CN1884256A - Process for preparing cycloalkanoimide betaine and use thereof - Google Patents
Process for preparing cycloalkanoimide betaine and use thereof Download PDFInfo
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- CN1884256A CN1884256A CNA2006100319205A CN200610031920A CN1884256A CN 1884256 A CN1884256 A CN 1884256A CN A2006100319205 A CNA2006100319205 A CN A2006100319205A CN 200610031920 A CN200610031920 A CN 200610031920A CN 1884256 A CN1884256 A CN 1884256A
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Abstract
The invention relates to a method for preparing naphthenic acid amide beet alkali and its application. Naphthenic acid amide or naphthenic acid imidazoline or mixture of them reacts with sodium monochloracetate, the molar proportion between naphthene base in naphthenic acid amide or imidazoline and sodium monochloracetate is 1.0: 4.8- 7.0, temperature is at 50-95 Deg. C, pH is about 10, and the reaction time is 8-18 hours. The product is used as water-soluble inhibitor for HCL-H2S-H2O system. The invention is characterized by low cost and simple process. The inhibiting property of said product is sound and compatibility with organic amine is good.
Description
Technical field
The present invention relates to the preparation method of cycloalkanoimide betaine and as the application of water soluble rust inhibitor.
Background technology
Naphthenic acid be mainly derived from refining of petroleum two, three-way alkaline residue.At present, China has more than about 30,000 t/a of naphthenic acid resource, but resource utilization is low, directly be used as boat coal additive and the mineral flotation agent except that a small amount of, the overwhelming majority is used for naphthenate production, and the naphthenic acid organic derivative, especially its Application and Development degree in aqueous media still is not enough.In the past, because naphthenic acid purity does not increase, when institute's corresponding organic derivative of synthetic is applied to aqueous media, there were a large amount of fulsome oily substances to separate out.The exploitation for preparing complete set technology along with high-purity naphthenic acid in recent years (is seen document 1: Shi Shuncun, open red. the preparation of high-purity naphthenic acid [J]. Xiangtan Mining Industry College's journal, 2001,16 (3): 47-50), crude naphthenic acid provides good basic substance through refining high-purity naphthenic acid for preparing water miscible naphthenic acid organic derivative.Compare with traditional lipid acid, the naphthenic acid organic derivative has the heat-resisting and antioxygen stability of good low-temperature fluidity and height, manipulates more convenient; And when being applied to the protection against corrosion field, compact protective film has better corrosion mitigating effect because of naphthenic acid deutero-naphthene group can form more in the metallic surface.
" one takes off three notes " (the ordinary decompression column top distillates line and annotates ammonia, annotates inhibiter, water filling) is still the main anti-corrosion measure that present refinery ordinary decompression column top condenser system adopts.This technological measure can prevent HCl-H preferably
2S-H
2The O corrosion, but still have two big weak points: the one, on-the-spot pH value fluctuation range is excessive, is difficult to regulation and control.On-the-spot pH value generally all is controlled at more than 8.5, and this has not only caused the significant wastage of ammoniacal liquor, and easily causes the NH4Cl crystallization to separate out, the serious fouling of equipment surface, and occluding device also causes underdeposit corrosion, influences equipment safety operation.The 2nd, because the vapour pressure height of ammonia is difficult for entering the acidic medium that the liquid phase neutralization causes dew point corrosion in the initial set district, the corrosion at dew point position, initial set district is not had effective restraining effect, make that Atmospheric Tower volatilization line point corrosion is heavier.So more and more notes organic amines that adopt replace annotating ammoniacal liquor to guarantee the etch-proof effect of neutralization.Simultaneously, be the technical process that simplifies the operation, " one takes off three notes " that refinery ordinary decompression column top condenser system is adopted changes " one takes off two notes " into, people be very willing to adopt integrate " neutralization " and " inhibition " function in and inhibiter.At present, still more generally adopt 7019 (ricinolic acid acid amide type) water soluble rust inhibitor on the market, 7019 belong to the long chain type organic inhibitors, under the strong basicity environment, and the long-chain decomposition of can rupturing, this keeps higher corrosion inhibition totally unfavorable to medicament for a long time.So still press for can with the direct composite new type water-solubility inhibiter together of organic amine.
Document [2] Wu Yufeng, Zhou Kunping, Liang Jing is next. the synthetic and performance study [J] of imidazoline quaternary ammonium salt water soluble rust inhibitor NH-1. Speciality Petrochemicals, 2001, (5): 39-42; Document [3] Li Bang. the synthetic and performance evaluation [J] of water-soluble imidazoline quaternary inhibiter. Speciality Petrochemicals, 2005, (4): 44-46; Disclosed the reaction of organic polyamines such as naphthenic acid and triethylene tetramine or diethylenetriamine and generated tetrahydroglyoxaline, adopted methyl-sulfate or ethyl sulfate to carry out alkylated reaction then and become the imidazoline quaternary ammonium salt water soluble rust inhibitor, and at HCl-H
2S-H
2Has good corrosion inhibition in the O system.But they all can't be directly composite with organic amine because of separating out under alkalescence; And on-site experience shows that when annotating organic amine, its corrosion mitigating effect reduces greatly.
