CN104436997A - Method for inhibiting degradation of desulfurization amine absorbent - Google Patents
Method for inhibiting degradation of desulfurization amine absorbent Download PDFInfo
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- CN104436997A CN104436997A CN201310422402.6A CN201310422402A CN104436997A CN 104436997 A CN104436997 A CN 104436997A CN 201310422402 A CN201310422402 A CN 201310422402A CN 104436997 A CN104436997 A CN 104436997A
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- amine
- antioxidant
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- ethylene glycol
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Abstract
The present invention relates to a method for inhibiting degradation of a desulfurization amine absorbent, specifically to addition of a certain amount of an antioxidant to an amine absorbent to inhibit the degradation of the amine absorbent, wherein the antioxidant is a composite antioxidant comprising at least two selected from sodium sulfite (Na2SO3), sodium molybdate (Na2MoO4) and ethylene glycol (EG), has the significant anti-oxidation effect, and can be used under the conditions of low addition amount, high temperature and wide oxygen content so as to substantially inhibit the degradation of the amine aqueous solution. With the method of the present invention, the corrosion of the absorption solvent on the equipment is reduced while the loss of the absorbent is reduced.
Description
Technical field
The invention belongs to field of gas purification, be specifically related to a kind of novel antioxidant suppressing organic amine desulfurizer oxidative degradation.
Background technology
Alkanolamine method is remove H from the unstripped gas of natural gas, oil and processing industry thereof always
2the main stream approach of S.Nearly decades, amine method technology development, achieves rapid progress, defines multiple alternative amine desulfurization decarbonizing solution, as monoethanolamine, diethanol amine, triethanolamine, methyl-ethanolamine and methyl diethanolamine etc.But alcohol amine solvent in use for some time, can degrade, thus cause hydraulic performance decline, cause the production such as solution foaming, corrosion problem.
Summary of the invention
The object of the invention is to, propose a kind of novel antioxidant, by interrupting the principle of oxidation reaction chain Sum decomposition oxidative breakdown product, the degraded of amine aqueous solution can be suppressed largely.
The present invention suppresses amine absorbent to be degraded by adding a certain amount of antioxidant in amine absorbent.
Main technical schemes of the present invention: the method suppressing the degraded of desulfurization amine absorbent, is characterized in that adding 0.1 ~ 5%(wt in amine aqueous solution) antioxidant, preferably 0.1 ~ 4%(wt).
Described antioxidant is sodium sulfite (Na
2sO
3), sodium molybdate (Na
2moO
4), the composite antioxidant of ethylene glycol (EG) at least two kinds composition.
Described antioxidant is sodium sulfite (Na
2sO
3) and sodium molybdate (Na
2moO
4) mixture that forms; Described antioxidant sodium sulfite (Na
2sO
3) account for amine aqueous solution 0.1 ~ 2.5%(wt), sodium molybdate (Na
2moO
4) account for amine aqueous solution 0.1 ~ 2.5%(wt).
Described antioxidant, is characterized in that, described antioxidant is sodium sulfite (Na
2sO
3) and the mixture that forms of ethylene glycol (EG); Described antioxidant sodium sulfite (Na
2sO
3) account for amine aqueous solution 0.1 ~ 2.5%(wt), ethylene glycol (EG) accounts for amine aqueous solution 0.1 ~ 2.5%(wt).
Described antioxidant is ethylene glycol (EG) and sodium molybdate (Na
2moO
4) mixture that forms; Described antioxidant ethylene glycol (EG) accounts for amine aqueous solution 0.1 ~ 2.5%(wt), sodium molybdate (Na
2moO
4) account for amine aqueous solution 0.1 ~ 2.5%(wt).
Described antioxidant is sodium sulfite (Na
2sO
3), sodium molybdate (Na
2moO
4) and the mixture that forms of ethylene glycol (EG); Described antioxidant sodium sulfite (Na
2sO
3) account for amine aqueous solution 0.1 ~ 1.5%(wt), sodium molybdate (Na
2moO
4) account for amine aqueous solution 0.1 ~ 1.5%(wt), ethylene glycol (EG) accounts for amine aqueous solution 0.1 ~ 2%(wt).
Amine of the present invention refers to N methyldiethanol amine (MDEA), monoethanolamine (MEA), diethanol amine (DEA), triethanolamine (TEA) and derivative thereof, one or more of methyl-ethanolamine (MMEA), piperazine, 2-amino-2-methyl-1-propanol, 2-piperidine ethanol, tert-butylamine base diethanol amine.
