CN102650056A - Composite corrosion inhibitor for butyl rubber chloromethane glycol dehydration and regeneration system - Google Patents
Composite corrosion inhibitor for butyl rubber chloromethane glycol dehydration and regeneration system Download PDFInfo
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- CN102650056A CN102650056A CN2012101344801A CN201210134480A CN102650056A CN 102650056 A CN102650056 A CN 102650056A CN 2012101344801 A CN2012101344801 A CN 2012101344801A CN 201210134480 A CN201210134480 A CN 201210134480A CN 102650056 A CN102650056 A CN 102650056A
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Abstract
The invention relates to a composite corrosion inhibitor for a butyl rubber chloromethane glycol dehydration and regeneration system. The composite corrosion inhibitor comprises at least two compounds, wherein the compounds are selected from heterocyclic compounds; the heterocyclic compounds are selected from nitrogen heterocyclic compounds and sulfur heterocyclic compounds, preferably the compounds are all selected from the nitrogen heterocyclic compounds, or the nitrogen heterocyclic compounds and the sulfur heterocyclic compounds; the nitrogen heterocyclic compounds are selected from a pyrrole compound, an imidazole compound, a pyrazol compound, a pyridine compound, a pyrazine compound, a miazine compound, a quinoline compound, an isoquinoline compound and a benzotriazole compound; and the sulfur heterocyclic compounds are thiazole compounds. According to the composite corrosion inhibitor, the problem of system corrosion due to accumulation of hydrochloric acid in the chloromethane glycol dehydration system can be effectively solved.
Description
The application is 200910087787.9 divides an application, and its applying date is: on 06 26th, 2009, denomination of invention was: a kind of composite corrosion inhibitor of butyl rubber chloromethane glycol dehydrating regeneration system.
Technical field
The present invention relates to a kind of composite corrosion inhibitor of butyl rubber chloromethane glycol dehydrating regeneration system; When relating in particular to a kind of emphasis and solving the butyl rubber production equipment and remove in the methyl chloride minor amount of water, because methyl chloride hydrolysis generation hydrochloric acid in glycol causes system's corroding method with glycol.
Background technology
The production technique of butyl rubber generally is to adopt methyl chloride to produce as the slurry process low temperature polymerization of solvent; With high-purity isobutylene, isoprene is raw material; Use high-purity chloro methane to be thinner, the employing aluminum chloride is a catalyzer, about-100 ℃, carries out the cationic copolymerization reaction; Polymerisate is suspended in and forms slurry in the thinner, so be called slurry process.
In the butyl rubber production process; Participate in the solvent methyl chloride of reaction and react unconverted monomer iso-butylene and isoprene need dehydrate refining reuse afterwards; Usually the dry refining alumina desiccant that adopts, but owing to be periodical operation, the aluminum oxide life cycle is short; Regeneration is frequent, and labour intensity is big.Cause fluctuation of service, the methyl chloride loss is big, and environmental pollution is serious, and aluminum oxide is short work-ing life, has a strong impact on the quality of butyl rubber product and the stability of production, and production cost is high.
Absorb after the minor amount of water in the methyl chloride with glycol and can solve the problem that single alumina desiccant produces with the dry combination process of alumina desiccant again; This combination process can delay the recovery time of alumina desiccant greatly, generally can extend to 5 days even longer.
U.S. Pat 3005808 discloses and has prolonged the alumina desiccant method in work-ing life, removes quantity many water and is handling with glycol through before the alumina desiccant through compression and cooling.In glycol absorber, absorb the water in the methyl chloride with glycol, the glycol that comes out in the absorption tower contains a large amount of water and dissolved methyl chloride, after through the glycol reclamation system it being regenerated glycol is back to glycol absorber.
