CN103157348A - High efficient desulfurizing agent with low energy consumption - Google Patents
High efficient desulfurizing agent with low energy consumption Download PDFInfo
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- CN103157348A CN103157348A CN2013101172602A CN201310117260A CN103157348A CN 103157348 A CN103157348 A CN 103157348A CN 2013101172602 A CN2013101172602 A CN 2013101172602A CN 201310117260 A CN201310117260 A CN 201310117260A CN 103157348 A CN103157348 A CN 103157348A
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- desulfurizing agent
- mdea
- desulfurizing
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- organic sulfur
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Abstract
The invention discloses a high efficient desulfurizing agent with low energy consumption. The desulfurizing agent contains the following components by mass percent: 93-98% of MDEA (methyldiethanolamine), 0.1-2% of desulfurizing defoaming agent, 0.1-2% of MDEA degradation inhibitor, 0.5-4% of organic sulfur adsorbent and 0.1-2% of hydrotropy agent. The novel desulfurizing agent can work under high concentration without foaming, and has high desulfurizing efficiency for H2S (hydrogen sulfide); the desulfurizing agent is also capable of desulfurizing the organic sulfur; the novel desulfurizing agent has large sulfur capacity and high using concentration and is a saving type solvent; and the novel desulfurizing agent has small corrosion to a gasometer, and does not degrade, foam, and discolor easily.
Description
Technical field:
The invention belongs to the petrochemical technology field.A kind of high-efficiency low energy consumption desulfurize agent of specific design.In the oil refining petrochemical industry, desulfurizing agent is used for removing of refinery's gas (catalysis drying gas, liquefied gas, hydrogenation dry gas, tail gas, sulphur hydrogen reduction gas, natural gas) hydrogen sulfide.
Technical background:
The N methyldiethanol amine (MDEA) of China's multiplex alkalescence in refinery is made absorbent, with H
2S, CO
2Absorb in the lump, remove after desorb Deng sour gas.Due to CO
2In most of the cases do not have harmfulness, the necessity that does not remove is if can optionally only remove H
2S reduces CO
2The amount of removing must make that the solvent internal circulating load reduces, equipment size and investment and operating cost reduce, and makes the regeneration Energy Intensity Reduction; And, after desorb in sour gas, H
2S concentration will raise, and the unstripped gas of high-quality is provided for Crouse (CLAUS) sulfur recovery unit, and will be very favourable to reclaiming sulphur.Conventional MDEA desulfurizing agent is in sweetening process, and desulfurizing agent is 99.5%, to CO
2Removal efficiency is 80%, easily degrades simultaneously, foaming, variable color.Because improve because of working ability refinery in the system of China Petroleum Chemicals Corporation, or because mixing the refining sour crude, dry gas, situation that the liquid hydrocarbon desulfurization degree of depth is inadequate all appearred, a kind of desulfurizing agent of high-efficiency low energy consumption need to be provided.
Summary of the invention:
The object of the present invention is to provide a kind of high-efficiency low energy consumption desulfurize agent.
Purpose of the present invention is achieved through the following technical solutions:
A kind of desulfurizing agent by the quality percentage composition, comprises following component:
MDEA 93%~98%
Desulfurization defoamer 0.1% ~ 2%
MDEA degradation inhibitor 0.1% ~ 2%
Organic sulfur adsorbent 0.5% ~ 4%
Cosolvent 0.1% ~ 2%.
Above-mentioned desulfurizing agent, the content of its each component is preferably:
MDEA 94%~97%
Desulfurization defoamer 0.5% ~ 1%
MDEA degradation inhibitor 0.5% ~ 1%
Organic sulfur adsorbent 1% ~ 3%
Cosolvent 0.5% ~ 2%.
Described desulfurization defoamer is the organic silicone oil of modification, for example: polyether modified silicon oil.
Described MDEA degradation inhibitor is water miscible antioxidant, for example: antioxidant 264.
Described organic sulfur adsorbent is sulfolane.
Described cosolvent is isopropyl alcohol.
The purity of described MDEA 〉=97%.
N methyldiethanol amine (MDEA) is a kind of tertiary amines material.Molecular formula is CH
3N (CH
2CH
2OH)
2, molecular weight is 119.16, proportion 1.0418, and 247 ℃ of boiling points, the viscosity in the time of 12 ℃ is 101cp, 48 ℃ of Ning Gu Dian – can be all soluble in water.MDEA can adopt the commercially available prod, also can adopt existing technique preparation.In the present invention, the production technology of MDEA adopts state-of-the-art channelization reaction in the world, and namely oxirane and single methylamine in tubular reactor, react under 2.5MPa pressure, and through distillation, rectifying obtains MDEA, purity 〉=97%.
