CN101717659A - Deep desulfurization method for diesel by coupling of oxidation and extraction - Google Patents
Deep desulfurization method for diesel by coupling of oxidation and extraction Download PDFInfo
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- CN101717659A CN101717659A CN200910232076A CN200910232076A CN101717659A CN 101717659 A CN101717659 A CN 101717659A CN 200910232076 A CN200910232076 A CN 200910232076A CN 200910232076 A CN200910232076 A CN 200910232076A CN 101717659 A CN101717659 A CN 101717659A
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Abstract
The invention relates to a deep desulfurization method for diesel by coupling of oxidation and extraction, that is a catalyzed oxidation desulfurization method for diesel in petroleum refining technologies. The method comprises the following steps of crushing and fine grinding a zirconium hydroxide carrier, dipping into impregnation liquid formed by aqueous ammonium meta-tungstate solution, placing the impregnation liquid in an ultrasonic generator to carry out ultrasonic facilitating impregnation, boiling off water after the impregnation is finished, drying and baking at high temperature to obtain a WO3/ZrO2 super solid acidic catalyst; adding aqueous hydrogen peroxide solution, extraction solvent and the WO3/ZrO2 super solid acidic catalyst in diesel containing sulfur, carrying out catalyzed oxidation desulfurization reaction under the action of power ultrasonics, cooling to the room temperature after the reaction is finished, separating and recycling the solid catalyst, standing and layering, wherein the upper layer is desulfurized diesel and the lower layer can be reused after regeneration. The invention has simple process, mild condition, high desulfurization degree and gasoline recovery, low cost and no pollution to environment and can obtain ultra-low sulfur clean diesel products.
Description
Technical field
The present invention relates to diesel oil catalytic oxidation desulfurization method in the petroleum refining process.
Background technology
Along with the enhancing of people's environmental consciousness and the raising of vehicle fuel exhaust emission standard, many in the world countries all formulate strict day by day restriction index to sulphur content in the oil fuel, and production and use super low sulfur oil fuel are imperative.Thereby research environment close friend's diesel deep desulfurization technology, meet the new opportunity and the new challenge of Clean Fuel Production, have important practical significance.
Aspect deep desulfuration, traditional hydrodesulfurization (HDS) severe reaction conditions, facility investment and process cost height remove difficulty to the serial sulfide of sterically hindered big dibenzothiophene (DBT), are difficult to reach the deep desulfuration requirement.Therefore, other non-hydrodesulfurizationprocess process is subjected to investigator's extensive concern, wherein, the facility investment simple of diesel oxidation desulfurizing technology with its desulfurization degree height, reaction conditions gentleness, technical process and process cost is low, can effective elimination DBT series sulfide etc. advantages just becoming the focus of domestic and international research, thought a kind of very promising ultra-deep desulfurization method by industry member.
Oxidative desulfurization techniques is under normal temperature, normal pressure and catalyzer existence condition, utilize oxygenant that the selective oxidation of sulfur containing compounds in particular that thiophene-based in the oil fuel etc. is difficult to remove is become the stronger sulfoxide of polarity, sulfone class S-contained substance, then sulfoxide, sulfone class sulfide are separated from oil fuel by methods such as extractions and remove, thereby reach the purpose of deep desulfuration.
Can the oxidation sweetening method become one of major technique of the super low sulfur of countries in the world production from now on clean diesel, and key is to develop high desulfurization rate, high oil product yield, low-cost expense, oxidation-extraction desulfurization system free from environmental pollution.