English Patent GB1275574 discloses the renovation process of the glycol siccative that is used for butyl rubber production; The methyl chloride thinner contacts and obtains drying with glycol in the absorption tower, it is that 45-85F, pressure are the flashing tower of 15-25psia that the glycol after the suction gets into temperature from the absorption tower.Volatile part is flashed away; Moisture liquid glycol logistics with other impurity enters into counter-current tower (self-refluxing tower) by the flashing tower bottom; Get into reboiler through glycol mixed solution at the bottom of the tower behind the counter-current tower; The gas that forms after boiling is again partly got back to counter-current tower and moisture and liquid glycol adverse currents other impurity, and the glycol after liquid portion is promptly regenerated takes out from the reboiler bottom.
Above-mentioned two patents are being that siccative is when removing the water in the thinner methyl chloride that butyl rubber produces with the glycol; The glycol that comes out from glycol absorber need pass through flashing tower, regenerator column (or counter-current tower), reboiler etc.; To remove water and other impurity in the glycol; Remove and to anhydrate and the glycol of other impurity is recycled to glycol absorber, send into water to glycol in the glycol absorber dechlorination methane from glycol and after above-mentioned a series of processing, be recycled to glycol absorber and be called chloromethane glycol dehydrating regeneration system, this chloromethane glycol dehydrating regeneration system is in secular running; Equipment corrosion is serious, finds mainly to contain in the on-the-spot triglycol through detecting: Fe
2+, Fe
3+, H
+And Cl
-Plasma, each ionic source and mechanism of corrosion are:
The hydrolysis reaction of methyl chloride under hot conditions: CH
3Cl+H
2O=CH
3OH+HCl
FeCl
2Source and balance: FeCl
2Mainly generated by the hcl corrosion carbon steel, its solubleness in water is very big, is the main existence form of cl ions, high density F eCl under hot conditions
2Hydrolysis possibly take place generate FeO and HCl accelerated corrosion, FeCl under aerobic conditions in addition
2Possibly be oxidized to FeCl
3
The reaction of hcl corrosion carbon steel: Fe+2HCl=FeCl
2+ H
2
FeCl
2Hydrolysis reaction under hot conditions: FeCl
2+ H
2O=FeO+2HCl
FeCl
3Source and balance: FeCl under aerobic conditions
2Possibly be oxidized to FeCl
3, because FeCl
3Oxidisability more intense, it can be rapidly and the iron reaction generate FeCl
2So, FeCl
3Exist concentration not high, but that the effect of corrosion of carbon steel is quickened in its catalysis is very big, correlated response is following:
4FeCl
2+4HCl+O
2＝4FeCl
3+2H
2O
Fe+2FeCl
3＝3FeCl
2
In addition, the hydrolysis of methyl chloride in glycol is a running balance, under acidic conditions; Methyl chloride is after the glycol hydrolysis, and the cl ions of system can remain on a level, as at 70 ℃; The equilibrium concentration of cl ions is about 400mg/L, and temperature perchlormethane hydrolysis rate more is fast more.Certainly in the system because hydrogen ion and cl ions existence are arranged; The corrosion of system is difficult to avoid; Corrosion can be broken the methyl chloride hydrolysising balance, owing to added composite corrosion inhibitor in the system, the methyl chloride hydrolysising balance is broken not obvious; The increasing amount of cl ions and iron ion can make cl ions and iron ion remain on certain level through the glycol solution of replacing in a small amount of system; If but do not have composite corrosion inhibitor, because hydrochloric acid and carbon steel reaction are being carried out always, therefore, the hydrolysising balance of methyl chloride would just be broken always, causes cl ions in the system, iron ion raising always.
Summary of the invention
In order to solve the etching problem in the glycol dehydration regeneration system rapidly, the contriver discovers: the butyl rubber device adds composite corrosion inhibitor when removing in the methyl chloride minor amount of water with glycol, can solve the etching problem of this system effectively.
The object of the present invention is to provide a kind of composite corrosion inhibitor of butyl rubber chloromethane glycol dehydrating regeneration system, can solve the salt acid accumulation effectively and bring system's etching problem, thereby suppress the corrosion in the glycol dehydration regeneration system rapidly.