Described amine aqueous solution is the aqueous solution that wherein one or more amine are composite, and its scope is 20 ~ 65%(wt).
Antioxidant serviceability temperature scope 36 ~ 130 DEG C of the present invention, pressure limit 0.2 ~ 7.5MPa, O2 concentration range is 0 ~ 5%.
Antioxidant of the present invention has following distinguishing feature: add less, and antioxidant effect is remarkable, can use, suppress the degraded of amine aqueous solution largely in high temperature, oxygen content higher; Ensure that the stability of lyosoption, reduce lyosoption and absorbent loss is again reduced to the extent of corrosion of equipment simultaneously, greatly reduce production cost.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in detail, but be not limited only to content described in following examples.
Embodiment 1: using 100g wherein total amine content be 45%(wt) MDEA as absorbent, mist composition (mol ratio): CO
230%, H
2s 16%, all the other O
2, at 80 DEG C, mist enters through and adds in aqueous alkanolamine, with the speed of 120ml/min, measures its degradation rate after reaching the reaction time.The results are shown in subordinate list.
Embodiment 2: by 100g wherein total amine content be the MDEA(wt of 45%), the Na of 1%
2sO
3(wt), the Na of 0.5%
2moO
4(wt) mixed liquor is as absorbent, mist composition (mol ratio): CO
230%, H
2s 16%, all the other O
2, at 80 DEG C, mist enters through in the aqueous alkanolamine adding composite antioxidant, with the speed of 120ml/min, measures its degradation rate after reaching the reaction time.The results are shown in subordinate list.
Embodiment 3: by 100g wherein total amine content be the MDEA(wt of 20%), the MEA(wt of 20%) mixed liquor as absorbent, mist composition (mol ratio): CO
230%, H
2s 16%, all the other O
2, at 80 DEG C, mist enters in aqueous alkanolamine, with the speed of 120ml/min, measures its degradation rate after reaching the reaction time.The results are shown in subordinate list.
Embodiment 4: by 100g wherein total amine content be the MDEA(wt of 20%), the MEA(wt of 20%), the Na of 1%
2moO
4(wt), ethylene glycol (EG) (wt) mixed liquor of 1.5% is as absorbent, and mist forms (mol ratio): CO
230%, H
2s 16%, all the other O
2, at 80 DEG C, mist enters through in the aqueous alkanolamine adding composite antioxidant, with the speed of 120ml/min, measures its degradation rate after reaching the reaction time.The results are shown in subordinate list.
Embodiment 5: by 100g wherein total amine content be the MEA(wt of 30%), the DEA(wt of 15%) mixed liquor as absorbent, mist composition (mol ratio): CO
230%, H
2s 16%, all the other O
2, at 80 DEG C, mist enters in aqueous alkanolamine, with the speed of 120ml/min, measures its degradation rate after reaching the reaction time.The results are shown in subordinate list.
Embodiment 6: by 100g wherein total amine content be the MEA(wt of 30%), the DEA(wt of 15%), the Na of 1%
2moO
4(wt), 0.5%Na
2moO
4(wt), ethylene glycol (EG) (wt) mixed liquor of 1.5% is as absorbent, and mist forms (mol ratio): CO
230%, H
2s 16%, all the other O
2, at 80 DEG C, mist enters through in the aqueous alkanolamine adding composite antioxidant, with the speed of 120ml/min, measures its degradation rate after reaching the reaction time.The results are shown in subordinate list.
Non-oxidizability experimental result sees the following form:
| Numbering | Reaction time (h) | Amine liquid degradation rate (%) |
| Example 1 | 6 | 4.7 |
| Example 2 | 6 | 2.1 |
| Example 3 | 8 | 5.2 |
| Example 4 | 8 | 1.9 |
| Example 5 | 10 | 5.8 |
| Example 6 | 10 | 2.4 |
Result shows: by contrast, composite antioxidant of the present invention significantly can reduce the degradation rate of alkanolamine solution.
Claims (9)
1. the method suppressing desulfurization amine absorbent to be degraded, is characterized in that adding 0.1 ~ 5%(wt in amine aqueous solution) antioxidant; Described antioxidant is sodium sulfite, sodium molybdate, the composite antioxidant of ethylene glycol at least two kinds composition.
2. method according to claim 1, is characterized in that adding 0.1 ~ 4%(wt in amine aqueous solution) antioxidant.