At above situation, we invent out a kind of being fit to and the composite new type water-solubility inhibiter-cycloalkanoimide betaine together of high density organic amine.In addition, the contriver yet there are no the relevant report of cycloalkanoimide betaine application facet.
Summary of the invention
It is lower that purpose of the present invention aims to provide a kind of cost, prepares the preparation method of cycloalkanoimide betaine simply and easily.
Another object of the present invention aims to provide the application as water soluble rust inhibitor of the cycloalkanoimide betaine that gone out by method for preparing, and its corrosion inhibition is excellent and good with the organic amine intermiscibility, helps industrial applications.
The objective of the invention is to realize by following manner:
The cycloalkanoimide betaine preparation method:
With cycloalkanoimide or naphthenic acid imidazoline or both mixtures and sodium chloroacetate reaction, in the reaction in cycloalkanoimide or the tetrahydroglyoxaline in contained cycloalkyl and the sodium chloroacetate solution total mol ratio of contained sodium chloroacetate be 1.0: 4.8～7.0,50～95 ℃ of controlled temperature, pH8～10 scope internal reactions, 8～18h, promptly synthetic cycloalkanoimide betaine product.
Described cycloalkanoimide or naphthenic acid imidazoline or both mixtures and sodium chloroacetate reaction, carry out in two steps, mol ratio by contained sodium chloroacetate in contained cycloalkyl and the sodium chloroacetate solution in cycloalkanoimide or the tetrahydroglyoxaline is 1.0: 3.0～5.0 temperature reactions gradually under agitation earlier, reach 5～8h when the reaction times, under the situation that the pH value does not descend, be 1.0: 0.5～3.0 mode again by the mol ratio of contained sodium chloroacetate in contained cycloalkyl and the sodium chloroacetate solution in cycloalkanoimide or the tetrahydroglyoxaline, stir and add sodium chloroacetate solution down, stirring and refluxing reaction 3～10h.
Described cycloalkanoimide or naphthenic acid imidazoline are that naphthenic acid and diethylenetriamine are generated through the condensation dehydration.
More excellent pH is 8.5～9.5 in the reaction process.
Described naphthenic acid is acid content 〉=85% massfraction, thick acid number 〉=185mgKOH/g.
Cycloalkanoimide betaine is applied to HCl-H
2S-H
2The O system is as water soluble rust inhibitor.
Cycloalkanoimide betaine is applied to refinery ordinary decompression column top condenser system, as water soluble rust inhibitor.Its corrosion inhibition is excellent and good with the organic amine intermiscibility, helps industrial applications.
(1) technological line of the present invention and reaction principle
(1) naphthenic acid and diethylenetriamine generate cycloalkanoimide or tetrahydroglyoxaline through the condensation dehydration:
In the formula: R---by naphthenic acid deutero-alkyl group; Down together.
(2) reaction of cycloalkanoimide and sodium chloroacetate generates cycloalkanoimide betaine:
RCONHCH
2CH
2NHCH
2CH
2NH
2+5ClCH
2COONa+3NaOH
(3) naphthenic acid imidazoline also can obtain the cycloalkanoimide betaine identical with following formula in following ring opening hydrolysis limit of alkaline condition and sodium chloroacetate reaction.
In addition, when the sodium chloroacetate proportional quantity more after a little while, also can generate following type only with the cycloalkanoimide betaine of a positive charge:
Or:
(2) implementation step
In the there-necked flask reaction unit of the charged heating jacket that thermometer, water trap and prolong thereof are housed; the naphthenic acid and the technical grade diethylenetriamine that add acid content 〉=85% (massfraction), thick acid number 〉=185mgKOH/g successively; make azeotropic agent with dimethylbenzene; under the logical nitrogen protection, heat up gradually and carry out the condensation dehydration reaction.150～230 ℃ of internal reaction 6～15h of temperature generate cycloalkanoimide to product acid number≤15mgKOH/g, perhaps 150～280 ℃ of internal reaction 15～24h of temperature are to product acid number≤6mgKOH/g and after generating naphthenic acid imidazoline, promptly retortablely remove dimethylbenzene and change next step reaction over to.