Consider the requirement of cleaner production, majority adopts hydrogen peroxide as oxygenant in the various oxidation desulfurizing methods of having reported, and uses organic acid as catalyzer usually.H
2O
2Though/organic acid oxidation sweetening system can reach than high desulfurization rate, organic acid is partially soluble in influences the oil fuel quality in the oil product, and the easy etching apparatus of organic acid, and recovery cost is higher.Research report about heteropolyacid catalyst and catalysis of solid catalyst hydrogen peroxide oxidation desulfurization system is a lot of both at home and abroad in recent years.Adopt heteropolyacid to make catalyzer, though sweetening effectiveness is better, the Preparation of Catalyst operation is comparatively complicated, and the recycling difficulty is bigger.And adopt solid catalysts such as HTS and solid super-strong acid to be used for oxidation sweetening, then can simplify the reprocessing cycle link of catalyzer, catalyzer is easy to Separation and Recovery, do not influence the fuel oil quality, prepared using is abundant, and in the catalytic oxidation desulfurization reaction, showing good activity and selectivity, desulfurization degree is higher.
In sum, existing oxidative desulfurization techniques need be separated sulfoxide, sulfone class oxidation products by methods such as extractions mostly and remove behind catalytic oxidation from oil fuel, thereby the process cost increase, and desulphurization cost is higher, and influences the oil product yield.
Summary of the invention
The object of the present invention is to provide the diesel oil catalytic oxidation desulfurization method that a kind of technical process is simple, cost is cheap, sweetening effectiveness is good, free from environmental pollution.
The present invention includes following steps:
1) the zirconium hydroxide carrier is pulverized fine ground back and immersed in the steeping fluid that ammonium metatungstate aqueous solution constitutes, described steeping fluid is placed carry out ultrasonic facilitating impregnation in the ultrasonic generator, dipping boils off moisture after finishing, drying, and make WO through high-temperature roasting
3/ ZrO
2Solid super acid catalyst;
2) in sulfur-containing diesel, add aqueous hydrogen peroxide solution, extraction solvent and WO
3/ ZrO
2Solid super acid catalyst carries out catalytic oxidation desulfurization reaction under the power ultrasonic effect, reaction finishes postcooling to room temperature, the Separation and Recovery solid catalyst, and standing demix then, the upper strata then be a desulfurized diesel oil, lower floor recycles after regenerating.
Above-mentioned steps 1) volumetric molar concentration of described ammonium metatungstate aqueous solution is 0.015～0.025M.
Zirconium hydroxide carrier described in the step 1) accounts for 20～40% of steeping fluid weight.
Maturing temperature described in the step 1) is 750～900 ℃.
The weight percent concentration of the aqueous hydrogen peroxide solution step 2) is 30%～35%, and aqueous hydrogen peroxide solution accounts for 10～25% of sulfur-containing diesel weight.
Step 2) extraction solvent described in is N, dinethylformamide, and N, the volume ratio of dinethylformamide and sulfur-containing diesel is 2: 1～1: 2.N, dinethylformamide are extraction agent, carry out the reaction of oxidation-extraction coupled diesel deep desulfurization under the power ultrasonic strengthening effect, and diesel fuel desulfurization rate and oil product yield all are higher than 98%.
Step 2) WO described in
3/ ZrO
2Solid super acid catalyst accounts for 1～5% of sulfur-containing diesel weight.
The temperature of the catalytic oxidation desulfurization reaction step 2) is 40～80 ℃, and the time is 30～70min.
The ultrasonic frequency of the power ultrasonic effect step 2) is 50～70kHz, and ultrasonic power is 350～450W.
The present invention gets the WO of high catalytic activity, easily separated recovery by ultrasonic facilitating impregnation legal system
3/ ZrO
2Solid super acid catalyst is used for the catalytic oxidation desulfurization system, and with the coupling of oxidizing reaction and extracting and separating, make sulfoxide, sulfone class oxidation products in time be transferred to extraction solvent mutually in, degree of oxidation obviously improves, with the further strengthening process of power ultrasonic, sweetening effectiveness is more remarkable simultaneously.Compare with existing oxidative desulfurization techniques, it is catalyzer that the present invention proposes with the solid super-strong acid, the oxidation-extraction coupling also is aided with the sulfur removal technology route that power ultrasonic is strengthened, flow process is simple, and condition relaxes, the desulfurization degree height, and oil product yield height, cost is low, and is free from environmental pollution, can obtain super low sulfur clean diesel product.Therefore this catalytic oxidation desulfurization technology has better industrial application prospect, can produce high economic benefit and social benefit.
