CN102650055B - 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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- CN102650055B CN102650055B CN201210134479.9A CN201210134479A CN102650055B CN 102650055 B CN102650055 B CN 102650055B CN 201210134479 A CN201210134479 A CN 201210134479A CN 102650055 B CN102650055 B CN 102650055B
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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 the divisional application of 200910087787.9, 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, relate in particular to a kind of emphasis and solve isoprene-isobutylene rubber production equipment glycol when removing minor amount of water in methyl chloride, cause the method for system corrosion because methyl chloride be hydrolyzed generation hydrochloric acid in glycol.
Background technology
The production technique of isoprene-isobutylene rubber is generally adopt methyl chloride to produce as the slurry process low temperature polymerization of solvent, with high-purity isobutylene, isoprene for raw material, be thinner with high-purity chloro methane, employing aluminum chloride is catalyzer, cationic copolymerization reaction is carried out at about-100 DEG C, polymerisate is suspended in thinner and forms slurry, therefore is called slurry process.
In isoprene-isobutylene rubber production process, do not participate in reaction solvent methyl chloride and react unconverted monomer iso-butylene and isoprene need dehydrate refining after reuse, usual drying is refining adopts alumina desiccant, but owing to being periodical operation, aluminum oxide life cycle is short, regeneration is frequent, and labour intensity is large.Cause fluctuation of service, methyl chloride loss is large, and environmental pollution is serious, and aluminum oxide is short for work-ing life, and have a strong impact on the quality of isoprene-isobutylene rubber product and the stability of production, production cost is high.
Can solve with the dry combination process of alumina desiccant the problem that single alumina desiccant produces again absorb the minor amount of water in methyl chloride with glycol after, this combination process can delay the recovery time of alumina desiccant greatly, generally can extend to 5 days even longer.
US Patent No. 3005808 discloses the method extending alumina desiccant work-ing life, by compressing and cooling the many water of removing quantity and used glycol process before by alumina desiccant.In glycol absorber, absorb the water in methyl chloride with glycol, absorption tower glycol out contains a large amount of water and the methyl chloride of dissolving, after glycol reclamation system regenerates it, glycol is back to glycol absorber.
English Patent GB1275574 discloses the renovation process of the glycol siccative produced for isoprene-isobutylene rubber, methyl chloride diluent contacts with the glycol in absorption tower and obtains drying, and the glycol after water suction enters from absorption tower that temperature is 45-85F, pressure is the flashing tower of 15-25psia.Volatile part is flashed away, the liquid glycol logistics of moisture and other impurity is by entering into counter-current tower (self-refluxing tower) bottom flashing tower, at the bottom of tower after counter-current tower, glycol mixed solution enters reboiler, the gas fraction formed after boiling again gets back to counter-current tower and moisture and liquid glycol adverse current that is other impurity, and the glycol after namely liquid portion regenerates takes out bottom reboiler.
Above-mentioned two patents with glycol be siccative remove isoprene-isobutylene rubber produce thinner methyl chloride in water time, need through flashing tower from glycol absorber glycol out, regenerator column (or counter-current tower), reboiler etc., to remove water in glycol and other impurity, except to anhydrate and the glycol of other impurity is recycled to glycol absorber, after above-mentioned a series of process, be recycled to glycol absorber to glycol from the glycol water sent in glycol absorber dechlorination methane and be called chloromethane glycol dehydrating regeneration system, this chloromethane glycol dehydrating regeneration system is in long-term running, equipment corrosion is serious, find after testing mainly to contain in on-the-spot triglycol: Fe
2+, Fe
3+, H
+and Cl
-plasma, the source of each ion and mechanism of corrosion are:
Methyl chloride hydrolysis reaction under the high temperature conditions: CH
3cl+H
2o=CH
3oH+HCl
FeCl
2source and balance: FeCl
2generate primarily of hcl corrosion carbon steel, its solubleness in water is very large, is the main existence form of chlorion, the FeCl of high density under the high temperature conditions
2hydrolysis may be there is and generate FeO and HCl accelerated corrosion, FeCl under aerobic conditions in addition
2feCl may be oxidized to
3.
