CN1273643C - Preparation process for gas phase corosion inhibitor of morpholine adrivative - Google Patents
Preparation process for gas phase corosion inhibitor of morpholine adrivative Download PDFInfo
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- CN1273643C CN1273643C CNB2004100169209A CN200410016920A CN1273643C CN 1273643 C CN1273643 C CN 1273643C CN B2004100169209 A CNB2004100169209 A CN B2004100169209A CN 200410016920 A CN200410016920 A CN 200410016920A CN 1273643 C CN1273643 C CN 1273643C
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Abstract
The present invention relates to a preparation method for a vapor phase inhibitor of morpholine derivatives, which comprises the steps that after morpholine and secondary amine are mixed, a formaldehyde solution or an acetaldehyde solution is added to the mixture in drops; the mixture is homogeneously mixed and reacts; then, the mixed solution and fatty acid or benzoic acid are treated by acid curing reaction, stirred and filtered to acquire a target product. The present invention has the advantages of easy acquirement and low price of used raw materials, such as morpholine, secondary amine, formaldehyde or acetaldehyde, fatty acid and benzoic acid and is suitable for large-scale industrial production. The present invention only has three relatively simple steps for preparing the target product, all reaction completed under the conventional condition and low requirements for equipment and further reduces the cost of the industrial preparation of the vapor phase inhibitor of morpholine derivatives. In addition, various corrosion resistant experiments indicate that the target product of the vapor phase inhibitor of morpholine derivatives, which is prepared by the present invention, has good corrosion inhibition performance.
Description
Technical field
The present invention relates to a kind of preparation has the alkyl that is replaced by heteroatoms, is connected in the method for the compound on the theheterocyclic nitrogen atom, particularly relates to a kind of method for preparing the morpholine derivative vapour-phase inhibitor.
Background technology
Atomospheric corrosion is to have the most a kind of corrosion, and the loss that is caused accounts for the over half of whole corrosion loss, and that the vapor phase corrosion inhibitor technology has is easy to use, clean, the characteristics of cleaning, is an important directions of present weather-resistant technical development.Morpholine and morpholine derivative vapour-phase inhibitor be not because contain the concern that environmentally hazardous nitrite especially is subjected to the scientific research personnel.Morpholine is industrial important cyclammonium, have nitrogen oxygen heterocyclic characteristics, in the 1980's, the Texaco lnc. of the U.S. succeeds in developing the glycol ether catalytic ammoniation and prepares the morpholine novel process, glycol ether is the byproduct of oxyethane hydrolysis preparing ethylene glycol, and ethylene glycol is the main raw material of synthetic terylene (PET) material.China also builds up 700 tons of/year full scale plants that many cover glycol ether catalytic ammoniations prepare morpholine in nineteen ninety in succession for the later stage, along with the China's Petrochemical number overlaps being constructed and put into operation that 200,000 tons/year PET (terylene) device and supporting large-scale EC (ethylene glycol) install, the glycol ether quantity of by-product can increase, make the morpholine raw material sufficient more, will lay a good foundation for the development of the fine chemical product in morpholine downstream.Morpholine is one of inhibiter of adopting the earliest of steam and condensate system, has low toxicity, and morpholine and derivative thereof also can be widely used in corrosion of metal and protection.South african patent ZA9406477 discloses the morpholine derivative preparation method as a kind of vapour-phase inhibitor, it is characterized in that morpholine and secondary amine effect generate morpholine Mannich alkali, wherein secondary amine comprises dimethyl amine, di-n-butyl amine, diisopropylamine, dicyclohexylamine, diphenylamine etc., but this invention product be a kind of oily liquids, use very inconvenient.
Summary of the invention
The objective of the invention is on the basis of prior art for preparing morpholine Mannich alkali, a kind of method for preparing the morpholine derivative vapour-phase inhibitor is provided, generate morpholine derivative vapour-phase inhibitor solid by the acid cure reaction, the morpholine derivative of this method preparation can improve the area coverage of vapour-phase inhibitor in the metallic surface, strengthens its vapor phase corrosion inhibitor ability.
