CN1261546C - Improved desulfurizing agent for petroleum refinery - Google Patents
Improved desulfurizing agent for petroleum refinery Download PDFInfo
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- CN1261546C CN1261546C CN 200410014931 CN200410014931A CN1261546C CN 1261546 C CN1261546 C CN 1261546C CN 200410014931 CN200410014931 CN 200410014931 CN 200410014931 A CN200410014931 A CN 200410014931A CN 1261546 C CN1261546 C CN 1261546C
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- alcohol amine
- desulfurizing agent
- sweetening agent
- petroleum refinery
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Abstract
The present invention relates to an improvement of an aerogenesis desulfurizing agent of a petroleum refinery, particularly to an improvement of a desulfurizing agent for alcohol amine compounds. The present invention is characterized in that the present invention is formed by compounding 20 to 70% WT of 1, 4 oxygen piperidine, 30 to 80 % WT of alcohol amine compounds, 0 to 10 % WT of pyridine compounds and 0 to 10% WT of sulpholane. Compared with an alcohol amine desulfurizing agent, the desulfurizing agent of the present invention has the advantages of high desulphurization activity, large sulfur carrying capacity, rapid reaction, high desulphurization efficiency, strong antidecomposition capability, low loss, long service life and less foam. Simultaneously, the present invention has good rust inhibition and has no toxicity to catalyst, and the present invention is suitable for the desulphurization of gas with high sulfur concentration. The present invention can reduce H2 S in the gas below 5 ppm, the elimination rate of organic sulfur can superlatively reach 85%, the total sulfur is reduced to about 100 ppm, and the agent consumption is only 0.014Kg per ton of oil.
Description
Technical field
The invention relates to petroleum refinery's output qi exhaustion sulphur with the improvement of sweetening agent, especially to the improvement of alcohol amine compound sweetening agent.
Background technology
Contain a large amount of sulfide in the oil (especially heavy oil, high-sulfur oils), thereby in refining of petroleum is produced, these sulphur are mostly with for example inorganic sulphide such as hydrogen sulfide, elemental sulfur and organic sulfides such as mercaptan, disulphide, be enriched in the refinery gas (liquefied gas for example of refining processing output, dry gas) in, if sulfide is not wherein removed (being reduced to bottom line), can cause environmental pollution and influence the derived product quality.Remove sulfide for this class sulfurous gas at present, mostly adopt by the composite hydramine sweetening agent of one or more mixing of alcohol amine compound (as Monoethanolamine MEA BASF, diethanolamine, N-methyl-thanomin, N methyldiethanol amine, Mono Methyl Ethanol Amine, diisopropanolamine (DIPA) etc.), alcohol amine compound content is usually about 95-97% in such sweetening agent.The hydramine sweetening agent shows removal effect preferably to inorganic sulfur, as hydrogen sulfide being taken off to trace, yet because of it selects universality high not enough to sulfide, show the organic sulfur removal effect relatively low, the organic sulfur removal rate is usually only about 15-30%, thereby cause the refinery gas total sulfur content still higher, total sulfur up to 300ppm about.The refinery gas sulphur content is higher, not only can cause environmental pollution (making fuel uses), but also can influence step deep processed product quality (making raw material uses) down; Secondly, hydramine sweetening agent and sulphur binding ability are not high enough, and ton finish consumption is big, and ton crude oil consumption sweetening agent needs about 0.7-1.0Kg approximately usually; Another deficiency of such sweetening agent is, boiling point is on the low side relatively, and according to different proportionings, boiling point is usually between 150-250 ℃, yet refining of petroleum production temperature is higher relatively, therefore can cause volatilization, the decomposition of sweetening agent effective ingredient, thereby influence recycles sweetening effectiveness, so often take place in actual applications along with prolong duration of service, sweetening effectiveness descends very fast, keep high sweetening effectiveness, then need constantly to replenish, also can cause the agent consumption to increase; The foam generation was big during such sweetening agent used besides, also was an one deficiency, not only influenced sweetening agent and refluxed, but also can cause the defoamer consumption to increase, and made desulphurization cost increase.Till the present invention occurred, the petroleum refinery used this class sweetening agent, removed the sulfide in the refining of petroleum processing output gas, and therefore still having is worth improved place.
