combined with each other without conflict.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Raw materials and reagents
N-methyl thiourea, ethylene glycol monomethyl ether, formamide, p-hydroxybenzoic acid, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, vinyl glycol ether, 3-methyl-2-pentene-4-alkynol, acetaldehyde methyl hexyl acetal, tall oil acid, isophorone diamine, phosphorus pentoxide and formaldehyde used in the invention are all purchased from Jiangtian chemical technology Limited in Tianjin.
Detection method of phosphoramidate water soluble corrosion inhibitor
Refer to standard SY/T5273-.
Example 1
Preparation of water soluble amido phosphate corrosion inhibitor:
1) Carrying out amidation on tall oil acid and isophorone diamine at the temperature of 120 ℃ for 8h according to the molar ratio of 1:1, cooling to 80 ℃ after the reaction is finished, and then adding phosphorus pentoxide, formaldehyde and water at the molar ratio of 1:1:1 for reacting for 3 hours to synthesize the phosphoramidate mixed solution.
2) And (2) fully dissolving and mixing 45 parts by weight of the mixed liquid of the phosphoramidate obtained in the step 1) with 4 parts by weight of N-methylthiourea, 5 parts by weight of ethylene glycol monomethyl ether, 5 parts by weight of formamide, 5 parts by weight of p-hydroxybenzoic acid, 1 part by weight of nonylphenol polyoxyethylene ether, 1 part by weight of octylphenol polyoxyethylene ether, 23.5 parts by weight of water, 8 parts by weight of vinyl glycol ether, 0.5 part by weight of 3-methyl-2-pentene-4-alkynol and 2 parts by weight of acetaldehyde methyl hexyl acetal at 60 ℃ to obtain the water-soluble phosphoramidate corrosion inhibitor.
Detection of phosphoramidate water soluble corrosion inhibitor：
Preparation of Cl-The content is 100000-120000 mg/L, HCO3 -The content of SO is 300-400 mg/L4 2-Ca in an amount of 300-350 mg/L2+The content of Na is 10000-11000 mg/L++K+The content of the simulated corrosion medium solution is 50000-60000 mg/L.
The specific process is as follows: weigh 0.235g NaHCO3，0.225gNa2SO4，27.75gCaCl2，7.831gMgCl2·6H2O, 2.4g of KCl and 126.08g of NaCl are poured into a 1L volumetric flask, 800mL of distilled water is added, stirring is carried out until all solids are dissolved uniformly, and then distilled water is used for fixing the volume to 1L to obtain the corrosion medium simulation liquid.
The obtained phosphoramidate water soluble corrosion inhibitor is added into a high-temperature autoclave filled with the prepared simulated liquid at the concentration of 30ppm, and CO is added2Partial pressure of 1MPa, H2The S partial pressure is 0.2MPa, and the corrosion environment temperature is 40 ℃. The corrosion rate of the gathering and transportation pipeline is detected by adopting a test method of United states cotest high-temperature autoclave and weightless hanging piece, and the result shows that the corrosion rate of the steel sheet can be reduced to be less than or equal to 0.076mm/a and is reduced by 97 percent compared with the blank corrosion rate by adding 30ppm of the phosphoramidate water-soluble corrosion inhibitor prepared by the embodiment, namely the corrosion inhibition efficiency is more than or equal to 97 percent.
Example 2
Preparation of water soluble amido phosphate corrosion inhibitor:
1) Carrying out amidation on tall oil acid and isophorone diamine at a molar ratio of 1:1 at 130 ℃ for 7h, cooling to 90 ℃ after the reaction is finished, adding phosphorus pentoxide, formaldehyde and water at a molar ratio of 1:1:1, and reacting for 6h to synthesize the phosphoramidate mixed solution.
2) Fully dissolving and mixing 42 parts by weight of phosphoramidate mixed solution, 4 parts by weight of N-methylthiourea, 6 parts by weight of ethylene glycol monomethyl ether, 6 parts by weight of formamide, 6 parts by weight of p-hydroxybenzoic acid, 2 parts by weight of nonylphenol polyoxyethylene ether, 1 part by weight of octylphenol polyoxyethylene ether, 20 parts by weight of water, 9 parts by weight of vinyl glycol ether, 1 part by weight of 3-methyl-2-pentene-4-alkynol and 3 parts by weight of acetaldehyde methyl hexyl acetal at 60 ℃ to obtain the phosphoramidate water-soluble corrosion inhibitor.