To achieve these goals, the technical scheme that the present invention takes: a kind of preparation method of morpholine derivative vapour-phase inhibitor, it is characterized in that, method is specially: the morpholine and the secondary amine mixing that with mol ratio are 1: 0.5～1: 2, in 40～50 ℃ of downhill reaction liquid, drip formaldehyde or acetaldehyde solution, the mol ratio of control morpholine and formaldehyde or acetaldehyde is 1: 1.2～1: 1.5, homogeneous reaction 2～4 hours; Add lipid acid or phenylformic acid in reaction solution, control morpholine and lipid acid or benzoic mol ratio are 1: 1.5～1: 2, add 50ml～80ml deionized water simultaneously, stir 2 hours to 4 hours; Filtration obtains morpholine derivative vapour-phase inhibitor solid; Described secondary amine is selected from dimethyl amine, di-n-butyl amine, diisopropylamine, dicyclohexylamine or diphenylamine; Described lipid acid is selected from the mixture of capric acid or Succinic Acid or capric acid and Succinic Acid; Described phenylformic acid is selected from cresotinic acid, Whitfield's ointment or tert-butylbenzene formic acid, or the mixture of above-mentioned two or more component of phenylformic acid.
Beneficial effect of the present invention is that described method raw material is easy to get, low price, is fit to large-scale industrial production.Its step is few, the reaction simple, and all reactions all can be finished under normal condition, to equipment require low.Can directly make target product by described method---morpholine derivative vapour-phase inhibitor solid.Every experiment to target product shows that the morpholine derivative vapour-phase inhibitor that the present invention prepares has good corrosion inhibition.
Description of drawings
Fig. 1 is the polarization curve of carbon steel electrode in simulation atomospheric corrosion water;
Fig. 2 is the electrochemical impedance Nyquist figure of carbon steel electrode in solution.
Embodiment
Below in conjunction with accompanying drawing the present invention is further specifically described: a kind of preparation method of morpholine derivative vapour-phase inhibitor, its step comprises: the morpholine and the secondary amine that (a) with mol ratio are 1: 0.5～1: 2 mix, and described secondary amine is selected from any one in dimethyl amine, di-n-butyl amine, diisopropylamine, dicyclohexylamine, the diphenylamine; (b) in 40～50 ℃ of downhill reaction liquid, drip formaldehyde or acetaldehyde solution, homogeneous reaction 2～4 hours, the mol ratio of control morpholine and formaldehyde or acetaldehyde is 1: 1.2～1: 1.5; (c) in reaction solution, add lipid acid or phenylformic acid, control morpholine and lipid acid or benzoic mol ratio are 1: 1.5～1: 2, agitation and filtration obtains morpholine derivative vapour-phase inhibitor solid, described lipid acid is selected from the mixture of capric acid or Succinic Acid or capric acid and Succinic Acid, described phenylformic acid is selected from any one in cresotinic acid, Whitfield's ointment, the tert-butylbenzene formic acid, or the mixture of above-mentioned two or more component of phenylformic acid.
The present invention further specifies by the following examples.
Embodiment 1
Get morpholine 1mol, the Diisopropylamine of itself and 1.2mol～1.5mol is mixed, drip the formaldehyde solution of 1mol～1.5mol, the phenylformic acid that adds 1.5mol to above-mentioned mixed solution, add 50ml～80ml deionized water simultaneously, stirred 2 hours to 4 hours, filter the 150g pressed powder, be the morpholine derivative vapour-phase inhibitor, be called inhibiter 1.
Embodiment 2
Get morpholine 1mol, the Di-n-Butyl Amine of itself and 1.2mol～1.5mol is mixed, be added dropwise to the formaldehyde solution of 1mol～1.5mol, the Whitfield's ointment that adds 1.5mol to above-mentioned mixed solution, add 50ml～80ml deionized water simultaneously, stirred 2 hours to 4 hours, filter the 130g pressed powder, be the morpholine derivative vapour-phase inhibitor, be called inhibiter 2.
Embodiment 3
Get morpholine 1mol, the dicyclohexyl amine of itself and 1mol～1.5mol is mixed, be added dropwise to the formaldehyde solution of 1mol～1.5mol, the phenylformic acid that adds 1.5mol to above-mentioned mixed solution, add 50ml～80ml deionized water simultaneously, stirred 2 hours to 4 hours, filter the 140g pressed powder, be the morpholine derivative vapour-phase inhibitor, be called inhibiter 3.
