CN101921609A - Method for simultaneously removing sulfur and nitrogen from diesel fuel by oxidization of Ce4+ under auxiliary action of ultrasonic waves - Google Patents
Method for simultaneously removing sulfur and nitrogen from diesel fuel by oxidization of Ce4+ under auxiliary action of ultrasonic waves Download PDFInfo
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- CN101921609A CN101921609A CN2009100926502A CN200910092650A CN101921609A CN 101921609 A CN101921609 A CN 101921609A CN 2009100926502 A CN2009100926502 A CN 2009100926502A CN 200910092650 A CN200910092650 A CN 200910092650A CN 101921609 A CN101921609 A CN 101921609A
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Abstract
The invention belongs to the field of inorganic chemistry and relates to a method for simultaneously removing sulfur and nitrogen from diesel fuel by oxidization of Ce4+ under the auxiliary action of ultrasonic waves. The method can be used for simultaneously removing sulfur-containing compounds and nitrogen-containing compounds from diesel fuel by utilizing the oxidization of Ce4+ under the auxiliary action of ultrasonic waves, wherein the Ce3+ generated after the diesel fuel is oxidized by the Ce4+ can be recycled after being electrochemically electrolyzed. Compared with the existing technology for removing sulfur and nitrogen, the method not only can be used for simultaneously removing sulfur-containing compounds and nitrogen-containing compounds harmful to the environment from the diesel fuel but also has higher efficiency for removing sulfur and nitrogen, thereby achieving the requirement for greatly removing sulfur and nitrogen. Simultaneously, the Ce4+ prepared by the electrochemical method has higher electrochemical activity. The method not only can ensure the clean production, but also can improve the economic benefit; moreover, the burning quality of the oxidized diesel fuel is improved.
Description
Technical field:
The invention belongs to domain of inorganic chemistry, relate to a kind of method of diesel oxidation desulfurizing denitrogenation, specifically is to pass through Ce under hyperacoustic booster action
4+Oxygenizement remove sulfur-bearing class and nitrogenous class organic compound in the diesel oil.
Technical background:
Along with expanding economy, the demand of diesel vehicle is increasing, and sulphur in the diesel oil, nitrogen content are more and more higher, make the content of vehicle exhaust sulphur oxide and oxynitride increase, cause following harm: 1, form acid rain, corrosion buildings, harm plant and physical environment; 2, cause being used for the poisoning of catalyst that vehicle exhaust is handled, shorten catalyzer work-ing life, influence the vent gas treatment effect; 3, engine be can corrode, its performance and work-ing life reduced.Therefore, sulphur, nitrogen content that environmental legislation requires are more and more lower, how to reduce the sulphur in the diesel oil, the key problem in technology that nitrogen content also becomes each refinery.Past great majority research all concentrates in hydrogenation deep desulfuration, the denitrogenation, though this method is ripe, on economizing on resources, also have great advantage, but deep hydrogenation can influence the quality of oil, shallow degree hydrogenation can cause the desulfurization removing nitric rate not high again, and this arts demand has enough hydrogen sources, expensive equipment, a large amount of investments, widespread usage has significant limitation at home.Simultaneously, the microbial method desulfurization removing nitric also is the focus of Recent study, and this method has overcome investment and the high problem of process cost, the reaction conditions gentleness, but microbial growth is affected by environment very big, and experimental period is longer, therefore also is not applied in the industrial production.In recent years, have the people that the method for ultrasonic wave and oxygenant coupling is applied in the diesel fuel desulfurization, the oxygenant that great majority adopt is H
2O
2And H
2O
2With catalyst Fe
2+The Fenton reagent of coupling, but there is oxygenant price height in the oxidative desulfurization techniques of this diesel oil, diesel yield is low and problems such as sour water discharging are arranged.Therefore, seeking a kind of economic benefit is the key issue that we need solve at present than high desulfurizing and denitrifying method.