Detection of phosphoramidate water soluble corrosion inhibitor：
Preparation of Cl-The content is 100000-120000 mg/L, HCO3 -The content of SO is 300-400 mg/L4 2-Ca in an amount of 300-350 mg/L2+The content of Na is 10000-11000 mg/L++K+The content of the simulated corrosion medium solution is 50000-60000 mg/L.
The specific process is as follows: weigh 0.235g NaHCO3，0.225gNa2SO4，27.75gCaCl2，7.831gMgCl2·6H2O, 2.4g of KCl and 126.08g of NaCl are poured into a 1L volumetric flask, 800mL of distilled water is added, stirring is carried out until all solids are dissolved uniformly, and then distilled water is used for fixing the volume to 1L to obtain the corrosion medium simulation liquid.
The obtained phosphoramidate water soluble corrosion inhibitor is added into a high-temperature autoclave filled with the prepared simulated liquid at the concentration of 30ppm, and CO is added2Partial pressure of 2MPa, H2The S partial pressure is 0.2MPa, and the corrosion environment temperature is 45 ℃. The corrosion rate of the gathering and transportation pipeline is detected by adopting a test method of United states cotest high-temperature autoclave and weightless hanging piece, and the result shows that the corrosion rate of the steel sheet can be reduced to be less than or equal to 0.076mm/a and is reduced by 97 percent compared with the blank corrosion rate by adding 30ppm of the phosphoramidate water-soluble corrosion inhibitor prepared by the embodiment, namely the corrosion inhibition efficiency is more than or equal to 97 percent.
Example 3
Preparation of water soluble amido phosphate corrosion inhibitor:
1) Carrying out amidation on tall oil acid and isophorone diamine at 140 ℃ for 6h according to the molar ratio of 1:1, cooling to 100 ℃ after the reaction is finished, adding phosphorus pentoxide, formaldehyde and water according to the molar ratio of 1:1:1, and reacting for 5 hours to synthesize the phosphoramidate mixed solution.
2) Fully dissolving and mixing 40 parts by weight of phosphoramidate mixed solution, 5 parts by weight of N-methylthiourea, 7 parts by weight of ethylene glycol monomethyl ether, 6 parts by weight of formamide, 7 parts by weight of p-hydroxybenzoic acid, 3 parts by weight of nonylphenol polyoxyethylene ether, 1 part by weight of octylphenol polyoxyethylene ether, 16 parts by weight of water, 10 parts by weight of vinyl glycol ether, 1 part by weight of 3-methyl-2-pentene-4-alkynol and 4 parts by weight of acetaldehyde methyl hexyl acetal at 60 ℃ to obtain the phosphoramidate water-soluble corrosion inhibitor.
Detection of phosphoramidate water soluble corrosion inhibitor：
Preparation of Cl-The content is 100000-120000 mg/L, HCO3 -The content of SO is 300-400 mg/L4 2-Ca in an amount of 300-350 mg/L2+The content of Na is 10000-11000 mg/L++K+The content of the simulated corrosion medium solution is 50000-60000 mg/L.
The specific process is as follows: weigh 0.235g NaHCO3，0.225gNa2SO4，27.75gCaCl2，7.831gMgCl2·6H2O, 2.4g of KCl and 126.08g of NaCl are poured into a 1L volumetric flask, 800mL of distilled water is added, stirring is carried out until all solids are dissolved uniformly, and then distilled water is used for fixing the volume to 1L to obtain the corrosion medium simulation liquid.
The obtained phosphoramidate water soluble corrosion inhibitor is added into a high-temperature autoclave filled with the prepared simulated liquid at the concentration of 30ppm, and CO is added2Partial pressure of 3MPa, H2The S partial pressure is 0.3MPa, and the temperature of the corrosion environment is 50 ℃. The corrosion rate of the gathering and transportation pipeline is detected by adopting a test method of United states cotest high-temperature autoclave and weightless hanging piece, and the result shows that the corrosion rate of the steel sheet can be reduced to be less than or equal to 0.076mm/a and is reduced by 96% compared with the blank corrosion rate by adding 30ppm of the phosphoramidate water-soluble corrosion inhibitor prepared by the embodiment, namely the corrosion inhibition efficiency is more than or equal to 96%.
