CN103436287B - A kind of metal oxide modified nano iron oxide catalyst carries out the method for diesel oxidation desulfurizing - Google Patents
A kind of metal oxide modified nano iron oxide catalyst carries out the method for diesel oxidation desulfurizing Download PDFInfo
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Abstract
The invention discloses a kind of method that metal oxide modified nano iron oxide catalyst carries out diesel oxidation desulfurizing, comprise the steps: 1) metal-salt of solubility is dissolved in distilled water, by nanometer α-Fe
2o
3impregnated in this solution, ultrasonic disperse, dry, roasting in retort furnace; 2) using hydrogen peroxide-acid reagent as oxidation system, add hydrogen peroxide-acid oxidant and catalyzer, organic sulfide is converted primarily into sulfone class, sulfoxide type; 3) separating catalyst and diesel oil; 4) in diesel oil, sulfur product, by mixing with extraction agent, leaves standstill phase-splitting, obtains phase oil phase and lower phase extraction phase, measures sulphur content in diesel oil with Microcoulomb instrument.The present invention adopts has higher selective oxidizing and strong acid center, has highly active diesel oxidation desulfurizing catalyzer and carries out oxidation sweetening, effectively remove various sulfide in diesel oil, and can reach the object of deep desulfuration.
Description
Technical field
The present invention relates to a kind of sulfur method, be specifically related to a kind of method that metal oxide modified nano iron oxide catalyst carries out diesel oxidation desulfurizing, belong to chemical technology field.
Background technology
Universal along with industrial expansion and automobile, petrol and diesel oil demand rapid growth, the proportion that diesel oil accounts in fuel is increasing, wherein thereupon produces environmental issue containing a large amount of sulfide.Sulfide in diesel oil is one of main source of acid rain formation; Sulfide after burning produces poisoning to the three-way catalyst of mechanical engine exhaust gas purification system, the corrosion of boost engine and wearing and tearing; Have obvious promoter action containing the discharge of sulfide to particulate matter (PM) in fuel, the oxysulfide formed after fuel combustion easily changes into calcium sulfate, forms fine particle; More polycyclic aromatic sulfur has carcinogenesis to a certain degree to human body.
Europe performs the Europe IV standard in 2005, on market, diesel oil sulphur content is not more than 50 μ g/g, and China 2012 perform be state III standard, diesel oil sulphur content is 7 times of Europe, along with " haze " weather that the further serious and each big and medium-sized cities of recent municipal pollution occur, alarm bell is beaten to pollution problem, objectively also China has been produced and use clean fuel oil to have higher requirement.Therefore, the deep desulfuration of diesel oil becomes one of environmental research problem of countries in the world urgent need solution.
Traditional sulfur method is hydrodesulfurization (HDS), is also comparatively ripe technique.Its principle is by High Temperature High Pressure under catalyst action, and in hydrogen and oil product, organic sulfide generates H2S and then removes.Patent CN1488715 and CN1576351 discloses petrol and diesel oil cut fraction hydrogenation desulfurization catalyst and hydrodesulfurizationprocess process, selects the metal-modified aluminum oxide such as iron, cobalt, nickel, copper to carry out hydrodesulfurization reaction as catalyzer in the catalyst.From current hydrogenating desulfurization technically, diesel fuel desulfurization is easy to realize to 300-500 μ g/g, reach deep desulfuration and then need very harsh condition, such as improve the huge facility investment that hydrogen dividing potential drop is brought with reduction reaction velocity, and the novel hydro-desulfurizatiocatalyst catalyst that selectivity is stronger.Hydrogenating desulfurization technical fee is high, and processing condition are harsh, and need to react at high temperature under high pressure, and need a large amount of hydrogen, equipment cost is high, so all make great efforts both at home and abroad to develop non-hydrodesulfurization.
