CN1283837C - Water-soluble corrosion inhibition neutralizer and preparation method thereof - Google Patents
Water-soluble corrosion inhibition neutralizer and preparation method thereof Download PDFInfo
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- CN1283837C CN1283837C CN 03147792 CN03147792A CN1283837C CN 1283837 C CN1283837 C CN 1283837C CN 03147792 CN03147792 CN 03147792 CN 03147792 A CN03147792 A CN 03147792A CN 1283837 C CN1283837 C CN 1283837C
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- 230000005764 inhibitory process Effects 0.000 title claims abstract description 39
- 238000005260 corrosion Methods 0.000 title claims abstract description 32
- 230000007797 corrosion Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 claims abstract description 46
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229920000768 polyamine Polymers 0.000 claims abstract description 15
- 150000004291 polyenes Chemical class 0.000 claims abstract description 12
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 35
- 230000003472 neutralizing effect Effects 0.000 claims description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 20
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 18
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 150000008065 acid anhydrides Chemical class 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 6
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 6
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 6
- 229960001124 trientine Drugs 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- YHASWHZGWUONAO-UHFFFAOYSA-N butanoyl butanoate Chemical compound CCCC(=O)OC(=O)CCC YHASWHZGWUONAO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- MHZGKXUYDGKKIU-UHFFFAOYSA-N Decylamine Chemical compound CCCCCCCCCCN MHZGKXUYDGKKIU-UHFFFAOYSA-N 0.000 claims 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 10
- 239000003112 inhibitor Substances 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000012423 maintenance Methods 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 125000005608 naphthenic acid group Chemical group 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- 238000007670 refining Methods 0.000 description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- -1 HCL or H2S or liquid Chemical compound 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 229910000926 A-3 tool steel Inorganic materials 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000975 Carbon steel Inorganic materials 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 239000010962 carbon steel Substances 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012453 solvate Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000003211 malignant effect Effects 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000002769 thiazolinyl group Chemical group 0.000 description 1
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a water-soluble corrosion inhibition neutralizer mainly used for metal corrosion protection of low-temperature light oil part of an oil refinery and a preparation method thereof, the corrosion inhibition neutralizer is a naphthenic acid imidazoline corrosion inhibitor prepared by using naphthenic acid, polyene polyamine and organic acid anhydride or ethylene oxide as raw materials, and then the corrosion inhibition neutralizer and the solvent are compounded to prepare the corrosion inhibitor2S-H2Corrosion and scaling of OThe energy consumption is low, the service cycle of the equipment is obviously prolonged, and the maintenance frequency is reduced.
Description
Technical field:
The present invention relates to mixture and preparation method thereof in the water soluble corrosion inhibition that a kind of anti-corrosion of metal uses, relate to a kind ofly by imidazoline type inhibiter and the composite inhibition neutralizing agent that forms of neutralizing agent in particular, it is anticorrosion to be mainly used in factory of petrochemical refining low temperature lightweight oil position.
Background technology:
Imidazoline inhibitor becomes the most active both at home and abroad with its outstanding excellent corrosion inhibition, most widely used inhibiter of new generation.In the oil refining petrochemical plant, be mainly used in the equipment that atmospheric and vacuum distillation unit and other can produce sour gas such as HCL or H2S or liquid, device and pipeline corrosion protection.The anti-corrosion measure commonly used of past atmospheric and vacuum distillation unit low temperature light oil position is " one takes off four notes ", " one takes off " is electric desalting, " four annotate " promptly annotated ammonia, annotates alkali, annotated inhibiter, and wherein, annotating inhibiter is a kind of main anticorrosion auxiliary agent of factory of the petrochemical refining anticorrosion usefulness in low temperature lightweight oil position.This inhibiter has oil soluble and water-soluble branch, and is each has something to recommend him on the performance.Introduced a kind of imidazoline amide compound as CN1091781A, can be used for the anticorrosion position of refinery low temperature lightweight oil, but this agent has been an oil-soluble inhibitor with organic acid and polyethylene polyamine preparation.It is the oil well acidation water soluble rust inhibitor that raw material obtains through the hydrochloric acid quaternary ammonium reaction with naphthenic acid imidazoline diamide Soxylat A 25-7 that CN1163301A discloses a kind of.US3510282, US3827874 have all reported a kind of organic acid such as lipid acid, have had substituent di-carboxylic acid and polyamines synthetic imidazoline inhibitor, but it is anticorrosion really naphthenic acid imidazoline water soluble rust inhibitor and the composite inhibition neutralizing agent that forms of neutralizing agent to be used for factory of petrochemical refining low temperature light oil position, does not see relevant report as yet.At present, also there is certain defective in the inhibiter of factory of petrochemical refining practical application: the consumption that has is higher, and inhibition efficiency is on the low side, causes carbon steel spot corrosion to occur.The sour gas that has can not get effectively neutralization and has the Malignant stink.The solubility property that has is relatively poor, stops up when often causing inhibiter line of pipes and nozzle injecting.The inhibitor effectiveness height that has, but function singleness is made troubles to execute-in-place.