Synthesize good cycloalkanoimide or tetrahydroglyoxaline and be cooled to below 110 ℃, it by total mol ratio of contained sodium chloroacetate in contained cycloalkyl and the sodium chloroacetate solution in cycloalkanoimide or the tetrahydroglyoxaline 1.0: 4.8～7.0 mode, successively add sodium chloroacetate solution in two batches, 50～95 ℃ of controlled temperature, pH8～10 scope internal reactions, 8～18h, the cycloalkanoimide betaine product of promptly synthetic amphoteric ion type.Reaction is when reaching home, and product is water-soluble fully, and can be dissolved in 30%～40%NaOH solution or 20%～25% ethylenediamine solution and do not separate out, do not have precipitation.Cycloalkanoimide betaine product physical index after synthesizing well is as follows: outward appearance is the reddish-brown transparent liquid, pH8.5～10, and about density 1.2kg/L, solid content 〉=40%.
(3) characteristics of the technology of the present invention and effect
(1) corrosion inhibition excellence and product cost are lower
Because amide group and hydroxy-acid group in the cycloalkanoimide betaine all can produce good adsorption with metallic iron; and can form more compact protective film in the metallic surface by naphthenic acid deutero-naphthene group; so the new type water-solubility inhibiter of being invented has excellent corrosion inhibition.It is at HCl-H
2S-H
2Corrosion inhibition rate to carbon steel in O (pH6.5～7.5) system is more than the twice of traditional 7019 water soluble rust inhibitors.
Cycloalkanoimide or naphthenic acid imidazoline can be feedstock production by naphthenic acid, and naphthenic acid through-stone oil refining by product, so the present invention except that the naphthenic acid resource can obtain the better utilised, also can reduce product cost.According to existing market, cycloalkanoimide betaine product comprehensive cost≤1.2 ten thousand yuan/ton, low than 7019 inhibiter.
(2) inhibiter and organic amine intermiscibility are good
The place of a key of the inhibiter that we invented has solved the problem of inhibition component decomposition failure under the strong basicity environment exactly.Because 7019 (ricinolic acid acid amide type) water soluble rust inhibitor is the long chain type organic inhibitor, under the strong basicity environment, long-chain can rupture decomposition and medicament was lost efficacy, so can not be compound with organic amine.We are the synthetic cycloalkanoimide betaine of raw material by the naphthenic acid that employing has highly alkaline-resisting heat-resistant stability, have solved this problem effectively.Applicating evaluating is the result show, the water soluble rust inhibitor that we invented, have the dissolved characteristics of not separating out, not having precipitation in 30%～40%NaOH solution or 20%～25% ethylenediamine solution and can keep higher corrosion inhibition for a long time, so in can being mixed with efficiently with organic amine etc. and inhibiter.
(3) technological operation flow process is greatly simplified
For in guaranteeing and anticorrosion ability, people are more and more to adopt and annotates organic amines and replace annotating ammoniacal liquor.Compare with inhibiter in the past, since the cycloalkanoimide betaine water soluble rust inhibitor can with organic amine be mixed with efficient in and inhibiter, so the technological operation flow process that refinery ordinary decompression column top condenser system adopts can greatly be simplified, promptly be reduced to " one takes off two notes " by original " one takes off three notes " (the ordinary decompression column top distillates line and annotates ammonia, annotates inhibiter, water filling).
(4) help the pH of system value stabilization and operation thereof
According to the titration curve of neutralization of Experiment of Analytical Chemistry as can be known, during ammonia water titration hydrochloric acid, the pH value has a hop between 4.0～8.5, and the pH value is difficult to be controlled at preferable neutral range; And adopting suitable organic amine, mutation range is very little, thereby can comparatively stably the pH value be controlled within the desired scope (pH6.5～7.5).The new type water-solubility inhibiter that we invented, since can with organic amine be composited efficient in and inhibiter, so when simplifying the technological operation flow process, also can make the pH of system value stabilization, be easy to control, no ammonium salt dirt, do not stop up, do not corrode, thereby help equipment " peace, steady, long, full, excellent " operation.
(5) easy for operation
Compare with traditional lipid acid, the naphthenic acid organic derivative has the heat-resisting and antioxygen stability of good low-temperature fluidity and height; Experimental result also shows that institute's synthetic cycloalkanoimide betaine product is for being easy to mobile reddish-brown transparent liquid, so manipulate more convenient.
In sum, preparation method of the present invention has simple, the convenience operation of technology, and raw materials cost used in the present invention is low, has improved the utilization ratio of resource and fund.Cycloalkanoimide betaine as the application of water soluble rust inhibitor especially the contriver propose first because the excellent corrosion inhibition that product of the present invention shows in this respect and with the good intermiscibility of organic amine, provide best mode for industrial utilization especially.
