CN101153225A - Oxidization-abstraction desulfurization technology of petroleum product based on ion liquid - Google Patents
Oxidization-abstraction desulfurization technology of petroleum product based on ion liquid Download PDFInfo
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- CN101153225A CN101153225A CNA2007101216709A CN200710121670A CN101153225A CN 101153225 A CN101153225 A CN 101153225A CN A2007101216709 A CNA2007101216709 A CN A2007101216709A CN 200710121670 A CN200710121670 A CN 200710121670A CN 101153225 A CN101153225 A CN 101153225A
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- oxidation
- carboxyalkyl
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Abstract
The present invention relates to a technology suitable for desulfurization of fuel oil products. In the oxidizing-extracting process to sulfur-containing oil products, the technology uses ionic liquid as reaction medium, catalyst and extracting agent to remove organic sulfur or inorganic sulfur in the oil products. Compared with the prior oxidative desulfurizing and extraction desulfurizing method, the present invention improves desulphurization effect to over 99 percent from about 50 percent; meanwhile, the added carboxyl alkyl functionalized ionic liquid has low vapor pressure and high boiling point, which is convenient for recycling. The novel desulfurization process can obviously improve desulphurization effect, simplifies production process, saves energy, and has the advantages of simple equipment, convenient operation, little investment, easy realization of industrialization, etc.
Description
Technical field: the present invention relates to oil product in the oxidation-extraction desulfurization process with a kind of desulfurization technology of ionic liquid as reaction medium, catalyzer and extraction agent.
Background technology:
Along with the aggravation of environmental pollution and the enhancing of people's environmental consciousness, people more and more focus in oil product processing and the use destruction to ecotope such as the acid rain that the discharging owing to sulfide causes, for example be discharged into atmosphere behind the combustion of sulfur in the gasoline and not only can influence environment, the SO of generation
xAlso can reduce the vehicle exhaust convertor to NO
x, imperfect combustion hydro carbons and particulate matter etc. transformation efficiency.And the continuous minimizing of crude oil reserve, make the poor quality degree of oil product constantly aggravate, in China, the gasoline that high-sulfur crude oil is produced through catalytic cracking (FCC) accounts for more than 80% of gasoline ultimate production, but its sulphur content is far above foreign level, therefore extensively carry out the desulfurizing oil Research on New, become the task of top priority of China's oil refining industry.
As green solvent, unique character such as ionic liquid has that polarity is strong, solvability good, low-steam pressure, structure can design, have broad application prospects in fields such as extracting and separating, catalyzed reactions, especially replacing traditional catalyzer, the easy volatile solvent, aspects such as reduction VOC pollution have remarkable advantages.Caused people's attention as sweetening agent with the sulfocompound that removes in the gasoline with ionic liquid.At present, R﹠D institutions such as Akzo Nobel company have carried out research in this regard, have proved the feasibility of this method.
But mainly concentrating on, existing at present research adopt ionic liquid to carry out the abstraction desulfurization experiment, as studies show that glyoxaline ion liquid is to thiophene, thionaphthene, main sulfurous organic compound has solvability (as: patent CN200610066595, CN200410037677 and CN03137916) preferably in the oil fuel such as dibenzothiophene.Desulfuration efficiency is low, the ionic liquid consumption is big, viscosity is high, thereby oil product intermediate ion liquid residue content height influences oil quality, the high deficiency of desulphurization cost but these class methods exist, and is difficult to be well used in industry.And traditional oxidation sweetening adopts organic acid as catalyzer mostly, and organic solvents such as alcohols or acetonitrile are as extraction agent.UniPure company has applied for multinomial patent in this respect, as patent WO02/18518, and US2002/0029997, US6406166 and US6402940 disclose use 30%H
2O
2Oxidation-extraction (or absorption) is handled the method for fraction oil of petroleum deep desulfuration.The consumption of its formic acid is big, and requires its concentration height, has the operating procedure complexity, and organic solvent is easy to volatilization and causes deficiencies such as secondary pollution, sweetening agent loss are big.Based on above present Research, the present invention with green solvent-ionic liquid as reaction medium, catalyzer and extraction agent, under the oxygenant existence condition, oil product is carried out desulfurization, it is advantageous that and to improve sweetening effectiveness greatly, simplified oxidation desulfuration process, secondary pollution that ionic liquid aqueous solution effectively reduced liquid viscosity, reduce ion liquid consumption, form when avoiding using organic kind solvent etc. has broad application prospects.
Summary of the invention
The present invention relates to the carboxyalkyl imidazoles, the carboxyalkyl pyridine, the mixture of one or more in carboxyalkyl quaternary amine and the carboxyalkyl quaternary phosphonium class ionic liquid is reaction medium, catalyzer and extraction agent, is oxygenant with the organic or inorganic superoxide, oil product is carried out the novel method of oxidation-extraction desulfurization.Oil product involved in the present invention comprises the work in-process oil in crude oil, oil fuel and the crude oil refining process.