Desulfurization defoamer, MDEA degradation inhibitor, organic sulfur adsorbent and isopropyl alcohol related in the present invention are the commercially available prod.
Conventional MDEA desulfurizing agent is in sweetening process, and desulfurizing agent is to H
2The removal efficiency of S is 99.5%, to CO
2Removal efficiency 80% is easily degraded simultaneously, foaming, variable color.Because improve because of working ability refinery in the system of China Petroleum Chemicals Corporation, or because mixing the refining sour crude, dry gas, situation that the liquid hydrocarbon desulfurization degree of depth is inadequate all appearred.Fully to demonstrate its sulfur capacity large for the efficient desulfurizing agent of the present invention take MDEA as host in this case, selective good advantage.Because the working concentration of desulfurizing agent of the present invention can be up to 50% ~ 65%, so its internal circulating load can greatly reduce, and it can absorb under high gas-liquid ratio or high liquid liquor ratio, and the regeneration heat of desorption of MDEA is smaller, thereby has reduced the regeneration heat dissipation.In a word, can significantly reduce energy consumption with the MDEA acid gas removal, finally reduce running cost.
New selective desulfurizing agent of the present invention is take MDEA as host, has added the composite desulfurizing agent of highly sterically hindered amine desulfurizing agent and physical solvent.Have for H
2The S absorption selectivity is good, simultaneously part organic sulfide removal effect.CO in sour gas
2/ H
2The ratio of S can save energy 10% greater than 3 o'clock, significantly was better than best similar desulfurizing agent at present.Capable of reducing energy consumption, the solvent internal circulating load is reduced, remove to greatest extent H
2S, Heat stability is good be difficult for to form foam, and concentration non-corrosiveness when being 50% ~ 65%, and the working concentration of existing commercially available similar desulfurizing agent is only 25% ~ 40%.
Beneficial effect of the present invention:
This product is weak yellow liquid, can dissolve each other with water, is noninflammable general liquid.Compare with conventional desulfurizing agent when serviceability aspect difference, New Desulphurizers has the following advantages:
New Desulphurizers can move under high concentration and non-foaming, and therefore operating bubble damages little, and evaluation test shows, under identical simulated conditions, the foam height of conventional desulfurizing agent is 6.5cm, and New Desulphurizers 3.8cm only.
New Desulphurizers is to H
2The removal efficiency of S is high, to CO
2Removal efficiency more lower slightly.Evaluation test shows, under identical simulated conditions, to H
2The removal efficiency of S: conventional desulfurizing agent is 99.5%, and New Desulphurizers can reach 99.9%.But New Desulphurizers is organic sulfide removal 40% ~ 70% also, and conventional desulfurizing agent does not have desulfurized effect to organic sulfur.To CO
2Removal efficiency: conventional desulfurizing agent is 80%, and New Desulphurizers is 78%(v) left and right, a little less than New Desulphurizers, but this recovery process to sulphur is favourable.
The sulfur capacity of New Desulphurizers of the present invention is large, and working concentration is high, thereby can move under large " gas agent ratio " condition, is a kind of economizing type solvent.Evaluation test shows, under identical simulated conditions, if take sulfur capacity as 1, conventional desulfurizing agent sulfur capacity is only 1.6 times of MDEA, and New Desulphurizers can reach 3.23 times of MDEA.
The gas holder corrosion of New Desulphurizers of the present invention is little.Evaluation test shows, under identical simulated conditions, the gaseous corrosion of conventional desulfurizing agent is larger, and New Desulphurizers of the present invention is more little.
The color that is in operation is difficult for deepening.Evaluation test shows,, darken, and the New Desulphurizers color is almost constant after test at conventional desulfurizing agent under identical simulated conditions.
The removal effect that desulfurizing agent of the present invention is used for refinery's gas (catalysis drying gas, liquefied gas, hydrogenation dry gas, tail gas, sulphur hydrogen reduction gas, natural gas) hydrogen sulfide is good, help to reduce air pollution and improve environmental quality, can significantly reduce energy consumption when this desulfurizing agent uses in addition, reduce running cost, saving can be former.