Embodiment
By cycloalkanoimide or the synthetic cycloalkanoimide betaine of tetrahydroglyoxaline
First mol ratio by contained sodium chloroacetate in contained cycloalkyl and the sodium chloroacetate solution in cycloalkanoimide or the tetrahydroglyoxaline is 1.0: 3.0～5.0 mode, in the cycloalkanoimide or tetrahydroglyoxaline that are cooled to below 110 ℃, stir and add sodium chloroacetate solution down, perhaps in the sodium chloroacetate solution that has configured, stir and add synthetic good bad alkanoic acid acid amides or tetrahydroglyoxaline down, temperature reaction gradually under agitation then, temperature is controlled to be 50～95 ℃.In the reaction process, by dripping the control of NaOH solution pH8～10, preferably pH8.5～9.5.When the reaction times reaches 5～8h, stops to drip NaOH solution and under the situation that the pH value does not descend, be 1.0: 0.5～3.0 mode again by the mol ratio of contained sodium chloroacetate in contained cycloalkyl and the sodium chloroacetate solution in cycloalkanoimide or the tetrahydroglyoxaline, stir adding sodium chloroacetate solution down, continue stirring and refluxing reaction 3～10h in 70～95 ℃ of temperature.In cycloalkanoimide or the tetrahydroglyoxaline in contained cycloalkyl and the sodium chloroacetate solution total mol ratio of contained sodium chloroacetate be 1.0: 4.8～7.0, total reaction time is 8～18h.When reaction was reached home, can obtain with the cycloalkanoimide betaine was the target product of main ingredient.At this moment, product is water-soluble fully, and can be dissolved in 30%～40%NaOH solution or 20%～25% ethylenediamine solution and do not separate out, do not have precipitation.At last, adopt the static steel weight-loss method, with 1000mg/LHCl-100～500mg/LH
2S solution (pH transfers to 6.5～7.5) is medium, carries out the corrosion inhibition evaluation of product to carbon steel.
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1
At 500mL stirring, dropping funnel, temperature being housed takes into account in the four-hole boiling flask of reflux condensing tube, adding just synthetic good and being cooled to 109 ℃ acid number is that 14.60mgKOH/g, amine value are the cycloalkanoimide 51.0g (amounting to 0.0995 mole of cycloalkyl) of 219.05mgKOH/g, it by the mol ratio of contained sodium chloroacetate in contained cycloalkyl and the sodium chloroacetate solution in the cycloalkanoimide 1.0: 3.0 mode, stir the 31.18% sodium chloroacetate solution 111.5g (wherein containing 0.2985 mole of sodium chloroacetate) that adding has down configured, temperature reaction gradually under agitation then.Speed of response is very fast during beginning, and temperature of reaction is controlled at 50～60 ℃ of lower scopes.Along with the carrying out of reaction, reacting liquid pH value descends, and continues for guaranteeing reaction, and by dripping 30%NaOH solution control reacting liquid pH value, the pH value is controlled to be 8.5～9.5 scopes.Simultaneously, along with the carrying out of reaction, speed of response can descend, and is the speed of response that guarantees to suit, that is guarantees the rate of addition of NaOH solution under pH value 8.5～9.5 scopes, and temperature of reaction raises gradually.At last, temperature of reaction rises to 85～90 ℃.When the reaction times reaches 5h, stop to drip NaOH solution half an hour and the pH value does not descend.At this moment, be 1.0: 1.8 mode again by the mol ratio of contained sodium chloroacetate in contained cycloalkyl and the sodium chloroacetate solution in the cycloalkanoimide, stir adding 31.18% sodium chloroacetate solution 67.0g (wherein containing 0.1794 mole of sodium chloroacetate) down, continue stirring and refluxing reaction 3h in 90～95 ℃ of temperature.This reaction, in the cycloalkanoimide in contained cycloalkyl and the sodium chloroacetate solution total mol ratio of contained sodium chloroacetate be 1.0: 4.8, total reaction time is 8h.When reaction was reached home, promptly obtaining with the cycloalkanoimide betaine was the target product I of main ingredient.Product I is water-soluble fully, and can be dissolved in 30%NaOH solution or 20% ethylenediamine solution and do not separate out, do not have precipitation.
Target product I physical index is as follows: outward appearance is the reddish-brown transparent liquid, pH8.7, density 1.15kg/L, solid content 40.35%.Adopt the static steel weight-loss method, carry out the corrosion inhibition evaluation of product, its evaluation result such as table 1 carbon steel.