Example 4
Preparation of water soluble amido phosphate corrosion inhibitor:
1) Carrying out amidation on tall oil acid and isophorone diamine at a molar ratio of 1:1 at 150 ℃ for 5h, cooling to 110 ℃ after the reaction is finished, adding phosphorus pentoxide, formaldehyde and water at a molar ratio of 1:1:1, and reacting for 4h to synthesize the phosphoramidate mixed solution.
2) Fully dissolving and mixing 35 parts by weight of phosphoramidate mixed solution, 5 parts by weight of N-methylthiourea, 8 parts by weight of ethylene glycol monomethyl ether, 7 parts by weight of formamide, 8 parts by weight of p-hydroxybenzoic acid, 4 parts by weight of nonylphenol polyoxyethylene ether, 1 part by weight of octylphenol polyoxyethylene ether, 11 parts by weight of water, 14 parts by weight of vinyl glycol ether, 2 parts by weight of 3-methyl-2-pentene-4-alkynol and 5 parts by weight of acetaldehyde methyl hexyl acetal at 60 ℃ to obtain the phosphoramidate water-soluble corrosion inhibitor.
Detection of phosphoramidate water soluble corrosion inhibitor：
Preparation of Cl-The content is 100000-120000 mg/L, HCO3 -The content of SO is 300-400 mg/L4 2-Ca in an amount of 300-350 mg/L2+The content of Na is 10000-11000 mg/L++K+The content of the simulated corrosion medium solution is 50000-60000 mg/L.
The specific process is as follows: weigh 0.235g NaHCO3，0.225gNa2SO4，27.75gCaCl2，7.831gMgCl2·6H2O, 2.4g of KCl and 126.08g of NaCl are poured into a 1L volumetric flask, 800mL of distilled water is added, stirring is carried out until all solids are dissolved uniformly, and then distilled water is used for fixing the volume to 1L to obtain the corrosion medium simulation liquid.
The obtained phosphoramidate water soluble corrosion inhibitor is added into a high-temperature autoclave filled with the prepared simulated liquid at the concentration of 30ppm, and CO is added2Partial pressure 4MPa, H2The S partial pressure is 0.4MPa, and the temperature of the corrosion environment is 55 ℃. The corrosion rate of the gathering and transportation pipeline is detected by adopting a test method of United states cotest high-temperature autoclave and weightless hanging piece, and the result shows that the corrosion rate of the steel sheet can be reduced to be less than or equal to 0.076mm/a and is reduced by 96% compared with the blank corrosion rate by adding 30ppm of the phosphoramidate water-soluble corrosion inhibitor prepared by the embodiment, namely the corrosion inhibition efficiency is more than or equal to 96%.
Example 5
Preparation of water soluble amido phosphate corrosion inhibitor:
1) Carrying out amidation on tall oil acid and isophorone diamine at 160 ℃ for 4h according to the molar ratio of 1:1, cooling to 120 ℃ after the reaction is finished, adding phosphorus pentoxide, formaldehyde and water according to the molar ratio of 1:1:1, and reacting for 3 hours to synthesize the phosphoramidate mixed solution.
2) And fully dissolving and mixing 30 parts by weight of the obtained phosphoramidate mixed solution with 6 parts by weight of N-methylthiourea, 10 parts by weight of ethylene glycol monomethyl ether, 8 parts by weight of formamide, 9 parts by weight of p-hydroxybenzoic acid, 5 parts by weight of nonylphenol polyoxyethylene ether, 2 parts by weight of octylphenol polyoxyethylene ether, 6 parts by weight of water, 15 parts by weight of vinyl glycol ether, 2.5 parts by weight of 3-methyl-2-pentene-4-alkynol and 6.5 parts by weight of acetaldehyde methyl hexyl acetal at 50 ℃ to obtain the phosphoramidate water soluble corrosion inhibitor.