3. antioxidant according to claim 1, is characterized in that, described antioxidant is the mixture of sodium sulfite and sodium molybdate composition; Sodium sulfite accounts for amine aqueous solution 0.1 ~ 2.5%(wt), sodium molybdate accounts for amine aqueous solution 0.1 ~ 2.5%(wt).
4. antioxidant according to claim 1, is characterized in that, described antioxidant is the mixture of sodium sulfite and ethylene glycol composition; Sodium sulfite accounts for amine aqueous solution 0.1 ~ 2.5%(wt), ethylene glycol accounts for amine aqueous solution 0.1 ~ 2.5%(wt).
5. antioxidant according to claim 1, is characterized in that, described antioxidant is the mixture of ethylene glycol and sodium molybdate composition; Ethylene glycol accounts for amine aqueous solution 0.1 ~ 2.5%(wt), sodium molybdate accounts for amine aqueous solution 0.1 ~ 2.5%(wt).
6. antioxidant according to claim 1, is characterized in that, described antioxidant is the mixture of sodium sulfite, sodium molybdate and ethylene glycol composition; Sodium sulfite accounts for amine aqueous solution 0.1 ~ 1.5%(wt), sodium molybdate accounts for amine aqueous solution 0.1 ~ 1.5%(wt), ethylene glycol accounts for amine aqueous solution 0.1 ~ 2%(wt).
7. according to the method described in claim 1, it is characterized in that described amine is N methyldiethanol amine, monoethanolamine, diethanol amine, triethanolamine and derivative thereof, one or more of methyl-ethanolamine, piperazine, 2-amino-2-methyl-1-propanol, 2-piperidine ethanol, tert-butylamine base diethanol amine.
8. according to the method for claim 1 or 7, it is characterized in that described amine aqueous solution is the aqueous solution that wherein one or more amine are composite, its scope is 20 ~ 65%(wt).
9. method according to claim 1, is characterized in that antioxidant serviceability temperature scope 36 ~ 130 DEG C, and pressure limit 0.2 ~ 7.5MPa, O2 concentration range is 0 ~ 5%.
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|---|---|---|---|
| CN201310422402.6A CN104436997A (en) | 2013-09-17 | 2013-09-17 | Method for inhibiting degradation of desulfurization amine absorbent |
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|---|---|---|---|
| CN201310422402.6A CN104436997A (en) | 2013-09-17 | 2013-09-17 | Method for inhibiting degradation of desulfurization amine absorbent |
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|---|---|
| CN104436997A true CN104436997A (en) | 2015-03-25 |
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ID=52884213
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554127A (en) * | 2018-05-04 | 2018-09-21 | 南京万象新材料科技有限责任公司 | A kind of compound desulfurizing assistant agent and application |
| CN110252090A (en) * | 2019-07-05 | 2019-09-20 | 郑州轻工业学院 | A method of sodium sulfite sulfur removal technology absorptive capacity and utilization rate are improved using triethanolamine |
| CN112143536A (en) * | 2019-06-27 | 2020-12-29 | 中石化南京化工研究院有限公司 | Absorption liquid for corrosion prevention of decarburization system in natural gas |
| CN115501731A (en) * | 2021-06-07 | 2022-12-23 | 中国石油化工股份有限公司 | For removing H from sulfur-containing gases 2 S absorption liquid, preparation method and application |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108554127A (en) * | 2018-05-04 | 2018-09-21 | 南京万象新材料科技有限责任公司 | A kind of compound desulfurizing assistant agent and application |
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| CN112143536A (en) * | 2019-06-27 | 2020-12-29 | 中石化南京化工研究院有限公司 | Absorption liquid for corrosion prevention of decarburization system in natural gas |
| CN110252090A (en) * | 2019-07-05 | 2019-09-20 | 郑州轻工业学院 | A method of sodium sulfite sulfur removal technology absorptive capacity and utilization rate are improved using triethanolamine |
| CN110252090B (en) * | 2019-07-05 | 2022-03-04 | 郑州轻工业学院 | Method for improving absorption capacity and utilization rate of sodium sulfite desulfurization process by using triethanolamine |
| CN115501731A (en) * | 2021-06-07 | 2022-12-23 | 中国石油化工股份有限公司 | For removing H from sulfur-containing gases 2 S absorption liquid, preparation method and application |
| CN115501731B (en) * | 2021-06-07 | 2024-05-07 | 中国石油化工股份有限公司 | For removing H from sulfur-containing gases2S absorption liquid, preparation method and application |
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Application publication date: 20150325 |