Embodiment 2
At 500mL stirring, dropping funnel, temperature being housed takes into account in the four-hole boiling flask of reflux condensing tube, add the 38.20% sodium chloroacetate solution 142.9g (wherein containing 0.4684 mole of sodium chloroacetate) that has configured, it by the mol ratio of contained sodium chloroacetate in contained cycloalkyl and the sodium chloroacetate solution in the cycloalkanoimide 1.0: 4.0 mode, adding acid number under stirring is that 14.60mgKOH/g, amine value are the cycloalkanoimide 60.0g (amounting to 0.1171 mole of cycloalkyl) of 219.05mgKOH/g, temperature reaction gradually under agitation then.Speed of response is very fast during beginning, and temperature of reaction is controlled at 50～60 ℃ of lower scopes.Along with the carrying out of reaction, reacting liquid pH value descends, and continues for guaranteeing reaction, and by dripping 30%NaOH solution control reacting liquid pH value, the pH value is controlled to be 8.0～9.5 scopes.Simultaneously, along with the carrying out of reaction, speed of response can descend, and is the speed of response that guarantees to suit, that is guarantees the rate of addition of NaOH solution under pH value 8.0～9.5 scopes, and temperature of reaction raises gradually.At last, temperature of reaction rises to 85～90 ℃.When the reaction times reaches 8h, stop to drip NaOH solution half an hour and the pH value does not descend.At this moment, be 1.0: 3.0 mode again by the mol ratio of contained sodium chloroacetate in contained cycloalkyl and the sodium chloroacetate solution in the cycloalkanoimide, stir adding 38.20% sodium chloroacetate solution 107.2g (wherein containing 0.3513 mole of sodium chloroacetate) down, continue stirring and refluxing reaction 10h in 85～95 ℃ of temperature.This reaction, in the cycloalkanoimide in contained cycloalkyl and the sodium chloroacetate solution total mol ratio of contained sodium chloroacetate be 1.0: 7.0, total reaction time is 18h.When reaction was reached home, promptly obtaining with the cycloalkanoimide betaine was the target product II of main ingredient.Product II is water-soluble fully, and can be dissolved in 40%NaOH solution or 25% ethylenediamine solution and do not separate out, do not have precipitation.
Target product II physical index is as follows: outward appearance is the reddish-brown transparent liquid, pH9.0, density 1.19kg/L, solid content 45.30%.The static steel weight-loss method is to the corrosion inhibition evaluation result such as the table 1 of carbon steel.
Embodiment 3
At 500mL stirring, dropping funnel, temperature being housed takes into account in the four-hole boiling flask of reflux condensing tube, the 38.20% sodium chloroacetate solution 170.0g (wherein containing 0.5575 mole of sodium chloroacetate) that packs into earlier and configured, it by the mol ratio of contained sodium chloroacetate in contained cycloalkyl and the sodium chloroacetate solution in the naphthenic acid imidazoline 1.0: 5.0 mode, stirring slow down adding acid number is that 5.79mgKOH/g, amine value are the naphthenic acid imidazoline 52.0g (amounting to 0.1115 mole of cycloalkyl) of 240.63mgKOH/g, temperature reaction gradually under agitation then.Speed of response is very fast during beginning, and temperature of reaction is controlled at 50～60 ℃ of lower scopes.Along with the carrying out of reaction, reacting liquid pH value descends, and therefore, continues for guaranteeing reaction, and by dripping 30%NaOH solution control reacting liquid pH value, the pH value is controlled to be 8.5～10.Simultaneously, along with the carrying out of reaction, speed of response can descend, and is the speed of response that guarantees to suit, that is guarantees the rate of addition of NaOH solution under pH value 8.5～10 scopes, and temperature of reaction raises gradually.At last, temperature of reaction rises to 90～95 ℃.When the reaction times reaches 8h, stop to drip NaOH solution half an hour and the pH value does not descend.At this moment, be 1.0: 0.5 mode again by the mol ratio of contained sodium chloroacetate in contained cycloalkyl and the sodium chloroacetate solution in the naphthenic acid imidazoline, stir adding 38.20% sodium chloroacetate solution 17.0g (wherein containing 0.0558 mole of sodium chloroacetate) down, continue stirring and refluxing reaction 3h in 70～80 ℃ of temperature.This reaction, in the naphthenic acid imidazoline in contained cycloalkyl and the sodium chloroacetate solution total mol ratio of contained sodium chloroacetate be 1.0: 5.5, total reaction time is 11h.When reaction was reached home, promptly obtaining with the cycloalkanoimide betaine was the target product III of main ingredient.Product III is water-soluble fully, and can be dissolved in 30%NaOH solution or 20% ethylenediamine solution and do not separate out, do not have precipitation.
Target product III physical index is as follows: outward appearance is the reddish-brown transparent liquid, pH9.8, density 1.22kg/L, solid content 48.79%.The static steel weight-loss method is to the corrosion inhibition evaluation result such as the table 1～table 2 of carbon steel.