Oxidation sweetening is direction and the trend of diesel fuel desulfurization from now on.Oxidation sweetening method (ODS) principle is under normal temperature and catalysts conditions, oxygenant is utilized the organic sulfide in oil fuel to be oxidized to the stronger sulfone class of polarity and sulfoxide type, re-use extraction agent (DMSO, DMF etc.) sulfone class, sulfoxide type are removed, in extracting phase (containing a large amount of solvent and high sulfur crude), complete the reclaiming to extraction agent by water distilling apparatus.Oxidative desulfurization techniques have reaction conditions gentleness, need not hydrogen, the feature such as facility investment is low, technical process is simple, be one of effective ways of diesel oil non-hydrogenation desulfurization.Zhu Jinhong etc. are with H
2o
2/ formic acid system is oxygenant, has investigated H
2o
2/ HCOOH system is to the oxidation susceptibility of dibenzothiophene (DBT) in simulation diesel oil, and oxygenant and simulation diesel fuel volume are than under the condition of 1:15, and desulfurization degree can reach 98%.Hai Mei etc., under ultrasound condition, utilize H
2o
2for oxygenant, under one minute condition, desulfurization degree reaches 85%, is complete reaction in seven minutes.Publication number CN101850237 discloses a kind of preparation method of diesel oil desulfurizing agents, by FeCl
2, FeSO
4, FeCl
3deng mixing by a certain percentage, prepare the magnetic powder of tool, and with this sweetening agent for catalyzer is used for diesel fuel desulfurization, this sweetening agent is for removing the sulfocompound in diesel oil, and desulfurization degree can reach more than 85%.Publication number CN102453504 discloses a kind of oxidation desulfuration process, with K
2cr
2o
7be oxygenant with hydrochloric acid, the sulfurous organic compound in oxidated diesel oil, desulfurization degree reaches 85%.
In diesel fuel desulfurization, because benzothiophene kind sulfide exists the cut diesel oil being greater than more than 300 DEG C, so cause diesel yield low when carrying out oxidation sweetening to diesel oil, part straight chain hydrocarbon and aromatic hydrocarbons can be oxidized, thus oil product are deteriorated or yield reduction.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of and there is higher selective oxidizing and strong acid center, and there is highly active diesel oxidation desulfurizing Catalysts and its preparation method, and adopt this catalyzer to carry out oxidation sweetening.
For solving the problems of the technologies described above, the present invention adopts following technical scheme to realize:
Metal oxide modified nano iron oxide catalyst carries out a method for diesel oxidation desulfurizing, comprises the following steps:
(1) pickling process: be dissolved in by a certain percentage in distilled water by certain component with the metal-salt of the solubilities such as ammonium molybdate, single nickel salt, aluminum chloride, cobalt oxalate, Lanthanum trichloride, zirconyl oxalate, bariumchloride, zinc chloride, get the nanometer α-Fe of certain mass
2o
3impregnated in ultrasonic disperse in this solution, with 300 ~ 700 DEG C of roastings in retort furnace, control heat-up rate 1 ~ 5K/min, be warming up to 300 ~ 500 DEG C, constant temperature 2-5h, namely obtain with nanometer α-Fe
2o
3for the diesel oxidation desulfurizing catalyzer of carrier;
(2) 1% consumption being diesel oil weight according to catalyzer mixes with diesel oil, adds using hydrogen peroxide-acid reagent as oxygenant, is placed in water bath with thermostatic control, and under magnetic stirring action, react 30 ~ 120min, temperature is 303K ~ 373K;
(3), after diesel oil selective oxidation process, separating catalyst and diesel oil, in diesel oil, sulfur product is by mixing with extraction agent, leaves standstill phase-splitting, obtains phase oil phase and lower phase extraction phase, so repeatedly for several times, measures sulphur content in diesel oil with Microcoulomb instrument.
Metal oxide and nanometer α-Fe in metal-salt in step 1)
2o
3weight ratio be 0.5% ~ 30%.
Nanometer α-Fe described in step (1)
2o
3diameter of carrier is 20 ~ 50nm, and the charge capacity of catalyst metal oxide is between 0.5wt% to 30wt%.