The reaction of hcl corrosion carbon steel: Fe+2HCl=FeCl
2+ H
2
FeCl
2hydrolysis reaction under the high temperature conditions: FeCl
2+ H
2o=FeO+2HCl
FeCl
3source and balance: FeCl under aerobic conditions
2feCl may be oxidized to
3, due to FeCl
3oxidisability stronger, it can rapidly and iron react and generate FeCl
2, so FeCl
3to there is concentration not high, but the effect that corrosion of carbon steel is accelerated in its catalysis is very large, and correlated response is as follows:
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, in acid condition, methyl chloride is after glycol hydrolysis, and the chlorion of system can remain on a level, as at 70 DEG C, the equilibrium concentration of chlorion is about 400mg/L, and more perchlormethane hydrolysis rate is faster for temperature.Owing to having hydrogen ion and chlorion to exist in certain system, the corrosion of system is difficult to avoid, corrosion can break methyl chloride hydrolysising balance, owing to adding composite corrosion inhibitor in system, methyl chloride hydrolysising balance is broken not obvious, the increasing amount of chlorion and iron ion, remains on certain level by the glycol solution of replacing in a small amount of system to make chlorion and iron ion; If but there is no 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 chlorion in system, iron ion raising always.
Summary of the invention
In order to solve the etching problem in glycol dehydration regeneration system rapidly, contriver studies discovery: add composite corrosion inhibitor when Butyl Rubber glycol removes minor amount of water in methyl chloride, effectively can solve the etching problem of this system.
The object of the present invention is to provide a kind of composite corrosion inhibitor of butyl rubber chloromethane glycol dehydrating regeneration system, can effectively solve salt acid accumulation and bring system corrosion problem, thus suppress the corrosion in 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, being selected from heterogeneous ring compound, described heterogeneous ring compound is selected from nitrogen-containing heterocycle compound and sulfur heterocyclic compound.At least two kinds of compounds of the present invention preferably all select from nitrogen heterogeneous ring compound or from two compounds-namely select from nitrogen-containing heterocycle compound and sulfur heterocyclic compound.
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 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, Edaravone, 1,5 dimethyl-2-phenyl-4-amino-3-pyrazolones 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, bromide sixteen alkyls pyridine, halogenated phosphates and dipyridyl.
Pyrazine compounds of the present invention is selected from 2,3-dihydroxyl pyrazine and 2-HYDROXYPYRAZINE.
Pyrimidines of the present invention is selected from 2-amino-5-methoxy pyrimidine, amino-2, the 4-dimethyl pyrimidines of 6-, 2-amino-4-methoxyl-6-methylpyrimidine, amino-2, the 6-dimethoxypyridins of 4-and flucytosine.
Quinolines of the present invention is selected from 3-bromoquinoline, 4-toluquinoline, 5-toluquinoline, 6-quinolylamine, 3-ethyl quinolinium, 3,8-dimethyl quinolines, 2,4-dimethyl quinolines 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-2-amino thiazole and 2-aminobenzothiazole.
When composite corrosion inhibitor of the present invention is used for glycol dehydration regeneration system rapidly, the concentration summation of heterogeneous ring compound is: 3000-50000mg/L glycol, is preferably 15000-35000mg/L glycol.
In butyl rubber chloromethane glycol dehydrating regeneration system, add composite corrosion inhibitor, greatly can reduce the erosion rate of system, efficiently solve the corrosion that in system, salt acid accumulation produces.
Embodiment
The following examples will contribute to the present invention is described, but not limit to its scope.
