CN101457157A - Method for removing sulphur in gasoline by electrochemical oxidation - Google Patents
Method for removing sulphur in gasoline by electrochemical oxidation Download PDFInfo
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- CN101457157A CN101457157A CNA2007101792760A CN200710179276A CN101457157A CN 101457157 A CN101457157 A CN 101457157A CN A2007101792760 A CNA2007101792760 A CN A2007101792760A CN 200710179276 A CN200710179276 A CN 200710179276A CN 101457157 A CN101457157 A CN 101457157A
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Abstract
The present invention relates to a method to remove sulphur in gasolene by using electrochemistry measure, which comprises the following procedures: first mix gasolene with an electrolytic system that consists of polar solvent, supporting electrolyte and water and place the mixture into an isolated electric tank for electrolysis, then settling separate fat phase and electrolytic system phase, electrolytic oxidation product of sulfur-containing compound of gasoline enter into electrolytic system phase to be removed; volume ratio between gasolene and electrolytic system is 0.5-2; electrolytic temperature range is from 40 DEG C to 50 DEG C; supporting electrolytes/ polar solvent is 0.1-2mol/L; volume ration between water and dissolvent is 0.1-1; polar solvent is one of acetic acid and ethyl hydrate or the mixture; supporting electrolytes is sodium chloride or sodium acetate; water is used to provide oxygen source in the process; operation condition is mild; dissolvent and supporting electrolytes can be used for periodic duty in electrolytic process; zero discharge can be realized primarily; hydrogen gas is produced secondarily; octane ratio lowing down problem because of hydrogenation in oil-extraction plant gasoline catalysis and cracking process can be solved.
Description
Technical field
The present invention relates to a kind of selective oxidation of sulfur containing compounds in particular in the gasoline be become stronger sulfone of polarity or sulfoxide class sulfide, be extracted into the stronger electrolysis system of polarity and its electrochemical oxidation that removes removed the method for sulfur in gasoline in mutually from oil product.
Background technology
Strict day by day and production gasoline stocks trend heaviness and poor qualityization with environmental requirement, especially the sulphur and the aromaticity content of catalytic gasoline increase to cause gasoline, be difficult to satisfy the requirement of cleaning Oil Production, therefore, it is more and more urgent to fall aromatic hydrocarbons Research on New development requires for gasoline desulfur.
Catalytic desulfurhydrogenation is present topmost light-end products desulfurization means, usually adopt Ni-W, Mo-Ni series catalysts, difference according to raw material, the hydrogen branch of gasoline hydrofinishing process is pressed in 3～4MPa, service temperature changes between 300 ℃～400 ℃, the outer hydrogen supply gas of process need, and the octane value of gasoline descends a lot, very uneconomical hydrogenating desulfurization the time.
The on-catalytic hydrogenated gasoline desulfuration purification technology of research and development such as biological process (US5910440), absorption method (US5730860) and oxidation desulfurization etc. show good application prospects at present.Wherein especially be suitable for the deep desulfuration of gasoline with oxidation style.
The photocatalytic oxidation gasoline desulfur technology of research such as Hirai and Shiraishi.In acetonitrile, add photosensitizers, use λ the visible light of 400nm shines, and is polarity sulfide with selective oxidation of sulfur containing compounds in particular, enters extraction phase, again with separation of oil.
Petro Star company has researched and developed and has utilized Peracetic Acid or peroxyformic acid between 75～95 ℃ He under the condition of normal pressure gasoline being carried out oxidation for oxygenant, adding the sulfocompound of polar solvent after to oxidation then extracts, extraction agent and desulfurization oil product distillatory method separating and recovering extractant, the oil product after extraction is through solid phase adsorption such as aluminum oxide.This method can be that the oil fuel of 4200ppm drops to 10ppm with sulphur content.Aforesaid method has desulfurization degree height, operational condition gentleness, equipment characteristic of simple than the catalytic desulfurhydrogenation technology, but exists the oxidation desulfur reaction selectivity low, shortcomings such as oxygenant costliness such as hydrogen peroxide and peroxy acid.