According to " Liaoming Petrochemical Univ's journal " 2005,25 (4) reports, Han Xuesong etc. adopt ultrasonic wave and H
2O
2-acetate coupling technique oxidation sweetening, when ultrasonic frequency is 28kHz, the sound intensity is 0.4w/cm
2The time can make that sulphur content drops to 103 μ g/g by 1988 μ g/g in the high-sulfur FCC diesel oil, diesel oil density reduces, desulfurization degree reaches 95%;
According to " chemistry with bind " 2007,29 (3) reports, Dong Lixu etc. under ultrasound condition with H
2O
2(concentration is 30%) is oxygenant, is 28kHz in ultrasonic frequency, when power is 200w, makes the sulphur content in the catalytic cracking diesel oil drop to 99.73 μ g/g from 1936.48 μ g/g, and the diesel fuel desulfurization rate is 94.8%;
According to " chemistry of fuel journal " 2007,35 (2) reports, Dai Yongchuan etc. adopt ultrasonic wave and Fenton-like reagent C u
2+/ H
2O
2Coupling technique makes catalytic cracking diesel oil (sulphur content 1452.6 * 10
-6) in desulfurization degree reach 63.5%;
According to " Fuel processing technology " 2008, report, Yongchuan Dai etc. are oxygenant with Fenton reagent, are 28kHz by hyperacoustic booster action in ultrasonic frequency, power is 200w, Fe
2+/ H
2O
2Be 0.05mol/mol, pH equals can make the sulphur content in the diesel oil drop to 9.5 μ g/g from 568.75 μ g/g under 2.10 the condition, but does not carry out the desulfurization removing nitric research of the higher diesel oil of sulphur content.
Summary of the invention:
The present invention seeks to pass through to add Ce (SO at the higher diesel oil of sulphur content
4)
2.4H
2The mode of O powder and extraction agent under the ultrasonic wave booster action, removes sulfur-bearing class and nitrogenous class organic compound in the diesel oil.
A kind of ultrasonic wave is assisted Ce
4+The method of simultaneously removing sulfur and nitrogen from diesel fuel by oxidization is characterized in that the preparation pH of elder generation is 0.5～0.8 sulphuric acid soln, with Ce (SO
4)
2.4H
2The O powder is dissolved in the sulphuric acid soln that has prepared, makes Ce (SO in the sulphuric acid soln
4)
2.4H
2The O powder concn is 0.05～0.5mol/L, is filling 0.05～0.5mol/L Ce
4+Middle adding sulphur content 8000～11000 μ g/g of solution, the diesel oil of nitrogen content 100～144 μ g/g makes diesel oil and Ce
4+Liquor capacity is than between 1: 7～1: 10, is to be 100w ultrasonic reaction 30-70min with the frequency in 50～100 ℃ the ultrasonic generator in water temperature.
Carry out when guaranteeing the diesel fuel desulfurization denitrogenation, need to select suitable extraction agent DMF (N, dinethylformamide), diesel oil after the oxidation is extraction agent extraction three times with DMF, the volume ratio of diesel oil and extraction agent is chosen in 2: 1～between 1: 3, DMF extraction back selects water as the reextraction agent, and the volume ratio of diesel oil and water extracted 1-5 time between 1: 1～1: 4; Extraction phase is heated to certain temperature, and extraction agent is reclaimed in distillation, for recycling, measures total sulfur content, total nitrogen content, cetane value with WK22D type microcoulomb synthesis analyzer.
Ce after the oxidated diesel oil
4+Change Ce into
3+, with the reacted solution layering, oil sample extraction in upper strata is isolated lower floor's solution and is done ionogen with certain density sulphuric acid soln, and the Pb electrode is an anode, and Graphite Electrodes is a negative electrode, depresses with the M273 potentiostat at the constant groove of 3.1V and carries out electrolysis, Ce
3+Again be oxidized to Ce
4+, the Ce after the electrolysis
4+Still have good oxidation activity.
The present invention uses Ce
4+Diesel oil is carried out the simultaneous oxidation desulfurization removing nitric, by cavitation effect of ultrasonic waves, make the reaction conditions gentlenessization, under the temperature condition of self ultrasonic generation the oxidation sweetening denitrogenation is carried out smoothly, this method has improved reaction efficiency when reducing investment cost.In addition, can prepare active very high Ce with electrochemical method
4+, and Ce
4+Oxidation medium can recycling utilization, and higher desulfurization removing nitric efficient is arranged, and can reach the requirement of deep desulfuration denitrogenation, has both solved the cleaner production requirement, has solved the higher economical efficiency of cost again, and is simple.