Corrosion experiment adopts classical weight-loss method, and adopt 20# carbon steel lacing film, specification is 40 × 13 × 2mm, and surface-area is 12cm
2.Lacing film (under normal pressure) in the glycol corrosive medium of 160 DEG C soaks 4h, and direct use washes of absolute alcohol before soaking, need not de-oiling (oil removal treatment was done by producer), and drying is placed in moisture eliminator for subsequent use.By ten thousand/balance precise lacing film weight before experiment, first with resistanceization hydrochloric acid (10%HCl+0.5% hexamethylenetetramine) cleaning after corrosion, the corrosion product on removing surface, then use deionized water rinsing, remove the hydrochloric acid remaining in metallic surface, finally use washes of absolute alcohol, remove surface-moisture, dry up and be placed in moisture eliminator, treat that it is weighed, calculate with following formula.
v＝87600*M/(7.85*S*H)
Wherein v-erosion rate, mm/a
The quality that M-lacing film reduces, g
The surface-area of S-lacing film, 12cm
2
H-etching time, h
Embodiment 1
In triethylene glycol. solution, add concentrated hydrochloric acid makes the chlorion in triethylene glycol. solution be 6000mg/L, add 2-mercaptobenzothiazole, N-benzyl imidazole and 4-benzyl-pyridine more respectively, the concentration made it in triglycol is respectively 2000mg/L, 8000mg/L, 10000mg/L, be warmed up to 160 DEG C, after 4h, survey erosion rate.
Embodiment 2
In triethylene glycol. solution, add concentrated hydrochloric acid makes the chlorion in triethylene glycol. solution be 6000mg/L, add 2-ethyl-4-methylimidazole, 2-benzyl-pyridine and benzopyrrole more respectively, the concentration made it in triglycol is respectively 3000mg/L, 5000mg/L, 2000mg/L, be warmed up to 160 DEG C, after 4h, survey erosion rate.
Embodiment 3
In triethylene glycol. solution, add concentrated hydrochloric acid makes the chlorion in triethylene glycol. solution be 6000mg/L, add 3,5-diphenylpypazole, bromide sixteen alkyls pyridine respectively again, the concentration made it in triglycol is respectively 5000mg/L, 30000mg/L, be warmed up to 160 DEG C, after 4h, survey erosion rate.
Embodiment 4
In triethylene glycol. solution, add concentrated hydrochloric acid makes the chlorion in triethylene glycol. solution be 6000mg/L, add 2,3-dihydroxyl pyrazine, glyoxal ethyline more respectively, the concentration made it in triglycol is respectively 4000mg/L, 20000mg/L, be warmed up to 160 DEG C, after 4h, survey erosion rate.
Embodiment 5
In triethylene glycol. solution, add concentrated hydrochloric acid makes the chlorion in triethylene glycol. solution be 6000mg/L, add 2-amino-5-methoxy pyrimidine, 3-benzyl-pyridine more respectively, the concentration made it in triglycol is respectively 9000mg/L, 9000mg/L, is warmed up to 160 DEG C, surveys erosion rate after 4h.
Embodiment 6
In triethylene glycol. solution, add concentrated hydrochloric acid makes the chlorion in triethylene glycol. solution be 6000mg/L, add 3-bromoquinoline, benzotriazole, 4-phenylpyridine more respectively, the concentration made it in triglycol is respectively 30000mg/L, 1000mg/L, 2000mg/L, be warmed up to 160 DEG C, after 4h, survey erosion rate.
Embodiment 7
In triethylene glycol. solution, add concentrated hydrochloric acid makes the chlorion in triethylene glycol. solution be 6000mg/L, add bromo isoquinoline 99.9,2-aminobenzothiazole more respectively, the concentration made it in triglycol is respectively 10000mg/L, 30000mg/L, is warmed up to 160 DEG C, surveys erosion rate after 4h.