Summary of the invention
The objective of the invention is to develop and a kind ofly selective oxidation of sulfur containing compounds in particular in the gasoline become stronger sulfone of polarity or sulfoxide class sulfide by adopting the method for electrochemical oxidation, be extracted into the stronger electrolysis system of polarity mutually in and it is removed from oil product.
Electrolytic reaction is carried out in isolated electrolyzer, barrier film adopts sintered glass, carbon dioxide process carbon electrode is an anode, with plumbous, nickel is negative electrode, gasoline mixes by the electrolysis system be made up of solvent, supporting electrolyte and water and carries out electrolysis, settlement separate oil phase and electrolysis system mutually, the sulfocompound in the gasoline is become corresponding sulfone of strong polarity and sulfoxide compound at anode by electrolytic oxidation, be extracted and enter the stronger electrolysis system of polarity and remove mutually, simultaneously catholyte by-product hydrogen.
A kind of novel method of utilizing electrochemistry to carry out gasoline desulfur of the present invention, be gasoline to be mixed into by the electrolysis system of being made up of polar solvent, supporting electrolyte and water carry out electrolysis in the isolated electrolyzer, barrier film adopts inert material such as sintered glass, pottery etc.; With inertia resistance to oxidation material is anode, as Graphite Electrodes, carbon dioxide process carbon electrode etc.; With plumbous, nickel is negative electrode; Settlement separate oil phase and electrolysis system mutually, the electrolytic oxidation product of sulfocompound enters electrolysis system mutually and remove in the oil, simultaneously catholyte by-product hydrogen.
Gasoline of the present invention and electrolysis system volume ratio are 0.1～5, and be preferred 0.3～4, most preferably 0.5～2.The add-on of gasoline is too low, and the treatment capacity of meaning gasoline is little, and a large amount of electrolysis system circulations is also uneconomical, and the gasoline add-on is too high, also not exclusively dissolves each other with electrolysis system, is unfavorable for electrolytic carrying out.
Electrolysis temperature scope of the present invention is 10 ℃～90 ℃, preferred 25 ℃～75 ℃, and most preferably 40 ℃～50 ℃.The electrolysis temperature height, electrolytic reaction speed is fast, the current efficiency height, electrolysis temperature is too high, and solvent and gasoline volatilization are accelerated, and electrolysis needs to carry out in the reactor of pressurization, brings difficulty for design, processing and the operation of equipment.
Polar solvent of the present invention can be one or several mixtures in low carbon organic acid, low-carbon alcohol and the acetonitrile.
Low carbon organic acid of the present invention can be one or several mixtures in acetate, formic acid, the propionic acid.
Low-carbon alcohol of the present invention can be one or several mixtures in methyl alcohol, ethanol, propyl alcohol, the butanols.
Supporting electrolyte of the present invention can be one or several mixtures of an alkali metal salt of hydrochloric acid, Hydrogen bromide, formic acid, acetate.
Polar solvent is selected one or several mixtures of low carbon organic acid, low-carbon alcohol and acetonitrile isopolarity solvent, with acetate and alcohol mixed solvent is example, wherein to account for solvent volume per-cent be 10%～100% to acetate, and acetate can also make electrolysis system be acid, CH as solvent the time
3COO
-Or anode surface free radical O
aTransmission medium, CH
3COO
-+ O
a=CH
3COOO
-, the CH of formation
3COOO
-Can enter the sulfocompound that participates in the electrolysis system in the oxidation of gasoline.One or several mixtures that add an alkali metal salt of hydrochloric acid, Hydrogen bromide, formic acid, acetate are made supporting electrolyte, preferred sodium-chlor or sodium acetate, and its concentration is 0.1～2mol/L.The adding of supporting electrolyte can increase the conductivity of electrolysis system, Cl wherein on the other hand on the one hand
-And CH
3COO
-Also participate in reaction, Cl
-+ O
a=ClO
-The add-on of water can not be too low, too lowly can not provide the electrolytic oxidation desulfurization required oxygen, can not be too high, the electrolysis system of too high composition reduces the dissolving power of gasoline, be unfavorable for electrolytic carrying out, water and solvent volume are than should preferably being controlled in 0.1～1 the scope.Form electrolysis system like this.