Embodiment 4
Embodiment 1,2,3 gained target products are carried out volatile rust prevention differentiation test: put into the weighing bottle that fills the 1g vapor phase inhibitor at Erlenmeyer flask, A3 steel, brass and the aluminium test piece of 50mm * 25mm * 2mm are hung into, the saturated 2h of constant temperature in 50 ℃ of baking ovens.Do blank test simultaneously, inject the distilled water of 15ml then with transfer pipet, place thermostat container to keep 50 ℃ of temperature, heat 8h every day, every 24h is an one-period, carries out 7 periodic tests altogether, and observe once every day, the time that the record corrosion occurs.Wipe the corrosion product on test piece surface after the off-test with rubber, weigh, calculate corrosion rate, the results are shown in Table 1.
Table 1 volatile rust prevention differentiation test-results
| Test piece | Experimental period | Corrosion rate (mg/m 2.h) | ||||
| Inhibiter 1 | Inhibiter 2 | Inhibiter 3 | Inhibiter 1 | Inhibiter 2 | Inhibiter 3 | |
| Carbon steel brass aluminium | 7 cycles of 7 cycles, 7 cycles | 7 cycles of 7 cycles, 7 cycles | 7 cycles of 7 cycles, 7 cycles | 1.78 - - | 1.56 - - | 1.98 - - |
Embodiment 5
Embodiment 1,2,3 gained target products are carried out vapor inhibitability test: the good test piece concave surface of will polishing is pressed in No. 9 soft rubber balls, test is showed out part and is no more than 3mm, the dehydrated alcohol degreasing of test piece test face after press-fiting, hot blast drying, experimental installation is with reference to Machinery Ministry standard JB/T 6071-92.Inject 35% aqueous glycerin solution 10ml in the wide-necked bottle of 1000ml bottom, adjusting relative humidity is 90%, is even spreading 0.5g vapour-phase inhibitor in the vessel of 40 ± 2mm at diameter; Testing apparatus placed under 20 ± 2 ℃ the temperature, in aluminum pipe, fill with temperature behind the 20h and be 2.0 ± 0.5 ℃ frozen water, keep down pouring out behind the 3h at 20 ± 2 ℃ again, take off the cotton sample of cleaning of paper, dry up the back and check that there is non-corroding on the test piece surface with what be soaked with dehydrated alcohol.The result shows that the morpholine derivative vapour-phase inhibitor that the present invention prepares can make metal testing plate that corrosion does not take place.
Embodiment 6
Embodiment 1,2,3 gained target products are sealed up for safekeeping experiment, bottom at the moisture eliminator of diameter 24cm adds 20ml distilled water, the 0.5g vapour-phase inhibitor is placed small beaker and puts into moisture eliminator, put into materials such as A3 steel, copper, brass, fine aluminium, aluminium alloy in the moisture eliminator, the time of sealing up for safekeeping is 60d, seals result of experiment up for safekeeping and sees Table 2.
Table 2 is sealed test-results up for safekeeping
| Rust-preventive agent | The A3 steel | Copper | Brass | Fine aluminium | Aluminium alloy |
| Blank inhibiter 1 inhibiter 2 inhibiter 3 | Serious rusty surface is bright and clean substantially than glossy surface than glossy surface, and imperceptible erosion point is arranged | ⊙ ○ ○ ○ | ⊙ ○ ○ ○ | ⊙ ○ ⊙ ○ | ⊙ ⊙ ⊙ ⊙ |
⊙ represents variable color or a small amount of rust, the atomic variable color of zero representative.
Embodiment 7
Embodiment 3 gained target products are carried out electrochemical research.Atomospheric corrosion belongs to the most a kind of corrosion form, and its essence also is electrochemical process, is not in electrolytic solution with the development of other electrochemical process different is corrosion process, but in one deck electrolytic thin-membrane of metallic surface.By polarization curve and electrochemical impedance measurement Research the morpholine derivative vapour-phase inhibitor of the present invention preparation to the influence of carbon steel electrode electrochemical behavior.