Summary of the invention
The objective of the invention is to overcome the deficiency of above-mentioned prior art, provide a kind of wide the sulfide range of choice, strong with the sulphur bonding force, desulfuration efficiency height, especially removal of organic sulfur from efficient height, petroleum refinery's sweetening agent that the agent consumption is little.
Petroleum refinery of the present invention sweetening agent through test in a large number, selects to adopt 1,4 morpholine with the sulfide range of choice is wide, binding ability is strong to substitute part alcamines sweetening agent, selects universality to improve sweetening agent, improves and takes off total sulphur efficiency, the depressant consumption.Specifically, petroleum refinery of the present invention sweetening agent is characterized in that 1,4 morpholine by 20-70% (WT, together following), the alcohol amine compound of 30-80%, the pyridine compounds of 0-10%, the composite composition of the tetramethylene sulfone of 0-10%.
Sweetening agent of the present invention, 1,4 morpholine addition is very few, and as too much being less than 20%, then sweetening effectiveness is similar substantially to the hydramine sweetening agent, can not show clear superiority; Addition is too high, and is also influential to sweetening effectiveness as too much being higher than 70%, also can cause the too high increase of cost simultaneously, and therefore, the present invention is on a large amount of experimental basis, and it is comparatively suitable to propose 20-70%, also comparatively economical.
Sweetening agent of the present invention adds pyridine compounds, and for example pyridine, hexahydropyridine, Pyrrolizidine can strengthen the activity of sweetening agent, thereby improve desulfurization rate, also helps further depressant consumption.
Add tetramethylene sulfone in the sweetening agent of the present invention, more favourable to improving desulfurization rate.
In the sweetening agent of the present invention, the suitable consumption of 1,4 morpholine can be 30-60%, and alcohol amine compound is preferably 35-60%; Wherein a kind of more preferably 1,4 morpholine consumption is higher than alcohol amine compound.
The present invention is for strengthening the selectivity to sulfide, and alcohol amine compound better adopts multiple alcohol amine compound to be mixed, as being mixed with Monoethanolamine MEA BASF, diethanolamine, N-methyl-ethanolamine, N methyldiethanol amine, Mono Methyl Ethanol Amine etc.
The present invention makes sulfide selectivity and bonding force are shown bigger raising owing to adopt with the alternative part alcohol amine compound of 1,4 morpholine, and it is strong to hold the sulphur ability, and sweetening effectiveness is good, and the agent consumption is little, not only to H
2S still keeps selectivity and decreasing ratio preferably, and organic sulfides such as COS, RSH are also had higher decreasing ratio, and the organic sulfur removal rate reaches as high as 85%, and being used for the petroleum refinery can be with refinery gas (as liquefied gas) H
2S drops to below the 5ppm, and total sulfur drops to about 100ppm, total sulfur removal rate height.After adding pyridine compounds and tetramethylene sulfone, also can significantly improve the desulphurizing activated and desulfurization rate of sweetening agent, further depressant consumes, and the agent consumption only is a 0.014Kg/ ton oil.In addition, sweetening agent boiling point of the present invention up to 340 ℃ about, be difficult for to decompose, this also is favourable to the depressant consumption.Sweetening agent of the present invention has desulphurizing activated height than the hydramine sweetening agent, and it is big to take sulfur capacity, and reaction is fast, desulfuration efficiency is high, the anti-ability of separating is strong, long service life, and race is decreased low, and it is few to bubble, also has rust inhibition preferably simultaneously, to the catalyzer nontoxicity, especially applicable to higher sulphur concentration gas sweetening.
Sweetening agent of the present invention, owing to add 1,4 morpholine, its product color is yellow partially than the hydramine sweetening agent, density (20 ℃) is also big, reaches 1.05g/cm
3, than alcamines sweetening agent 1.04g/cm
3Slightly high, boiling point height (reaching about 340 ℃), this is the difference of sweetening agent outward appearance of the present invention and physical index and alcamines sweetening agent, can be used for simply distinguishing two class sweetening agents.