Gasoline joins electrolysis in the electrolysis system by a certain percentage, and preferred electrolytic potential is controlled at 1500～2500mV (with respect to reference electrode), and electrolytic potential is too low, and electrolytic reaction can not take place, and electrolytic potential is too high, and it is serious that anode is analysed oxygen, influences current efficiency.Sulfocompound in the gasoline is become corresponding sulfone of strong polarity and sulfoxide compound at anode by electrolytic oxidation, and the cathodic area produces hydrogen simultaneously, is high-purity hydrogen behind adsorbing and removing less water volatile matter.After finishing, electrolysis adds the entry extraction, solvent and supporting electrolyte in sulfone and sulfoxide compound and the electrolysis system enter water, water and upper strata gasoline layering, separating in the gasoline of back still has a spot of sulfone and sulfoxide compound not to be extracted, and further separates with adsorbents adsorb such as aluminum oxide, carclazytes.Isolating water returns as electrolysis system after removing portion water and recycles.
Electrochemistry of the present invention is carried out the novel method of gasoline desulfur, is to be that reaction provides oxygen source with water, does not need outer hydrogen supply gas and oxygenant, operational condition gentleness (being generally low temperature, normal pressure); Solvent and supporting electrolyte can be recycled in electrolytic process, realize zero release substantially; Can by-product hydrogen; Can reach the purpose of deep desulfuration, be reduced to below the 50ppm through sulphur content in the oil product after extraction, the absorption.Maximum benefit keeps octane value not reduce when being desulfurization.
Embodiment
Embodiment 1
Plate graphite is an anode, and dull and stereotyped lead is negative electrode, and the two poles of the earth surface-area is 4cm
2, barrier film is a sintered glass.The electrolysis system that adopts is " H
2O-EtOH-CH
3COOH-NaCl ".Take by weighing pure H
2O 7.50g, EtOH (ethanol) 10.67g (13.50ml), CH
3COOH (acetate) 1.58g (1.50ml), NaCl 1.98g (1.50mol/L).After mixing fully stirring, take out 3ml and be added to the cathodic area, all the other are added to the positive column, and adding 22.50ml content is thionaphthene-hexanaphthene organic solution of 650g/mL, the agent-oil ratio of this moment is 1:1, stirs 30 ℃ of constant temperature, the control electrolytic potential is that 1700mV carries out potentiostatic deposition 5hr, and thionaphthene content is reduced to 32mg/L from 353mg/L in the hexanaphthene.
Embodiment 2
Electrode and electrolysis system are with embodiment 1.Take by weighing pure H
2O 10.00g, EtOH 14.22g (18.00ml), CH
3COOH 2.11g (2.00ml), NaCl 2.63g (1.50mol/L).After mixing fully stirring, take out 3ml and be added to the cathodic area, all the other are added to the positive column, and adding the 15.00ml catalytically cracked gasoline, the agent-oil ratio of this moment is 2:1, stirs, 30 ℃ of constant temperature, the control electrolytic potential is 1700mV electrolysis 6hr, sulphur content is reduced to 54mg/L by 235mg/L in the oil sample.
Embodiment 3
Electrode and barrier film are with embodiment 1.Take by weighing pure H
2O 7.50g, EtOH 10.67g (13.50ml), CH
3COOH 1.58g (1.50ml), NaCl 1.98g (1.50mol/L).After mixing fully stirring, take out 3ml and be added to the cathodic area, all the other are added to the positive column, and adding the 22.50ml catalytically cracked gasoline, the agent-oil ratio of this moment is 1:1, stirs, 30 ℃ of constant temperature, the control electrolytic potential is 1700mV electrolysis 5hr, sulphur content is reduced to 67mg/L by 235mg/L in the oil sample.
Embodiment 4
Electrode, barrier film and electrolysis system are with embodiment 1.Take by weighing pure H
2O 7.50g, EtOH 10.67g (13.50ml), CH
3COOH 1.58g (1.50ml), NaCl 1.98g (1.50mol/L).After mixing fully stirring, and add the 11.25ml catalytically cracked gasoline, the agent-oil ratio of this moment is 2:1, and temperature is 50 ℃, and the control electrolytic potential is 1900mV electrolysis 8hr, separates oil sample and uses the 2g alumina adsorption again, and sulphur content is reduced to 16mg/L by 235mg/L in the oil sample.