The specific embodiment:
Embodiment 1:
The formula of desulfurizing agent: purity is 99.5% MDEA 95.5%, desulfurization defoamer (polyether modified silicon oil, precious chemical industry Co., Ltd in Qingdao) 0.5% MDEA degradation inhibitor (antioxidant 264,, the fast chemical industry of Guangzhou sheng Co., Ltd) 0.5%, organic sulfur adsorbent (sulfolane, Yingkou, Liaoning) 2.5%, isopropyl alcohol 1%.
Above each component is mixed in proportion namely make desulfurizing agent.
Embodiment 2:
The formula of desulfurizing agent: purity is 99.5% MDEA 95.5%, desulfurization defoamer (polyether modified silicon oil, precious chemical industry Co., Ltd in Qingdao) 0.5% MDEA degradation inhibitor (antioxidant 264,, the fast chemical industry of Guangzhou sheng Co., Ltd) 1%, organic sulfur adsorbent (sulfolane, Yingkou, Liaoning) 2%, isopropyl alcohol 1%.
Above each component is mixed in proportion namely make desulfurizing agent.
Embodiment 3:
The formula of desulfurizing agent: purity is 99.5% MDEA 94%, desulfurization defoamer (polyether modified silicon oil, precious chemical industry Co., Ltd in Qingdao) 1% MDEA degradation inhibitor (antioxidant 264,, the fast chemical industry of Guangzhou sheng Co., Ltd) 1%, organic sulfur adsorbent (sulfolane, Yingkou, Liaoning) 2%, isopropyl alcohol 2%.
Above each component is mixed in proportion namely make desulfurizing agent.
Embodiment 4:
The formula of desulfurizing agent: purity is 99.5% MDEA 97%, desulfurization defoamer (polyether modified silicon oil, precious chemical industry Co., Ltd in Qingdao) 0.5% MDEA degradation inhibitor (antioxidant 264,, the fast chemical industry of Guangzhou sheng Co., Ltd) 0.5%, organic sulfur adsorbent (sulfolane, Yingkou, Liaoning) 1%, isopropyl alcohol 1%.
Above each component is mixed in proportion namely make desulfurizing agent.
Embodiment 5:
The formula of desulfurizing agent: purity is 99.5% MDEA 93%, desulfurization defoamer (polyether modified silicon oil, precious chemical industry Co., Ltd in Qingdao) 1% MDEA degradation inhibitor (antioxidant 264,, the fast chemical industry of Guangzhou sheng Co., Ltd) 1.5%, organic sulfur adsorbent (sulfolane, Yingkou, Liaoning) 2.5%, isopropyl alcohol 2%.
Above each component is mixed in proportion namely make desulfurizing agent.
Embodiment 6:
The formula of desulfurizing agent: purity is 99.5% MDEA 98%, desulfurization defoamer (polyether modified silicon oil, precious chemical industry Co., Ltd in Qingdao) 0.2% MDEA degradation inhibitor (antioxidant 264,, the fast chemical industry of Guangzhou sheng Co., Ltd) 0.2%, organic sulfur adsorbent (sulfolane, Yingkou, Liaoning) 0.5%, isopropyl alcohol 1.1%.
Above each component is mixed in proportion namely make desulfurizing agent.
The desulfurizing agent of employing embodiment 1-6 and existing commercially available similar desulfurizing agent carry out removing of hydrogen sulfide to the catalysis drying gas of refinery.Its removal effect such as following table:
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Commercially available desulfurizing agent | |
| H 2The S removal efficiency | 99.91% | 99.93% | 99.90% | 99.90% | 99.89% | 99.88% | 99.5% |
| CO 2Removal efficiency | 78.2% | 78.1% | 78.0% | 78.9% | 77.6% | 79.1% | 80% |
| The organic sulfur removal rate | 69% | 70% | 65% | 66% | 55% | 45% | 0 |
Except in upper table, the desulfurizing agent of embodiment 1-6 with commercially available similar desulfurizing agent at H
2S removal efficiency, CO
2Outside the contrast of removal efficiency, organic sulfur removal rate, desulfurizing agent of the present invention also has following advantage:
Existing commercially available similar desulfurizing agent working concentration is 25% ~ 40%, and the working concentration of desulfurizing agent of the present invention can be up to 50% ~ 65%, therefore the internal circulating load of desulfurizing agent of the present invention can greatly reduce, it can absorb under high gas-liquid ratio or high liquid liquor ratio, the regeneration heat of desorption of MDEA is smaller, thereby has reduced the regeneration heat dissipation.Can significantly reduce energy consumption with the MDEA acid gas removal, finally reduce running cost.