The ion liquid positively charged ion that uses among the present invention is by the carboxyalkyl imidazoles, the carboxyalkyl pyridine, a kind of in carboxyalkyl quaternary amine and the carboxyalkyl quaternary phosphonium class, negatively charged ion is inorganic or organic neutrality or acidic anionic, wherein carboxyalkyl imidazoles positively charged ion is by 1-n carboxyalkyl-3-alkyl imidazole, the 1-n carboxyalkyl-3-n carboxyalkyl imidazoles of different side chain carbon numbers or contain a kind of wherein n=1～3 in the ion of carboxyalkyl glyoxaline structure, negatively charged ion can be stable inorganic or organic ion, as: Br
-, Cl
-, PF
6 -, BF
4 -, [CF
3COO]
-, [(CH
3COO]
-Deng.More than ion liquid structural formula can be exemplified below:
[CH
3COOHim] Br:1-carboxymethyl-3-Methylimidazole bromine salt
[CH
3COOHim] [BF
4]: 1-carboxymethyl-3-Methylimidazole fluoroborate
[C
2H
5COOHim] [BF
4]: 1-propyloic-3-Methylimidazole fluoroborate
[C
2H
5COOHim] [PF
6]: 1-propyloic-3-Methylimidazole fluorophosphate
Purified above-mentioned ion liquid dissolving in certain water gaging, is joined in a certain amount of sour product, at a certain temperature, add proper amount of oxidant and carry out desulfurization.The concentration range of ionic liquid aqueous solution is 0.1%～99.9%.Normal pressure or (be preferably under 1～10atm) at pressure 0.1atm～50atm, under 273K～373K temperature, reaction times oil product (the work in-process oil in crude oil, oil fuel and the crude oil refining process) to sulfur-bearing in 1～8h scope carries out the experiment that removes of sulfurous organic compound or inorganics.Can clear layering after absorbing saturated liquid and leaving standstill, recycle resulting solvent is renewable after the solvent layer underpressure distillation after the separation.
Embodiment:
The present invention illustrates with following embodiment, but the present invention is not limited to following embodiment, under the scope of described aim, changes and implements to be included in the technical scope of the present invention before and after not breaking away from.
Embodiment 1
With 2ml[CH
3COOHim] Br joins in the analog gasoline of 10ml sulfur-bearing (thiophene) 1500ppm, under normal pressure stirs, when being warming up to 343K, adds the H of 2ml
2O
2, behind the magnetic agitation 5h, leave standstill, layering, detect with gas-chromatography, the sulphur content in the oil product can be reduced to 10ppm.After finishing using, isolate gasoline, solvent layer underpressure distillation under the 353K condition can be reused.
Embodiment 2
With 2ml[CH
3COOHim] [BF
4] join in the analog gasoline of 10ml sulfur-bearing (thiophene) 1500ppm, under normal pressure stirs, when being warming up to 343K, add the H of 2ml
2O
2, behind the magnetic agitation 2h, leave standstill, layering, detect with gas-chromatography, the sulphur content in the oil product can be reduced to 10ppm.After finishing using, isolate gasoline, solvent layer underpressure distillation under the 353K condition can be reused.
Embodiment 3
With 5ml[CH
3COOHim] Br joins in the analog gasoline of 10ml sulfur-bearing (thiophene) 1500ppm, under normal pressure stirs, when being warming up to 313K, adds the H of 2ml
2O
2, behind the magnetic agitation 2h, leave standstill, layering, detect with gas-chromatography, the sulphur content in the oil product can be reduced to 10ppm.After finishing using, isolate gasoline, solvent layer underpressure distillation under the 353K condition can be reused.
Embodiment 4
With 5ml[CH
3COOHim] [BF
4] join in the analog gasoline of 10ml sulfur-bearing (thiophene) 1500ppm, under normal pressure stirs, when being warming up to 343K, add the H of 2ml
2O
2, behind the magnetic agitation 6h, leave standstill, layering, detect with gas-chromatography, the sulphur content in the oil product can be reduced to 6ppm.After finishing using, isolate gasoline, solvent layer underpressure distillation under the 353K condition can be reused.
Embodiment 5
With 2ml[CH
3COOHim] [BF
4] join in the analog gasoline of 10ml sulfur-bearing (thiophene) 1500ppm, under normal pressure stirs, when being warming up to 303K, add the H of 2ml
2O
2, behind the magnetic agitation 2h, leave standstill, layering, detect with gas-chromatography, the sulphur content in the oil product can be reduced to 15ppm.After finishing using, isolate gasoline, solvent layer underpressure distillation under the 353K condition can be reused.