Summary of the invention:
It is simple that purpose of the present invention just provides a kind of synthesis technique, potion multi-purpose water soluble corrosion inhibition neutralizing agent, during this agent has concurrently and the film forming double effects, can both bring into play good efficacy no matter make carbon steel at low temperature light oil position water or oil phase, overcome inhibition component decomposition failure problem under strong alkali environment easily, can not make oil product produce emulsification, meet water or oil and do not produce precipitation, enough chemical stabilities and thermostability are arranged in working medium.To following process, no negative interaction, low toxicity, free from extraneous odour, execute-in-place are more simple and convenient.
Inhibition neutralizing agent preparation method of the present invention is as follows:
(1) preparation naphthenic acid imidazoline inhibiter or naphthenic acid imidazoline Soxylat A 25-7 inhibiter: naphthenic acid and polyamines polyene were dropped in 1: 1 in molar ratio～1: 3, and adding charging capacity 5～30% varsols, under constantly stirring, be warming up to 100～250 ℃, refluxed 2～10 hours, with acid number control reaction depth, when the reactant acid number reaches 2.89mgKOH/g～9.65mgKOH/g, obtain naphthenic acid azoles quinoline intermediate, naphthenic acid imidazoline intermediate and organic acid anhydride are pressed 1: 0.5～1: 3 mol ratio, 5～40% varsol was carried out to reactant salt 0.5～5 hour under 10～120 ℃ of temperature actions, obtain water-soluble naphthenic acid imidazoline inhibiter or with naphthenic acid imidazoline intermediate and ethylene oxide 1: 5 in molar ratio～1: 15,115～140 ℃ were reacted 0.5～4 hour down, obtain water-soluble naphthenic acid imidazoline Soxylat A 25-7 inhibiter.
(2) preparation of inhibition neutralizing agent:
The inhibition neutralizing agent carries out composite mediation by following weight percent and forms
Naphthenic acid imidazoline inhibiter 10～40%
Neutralizing agent 10～40%
Solvent 20～80%
Naphthenic acid of the present invention can have saturated or unsaturated side chain on its naphthenic ring, and molecular weight is 100-350.Naphthenic acid can be the naphthenic acid that contains a certain amount of hydrocarbon ils, also can be to form through other purifying techniques such as soda acid-clay-filtered or ammonia alcoholic solvent are refining.This product has the commercially available prod, as the 65# naphthenic acid, and 75# naphthenic acid, 85# naphthenic acid etc.Its structural formula is: RCOOH
Wherein, R can be H, alkyl, thiazolinyl, cycloalkyl etc., n=1～20
Described polyamines polyene can be in diethylenetriamine, triethylene tetramine, the tetraethylene pentamine any one, also can be the above-mentioned mixture of polyamines polyene more than two kinds.Preferably wherein arbitrary single agent.
Described organic acid anhydride is the rudimentary acid anhydrides of liquid, as acetic anhydride, second third acid anhydride, butanoic anhydride etc., and preferred acetic anhydride and second third acid anhydride.
Described varsol plays dehydration in reaction, can be: benzene,toluene,xylene or mixed benzene also can be varsol oil.Preferred toluene, dimethylbenzene or varsol oil.