Easily degrade when existing commercially available similar desulfurizing agent uses, foaming, variable color, and do not have this situation during the use of desulfurizing agent of the present invention.
Under identical simulated conditions, if take sulfur capacity as 1, the sulfur capacity of existing commercially available similar desulfurizing agent is only 1.6 times of MDEA, and New Desulphurizers can reach 3.23 times of MDEA.The sulfur capacity of New Desulphurizers of the present invention is large, and working concentration is high, thereby can move under large " gas agent ratio " condition, is a kind of economizing type solvent.
Claims (7)
1. desulfurizing agent is characterized in that comprising following component by the quality percentage composition:
MDEA 93%~98%
Desulfurization defoamer 0.1% ~ 2%
MDEA degradation inhibitor 0.1% ~ 2%
Organic sulfur adsorbent 0.5% ~ 4%
Cosolvent 0.1% ~ 2%.
2. desulfurizing agent according to claim 1 is characterized in that the content of each component is:
MDEA 94%~97%
Desulfurization defoamer 0.5% ~ 1%
MDEA degradation inhibitor 0.5% ~ 1%
Organic sulfur adsorbent 1% ~ 3%
Cosolvent 0.5% ~ 2%.
3. desulfurizing agent according to claim 1 and 2, is characterized in that described desulfurization defoamer is the organic silicone oil of modification.
4. desulfurizing agent according to claim 1 and 2, is characterized in that described MDEA degradation inhibitor is water miscible antioxidant.
5. desulfurizing agent according to claim 1 and 2, is characterized in that described organic sulfur adsorbent is sulfolane.
6. desulfurizing agent according to claim 1 and 2, is characterized in that described cosolvent is isopropyl alcohol.
7. desulfurizing agent according to claim 1 and 2 is characterized in that the purity of described MDEA 〉=97%.
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| CN2013101172602A CN103157348A (en) | 2013-04-03 | 2013-04-03 | High efficient desulfurizing agent with low energy consumption |
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|---|---|---|---|
| CN2013101172602A CN103157348A (en) | 2013-04-03 | 2013-04-03 | High efficient desulfurizing agent with low energy consumption |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664698A (en) * | 2016-04-05 | 2016-06-15 | 江苏大海能源科技有限公司 | Compound liquid desulfurizing agent and application thereof |
| CN106009726A (en) * | 2016-06-20 | 2016-10-12 | 许昌金欧特沥青股份有限公司 | Asphalt modified with odorless rubber powder easy to melt |
| CN106009725A (en) * | 2016-06-20 | 2016-10-12 | 许昌金欧特沥青股份有限公司 | Odorless waste tire rubber powder modifying agent easy to melt |
| CN107586558A (en) * | 2017-09-04 | 2018-01-16 | 江苏创新石化有限公司 | A kind of selective minimum discharge desulfurizing agent |
| CN109865400A (en) * | 2018-10-16 | 2019-06-11 | 上海赛思特新能源科技有限公司 | Laminated desulfurizer and preparation method thereof |
| CN114452777A (en) * | 2022-01-25 | 2022-05-10 | 江苏创新石化有限公司 | Special ultralow-emission desulfurization solvent for SCOT tail gas of sulfur recovery device of oil refinery |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105664698A (en) * | 2016-04-05 | 2016-06-15 | 江苏大海能源科技有限公司 | Compound liquid desulfurizing agent and application thereof |
| CN106009726A (en) * | 2016-06-20 | 2016-10-12 | 许昌金欧特沥青股份有限公司 | Asphalt modified with odorless rubber powder easy to melt |
| CN106009725A (en) * | 2016-06-20 | 2016-10-12 | 许昌金欧特沥青股份有限公司 | Odorless waste tire rubber powder modifying agent easy to melt |
| CN107586558A (en) * | 2017-09-04 | 2018-01-16 | 江苏创新石化有限公司 | A kind of selective minimum discharge desulfurizing agent |
| CN109865400A (en) * | 2018-10-16 | 2019-06-11 | 上海赛思特新能源科技有限公司 | Laminated desulfurizer and preparation method thereof |
| CN114452777A (en) * | 2022-01-25 | 2022-05-10 | 江苏创新石化有限公司 | Special ultralow-emission desulfurization solvent for SCOT tail gas of sulfur recovery device of oil refinery |
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Application publication date: 20130619 |