Embodiment 8
In diethylene glycol solution, add concentrated hydrochloric acid makes the chlorion in diethylene glycol solution be 6000mg/L, add 2 respectively again, 5-pyrrolidine-diones, 1,5 dimethyl-2-phenyl-4-amino-3-pyrazolones, the concentration made it in glycol ether is respectively 5000mg/L, 5000mg/L, be warmed up to 160 DEG C, after 4h, survey erosion rate.
Embodiment 9
In diethylene glycol solution, add concentrated hydrochloric acid makes the chlorion in diethylene glycol solution be 6000mg/L, then adds 2,4-dimethyl quinoline, 6-amino-2 respectively, 4-dimethyl pyrimidine, the concentration made it in glycol ether is respectively 2000mg/L, 6000mg/L, is warmed up to 160 DEG C, surveys erosion rate after 4h.
Embodiment 10
In diethylene glycol solution, add concentrated hydrochloric acid makes the chlorion in diethylene glycol solution be 6000mg/L, add 5-nitroisoquinoline, thiazolamine respectively again, the concentration made it in glycol ether is respectively 2000mg/L, 1500mg/L, is warmed up to 160 DEG C, surveys erosion rate after 4h.
Embodiment 11
In triethylene glycol. solution, add concentrated hydrochloric acid makes the chlorion in triethylene glycol. solution be 6000mg/L, add 6-quinolylamine, flucytosine respectively again, the concentration made it in triglycol is respectively 4000mg/L, 2500mg/L, is warmed up to 160 DEG C, surveys erosion rate after 4h.
Comparative example 1
In triethylene glycol. solution, add concentrated hydrochloric acid makes the chlorion in triethylene glycol. solution be 6000mg/L, is warmed up to 160 DEG C, surveys erosion rate after 4h.
Comparative example 2
In diethylene glycol solution, add concentrated hydrochloric acid makes the chlorion in diethylene glycol solution be 6000mg/L, is warmed up to 160 DEG C, surveys erosion rate after 4h.
Above-mentioned experiment the results are shown in Table 2.
Table 2 adds the corrosion mitigating effect after 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 example 1 | 10.3 |
| Comparative example 2 | 11.5 |
Claims (5)
1. the purposes of a composite corrosion inhibitor in butyl rubber chloromethane glycol dehydrating regeneration system, composite corrosion inhibitor is it is characterized in that to add in butyl rubber chloromethane glycol dehydrating regeneration system, described composite corrosion inhibitor consist of at least two kinds of heterogeneous ring compounds, be selected from azoles and pyrazole compound, described azoles is selected from 2,5-pyrrolidine-diones, benzopyrrole and dibenzopyrrole; Described pyrazole compound is selected from 3,5-diphenylpypazole, Edaravone, 1,5 dimethyl-2-phenyl-4-amino-3-pyrazolones and 1-phenyl-5-amino-pyrazol.
2. purposes according to claim 1, is characterized in that it consists of two kinds of heterogeneous ring compounds, is selected from azoles and pyrazole compound respectively.
3. purposes according to claim 1 and 2, is characterized in that described azoles is 2,5-pyrrolidine-diones, described pyrazole compound is 1,5 dimethyl-2-phenyl-4-amino-3-pyrazolones.
4. purposes according to claim 1 and 2, is characterized in that the concentration summation of heterogeneous ring compound is: 3000-50000mg/L glycol.
5. purposes according to claim 4, is characterized in that the concentration summation of heterogeneous ring compound is: 15000-35000mg/L glycol.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1527747A (en) * | 2000-09-19 | 2004-09-08 | ϣ | Process for treating adhesion promoted metal surfaces |
| CN1966594A (en) * | 1997-07-28 | 2007-05-23 | 卡伯特微电子公司 | Polishing composition for metal cmp |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1966594A (en) * | 1997-07-28 | 2007-05-23 | 卡伯特微电子公司 | Polishing composition for metal cmp |
| CN1527747A (en) * | 2000-09-19 | 2004-09-08 | ϣ | Process for treating adhesion promoted metal surfaces |
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