Embodiment 4
At 500mL stirring, dropping funnel, temperature being housed takes into account in the four-hole boiling flask of reflux condensing tube, adding acid number earlier is that 5.79mgKOH/g, amine value are the naphthenic acid imidazoline 52.0g (amounting to 0.1115 mole of cycloalkyl) of 240.63mgKOH/g, it by the mol ratio of contained sodium chloroacetate in contained cycloalkyl and the sodium chloroacetate solution in the naphthenic acid imidazoline 1.0: 3.0 mode, stir the 31.18% sodium chloroacetate solution 125.0g (wherein containing 0.3345 mole of sodium chloroacetate) that slow adding has down configured, temperature reaction gradually under agitation then.Speed of response is very fast during beginning, and temperature of reaction is controlled at 50～60 ℃ of lower scopes.Along with the carrying out of reaction, reacting liquid pH value descends, and continues for guaranteeing reaction, and by dripping 30%NaOH solution control reacting liquid pH value, the pH value is controlled to be 8.0～9.5 scopes.Simultaneously, along with the carrying out of reaction, speed of response can descend, and is the speed of response that guarantees to suit, that is guarantees the rate of addition of NaOH solution under pH value 8.0～9.5 scopes, and temperature of reaction raises gradually.At last, temperature of reaction rises to 90～95 ℃.When the reaction times reaches 6h, stop to drip NaOH solution half an hour and the pH value does not descend.At this moment, be 1.0: 3.0 mode again by the mol ratio of contained sodium chloroacetate in contained cycloalkyl and the sodium chloroacetate solution in the naphthenic acid imidazoline, stir adding 31.18% sodium chloroacetate solution 125.0g (wherein containing 0.3345 mole of sodium chloroacetate) down, continue stirring and refluxing reaction 10h in 85～95 ℃ of temperature.This reaction, in the naphthenic acid imidazoline in contained cycloalkyl and the sodium chloroacetate solution total mol ratio of contained sodium chloroacetate be 1.0: 6.0, total reaction time is 16h.When reaction was reached home, promptly obtaining with the cycloalkanoimide betaine was the target product IV of main ingredient.Product IV is water-soluble fully, and can be dissolved in 33%NaOH solution or 22% ethylenediamine solution and do not separate out, do not have precipitation.
Target product IV physical index is as follows: outward appearance is the reddish-brown transparent liquid, pH9.0, density 1.15kg/L, solid content 40.16%.The static steel weight-loss method is to the corrosion inhibition evaluation result such as the table 1 of carbon steel.
Embodiment 5
At 500mL stirring is housed, dropping funnel, temperature is taken into account in the four-hole boiling flask of reflux condensing tube, earlier adding acid number respectively is 14.60mgKOH/g, the amine value is that cycloalkanoimide 30.0g (amounting to 0.0585 mole of cycloalkyl) and the acid number of 219.05mgKOH/g is 5.79mgKOH/g, the amine value is the naphthenic acid imidazoline 25.0g (amounting to 0.0536 mole of cycloalkyl) of 240.63mgKOH/g, it by the mol ratio of contained sodium chloroacetate in contained total cycloalkyl and the sodium chloroacetate solution in cycloalkanoimide and the tetrahydroglyoxaline thereof 1.0: 4.0 mode, stir the 38.20% sodium chloroacetate solution 136.8g (wherein containing 0.4484 mole of sodium chloroacetate) that slow adding has down configured, temperature reaction gradually under agitation then.Speed of response is very fast during beginning, and temperature of reaction is controlled at 50～60 ℃ of lower scopes.Along with the carrying out of reaction, reacting liquid pH value descends, and continues for guaranteeing reaction, and by dripping 30%NaOH solution control reacting liquid pH value, the pH value is controlled to be 8～10 scopes.Simultaneously, along with the carrying out of reaction, speed of response can descend, and is the speed of response that guarantees to suit, that is guarantees the rate of addition of NaOH solution under pH value 8～10 scopes, and temperature of reaction raises gradually.At last, temperature of reaction rises to 90～95 ℃.When the reaction times reaches 7h, stop to drip NaOH solution half an hour and the pH value does not descend.At this moment, be 1.0: 2.5 mode again by the mol ratio of contained sodium chloroacetate in contained total cycloalkyl and the sodium chloroacetate solution in cycloalkanoimide and the tetrahydroglyoxaline thereof, stir adding 38.20% sodium chloroacetate solution 85.5g (wherein containing 0.280 mole of sodium chloroacetate) down, continue stirring and refluxing reaction 10h in 80～90 ℃ of temperature.This reaction, in cycloalkanoimide and the tetrahydroglyoxaline thereof in contained total cycloalkyl and the sodium chloroacetate solution total mol ratio of contained sodium chloroacetate be 1.0: 6.5, total reaction time is 17h.When reaction was reached home, promptly obtaining with the cycloalkanoimide betaine was the target product V of main ingredient.Product V is water-soluble fully, and can be dissolved in 36%NaOH solution or 23% ethylenediamine solution and do not separate out, do not have precipitation.