Embodiment 5
Electrode and barrier film are with embodiment 1.The electrolysis system that adopts is " H
2O-EtOH-CH
3COOH-CH
3COONa ".Take by weighing pure H
2O 11.25g, CH
3CN 5.25mL CH
3COOH 6.3g (6ml), CH
3COONa0.93g (0.50mol/L).After mixing fully stirring, take out 3ml and be added to the cathodic area, all the other are added to the positive column, and adding the 22.50ml catalytically cracked gasoline, the agent-oil ratio of this moment is 1:1, stirs, 30 ℃ of temperature, the control electrolytic potential is 1700mV electrolysis 5hr, sulphur content is reduced to 34mg/L by 235mg/L in the oil sample.
Claims (1)
1. an electrochemical oxidation removes the method for sulfur in gasoline, it is characterized in that: at first gasoline is mixed with the electrolysis system of being made up of polar solvent, supporting electrolyte and water, enter and carry out electrolysis in the isolated electrolyzer, settlement separate oil phase and electrolysis system mutually, the electrolytic oxidation product of sulfocompound enters electrolysis system mutually and remove in the oil;
Gasoline and electrolysis system volume ratio are 0.5～2;
The electrolysis temperature scope is 40 ℃～50 ℃;
Supporting electrolyte/polar solvent is 0.1～2mol/L;
Water and polar solvent volume ratio are 0.1～1;
Polar solvent is an a kind of or mixture of acetate and alcoholic acid;
Supporting electrolyte is sodium-chlor or sodium acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101792760A CN101457157A (en) | 2007-12-12 | 2007-12-12 | Method for removing sulphur in gasoline by electrochemical oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2007101792760A CN101457157A (en) | 2007-12-12 | 2007-12-12 | Method for removing sulphur in gasoline by electrochemical oxidation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101457157A true CN101457157A (en) | 2009-06-17 |
Family
ID=40768280
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2007101792760A Pending CN101457157A (en) | 2007-12-12 | 2007-12-12 | Method for removing sulphur in gasoline by electrochemical oxidation |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2462501C1 (en) * | 2011-05-27 | 2012-09-27 | Государственное образовательное учреждение Высшего профессионального образования Национальный исследовательский Томский политехнический университет | Method of demetallisation and crude oil desulfurisation in flow |
| CN103242897A (en) * | 2013-04-23 | 2013-08-14 | 上海交通大学 | Method for removing sulfur from fuel oil through electrolytic reduction |
| CN103998576A (en) * | 2011-07-29 | 2014-08-20 | 沙特阿拉伯石油公司 | Process for in-situ electrochemical oxidative generation and conversion of organosulfur compounds |
| CN106833722A (en) * | 2017-03-28 | 2017-06-13 | 刘望舒 | A kind of lightweight desulfurating agent and preparation method thereof |
-
2007
- 2007-12-12 CN CNA2007101792760A patent/CN101457157A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2462501C1 (en) * | 2011-05-27 | 2012-09-27 | Государственное образовательное учреждение Высшего профессионального образования Национальный исследовательский Томский политехнический университет | Method of demetallisation and crude oil desulfurisation in flow |
| CN103998576A (en) * | 2011-07-29 | 2014-08-20 | 沙特阿拉伯石油公司 | Process for in-situ electrochemical oxidative generation and conversion of organosulfur compounds |
| CN103998576B (en) * | 2011-07-29 | 2016-03-16 | 沙特阿拉伯石油公司 | The electrochemical in-situ oxidation of organosulfur compound generates and method for transformation |
| CN103242897A (en) * | 2013-04-23 | 2013-08-14 | 上海交通大学 | Method for removing sulfur from fuel oil through electrolytic reduction |
| CN103242897B (en) * | 2013-04-23 | 2015-04-22 | 上海交通大学 | Method for removing sulfur from fuel oil through electrolytic reduction |
| CN106833722A (en) * | 2017-03-28 | 2017-06-13 | 刘望舒 | A kind of lightweight desulfurating agent and preparation method thereof |
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Open date: 20090617 |