We are with Ce
4+Be oxygenant, by hyperacoustic cavitation, impact the generation involve the reaction of microjet effect assisted oxidation and then removing of organosulfur, nitrogen in the diesel oil studied, make Ce by electrochemical method simultaneously
4+The oxidation medium recycling had both met the demand of cleaner production, had solved the higher economical efficiency of cost again, had the favorable economic benefit ratio, met the trend of Green Chemistry development.
Embodiment
Example 1: concentration is 0.05～0.5mol/L Ce under the ultrasonic wave booster action
4+Oxidated diesel oil (sulphur content 8000 μ g/g, nitrogen content 144 μ g/g) desulfurization removing nitric experiment simultaneously.
1.1. with Ce (SO
4)
2.4H
2The O powder is dissolved in pH in 0.5～0.8 the sulphuric acid soln, makes Ce (SO
4)
2The concentration of solution is 0.05～0.5mol/L.Filling Ce (SO
4)
2Add diesel oil (sulphur content 8000 μ g/g in the Erlenmeyer flask of solution, nitrogen content 144 μ g/g), making diesel oil in the Erlenmeyer flask and water is to be ultrasonic assisted reaction 30～70min of 100w with the frequency in 50～100 ℃ the ultrasonic generator by 1: 7～1: 10 volume ratio in water temperature.Oil phase DMF (N, dinethylformamide) extraction is three times, between the volume ratio of diesel oil and extraction agent 2: 1～1: 3, reextraction was carried out repeatedly with the volume ratio of diesel oil and water in DMF extraction back between 1: 1～1: 4, extraction phase is heated to certain temperature, extraction agent is reclaimed in distillation, for recycling.Ce
4+Change Ce after the oxidation medium oxidated diesel oil into
3+, with the reacted solution layering, oil sample extraction in upper strata is isolated lower floor's solution and is done ionogen with certain density sulphuric acid soln, and the Pb electrode is an anode, and Graphite Electrodes is a negative electrode, depresses with the M273 potentiostat at the constant groove of 3.1V and carries out electrolysis, Ce
3+Again be oxidized to Ce
4+, the Ce after the electrolysis
4+Still have good oxidation activity.
1.2 the analysis of sulphur, nitrogen content, cetane value in the diesel oil
Diesel oil behind the ultrasonic oxidation is measured sulphur, nitrogen content and cetane value thereof through the microcoulomb synthesis analyzer, its result drops to 29.76 μ g/g for the total sulfur content in the diesel oil from 8000 μ g/g, measure simultaneously that total nitrogen content is 2.65 μ g/g in the diesel oil, cetane value is 58.8.
Concentration is 0.05～0.5mol/L Ce under the example 2 ultrasonic wave booster actions
4+Oxidated diesel oil (sulphur content 11000 μ g/g, nitrogen content 100 μ g/g) desulfurization removing nitric experiment simultaneously
2.1. with Ce (SO
4)
2.4H
2The O powder is dissolved in pH makes Ce (SO in 0.5～0.8 the sulphuric acid soln
4)
2Strength of solution is 0.05～0.5mol/L.Filling Ce (SO
4)
2Add diesel oil (sulphur content 11000 μ g/g in the Erlenmeyer flask of solution, nitrogen content 100 μ g/g), making diesel oil in the Erlenmeyer flask and water is that 50～100 ℃ ultrasonic generator is ultrasonic assisted reaction 30～70min of 100w with the frequency by 1: 7～1: 10 volume ratio in water temperature.Oil phase is with DMF (N, dinethylformamide) extraction three times, between the volume ratio of diesel oil and extraction agent 2: 1～1: 3, reextraction is repeatedly between 1: 1～1: 4 with the volume ratio of diesel oil and water in DMF extraction back, extraction phase is heated to certain temperature, and extraction agent is reclaimed in distillation, for recycling.Ce
4+Change Ce after the oxidation medium oxidated diesel oil into
3+, with the reacted solution layering, oil sample extraction in upper strata is isolated lower floor's solution and is done ionogen with certain density sulphuric acid soln, and the Pb electrode is an anode, and Graphite Electrodes is a negative electrode, depresses with the M273 potentiostat at the constant groove of 3.1V and carries out electrolysis, Ce
3+Again be oxidized to Ce
4+, the Ce after the electrolysis
4+Still have good oxidation activity.