Target product V physical index is as follows: outward appearance is the reddish-brown transparent liquid, pH9.5, density 1.18kg/L, solid content 44.86%.The static steel weight-loss method is to the corrosion inhibition evaluation result such as the table 1 of carbon steel.
Embodiment 1～5 corrosion inhibition evaluation result
To above-mentioned synthetic cycloalkanoimide betaine product I～V, with 1000mg/LHCl-100～500mg/LH
2S solution (pH transfers to 6.5～7.5) is medium, adopts the static steel weight-loss method, has carried out its corrosion inhibition evaluation to carbon steel, and has done contrast with 7019 traditional water soluble rust inhibitors.Its result such as following table 1～table 2.
Table 1 1000mg/LHCl-100mg/LH
2In the S solution inhibiter I～V and with 7019 comparative evaluation result
| Inhibiter | Blank corrosion rate (mm/a) before the neutralization | Neutralization back blank corrosion rate (mm/a) | Inhibiter consumption (mg/L) | Dosing post-etching rate (mm/a) | Corrosion inhibition rate # (％) | Total corrosion inhibition rate # (％) |
| I II III IV V 7019 | 4.714 4.714 4.714 4.714 4.714 4.714 | 0.442 0.442 0.442 0.442 0.442 0.442 | 20 20 20 20 20 20 | 0.043 0.065 0.056 0.070 0.061 0.264 | 90.3 85.3 87.3 84.2 86.2 40.3 | 99.1 98.6 98.8 98.6 98.7 94.4 |
#Corrosion inhibition rate is meant with pH and transfers to the contrast of 6.5～7.5 blank; And total corrosion inhibition rate is meant and the not corresponding blank contrast of adjust pH.Down together.
Find out 1000mg/LHCl-100mg/LH by table 1
2In the S medium, when pH transfers to 6.5～7.5 and when adding inhibiter, traditional total corrosion inhibition rate of 7019 water soluble rust inhibitors is less than 95%, its corrosion of carbon steel rate is up to more than the 0.25mm/a after the dosing, and the cycloalkanoimide betaine inhibiter all reaches more than 98% total corrosion inhibition rate of carbon steel, and its corrosion of carbon steel rate all can be controlled in below the 0.1mm/a after the dosing.Transfer to the contrast of 6.5～7.5 blank with pH, 7019 water soluble rust inhibitors have only about 40% the corrosion inhibition rate of carbon steel, and the corrosion inhibition rate of cycloalkanoimide betaine inhibiter all reaches more than 80%, and the latter is more than the former twice to the corrosion inhibition rate of carbon steel.
Table 2 1000mg/LHCl-100～500mg/LH
2In the S solution inhibiter III and with 7019 comparative evaluation result
| System | Blank corrosion rate (mm/a) before the neutralization | Neutralization back blank corrosion rate (mm/a) | Inhibiter and consumption thereof (mg/L) | Dosing post-etching rate (mm/a) | Corrosion inhibition rate # (％) | Total corrosion inhibition rate # (％) |
| 1000mg/LHCl- 100mg/LH 2S 1000mg/LHCl- 300mg/LH 2S 1000mg/LHCl- 500mg/LH 2S | 4.714 4.944 5.516 | 0.442 0.392 0.369 | III，20 7019，20 III，20 7019，20 III，20 7019，20 | 0.056 0.264 0.076 0.271 0.097 0.277 | 87.3 40.3 80.6 30.9 73.7 24.9 | 98.8 94.4 98.5 94.5 98.2 95.0 |
Find out 1000mg/LHCl-100～500mg/LH by table 2
2In the S solution, it is nearly 95% that 7019 traditional water soluble rust inhibitors, total corrosion inhibition rate only reach, and its corrosion of carbon steel rate transfers to 6.5～7.5 corresponding blank contrast all up to more than the 0.25mm/a with pH after the dosing, and its corrosion inhibition rate to carbon steel has only 25%～40%; Therewith accordingly, the total corrosion inhibition rate of cycloalkanoimide betaine amphoteric ion type water soluble rust inhibitor is all more than 98%, can reach 73%～87% and transfer to 6.5～7.5 the correlated corrosion inhibition rate of corresponding blank with pH, than exceeding more than a times of 7019 water-soluble corrosion inhibitors, the corrosion of carbon steel rate all can be controlled in below the 0.1mm/a after the dosing.
Therefore, the cycloalkanoimide betaine amphoteric ion type water soluble rust inhibitor that we invented has excellent corrosion inhibition, and it is at HCl-H
2S-H
2Corrosion inhibition rate to carbon steel in the system of O (pH transfers to 6.5～7.5) is more than the twice of traditional 7019 water soluble rust inhibitors.