For achieving the above object, the invention provides a kind of composite corrosion inhibitor of butyl rubber chloromethane glycol dehydration system, comprising at least two kinds of compounds, be selected from heterogeneous ring compound, said heterogeneous ring compound is selected from nitrogen-containing heterocycle compound and sulfur heterocyclic compound.At least two kinds of compounds of the present invention are preferably all selected from the nitrogen heterogeneous ring compound or from two compounds-promptly from nitrogen-containing heterocycle compound and sulfur heterocyclic compound, are selected.
Nitrogen-containing heterocycle compound of the present invention is selected from azoles, glyoxaline compound, pyrazole compound, pyridine compounds and their, pyrazine compounds, pyrimidines, quinolines, isoquinoline compound and benzotriazole compounds; Sulfur heterocyclic compound is a thiazole compound.
Azoles of the present invention is selected from 2,5-pyrrolidine-diones, benzopyrrole and dibenzopyrrole.
Glyoxaline compound of the present invention is selected from 2-ethyl-4-methylimidazole, benzoglyoxaline, N-benzyl imidazole, glyoxal ethyline, 4-methylimidazole and 2,4-methylimidazole.
Pyrazole compound of the present invention is selected from 3,5-diphenylpypazole, 3-methyl isophthalic acid-phenyl-5-pyrazolone, 1,5 dimethyl--2-phenyl-4-amino-3-pyrazolone and 1-phenyl-5-amino-pyrazol.
Pyridine compounds and their of the present invention is selected from 2-benzyl-pyridine, 3-benzyl-pyridine, 4-benzyl-pyridine, 2-phenylpyridine, 3-phenylpyridine, 4-phenylpyridine, bromohexadecane yl pyridines, chloro-hexadecane yl pyridines and dipyridyl.
Pyrazine compounds of the present invention is selected from 2,3-dihydroxyl pyrazine and 2-hydroxyl pyrazine.
Pyrimidines of the present invention is selected from 2-amino-5-methoxy pyrimidine, 6-amino-2,4-dimethyl pyrimidine, 2-amino-4-methoxyl group-6-methylpyrimidine, 4-amino-2,6-dimethoxypyridin and flucytosine.
Quinolines of the present invention is selected from 3-bromoquinoline, 4-toluquinoline, 5-toluquinoline, 6-quinolylamine, 3-ethyl quinoline, 3,8-dimethyl quinoline, 2,4-dimethyl quinoline and 5,7-dichloro-8-hydroxyquinoline.
Isoquinoline compound of the present invention is selected from bromo isoquinoline 99.9 and 5-nitroisoquinoline.
Benzotriazole compounds of the present invention is selected from benzotriazole and Methylbenzotriazole (sodium).
Thiazole compound of the present invention is selected from 2-mercaptobenzothiazole, thiazolamine, 4-methyl-thiazolamine and 2-aminobenzothiazole.
When composite corrosion inhibitor of the present invention was used for the glycol dehydration regeneration system rapidly, the concentration summation of heterogeneous ring compound was: the 3000-50000mg/L glycol is preferably the 15000-35000mg/L glycol.
In butyl rubber chloromethane glycol dehydrating regeneration system, add composite corrosion inhibitor, can reduce the erosion rate of system greatly, efficiently solve the corrosion that the salt acid accumulation produces in the system.
Embodiment
Following embodiment will help to explain the present invention, but not limit to its scope.
Corrosion experiment adopts classical weight-loss method, adopts 20# carbon steel lacing film, and specification is 40 * 13 * 2mm, and surface-area is 12cm
2Lacing film (under normal pressure) in 160 ℃ glycol corrosive medium soaks 4h, directly cleans with absolute ethyl alcohol before the immersion, need not de-oiling (producer had done oil removal treatment), and drying is placed in the moisture eliminator subsequent use.With the accurate weighing lacing film of ten thousand/balance weight, the corrosion back is cleaned with resistanceization hydrochloric acid (10%HCl+0.5% hexamethylenetetramine) earlier, removes the corrosion product on surface before the experiment; Use deionized water rinsing then, remove the hydrochloric acid that remains in the metallic surface, clean with absolute ethyl alcohol at last; Remove surface-moisture; Dry up and be placed in the moisture eliminator, treat it and weigh, use computes.