2.2 the analysis of total sulfur, total nitrogen content, cetane value in the diesel oil
Diesel oil behind the ultrasonic oxidation is measured sulphur, nitrogen content and cetane value thereof through the microcoulomb synthesis analyzer, its result drops to 70.96 μ g/g for the total sulfur content in the diesel oil from 11000 μ g/g, total nitrogen content drops to 6.98 μ g/g from 100 μ g/g, and cetane value is 65.5.
Conclusion
By to utilizing cavitation effect of ultrasonic waves to assist Ce
4+Studies show that of sulfocompound in the oxidation removal diesel oil and nitrogenous compound, the desulfurization removing nitric rate of diesel oil is relevant with diesel oil sulfur-bearing nitrogen content, this laboratory is respectively to sulphur content 8000～11000 μ g/g, the diesel oil of nitrogen content 100～144 μ g/g has carried out the research of oxidation sweetening denitrogenation, is 0.05～0.5mol/L Ce through concentration
4+In the volume ratio of diesel oil and oxygenant is under 1: 7～1: 10 condition after the oxidation, extract repeatedly with DMF, the volume ratio of diesel oil and extraction agent is between 2: 1～1: 3, DMF extraction back selects water as the reextraction agent, reextraction repeatedly can make sulphur content 8000 μ g/g under the oil-water ratio between 1: 1～1: 4, and the diesel oil sulphur content of nitrogen content 144 μ g/g drops to 29.76 μ g/g, total nitrogen content drops to 2.65 μ g/g, and cetane value is 58.8 after the oxidation; To sulphur content is 11000 μ g/g, and nitrogen content is that the diesel oil employing concentration of 100 μ g/g is 0.05～0.5mol/L Ce
4+In the volume ratio of diesel oil and oxygenant is under 1: 7～1: 10 condition after the oxidation, extract repeatedly with DMF, the volume ratio of diesel oil and extraction agent is between 2: 1～1: 3, DMF extraction back selects water as the reextraction agent, under the oil-water ratio between 1: 1～1: 4 reextraction repeatedly, the total sulfur content in the diesel oil can drop to 70.96 μ g/g, total nitrogen content 6.98 μ g/g, diesel-fuel cetane number is 65.5 after the oxidation, and the burning quality of diesel oil raises.
Claims (2)
1. a ultrasonic wave is assisted Ce
4+The method of simultaneously removing sulfur and nitrogen from diesel fuel by oxidization is characterized in that the preparation pH of elder generation is 0.5～0.8 sulphuric acid soln, with Ce (SO
4)
2.4H
2The O powder is dissolved in the sulphuric acid soln that has prepared, makes Ce (SO in the sulphuric acid soln
4)
2.4H
2The O powder concn is 0.05～0.5mol/L, is filling 0.05～0.5mol/L Ce
4+Middle adding sulphur content 8000～11000 μ g/g of solution, the diesel oil of nitrogen content 100～144 μ g/g makes diesel oil and Ce
4+Liquor capacity is than between 1: 7～1: 10, is to be 100w ultrasonic reaction 30-70min with the frequency in 50～100 ℃ the ultrasonic generator in water temperature.
2. a kind of ultrasonic wave as claimed in claim 1 is assisted Ce
4+The method of simultaneously removing sulfur and nitrogen from diesel fuel by oxidization, it is characterized in that carrying out when guaranteeing the diesel fuel desulfurization denitrogenation, slective extraction agent DMF is N, dinethylformamide, diesel oil after the oxidation is extraction agent extraction three times with DMF, the volume ratio of diesel oil and extraction agent is chosen in 2: 1～and between 1: 3, DMF extraction back selects water as the reextraction agent, and the volume ratio of diesel oil and water extracted 1-5 time between 1: 1～1: 4; Extraction phase is heated to certain temperature, and extraction agent is reclaimed in distillation, for recycling.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173188A (en) * | 2006-10-12 | 2008-05-07 | 高化环保技术有限公司 | Process for preparing an organic acid or its derivatives using a homogeneous mc-type catalyst and an o2/co2 mixture |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101173188A (en) * | 2006-10-12 | 2008-05-07 | 高化环保技术有限公司 | Process for preparing an organic acid or its derivatives using a homogeneous mc-type catalyst and an o2/co2 mixture |
Non-Patent Citations (1)
| Title |
|---|
| 张秀兰: "柴油脱氮方法的研究及应用", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
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Application publication date: 20101222 |