Electrochemical measurement adopts three electrode forms, and adopting biliquid to connect saturated calomel electrode is reference electrode, and Pt is a supporting electrode.The carbon steel electrode that Resins, epoxy seals admittedly is a working electrode, and exposed area is 0.7cm
2, polish step by step through 1#-6# abrasive paper for metallograph (Shanghai sand paper factory) in the surface, the alcohol degreasing, and deionized water rinsing is clean.Polarization curve is measured and is adopted EG﹠amp; The GPARCMODEL283 potentiostat is measured automatically, and data processing adopts EG﹠amp; G M352 corrosion analysis software.Sweep velocity is 1mV/s, and scanning start-stop current potential is-800mV～700mV.The electrochemical impedance experiment is carried out under room temperature and corrosion potential, and test impedance frequency scope is 0.01～105Hz, and ac-excited signal amplitude is 5mv.Adopt ASTM simulation atomospheric corrosion water (0.1g/L NaCl, 0.1g/L NaHCO
3, 0.1g/L Na
2SO
4) be supporting electrolyte.Given current potential is the current potential with respect to saturated calomel electrode (SCE) in the specification sheets.From polarization curve as can be seen, add the corrosion potential that makes carbon steel electrode behind the inhibiter 3 from-550mV is negative to move on to-740mV, the restraining effect of 3 pairs of carbon steel electrode cathodic polarizations of inhibiter electric current is bigger, its inhibition mechanism belongs to cathodic polarization type vapor phase inhibitor.It is generally acknowledged that organic amine can play corrosion inhibition by the chemisorption of lone-pair electron on the N atom and the physical adsorption of formation quaternary ammonium salt positive ion; inhibiter 3 vapor phase inhibitor intramolecularly contain heteroatomss such as a plurality of nitrogen and oxygen; can polycentric adsorption take place with the metallic surface; strengthened adsorptive power in the metallic surface; thereby show the better protecting performance, as shown in Figure 1.
As shown in Figure 2, the electrochemical impedance Nyquist figure of carbon steel electrode in solution wherein 1 represent blankly, and 2 to represent concentration be the inhibiter 3 that 10mg/L is prepared by embodiment 3.As can be seen from Figure 2; electrochemical impedance at solution medium carbon steel electrode is a capacitive reactance arc at high band; obviously shrink at the low-frequency range impedance spectrum; add after the inhibiter; the impedance spectrum of carbon steel electrode is similar with the impedance spectrum of blank electrode, shows as a capacitive reactance arc, and the more blank electrode capacitive reactance of the radius of its capacitive reactance arc arc radius increases; have bigger resistance value, this morpholine derivative vapour-phase inhibitor that shows that the present invention prepares has provide protection to carbon steel electrode.
Claims (1)
1. the preparation method of a morpholine derivative vapour-phase inhibitor, it is characterized in that, method is specially: the morpholine and the secondary amine mixing that with mol ratio are 1: 0.5～1: 2, in 40～50 ℃ of downhill reaction liquid, drip formaldehyde or acetaldehyde solution, the mol ratio of control morpholine and formaldehyde or acetaldehyde is 1: 1.2～1: 1.5, homogeneous reaction 2～4 hours; Add lipid acid or phenylformic acid in reaction solution, control morpholine and lipid acid or benzoic mol ratio are 1: 1.5～1: 2, add 50ml～80ml deionized water simultaneously, stir 2 hours to 4 hours; Filtration obtains morpholine derivative vapour-phase inhibitor solid; Described secondary amine is selected from dimethyl amine, di-n-butyl amine, diisopropylamine, dicyclohexylamine or diphenylamine; Described lipid acid is selected from the mixture of capric acid or Succinic Acid or capric acid and Succinic Acid; Described phenylformic acid is selected from cresotinic acid, Whitfield's ointment or tert-butylbenzene formic acid, or the mixture of above-mentioned two or more component of phenylformic acid.
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| CN100381637C (en) * | 2006-01-06 | 2008-04-16 | 华南理工大学 | Preparation method of thermostable paper cushion for protecting stainless steel |
| CN100383337C (en) * | 2006-01-06 | 2008-04-23 | 华南理工大学 | Preparation method of paper cushion for protecting stainless steel |
| CN103103535B (en) * | 2012-11-13 | 2015-11-18 | 铜陵祥云消防科技有限责任公司 | A kind of metal antirusting agent |
| CN104633447A (en) * | 2014-12-07 | 2015-05-20 | 中国石油化工股份有限公司 | Nitrogen-contained type natural gas drag-reduction agent and synthesis method of nitrogen-contained type natural gas drag-reduction agent |
| CN104633448A (en) * | 2014-12-07 | 2015-05-20 | 中国石油化工股份有限公司 | Nitrogenous natural gas drag reducing agent and synthetic method thereof |
| CN108642497B (en) * | 2018-05-17 | 2019-11-15 | 杭州意能电力技术有限公司 | A kind of Shut-down Protection method of vapour phase inhibitor, preparation method and therrmodynamic system |
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