Described neutralizing agent can be mineral alkali NaOH, KOH or ammonia, also can be the lower molecular weight organic amine: methylamine, ethamine, quadrol, dimethylamine, Trimethylamine 99, diethylamine, triethylamine etc.Methylamine, ethamine, quadrol or diethylamine in the preferred above-mentioned mineral alkali in any one or the organic amine.
Described solvent mainly is the low mass molecule alcohol class that can dissolve each other with water, as methyl alcohol, ethanol.
Preparation naphthenic acid imidazoline inhibiter, the mol ratio that naphthenic acid and polyamines polyene reaction are best is 1: 1～1: 1.7, the varsol amount is advisable can keep reflux state, best varsol amount is 5～15% of a charging capacity, temperature is 150～230 ℃, the reaction optimum mole ratio of tetrahydroglyoxaline intermediate and organic acid anhydride 1: 0.5～1: 2, temperature of reaction is below 80 ℃, hold in the presence of the agent 5～20% at hydro carbons, react and got final product in 0.5～3 hour, or with synthetic tetrahydroglyoxaline intermediate and ethylene oxide reaction, 1: 7～1: 13 mol ratio of optimum process condition, reaction is 0.5-4 hour under 120～125 ℃ of temperature, its chemical reaction equation of naphthenic acid imidazoline polyvinyl ether inhibiter
In the formula, R1 is a cycloalkyl, n=1～3
In the formula, x=1～10
Inhibiter main component by above-mentioned processing condition preparation is the cycloalkanes tetrahydroglyoxaline, does not contain the reaction raw materials naphthenic acid.Its quality and technical index is: outward appearance: reddish-brown, even matter liquid, density (20 ℃): be not less than 850Kg/m
3, pH value: be not less than 9, solvability: water-soluble, corrosion inhibition rate: in the corrosive medium of the H2S of the HCL+1000mg/L of 1000mg/L, add 50mg/L tetrahydroglyoxaline inhibition of the present invention neutralizing agent, the inhibition efficiency of A3 steel test piece is not less than 90%.
The present invention compares with similar inhibiter, has good water solubility, inhibition efficiency high chemical stability and Heat stability is good, the characteristics that dosage is suitable, integrated film inhibition with in and double effects, make execute-in-place more simple, changed conventional " one takes off four notes " technology, be reduced to " one takes off notes " technology, reduce the corrosion and scaling of overhead condensation cooling system low-temperature section HCL-H2S-H2O, cut down the consumption of energy, obviously improved the life cycle of equipment, reduce the maintenance number of times, have outstanding economic benefit.
Embodiment:
Embodiment 1
With thick acid number be the 85# naphthenic acid of 185.4mgKOH/g and diethylenetriamine by 1: 1MOL/MOL drops in the reactor, adds 5% 120# solvent oil, and 100 ℃ of following back flow reaction 2 hours, obtaining acid number was the naphthenic acid imidazoline intermediate of 2.89mgKOH/g.This intermediate and second third acid anhydride were dropped in the reactor in 1: 0.5 in molar ratio again, add 5% methanol solvate, reaction is 0.5 hour under the room temperature, and control reaction temperature is no more than 80 ℃ and obtains water-soluble naphthenic acid imidazoline inhibiter.Prepared this inhibiter of 50mg/L is incorporated in the corrosive medium of H2S of HCL+1000mg/L of 1000mg/L, under 85 ℃, to the inhibition speed of A3 steel test piece, by the 24.75g/m of blank sample
2.h reduce to 0.61g/m
2.h, inhibition efficiency is 97.5%.With the methanol solvate of this inhibiter 10% with neutralizing agent methylamine 10%, 80%, be in harmonious proportion half an hour at 50 ℃, promptly obtain the inhibition neutralizing agent.After tested, its every performance all reaches the product quality indicator requirement.