Embodiment 6
With 2ml[CH
3COOHim] [BF
4] join in the analog gasoline of 10ml sulfur-bearing (thionaphthene) 1500ppm, under normal pressure stirs, when being warming up to 303K, add the H of 2ml
2O
2, behind the magnetic agitation 2h, leave standstill, layering, detect with gas-chromatography, the sulphur content in the oil product can be reduced to 18ppm.After finishing using, isolate gasoline, under the 493K condition, check distillation to reuse solvent layer.
Claims (8)
1. one kind based on ion liquid oil oxidation-extraction desulfurization technique, it is characterized in that choosing with the carboxyalkyl imidazoles, the carboxyalkyl pyridine, the mixture of one or more in carboxyalkyl quaternary amine and the carboxyalkyl quaternary phosphonium class ionic liquid is a reaction medium, catalyzer and extraction agent, in the presence of oxygenant, utilize the limit oxidation, the principle desulfurization of limit extraction, it is characterized in that ionic liquid is the functionalized ion liquid that contains carboxyalkyl, adopt the extraction of oxidation limit, one pot of addition method limit, ionic liquid again as the extraction agent in the extraction process, is used for removing the organosulfur or the inorganic sulfur of oil product as reaction medium in the oxidising process and catalyzer.
2. according to claim 1 a kind of based on ion liquid oil oxidation-extraction desulfurization technique, it is characterized in that the carboxyalkyl in the ionic liquid that this oxidation-extraction desulfurization technique uses is monobasic carboxyalkyl, binary carboxyalkyl or ternary carboxyalkyl.
3. according to claim 1 a kind of based on ion liquid oil oxidation-extraction desulfurization technique, it is characterized in that the oil product that this oxidation-extraction desulfurization technique removes comprises crude oil, the work in-process oil in oil fuel and the crude oil refining process.
4. according to claim 1 a kind of based on ion liquid oil oxidation-extraction desulfurization technique, the temperature that it is characterized in that desulfurization is between 273K and 373K.
5. according to claim 1 a kind of based on ion liquid oil oxidation-extraction desulfurization technique, the pressure range that it is characterized in that this sweetening process is preferably between 1～10atm between 0.1～50atm.
6. according to claim 1 a kind of based on ion liquid oil oxidation-extraction desulfurization technique, the concentration that it is characterized in that this desulfurization technology intermediate ion liquid aqueous solution is 0.1%～99.9%.
7. according to claim 1 a kind of based on ion liquid oil oxidation-extraction desulfurization technique, it is characterized in that agent-oil ratio in this desulfurization technology is between 1: 8～2: 1.
8. oxidation-extraction desulfurization method according to claim 1 is characterized in that desulfurization time is controlled between 0.2h～10h.
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|---|---|---|---|
| CN2007101216709A CN101153225B (en) | 2007-09-12 | 2007-09-12 | Oxidization-abstraction desulfurization technology of petroleum product based on ion liquid |
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| CN101153225B CN101153225B (en) | 2012-06-27 |
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|---|---|---|---|---|
| CN102199442A (en) * | 2011-04-14 | 2011-09-28 | 大连大学 | Method for applying amine proton-type ionic liquid extractant in desulfurization of oil product and recovering extractant |
| CN102408915A (en) * | 2010-09-21 | 2012-04-11 | 中国科学院大连化学物理研究所 | Method for oil product desulfurization through oxidation and extraction |
| CN102690676A (en) * | 2012-05-14 | 2012-09-26 | 辽宁大学 | FCC (fluid catalytic cracking) gasoline oxidation desulfurization method by utilizing ionic liquids |
| CN102746874A (en) * | 2012-07-31 | 2012-10-24 | 中国石油天然气股份有限公司抚顺石化分公司 | Method for FCC (Fluid Catalytic Cracking) gasoline oxidation sweetening with ionic liquid |
| CN103242903A (en) * | 2012-02-06 | 2013-08-14 | 郑舜升 | Fuel desulfurization method |
| CN103450088A (en) * | 2013-09-22 | 2013-12-18 | 辽宁石油化工大学 | Novel sulfonic acid functionalized rhenium ionic liquid and preparation method and application thereof |
| CN103467384A (en) * | 2013-09-22 | 2013-12-25 | 辽宁石油化工大学 | Novel carboxylic acid functional rhenium iron liquid and preparation method and application thereof |