Detection of phosphoramidate water soluble corrosion inhibitor：
Preparation of Cl-The content is 100000-120000 mg/L, HCO3 -The content of SO is 300-400 mg/L4 2-Ca in an amount of 300-350 mg/L2+The content of Na is 10000-11000 mg/L++K+The content of the simulated corrosion medium solution is 50000-60000 mg/L.
The specific process is as follows: weigh 0.235g NaHCO3，0.225gNa2SO4，27.75gCaCl2，7.831gMgCl2·6H2O, 2.4g of KCl and 126.08g of NaCl are poured into a 1L volumetric flask, 800mL of distilled water is added, stirring is carried out until all solids are dissolved uniformly, and then distilled water is used for fixing the volume to 1L to obtain the corrosion medium simulation liquid.
The obtained phosphoramidate water soluble corrosion inhibitor is added into a high-temperature autoclave filled with the prepared simulated liquid at the concentration of 30ppm, and CO is added2Partial pressure of 5MPa, H2The S partial pressure is 0.5MPa, and the temperature of the corrosion environment is 60 ℃. The corrosion rate of the gathering and transportation pipeline is detected by adopting a test method of United states cotest high-temperature autoclave and weightless hanging piece, and the result shows that the corrosion rate of the steel sheet can be reduced to be less than or equal to 0.076mm/a and is reduced by 95% compared with the blank corrosion rate by adding 30ppm of the phosphoramidate water-soluble corrosion inhibitor prepared by the embodiment, namely the corrosion inhibition efficiency is more than or equal to 95%％。
The corrosion rate of the gathering and transportation pipeline is detected by adopting an American cotest high-temperature autoclave and a weightless hanging piece test method, and the results show that the phosphoramidate water-soluble corrosion inhibitor prepared in the embodiments 1-5 has excellent corrosion inhibition performance, as shown in the following table 1.
TABLE 1 results of performance testing of the phosphoramidate water soluble corrosion inhibitors described in examples 1-5
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (3)
1. An aminophosphate water soluble corrosion inhibitor comprises the following components in parts by weight: 30-45 parts of an phosphoramidate mixed solution, 4-6 parts of N-methylthiourea, 5-10 parts of ethylene glycol monomethyl ether, 5-8 parts of formamide, 5-9 parts of p-hydroxybenzoic acid, 1-5 parts of nonylphenol polyoxyethylene ether, 1-2 parts of octylphenol polyoxyethylene ether, 6-23.5 parts of water, 8-15 parts of vinyl glycol ether, 0.5-2.5 parts of 3-methyl-2-pentene-4-alkynol and 2-6.5 parts of acetaldehyde methyl hexyl acetal,
the phosphoramidate mixed solution is synthesized by reacting tall oil acid, isophorone diamine, phosphorus pentoxide and formaldehyde, wherein the molar ratio of the tall oil acid to the isophorone diamine is 1: 1.
2. A method for preparing the phosphoramidate water soluble corrosion inhibitor of claim 1, which comprises:
(1) amidating tall oil acid and isophorone diamine in a molar ratio of 1:1, adding phosphorus pentoxide, formaldehyde and water in a molar ratio of 1:1:1, and reacting for 3-6 hours to synthesize an aminophosphate mixed solution;
(2) according to the weight parts, 30-45 parts of the phosphoramidate mixed solution, 4-6 parts of N-methyl thiourea, 5-10 parts of ethylene glycol monomethyl ether, 5-8 parts of formamide, 5-9 parts of p-hydroxybenzoic acid, 1-5 parts of nonylphenol polyoxyethylene ether, 1-2 parts of octylphenol polyoxyethylene ether, 6-23.5 parts of water, 8-15 parts of vinyl glycol ether, 0.5-2.5 parts of 3-methyl-2-pentene-4-alkynol and 2-6.5 parts of acetaldehyde methyl hexyl acetal are mixed and stirred uniformly at 50-60 ℃ to obtain the phosphoramidate water soluble corrosion inhibitor.
3. The preparation method of the phosphoramidate water soluble corrosion inhibitor according to claim 2, wherein the amidation reaction temperature of the tall oil acid and the isophorone diamine is 120-160 ℃, the reaction time is 4-8h, and the temperature is reduced to 80-120 ℃ after the reaction is completed.
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