Embodiment 2
Under 120-125 ℃, reacted 0.5 hour by 1: 5 mol ratio by embodiment 1 condition synthetic naphthenic acid imidazoline intermediate and ethylene oxide, promptly obtain naphthenic acid imidazoline polyoxyethylene mystery inhibiter.Under the corrosive medium and etching condition identical with embodiment 1, the inhibition speed that records this product is 2.45g/m
2.h, inhibition efficiency 90.1%.With this inhibiter 20%, neutralizing agent ethamine 20%, concentration is 10% the NaOH aqueous solution 20%, and methyl alcohol 30% is in harmonious proportion down half an hour at 50 ℃, promptly obtains inhibition neutralizing agent product.Test by analysis, its physicochemical property all reaches the product quality indicator requirement.
Embodiment 3-12 (seeing Table one)
Embodiment 13-18 (seeing Table two)
Synthetic inhibition neutralizing agent and corrosion mitigating effect under table one different condition
| The naphthenic acid imidazoline intermediate | The naphthenic acid imidazoline inhibiter | Test-results | |||||||||||||
| Embodiment | Naphthenic acid | Polyamines polyene | Acid: polyamines mol/mol | Solvent | Solvent load % | Temperature of reaction ℃ | Reaction times h | Acid number mgkoH/g | A or b title * | Intermediate: a or b* mol/mol | Temperature of reaction ℃ | Reaction times h | Erosion rate g/m 2·h | Corrosion inhibition rate % | The product code name |
| 3 | 65# | Tetraethylene pentamine | 1∶2 | Sherwood oil | 25 | 250 | 4 | 7.14 | Acetic anhydride | 1∶0.8 | 60～100 | 0.5 | 1.61 | 93.5 | A |
| 4 | 75# | Triethylene tetramine | 1∶1.7 | Dimethylbenzene | 20 | 230 | 5 | 6.89 | Ethylene oxide | 1∶7 | 115～125 | 3 | 1.81 | 92.7 | B |
| 5 | 55# | Triethylene tetramine | 1∶3 | Toluene | 30 | 180 | 8 | 7.85 | Second third acid anhydride | 1∶3 | 110 | 1.5 | 0.86 | 96.6 | C |
| 6 | 85# | Tetraethylene pentamine | 1∶1.5 | The 120# solvent oil | 10 | 150 | 10 | 9.65 | Ethylene oxide | 1∶13 | 115～125 | 3.5 | 1.21 | 95.1 | D |
| 7 | 75# | Tetraethylene pentamine | 1∶2.5 | Dimethylbenzene | 15 | 200 | 6 | 7.43 | Ethylene oxide | 1∶15 | 125～140 | 4 | 2.06 | 91.7 | E |
| 8 | 65# | Triethylene tetramine | 1∶2.2 | Mix benzene | 22 | 210 | 7 | 6.43 | Second third acid anhydride | 1∶2 | 80～120 | 1.5 | 0.83 | 96.6 | F |
| 9 | 55# | Diethylenetriamine | 1∶2.7 | Sherwood oil | 12 | 190 | 9 | 7.07 | Acetic anhydride | 1∶1.5 | 10～60 | 1.0 | 0.97 | 96.1 | G |
| 10 | 65# | Diethylenetriamine | 1∶1.1 | Toluene | 8 | 120 | 10 | 5.42 | Butanoic anhydride | 1∶2 | 100～120 | 5 | 2.25 | 90.9 | H |
| 11 | 75# | Polyamines polyene | 1∶1.3 | Mix benzene | 10 | 140 | 8 | 8.02 | Acetic anhydride | 1∶2.5 | 60～80 | 2.5 | 1.14 | 95.4 | I |
| 12 | 55# | Polyamines polyene | 1∶1.5 | The 120# solvent oil | 18 | 170 | 10 | 6.79 | Ethylene oxide | 1∶10 | 120～130 | 2 | 2.03 | 91.8 | J |
After the part inhibiter of table two table one and neutralizing agent are composite, the on-the-spot example as a result that uses of inhibition neutralizing agent.