v＝87600*M/(7.85*S*H)
V-erosion rate wherein, mm/a
The quality that the M-lacing film reduces, g
The surface-area of S-lacing film, 12cm
2
The H-etching time, h
Embodiment 1
In triglycol solution, adding concentrated hydrochloric acid, to make the cl ions in the triglycol solution be 6000mg/L; Add 2-mercaptobenzothiazole, N-benzyl imidazole and 4-benzyl-pyridine more respectively; The concentration that makes it in triglycol is respectively 2000mg/L, 8000mg/L, 10000mg/L; Be warmed up to 160 ℃, survey erosion rate behind the 4h.
Embodiment 2
In triglycol solution, adding concentrated hydrochloric acid, to make the cl ions in the triglycol solution be 6000mg/L; Add 2-ethyl-4-methylimidazole, 2-benzyl-pyridine and benzopyrrole more respectively; The concentration that makes it in triglycol is respectively 3000mg/L, 5000mg/L, 2000mg/L; Be warmed up to 160 ℃, survey erosion rate behind the 4h.
Embodiment 3
In triglycol solution, adding concentrated hydrochloric acid, to make the cl ions in the triglycol solution be 6000mg/L; Add 3 respectively again, 5-diphenylpypazole, bromohexadecane yl pyridines, the concentration that makes it in triglycol is respectively 5000mg/L, 30000mg/L; Be warmed up to 160 ℃, survey erosion rate behind the 4h.
Embodiment 4
In triglycol solution, adding concentrated hydrochloric acid, to make the cl ions in the triglycol solution be 6000mg/L; Add 2 respectively again, 3-dihydroxyl pyrazine, glyoxal ethyline, the concentration that makes it in triglycol is respectively 4000mg/L, 20000mg/L; Be warmed up to 160 ℃, survey erosion rate behind the 4h.
Embodiment 5
In triglycol solution, adding concentrated hydrochloric acid, to make the cl ions in the triglycol solution be 6000mg/L; Add 2-amino-5-methoxy pyrimidine, 3-benzyl-pyridine more respectively; The concentration that makes it in triglycol is respectively 9000mg/L, 9000mg/L, is warmed up to 160 ℃, surveys erosion rate behind the 4h.
Embodiment 6
In triglycol solution, adding concentrated hydrochloric acid, to make the cl ions in the triglycol solution be 6000mg/L; Add 3-bromoquinoline, benzotriazole, 4-phenylpyridine more respectively; The concentration that makes it in triglycol is respectively 30000mg/L, 1000mg/L, 2000mg/L; Be warmed up to 160 ℃, survey erosion rate behind the 4h.
Embodiment 7
In triglycol solution, adding concentrated hydrochloric acid, to make the cl ions in the triglycol solution be 6000mg/L; Add bromo isoquinoline 99.9,2-aminobenzothiazole more respectively; The concentration that makes it in triglycol is respectively 10000mg/L, 30000mg/L, is warmed up to 160 ℃, surveys erosion rate behind the 4h.
Embodiment 8
In diethylene glycol solution, adding concentrated hydrochloric acid, to make the cl ions in the diethylene glycol solution be 6000mg/L; Add 2 respectively again; 5-pyrrolidine-diones, 1,5 dimethyl--2-phenyl-4-amino-3-pyrazolone, the concentration that makes it in glycol ether is respectively 5000mg/L, 5000mg/L; Be warmed up to 160 ℃, survey erosion rate behind the 4h.
Embodiment 9
In diethylene glycol solution, adding concentrated hydrochloric acid, to make the cl ions in the diethylene glycol solution be 6000mg/L, adds 2 respectively again, 4-dimethyl quinoline, 6-amino-2; The 4-dimethyl pyrimidine; The concentration that makes it in glycol ether is respectively 2000mg/L, 6000mg/L, is warmed up to 160 ℃, surveys erosion rate behind the 4h.