Acid reagent described in step (2) be acetic acid, formic acid, hydrochloric acid, oxalic acid, diacetyl oxide one or more, the volume ratio of acid reagent and hydrogen peroxide (30%) is 1 ~ 5, and the amount adding hydrogen peroxide-acid is agent-oil ratio 1:20 to 1:5.
Extraction agent described in step (3) be DMF, dimethyl sulfoxide (DMSO), methyl alcohol, sulfur oxychloride, N-methyl-p-nitroaniline one or more.
Catalyzer described in step (3) and diesel oil tripping device are decanter type or filtering type or centrifugal or vane-type solid-liquid separation device.
Beneficial effect of the present invention: use and there is higher selective oxidizing and strong acid center, and there is highly active diesel oxidation desulfurizing catalyzer carry out oxidation sweetening, effectively remove various sulfide in diesel oil, the object of deep desulfuration can be reached.
Accompanying drawing explanation
Fig. 1 is the NH of embodiment 1 catalyzer
3-TPD schemes.
Fig. 2 be embodiment 1 not equality of temperature desulfurization degree is affected.
Fig. 3 is the result of several oil sample of embodiment 2.
Embodiment
Below in conjunction with specific embodiment, the present invention is elaborated.
embodiment 1
Weigh 3g Ammonium Molybdate Tetrahydrate, be dissolved in 5ml distilled water, stirring and dissolving, add 10g nano-sized iron oxide wherein, at 40 DEG C of ultrasonic 30min; Ultrasonic rear standing 12h, 120 DEG C of oven dry, grind, 500 DEG C of roasting 2h in resistance furnace, obtain the MoO that charge capacity is 25% (wt)
3/ α-Fe
2o
3catalyzer.
In clean round-bottomed flask, add the above-mentioned catalyzer of 0.1g and 10ml diesel oil oil sample, at a certain temperature stirring reaction 90min, after stopping stirring, whizzer separating catalyst and diesel oil, extract with extraction agent DMF, Solvent quantity agent-oil ratio used is 1:1, and continuous extraction three times, gets upper oil phase, sulphur content is surveyed with Microcoulomb instrument, gasification temperature is 600 DEG C, and temperature of combustion is 810 DEG C, and stable section temperature is 700 DEG C, determine sulphur content before and after diesel oil, calculate desulfurization degree.As can be seen from Figure 1, after nano-sized iron oxide load active component, active ingredient provides stronger acidic site.As can be seen from Figure 2, when temperature is 60 DEG C, desulfurization degree is the highest, reaches 92%.
embodiment 2
Weigh Ammonium Molybdate Tetrahydrate, each 2g of single nickel salt, be dissolved in 5ml distilled water, stirring and dissolving, add 10g nano-sized iron oxide wherein, at 40 DEG C of ultrasonic 30min; Ultrasonic rear standing 12h, 120 DEG C of oven dry, grind, 500 DEG C of roasting 2h in resistance furnace, obtain the catalyzer that charge capacity is 30% (wt).
Get above-mentioned catalyzer 0.05g and 10ml diesel oil oil sample, according to embodiment 1 method, 60 DEG C of reactions, test sample.Fig. 3 is the result of several oil sample, and after reaction, the sulphur content in oil sample 1 diesel oil drops to 300ppm by 4000ppm, and in oil sample 2, diesel oil sulphur content drops to 250ppm by 3000ppm.
Above-described embodiment is only in order to illustrate technical scheme of the present invention; but not design of the present invention and protection domain are limited; those of ordinary skill of the present invention is modified to technical scheme of the present invention or equivalent replacement; and not departing from aim and the scope of technical scheme, it all should be encompassed in right of the present invention.
