CN103146416B - Method of separating disulfide from lye - Google Patents
Method of separating disulfide from lye Download PDFInfo
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- CN103146416B CN103146416B CN201110401464.XA CN201110401464A CN103146416B CN 103146416 B CN103146416 B CN 103146416B CN 201110401464 A CN201110401464 A CN 201110401464A CN 103146416 B CN103146416 B CN 103146416B
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- disulphide
- alkali lye
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- lye
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Abstract
The invention relates to a method of separating disulfide from lye. The method comprises that the lye enters into a liquid inlet of an overweight machine through a pump after heat exchange, gas enters into a gas inlet through a flowmeter, the lye and the gas are mixed in the overweight machine, the disulfide diffuses from a liquid phase to a vapor phase and is eliminated with the gas, and thus the disulfide in the liquid phase is removed and re-enters a liquefied gas extracting system, wherein the gas is nitrogen, air or fuel gas, a content of the oxygen is less than or equal to 20 % v/v, a temperature of the lye is between a normal temperature and 80 DEG C, a volume ratio of the gas and the liquid is 1-500 : 1, a rotating speed of the overweight machine is 100-2000 rpm, an operation pressure is between a normal pressure and 1.0 Mpa, and the lye contains 0.1-10000 ppm of dimethyl disulfide, 0.1-10000 ppm of methylethyl disulfide or/and 0.1-10000 ppm of diethyl disulfide. The method can reduce a content of the disulfide in the lye to 5 ppmw or less.
Description
Technical field
The present invention relates to liquefied gas caustic wash desulfuration field, be specifically related to the method being removed disulphide in alkali lye by hypergravity technique.
Background technology
Liquefied gas usually adopts the method mercaptan removal of alkali cleaning in treating process, general process is that liquefied gas contacts with alkali lye and carries out extracting, react in acid low molecule mercaptan and sodium hydroxide in liquefied gas and generate sodium mercaptides and enter alkali lye phase, the sulfide of liquefied gas is removed, and total sulfur is minimized.Alkali lye containing sodium mercaptides contacts with air in oxidizing tower, under cobalt sulfonated phthalocyanine effect, sodium mercaptides generates disulphide and sodium hydroxide, the disulphide generated is insoluble to alkali lye, be separated with alkali lye through the gravity settling of more than 1 hour in disulphide slurry tank, the alkali lye after regeneration reenters extraction tower and uses.
But during the alkali liquor oxidized device actual motion of routine, in regeneration alkali lye, sodium hydroxide cannot be separated completely with disulphide, the disulphide of 2000 ~ 10000ppm is still had to stay in regeneration alkali lye with microemulsion state, thus cause entering liquefied gas at extraction phases, cause the total sulfur of liquefied gas to exceed standard.And disulphide is constantly accumulated in regeneration alkali lye, need the total sulfur often changing alkali lye guarantee liquefied gas up to standard, waste lye quantity discharged is larger.
The disulphide one removed in regeneration alkali lye to prevent disulphide from entering liquefied gas, can effectively reduce liquefied gas total sulfur, and two is to reduce waste lye discharge, is very important for liquefied gas caustic wash desulfuration alcohol.
CN87101298 proposes and disulfide reduction in regeneration alkali lye is become the method for mercaptan, and by the catalysis of metal catalyst or electrochemical method by disulfide reduction remaining in alkali lye, this Technology is complicated, industrial application poor practicability.
CN200880115461.6 proposes a kind of method using disulphide in activated carbon adsorption alkali lye, and it declares to realize alkali lye medium sulphide content to be removed to below 5ppmw.Its shortcoming is apparent, and disulphide is adsorbed to activated carbon, because the Sulfur capacity of activated carbon is very low, if implement frequently to change activated carbon adsorbent.And the activated carbon having adsorbed disulphide cannot regenerate, turn increase high sulfur-containing solid treatment of wastes produced.
Adopting solvent-extracted method to realize being separated of alkali lye and disulphide (back suction is carried) is one of conventional method.CN200510132299.7, CN200710100287.5 and CN200880102073.4 disclose similar method, namely the regeneration alkali lye after gravity settling enters solvent tower, and after utilizing reformed gasoline, straight-run spirit, stable gasoline, hydrogenation, disulphide removes by petroleum naphtha or other solvents.This method widely uses in tunica fibrosa sulfur removal technology, and advantage is that waste lye discharge obviously reduces.But this method generally can only by alkali lye about 30% disulphide extract, limited efficiency, and extraction after sulfur-bearing solvent have to pass through process could use, add running cost.