Embodiment 10
In diethylene glycol solution, adding concentrated hydrochloric acid, to make the cl ions in the diethylene glycol solution be 6000mg/L; Add 5-nitroisoquinoline, thiazolamine more respectively; The concentration that makes it in glycol ether is respectively 2000mg/L, 1500mg/L, is warmed up to 160 ℃, surveys erosion rate behind the 4h.
Embodiment 11
In triglycol solution, adding concentrated hydrochloric acid, to make the cl ions in the triglycol solution be 6000mg/L; Add 6-quinolylamine, flucytosine more respectively; The concentration that makes it in triglycol is respectively 4000mg/L, 2500mg/L, is warmed up to 160 ℃, surveys erosion rate behind the 4h.
Comparative Examples 1
In triglycol solution, adding concentrated hydrochloric acid, to make the cl ions in the triglycol solution be 6000mg/L, is warmed up to 160 ℃, surveys erosion rate behind the 4h.
Comparative Examples 2
In diethylene glycol solution, adding concentrated hydrochloric acid, to make the cl ions in the diethylene glycol solution be 6000mg/L, is warmed up to 160 ℃, surveys erosion rate behind the 4h.
Above-mentioned result of experiment is seen table 2.
Table 2 adds the corrosion mitigating effect behind the inhibiter
| Embodiment | Erosion rate (mm/a) |
| Embodiment 1 | 0.65 |
| Embodiment 2 | 1.09 |
| Embodiment 3 | 0.76 |
| Embodiment 4 | 0.68 |
| Embodiment 5 | 0.73 |
| Embodiment 6 | 0.67 |
| Embodiment 7 | 0.51 |
| Embodiment 8 | 1.26 |
| Embodiment 9 | 1.61 |
| Embodiment 10 | 3.74 |
| Embodiment 11 | 2.55 |
| Comparative Examples 1 | 10.3 |
| Comparative Examples 2 | 11.5 |
Claims (6)
1. the composite corrosion inhibitor of a butyl rubber chloromethane glycol dehydrating regeneration system, it consists of two kinds of heterogeneous ring compounds, is selected from quinolines and pyrimidines respectively.
2. composite corrosion inhibitor according to claim 1; It is characterized in that described quinolines is selected from 3-bromoquinoline, 4-toluquinoline, 5-toluquinoline, 6-quinolylamine, 3-ethyl quinoline, 3; 8-dimethyl quinoline, 2,4-dimethyl quinoline and 5,7-dichloro-8-hydroxyquinoline.
3. composite corrosion inhibitor according to claim 1 and 2; It is characterized in that described pyrimidines is selected from 2-amino-5-methoxy pyrimidine, 6-amino-2; 4-dimethyl pyrimidine, 2-amino-4-methoxyl group-6-methylpyrimidine, 4-amino-2,6-dimethoxypyridin and flucytosine.
4. composite corrosion inhibitor according to claim 3 is characterized in that described quinolines is 6-quinolylamine or 2, and 4-dimethyl quinoline, described pyrimidines are 6-amino-2,4-dimethyl pyrimidine or flucytosine.
5. composite corrosion inhibitor according to claim 1 and 2 is characterized in that the concentration summation of heterogeneous ring compound is: the 3000-50000mg/L glycol.
6. composite corrosion inhibitor according to claim 5 is characterized in that the concentration summation of heterogeneous ring compound is: the 15000-35000mg/L glycol.
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|---|---|---|---|
| CN201210134480.1A CN102650056B (en) | 2009-06-26 | 2009-06-26 | Composite corrosion inhibitor for butyl rubber chloromethane glycol dehydration and regeneration system |
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|---|---|---|---|
| CN201210134480.1A CN102650056B (en) | 2009-06-26 | 2009-06-26 | Composite corrosion inhibitor for butyl rubber chloromethane glycol dehydration and regeneration system |
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| CN2009100877879A Division CN101928942A (en) | 2009-06-26 | 2009-06-26 | Composite inhibitor of butyl rubber chloromethane glycol dehydration regenerative system |
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| US3758480A (en) * | 1968-07-10 | 1973-09-11 | Mallinckrodt Chemical Works | S-triazolo(5,1-a)isoquinolines and derivatives thereof |
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