| Embodiment | Inhibiter | Consumption % | Neutralizing agent | Consumption % | Solvent | Be in harmonious proportion temperature ℃ | Mediation time h | Normal top water of condensation | Subtract the top water of condensation | |||
| Title | Consumption % | PH value | Fe 2+mg/L | PH value | Fe 2+mg/L | |||||||
| 13 | A | 15 | Ammonia | 15 | Ethanol | 70 | 50 | 0.5 | 4.78 | 16.87 | 5.84 | 11.8 |
| 14 | B | 20 | Quadrol | 20 | Ethanol | 60 | 50 | 0.5 | 6.44 | 10.25 | 7.46 | 7.08 |
| 15 | D | 30 | Triethylamine | 30 | Methyl alcohol | 40 | 50 | 0.5 | 8.24 | 8.59 | 5.82 | 12.1 |
| 16 | F | 40 | Dimethylamine | 40 | Ethanol | 20 | 50 | 0.5 | 8.68 | 9.38 | 6.51 | 8.4 |
| 17 | G | 25 | Trimethylamine 99 | 35 | Methyl alcohol | 45 | 50 | 0.5 | 6.02 | 13.92 | 4.29 | 9.72 |
| 18 | I | 35 | Diethylamine | 25 | Methyl alcohol | 45 | 50 | 0.5 | 6.32 | 12.37 | 5.16 | 10.29 |
Annotate: (1) a is an anhydrides, and b is an ethylene oxide;
(2) polyamines polyene is the mixture of diethylenetriamine, triethylene tetramine, tetraethylene pentamine;
(3) corrosion test condition: the H of the HCL+1000mg/L of corrosive medium 1000mg/L
2S solution, inhibiter add-on 50mg/L, 85 ℃ of corrosion temperatures, test piece A3 steel.
Claims (8)
1. the preparation method of a water soluble corrosion inhibition neutralizing agent, it is characterized in that: (1) water-soluble naphthenic acid imidazoline inhibiter of preparation or water-soluble naphthenic acid imidazoline Soxylat A 25-7 inhibiter: naphthenic acid and polyamines polyene were dropped in 1: 1 in molar ratio～1: 3, and add the varsol of the weight 5～30% that feeds intake, under constantly stirring, be warming up to 100～250 ℃, refluxed 2～10 hours, with acid number control reaction depth, when the mixture acid number of reaction reaches 2.89mgKOH/g～9.65mgKOH/g, obtain synthetic naphthenic acid imidazoline intermediate; Naphthenic acid imidazoline intermediate and organic acid anhydride are pressed 1: 0.5～1: 3 mol ratio input, and add the varsol of the weight 5～40% that feeds intake, under 10～120 ℃ of temperature, be carried out to reactant salt 0.5～5 hour, obtain water-soluble naphthenic acid imidazoline inhibiter, or with naphthenic acid imidazoline intermediate and ethylene oxide 1: 5 in molar ratio～1: 15,115～140 ℃ were reacted 0.5～4 hour down, obtain water-soluble naphthenic acid imidazoline Soxylat A 25-7 inhibiter; (2) preparation of water soluble corrosion inhibition neutralizing agent: the water soluble corrosion inhibition neutralizing agent carries out composite mediation by following weight percent and forms, naphthenic acid imidazoline inhibiter 10～40%, neutralizing agent is mineral alkali NaOH, KOH, ammonia or lower molecular weight organic amine 10～40%, the low mass molecule alcohol class 20～80% that can dissolve each other with water.
2. the preparation method of a kind of water soluble corrosion inhibition neutralizing agent according to claim 1, it is characterized in that: the mol ratio of naphthenic acid and polyamines polyene reaction is 1: 1～1: 1.7, the varsol amount is 5～15% of the weight that feeds intake, temperature is 150～230 ℃, naphthenic acid imidazoline intermediate and organic acid anhydride reaction mol ratio are 1: 0.5～1: 2, temperature of reaction is 10 ℃～80 ℃, in the presence of 5～20% varsols, reacted 0.5～3 hour, or with synthetic naphthenic acid imidazoline intermediate and ethylene oxide 1: 7 in molar ratio～1: 13, temperature is 120～125 ℃ and reacted 0.5～4 hour down.
3. the preparation method of a kind of water soluble corrosion inhibition neutralizing agent according to claim 1, it is characterized in that: have saturated or unsaturated side chain on the naphthenic ring of naphthenic acid, the naphthenic acid molecule amount is 100～350, and naphthenic acid is through making with extra care or do not pass through the purified naphthenic acid.