When the alkali liquor oxidized device actual motion of routine, the disulphide in alkali lye can be reduced by raising note air quantity.Principle is that oxidizing reaction generation disulphide has certain volatility, is easily diffused in gas phase.But because the operational condition of oxidizing tower limits, note air quantity can only be increased 5 times generally at most, otherwise oxidizing tower is difficult to stable operation.Based on above principle, the present invention proposes a kind of method adopting novel mass transfer apparatus to be separated to strengthen alkali lye with disulphide, and the equipment adopted is overweight machine or is called rotating packed bed.High-gravity technology has been widely used in the gas-liquid mass transfer strengthening fields such as nano material preparation, feedwater deoxidation, carbon dioxide absorption, is the representative of Novel chemical Reaction Separation technology.
Summary of the invention
The object of this invention is to provide a kind of method using high-gravity technology to remove disulphide in alkali lye, can by within alkali lye, the content of disulphide be down to 5ppmw.
The method being separated disulphide from alkali lye of the present invention is gas-liquid operate continuously, general process is as follows: alkali lye enters overweight machine liquid inlet through pump after heat exchange, gas enters gas inlet through under meter, gas-liquid carries out gas-liquid mixed in overweight machine, disulphide is diffused into gas phase from liquid phase, with air scavenge, in liquid phase, disulphide is removed, and reenters liquefied gas extraction system.
In method of the present invention, the gas used can be nitrogen, air or fuel gas, oxygen content≤20%v/v.
In method of the present invention, use overweight machine and rotating packed bed to be gas-liquid counter current and flow or baffling formal operations.
In method of the present invention, after overweight machine is generally placed on disulphide slurry tank, before also can being placed on disulphide slurry tank, or oxidizing tower outlet.
In method of the present invention, the temperature of alkali lye is generally normal temperature ~ 80 DEG C, and vapour-liquid ratio is generally at 1 ~ 500: 1 (v/v), and overweight machine rotating speed is generally at 100 ~ 2000rpm, and working pressure is normal pressure ~ 1.0MPa.
The disulphide contained in described alkali lye be the dimethyl disulfide of 0.1 ~ 10000ppm, 0.1 ~ 10000ppm the first and second base disulfides or/and the diethyl disulphide of 0.1 ~ 10000ppm.
Effect of the present invention: in the inventive method, the disulphide content in the alkali lye after hypergravity is separated is reduced to below 5ppmw.
Embodiment
Embodiment 1:
Alkali lye containing disulphide and nitrogen enter overweight machine respectively, and alkali liquid temperature is 40 DEG C, and vapour-liquid ratio is 200: 1 (v/v), rotating speed 1000rpm, atmospheric operation.In alkali lye before and after refining, disulphide content is in table 1.
Table 1
Embodiment 2:
Alkali lye containing disulphide and nitrogen enter overweight machine respectively, and alkali liquid temperature is 60 DEG C, and vapour-liquid ratio is 100: 1 (v/v), rotating speed 1000rpm, atmospheric operation.In alkali lye before and after refining, disulphide content is in table 2.
Table 2
Embodiment 3:
Alkali lye containing disulphide and air enter overweight machine respectively, and alkali liquid temperature is 40 DEG C, and vapour-liquid ratio is 200: 1 (v/v), rotating speed 600rpm, atmospheric operation.In alkali lye before and after refining, disulphide content is in table 3.
Table 3
Embodiment 4:
Alkali lye containing disulphide and air enter overweight machine respectively, and alkali liquid temperature is 60 DEG C, and vapour-liquid ratio is 100: 1 (v/v), rotating speed 2000rpm, atmospheric operation.In alkali lye before and after refining, disulphide content is in table 4.
Table 4
Embodiment 5:
Alkali lye containing disulphide and fuel gas (oxygen level 8%v/v) enter overweight machine respectively, and alkali liquid temperature is 40 DEG C, and vapour-liquid ratio is 200: 1 (v/v), rotating speed 1000rpm, atmospheric operation.In alkali lye before and after refining, disulphide content is in table 5.
Table 5
Embodiment 6:
Alkali lye containing disulphide and fuel gas (oxygen level 8%v/v) enter overweight machine respectively, and alkali liquid temperature is 40 DEG C, and vapour-liquid ratio is 200: 1 (v/v), rotating speed 1000rpm, working pressure 0.3MPa.In alkali lye before and after refining, disulphide content is in table 6.