Claims (4)
1. metal oxide modified nano iron oxide catalyst carries out a method for diesel oxidation desulfurizing, it is characterized in that: comprise the steps:
(1) at room temperature, the metal-salt of solubility is dissolved in distilled water, gets nanometer α-Fe
2o
3impregnated in this solution, ultrasonic disperse, 60 ~ 120 DEG C of oven dry, with 300 ~ 700 DEG C of roastings in retort furnace, control heat-up rate 1 ~ 5K/min, be warming up to 300 ~ 500 DEG C, constant temperature 2-5h, namely obtain with nanometer α-Fe
2o
3for the diesel oxidation desulfurizing catalyzer of carrier; Described nanometer α-Fe
2o
3diameter of carrier is 20 ~ 50nm, and the charge capacity of catalyst metal oxide is 0.5wt% ~ 30wt%; The metal-salt of described solubility is one or more in Ammonium Molybdate Tetrahydrate, single nickel salt, aluminum chloride, cobalt oxalate, Lanthanum trichloride, zirconyl oxalate, bariumchloride, zinc chloride; Metal oxide and nanometer α-Fe in metal-salt
2o
3weight ratio be 0.5% ~ 30%;
(2) using 30% hydrogen peroxide-acid reagent as oxidation system, the volume ratio of acid reagent and 30% hydrogen peroxide is 1 ~ 5, the amount adding hydrogen peroxide-acid is agent-oil ratio 1:20 to 1:5, carries out, organic sulfide is converted primarily into sulfone class, sulfoxide type at 303 ~ 373K temperature; Acid reagent is one or more in acetic acid, formic acid, hydrochloric acid, oxalic acid, diacetyl oxide;
(3) after diesel oil selective oxidation process, separating catalyst and diesel oil, catalyzer can be recycled;
(4) in diesel oil, sulfur product, by mixing with extraction agent, leaves standstill phase-splitting, obtains phase oil phase and lower phase extraction phase, 3 times so repeatedly, measures sulphur content in diesel oil with Microcoulomb instrument.
2. a kind of metal oxide modified nano iron oxide catalyst according to claim 1 carries out the method for diesel oxidation desulfurizing, it is characterized in that: in described step 4) extraction agent be DMF, dimethyl sulfoxide (DMSO), methyl alcohol, sulfur oxychloride, N-methyl-p-nitroaniline one or more.
3. a kind of metal oxide modified nano iron oxide catalyst according to claim 1 carries out the method for diesel oxidation desulfurizing, it is characterized in that: be decanter type or filtering type or centrifugal or vane-type solid-liquid separation device for catalyzer in described step 3) and diesel oil tripping device.
4. a kind of metal oxide modified nano iron oxide catalyst according to claim 1 carries out the method for diesel oxidation desulfurizing, it is characterized in that: Solvent quantity agent-oil ratio used in described step 4) is 1:1.
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| CN109455807A (en) * | 2018-09-18 | 2019-03-12 | 辽宁石油化工大学 | A kind of sulfur method of high sulfur content oilfield sewage |
| CN110747004B (en) * | 2019-11-15 | 2021-08-24 | 河南科技大学 | Application of spinel ferrite magnetic nano catalyst in oil product desulfurization |
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| CN1257254C (en) * | 2000-09-01 | 2006-05-24 | 尤尼普瑞公司 | Process for removing low amounts of organic sulfur from hydrocarbon fuels |
| CN1868572A (en) * | 2005-05-25 | 2006-11-29 | 中国石油天然气股份有限公司 | Catalyst for direct oxidation and desulphurization and its prepn. method |
| CN103084147A (en) * | 2011-11-08 | 2013-05-08 | 纳科石油化工有限公司 | Iron oxide magnetic nano particle, preparation method and application method thereof in desulfurization |
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| US20090242460A1 (en) * | 2008-03-26 | 2009-10-01 | General Electric Company | Oxidative desulfurization of fuel oil |
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| CN1257254C (en) * | 2000-09-01 | 2006-05-24 | 尤尼普瑞公司 | Process for removing low amounts of organic sulfur from hydrocarbon fuels |
| WO2002026916A1 (en) * | 2000-09-28 | 2002-04-04 | Sulphco. Inc. | Oxidative desulfurization of fossil fuels with ultrasound |
| CN1624081A (en) * | 2004-10-24 | 2005-06-08 | 西南石油学院 | Process for catalyzing oxygenizing desulfurizing diesel oil |
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