Attached: the static steel weight-loss method
The carbon steel lacing film of handling and weighing is fastened (be that the lacing film place wants pine, be not close to the lacing film surface, prevent to produce crevice corrosion) with anti-corrosion plastic ties, and immersion fills 1000mg/LHCl-100～500mg/LH fully
2S solution (pH transfers to 6.5～7.5) also adds in the wide-mouth or Erlenmeyer flask of inhibiter, and lacing film does not touch a bottle wall, and the suspension strop the other end is clamped fixing with bottle cap, static suspension 48～72h under the condition such as 85～90 ℃, oxygen barrier.Take out lacing film and handle also and weigh, do not add inhibiter pH and transfer under 6.5～7.5 blank and the same operation steps and do not add inhibiter and the not blank contrast of adjust pH respectively with under the same operation steps.By lacing film weightlessness, calculate corrosion inhibition rate and total corrosion inhibition rate respectively.
Claims (7)
1, the preparation method of cycloalkanoimide betaine, it is characterized in that: cycloalkanoimide or naphthenic acid imidazoline or both mixtures and sodium chloroacetate reaction, in the reaction in cycloalkanoimide or the tetrahydroglyoxaline in contained cycloalkyl and the sodium chloroacetate solution total mol ratio of contained sodium chloroacetate be 1.0: 4.8～7.0,50～95 ℃ of controlled temperature, pH8～10 scope internal reactions, 8～18h, promptly synthetic cycloalkanoimide betaine.
2, the preparation method of cycloalkanoimide betaine according to claim 1 is characterized in that: described cycloalkanoimide or naphthenic acid imidazoline are to be generated through the condensation dehydration by naphthenic acid and diethylenetriamine.
3, the preparation method of cycloalkanoimide betaine according to claim 1, it is characterized in that: cycloalkanoimide or naphthenic acid imidazoline or both mixtures and sodium chloroacetate reaction, carry out in two steps, mol ratio by contained sodium chloroacetate in contained cycloalkyl and the sodium chloroacetate solution in cycloalkanoimide or the tetrahydroglyoxaline is 1.0: 3.0～5.0 temperature reactions gradually under agitation earlier, reach 5～8h when the reaction times, under the situation that the pH value does not descend, be 1.0: 0.5～3.0 mode again by the mol ratio of contained sodium chloroacetate in contained cycloalkyl and the sodium chloroacetate solution in cycloalkanoimide or the tetrahydroglyoxaline, stir and add sodium chloroacetate solution down, stirring and refluxing reaction 3～10h.
4, according to the preparation method of claim 1 or 3 described cycloalkanoimide betaines, it is characterized in that: pH is 8.5～9.5 in the reaction process.
5, the preparation method of cycloalkanoimide betaine according to claim 2 is characterized in that: described naphthenic acid is acid content 〉=85% massfraction, thick acid number 〉=185mgKOH/g.
6, the application of cycloalkanoimide betaine is characterized in that: cycloalkanoimide betaine is applied to HCl-H
2S-H
2The O system is as water soluble rust inhibitor.
7, the application of cycloalkanoimide betaine according to claim 6 is characterized in that: cycloalkanoimide betaine is applied to refinery ordinary decompression column top condenser system, as water soluble rust inhibitor.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102205214A (en) * | 2011-04-28 | 2011-10-05 | 孙安顺 | N,N-dialkyl propanamide fatty alkyl betaine amphoteric surfactant, preparation method and application thereof in tertiary recovery |
| CN106244126A (en) * | 2016-07-03 | 2016-12-21 | 青岛大学 | A kind of method preparing heavy crude thinner for raw material with aphthenic acids |
| CN106518770A (en) * | 2016-09-30 | 2017-03-22 | 宿迁明江化工有限公司 | Preparation method of novel water soluble and non-salt soluble imidazoline corrosion inhibitor and application |
-
2006
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102205214A (en) * | 2011-04-28 | 2011-10-05 | 孙安顺 | N,N-dialkyl propanamide fatty alkyl betaine amphoteric surfactant, preparation method and application thereof in tertiary recovery |
| CN102205214B (en) * | 2011-04-28 | 2014-07-30 | 孙安顺 | N,N-dialkyl propanamide fatty alkyl betaine amphoteric surfactant, preparation method and application thereof in tertiary recovery |
| CN106244126A (en) * | 2016-07-03 | 2016-12-21 | 青岛大学 | A kind of method preparing heavy crude thinner for raw material with aphthenic acids |
| CN106244126B (en) * | 2016-07-03 | 2019-01-25 | 青岛大学 | A method of heavy crude thinner is prepared by raw material of aphthenic acids |
| CN106518770A (en) * | 2016-09-30 | 2017-03-22 | 宿迁明江化工有限公司 | Preparation method of novel water soluble and non-salt soluble imidazoline corrosion inhibitor and application |
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