Sweetening agent of the present invention, also can be used for the coal is the Coal Chemical Industry aerogenesis desulfurization sulphur removal of raw material.
Below in conjunction with several embodiments, further specify the present invention.
Embodiment
Embodiment 1: 1,4 morpholine with 25%, 75% N methyldiethanol amine and a small amount of defoamer (foaming in elimination or the minimizing Hybrid Production Process), mixed stirring.Products obtained therefrom organic sulfur removal rate can reach about 25%.
Embodiment 2: 1,4 morpholine with 35%, and 40% N methyldiethanol amine, 25% diethanolamine adds a small amount of defoamer, mixed stirring.Products obtained therefrom organic sulfur removal rate can reach about 40%.
Embodiment 3: 1,4 morpholine with 50%, and 25% N methyldiethanol amine, 20% diethanolamine, 5% tetramethylene sulfone adds a small amount of defoamer, mixed stirring.Products obtained therefrom organic sulfur removal rate can reach about 60%.
Embodiment 4: 1,4 morpholine with 65%, and 10% N methyldiethanol amine, 8% Monoethanolamine MEA BASF, 8% diethanolamine, 5% tetramethylene sulfone, 4% pyridine adds a small amount of defoamer, mixed stirring.Products obtained therefrom organic sulfur removal rate can reach about 85%.
By the foregoing description as can be known, along with the increase of 1,4 morpholine amount, desulfuration efficiency is improving.
Claims (6)
1, a kind of petroleum refinery sweetening agent is characterized in that 1,4 morpholine by 20-70%wt, the alcohol amine compound of 30-80%wt, the pyridine compounds of 0-10%wt, the composite composition of the tetramethylene sulfone of 0-10%wt.
2,, it is characterized in that said 1,4 morpholine consumption is 30-60%wt according to the described petroleum refinery of claim 1 sweetening agent.
3,, it is characterized in that said alcohol amine compound consumption is 35-60%wt according to claim 1 or 2 described petroleum refinery sweetening agents.
4,, it is characterized in that said alcohol amine compound is mixed by two or more alcohol amine compound to form according to the described petroleum refinery of claim 3 sweetening agent.
5,, it is characterized in that said 1,4 morpholine consumption is higher than alcohol amine compound according to claim 1,2 or 4 described petroleum refinery sweetening agents.
6, according to the described petroleum refinery of claim 3 sweetening agent, its feature is higher than alcohol amine compound at said 1,4 morpholine consumption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410014931 CN1261546C (en) | 2004-05-15 | 2004-05-15 | Improved desulfurizing agent for petroleum refinery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410014931 CN1261546C (en) | 2004-05-15 | 2004-05-15 | Improved desulfurizing agent for petroleum refinery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1580201A CN1580201A (en) | 2005-02-16 |
| CN1261546C true CN1261546C (en) | 2006-06-28 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 200410014931 Expired - Fee Related CN1261546C (en) | 2004-05-15 | 2004-05-15 | Improved desulfurizing agent for petroleum refinery |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051244B (en) * | 2009-10-28 | 2014-04-02 | 中国石油化工股份有限公司 | High-efficiency purification desulfurizer for high-acid oil and gas |
| CN102304383B (en) * | 2011-08-05 | 2013-10-16 | 天津迪赛福技术有限公司 | Oil product desulfurizer and use thereof |
| CN106381182B (en) * | 2016-09-27 | 2019-04-19 | 中国石油化工股份有限公司 | A kind of liquid-absorbant and its application for removing hydrogen sulfide |
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Owner name: JIANGSU JINLU ENVIRONMENTAL PROTECTION TECHNOLOGY Free format text: FORMER NAME: XINGDA CATALYST PLANT, YIXING CITY |
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| CP01 | Change in the name or title of a patent holder |
Address after: The big town Jiangsu city Yixing province Dapu village 214226 Patentee after: Jiangsu Jin Lu Environmental Protection Technology Co., Ltd. Address before: The big town Jiangsu city Yixing province Dapu village 214226 Patentee before: Xingda Catalyst Plant, Yixing City |
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Granted publication date: 20060628 Termination date: 20170515 |
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| CF01 | Termination of patent right due to non-payment of annual fee |