| CN103525453A (en) * | 2013-09-16 | 2014-01-22 | 烟台大学 | Oxidative coupling extraction desulfurization of petroleum product as well as ionic liquid and preparation method thereof |
| CN103626706A (en) * | 2013-12-02 | 2014-03-12 | 辽宁大学 | Novel efficient ionic liquid with desulfuration function as well as preparation method and application thereof |
| CN103740398A (en) * | 2014-01-09 | 2014-04-23 | 江苏大学 | Method for desulfurizing fuel oil through catalytic oxidation by adopting piperidine ionic liquid |
| CN103834432A (en) * | 2014-03-24 | 2014-06-04 | 中国科学院山西煤炭化学研究所 | Method for extracting, oxidizing and desulfuring fuel oil in ionic liquid |
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| CN105623710A (en) * | 2016-04-06 | 2016-06-01 | 成都天丰清洁能源发展有限公司 | Method for desulfurizing gasoline product by using ionic liquid |
| CN105778980A (en) * | 2016-02-28 | 2016-07-20 | 辽宁石油化工大学 | Method for regenerating hydrophilic type ionic liquid desulfurizing agent through reverse extraction |
| CN108504868A (en) * | 2018-05-15 | 2018-09-07 | 中国科学院过程工程研究所 | A kind of method of lithium metal in recycling waste and old lithium ion battery |
| CN108822884A (en) * | 2018-06-04 | 2018-11-16 | 湖南省林业科学院 | A kind of abstraction desulfurization agent, preparation method and biodiesel desulfurization refining method |
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| US6274026B1 (en) * | 1999-06-11 | 2001-08-14 | Exxonmobil Research And Engineering Company | Electrochemical oxidation of sulfur compounds in naphtha using ionic liquids |
| CN1827747A (en) * | 2006-04-03 | 2006-09-06 | 中国石油大学(北京) | Diesel oil coupled desulfurization method |
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| CN102408915A (en) * | 2010-09-21 | 2012-04-11 | 中国科学院大连化学物理研究所 | Method for oil product desulfurization through oxidation and extraction |
| CN102199442B (en) * | 2011-04-14 | 2013-11-06 | 大连大学 | Method for applying amine proton-type ionic liquid extractant in desulfurization of oil product and recovering extractant |
| CN102199442A (en) * | 2011-04-14 | 2011-09-28 | 大连大学 | Method for applying amine proton-type ionic liquid extractant in desulfurization of oil product and recovering extractant |
| US9127214B2 (en) | 2012-02-06 | 2015-09-08 | Shun-Sheng Cheng | Fuel desulfurization method |
| CN103242903A (en) * | 2012-02-06 | 2013-08-14 | 郑舜升 | Fuel desulfurization method |
| CN102690676A (en) * | 2012-05-14 | 2012-09-26 | 辽宁大学 | FCC (fluid catalytic cracking) gasoline oxidation desulfurization method by utilizing ionic liquids |
| CN102746874A (en) * | 2012-07-31 | 2012-10-24 | 中国石油天然气股份有限公司抚顺石化分公司 | Method for FCC (Fluid Catalytic Cracking) gasoline oxidation sweetening with ionic liquid |
| CN102746874B (en) * | 2012-07-31 | 2014-10-15 | 中国石油天然气股份有限公司抚顺石化分公司 | Method for FCC (Fluid Catalytic Cracking) gasoline oxidation sweetening with ionic liquid |
| CN103525453A (en) * | 2013-09-16 | 2014-01-22 | 烟台大学 | Oxidative coupling extraction desulfurization of petroleum product as well as ionic liquid and preparation method thereof |
| CN103450088A (en) * | 2013-09-22 | 2013-12-18 | 辽宁石油化工大学 | Novel sulfonic acid functionalized rhenium ionic liquid and preparation method and application thereof |
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| CN103467384B (en) * | 2013-09-22 | 2015-05-13 | 辽宁石油化工大学 | Novel carboxylic acid functional rhenium iron liquid and preparation method and application thereof |
| CN103626706A (en) * | 2013-12-02 | 2014-03-12 | 辽宁大学 | Novel efficient ionic liquid with desulfuration function as well as preparation method and application thereof |
| CN103740398A (en) * | 2014-01-09 | 2014-04-23 | 江苏大学 | Method for desulfurizing fuel oil through catalytic oxidation by adopting piperidine ionic liquid |
| CN103740398B (en) * | 2014-01-09 | 2015-07-01 | 江苏大学 | Method for desulfurizing fuel oil through catalytic oxidation by adopting piperidine ionic liquid |
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| CN105778980A (en) * | 2016-02-28 | 2016-07-20 | 辽宁石油化工大学 | Method for regenerating hydrophilic type ionic liquid desulfurizing agent through reverse extraction |
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| CN108822884A (en) * | 2018-06-04 | 2018-11-16 | 湖南省林业科学院 | A kind of abstraction desulfurization agent, preparation method and biodiesel desulfurization refining method |
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