Table 6
Comparative example 1
In the glass flask of a 500mL, add the alkali lye 300mL containing disulphide, pass into nitrogen by airway at drag, nitrogen flow 60L/h, reaction carries out 1h, temperature 40 DEG C, atmospheric operation, stir speed (S.S.) 200rpm.In alkali lye before and after refining, disulphide content is in table 7.
Table 7
Comparative example 2
In the glass flask of a 500mL, add the alkali lye 300mL containing disulphide, pass into air by airway at drag, nitrogen flow 60L/h, reaction carries out 1h, temperature 60 C, atmospheric operation, stir speed (S.S.) 200rpm.In alkali lye before and after refining, disulphide content is in table 8.
Table 8
Claims (2)
1. one kind is separated the method for disulphide from alkali lye, it is characterized in that: alkali lye enters overweight machine liquid inlet through pump after heat exchange, gas enters gas inlet through under meter, gas-liquid carries out gas-liquid mixed in overweight machine, disulphide is diffused into gas phase from liquid phase, with air scavenge, in liquid phase, disulphide is removed, and reenters liquefied gas extraction system;
The gas used is nitrogen, air or fuel gas, oxygen content≤20%v/v;
The temperature of alkali lye is normal temperature ~ 80 DEG C, and gas-liquid volume ratio is 1 ~ 500: 1, and overweight machine rotating speed is 100 ~ 2000rpm, and working pressure is normal pressure ~ 1.0Mpa;
The dimethyl disulfide of 0.1 ~ 10000ppm, the first and second base disulfides of 0.1 ~ 10000ppm are contained or/and contain the diethyl disulphide of 0.1 ~ 10000ppm in described alkali lye.
2. the method being separated disulphide from alkali lye according to claim 1, is characterized in that: the overweight machine used is for gas-liquid counter current and stream or the rotating packed bed of baffling formal operations.
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| CN201110401464.XA CN103146416B (en) | 2011-12-06 | 2011-12-06 | Method of separating disulfide from lye |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104624033B (en) * | 2013-11-13 | 2017-08-04 | 中国石油天然气股份有限公司 | A kind of liquefied gas deep desulfuration combined method |
| CN104694160B (en) * | 2013-12-06 | 2017-02-15 | 中国石油天然气股份有限公司 | A combined method of light gasoline desulphurization by alkali washing |
| CN104694151B (en) * | 2013-12-06 | 2016-08-17 | 中国石油天然气股份有限公司 | A kind of oxidized regenerating method containing mercaptides alkali liquor |
| CN103880722B (en) * | 2014-03-31 | 2016-08-31 | 宁波中一石化科技股份有限公司 | A kind of method preparing high-purity diethyl disulphide |
| CN104743726B (en) * | 2015-03-02 | 2018-06-26 | 宁波中一石化科技股份有限公司 | A kind of device and method based on hypergravity oxidative treatment refinery basic sewage |
| CN106929089B (en) * | 2015-12-29 | 2019-05-07 | 中国石油天然气股份有限公司 | A kind of pre-oxidation regeneration method of sulfur-bearing alkoxide lye |
| CN108704480B (en) | 2018-04-13 | 2020-11-06 | 中国石油天然气股份有限公司 | Regeneration method of liquefied gas desulfurized alcohol alkali liquor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101234791A (en) * | 2008-02-26 | 2008-08-06 | 刘泽政 | Hypergravity purifying method for ammonia nitrogen sewage and hypergravity machine used in the same |
| CN101962566A (en) * | 2009-07-21 | 2011-02-02 | 宁波中一石化科技有限公司 | Mercaptan removed alkali liquid oxidation regeneration method and device thereof |
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| US6306288B1 (en) * | 1998-04-17 | 2001-10-23 | Uop Llc | Process for removing sulfur compounds from hydrocarbon streams |
| CN101371967B (en) * | 2007-08-24 | 2011-03-30 | 宁波中一石化科技有限公司 | Liquid gas sweetening alkali liquor oxidized regeneration method and apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101234791A (en) * | 2008-02-26 | 2008-08-06 | 刘泽政 | Hypergravity purifying method for ammonia nitrogen sewage and hypergravity machine used in the same |
| CN101962566A (en) * | 2009-07-21 | 2011-02-02 | 宁波中一石化科技有限公司 | Mercaptan removed alkali liquid oxidation regeneration method and device thereof |
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