4. the preparation method of a kind of water soluble corrosion inhibition neutralizing agent according to claim 1 is characterized in that: described polyamines polyene is a kind of in diethylenetriamine, triethylene tetramine, the tetraethylene pentamine or two or more mixture arbitrarily.
5. the preparation method of a kind of water soluble corrosion inhibition neutralizing agent according to claim 1 is characterized in that: described organic acid anhydride is any one in acetic anhydride, second third acid anhydride or the butanoic anhydride.
6. the preparation method of a kind of water soluble corrosion inhibition neutralizing agent according to claim 1 is characterized in that: described varsol is any one in benzene,toluene,xylene, benzene mixed or the varsol oil.
7. the preparation method of a kind of water soluble corrosion inhibition neutralizing agent according to claim 1 is characterized in that: the lower molecular weight organic amine is methylamine, ethamine, quadrol, dimethylamine, Trimethylamine 99, diethylamine or triethylamine.
8. the preparation method of a kind of water soluble corrosion inhibition neutralizing agent according to claim 1 is characterized in that: the low mass molecule alcohol class that can dissolve each other with water is methyl alcohol or ethanol.
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Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1309869C (en) * | 2005-11-15 | 2007-04-11 | 中国石油天然气集团公司 | Corrosion inhibition neutralizer |
| CN101190896B (en) * | 2006-12-01 | 2012-01-11 | 湖南科技大学 | Method for preparing naphthenic acid imidazolines and betaine of amide thereof, and application of the same in HCl-H2S-H2O system |
| CN101455199B (en) * | 2008-11-11 | 2011-11-09 | 北京迪威尔石油天然气技术开发有限公司 | Naphthenic acid imidazoline and preparation method thereof |
| CN102953064B (en) * | 2011-08-19 | 2014-11-12 | 中国石油天然气股份有限公司 | Mannich base corrosion-inhibiting neutralizer and preparation method thereof |
| CN102953065B (en) * | 2011-08-19 | 2014-10-15 | 中国石油天然气股份有限公司 | Corrosion inhibition neutralizer for metal corrosion prevention and preparation method thereof |
| CN104099075B (en) * | 2013-04-03 | 2016-09-07 | 中国石油天然气股份有限公司 | Solid corrosion inhibitor for oil and gas well and preparation method thereof |
| CN104099615B (en) * | 2014-06-20 | 2016-08-24 | 黄河三角洲京博化工研究院有限公司 | With corrosion inhibiter and preparation method thereof in a kind of imidazoline type |
| CN105063628A (en) * | 2015-07-20 | 2015-11-18 | 武汉三友石化有限公司 | Corrosion inhibition neutralizer |
| CN106435597A (en) * | 2015-08-06 | 2017-02-22 | 胜利油田胜利化工有限责任公司 | Formula of protective agent for J55 steel for oil field exploitation and production process |
| CN105132922B (en) * | 2015-09-14 | 2019-03-01 | 中国石油大学(华东) | A kind of preparation method for the oil-soluble inhibitor for inhibiting fractionation tower top to follow corrosion |
| CN111058043A (en) * | 2018-10-17 | 2020-04-24 | 中国石油化工股份有限公司 | Organic composite corrosion inhibitor and method for inhibiting carbon steel corrosion in Fischer-Tropsch synthesis reaction water by using same |
| CN109797003A (en) * | 2019-02-01 | 2019-05-24 | 北京乐文科技发展有限公司 | A kind of oil-soluble inhibitor and preparation method thereof |
| CN110344063A (en) * | 2019-08-27 | 2019-10-18 | 山东益丰生化环保股份有限公司 | A kind of modified imidazoline corrosion inhibiter and preparation method thereof |
| CN111945168B (en) * | 2020-07-28 | 2022-05-24 | 广东粤首新科技有限公司 | Neutralization corrosion inhibitor and application thereof |
| CN112176348A (en) * | 2020-09-27 | 2021-01-05 | 北京乐文科技发展有限公司 | Water-soluble corrosion inhibitor and preparation method thereof |
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