Embodiment
Used analytical procedure is a GB/T380-88 petroleum products sulphur content determination method in following examples, desulfurization degree=1-(diesel oil sulphur content after the desulfurization/raw material diesel oil sulphur content).
One, preparation WO
3/ ZrO
2Solid super acid catalyst:
To make the zirconium hydroxide carrier pulverizes in the steeping fluid of fine ground back with solid-liquid weight ratio immersion 0.015～0.025M (preferred 0.020M) ammonium metatungstate aqueous solution formation of 1: 3, this steeping fluid placed carry out ultrasonic facilitating impregnation in the ultrasonic generator, dipping boils off moisture after finishing, 80 ℃ of dryings, and make WO through 750～900 ℃ of high-temperature roastings
3/ ZrO
2Solid super acid catalyst.
Two, diesel catalytic oxidation desulfurization:
Embodiment 1
Adding the 100ml sulphur content in the 250ml Erlenmeyer flask is the mixing straight-run diesel oil of 1703 μ g/g, and 10ml concentration is the aqueous hydrogen peroxide solution and the 100ml N of 30% (weight percent), dinethylformamide (DMF) extraction agent and the homemade WO of 2g
3/ ZrO
2Solid super acid catalyst is 50～70kHz in ultrasonic frequency, and preferred 59kHz, ultrasonic power are 350～450W, and in 40～80 ℃, preferred 60 ℃ are carried out catalytic oxidation desulfurization reaction 30～70min, preferred 60min under the power ultrasonic effect of preferred 350W.Reaction finishes postcooling to room temperature, isolates solid catalyst recovery set usefulness, standing demix then, and the upper strata obtains the desulfurized diesel oil that sulphur content is 28.5 μ g/g by analysis, and desulfurization degree is 98.3%, and the oil product yield is 98.7%, and lower floor then recycles after regeneration.
Embodiment 2
Adding the 100ml sulphur content in the 250ml Erlenmeyer flask is the mixing straight-run diesel oil of 1703 μ g/g, and 20ml concentration is the aqueous hydrogen peroxide solution and the 100ml N of 30% (weight percent), dinethylformamide (DMF) extraction agent and the homemade WO of 2g
3/ ZrO
2Solid super acid catalyst, all the other are operated with example 1, obtain the desulfurized diesel oil that sulphur content is 26.8 μ g/g, and desulfurization degree is 98.4%, and the oil product yield is 98.2%.
Embodiment 3
Adding the 50ml sulphur content in the 250ml Erlenmeyer flask is the mixing straight-run diesel oil of 1703 μ g/g, 10ml concentration is the aqueous hydrogen peroxide solution and the 100ml N of 30% (weight percent), dinethylformamide (DMF) extraction agent and 2g are from controlling catalyst, all the other operations are with example 1, obtain the desulfurized diesel oil that sulphur content is 23.8 μ g/g, desulfurization degree is 98.6%, and the oil product yield is 93.1%.
Embodiment 4
Adding the 100ml sulphur content in the 250ml Erlenmeyer flask is the mixing straight-run diesel oil of 1703 μ g/g, 10ml concentration is that the aqueous hydrogen peroxide solution of 30% (weight percent) and 100ml dimethyl sulfoxide (DMSO) (DMSO) extraction agent and 2g are from controlling catalyst, all the other operations are with example 1, obtain the desulfurized diesel oil that sulphur content is 177.4 μ g/g, desulfurization degree is 89.6%, and the oil product yield is 98.5%.
Embodiment 5
Adding the 100ml sulphur content in the 250ml there-necked flask is the mixing straight-run diesel oil of 1703 μ g/g, 10ml concentration is the aqueous hydrogen peroxide solution and the 100ml N of 30% (weight percent), dinethylformamide (DMF) extraction agent and 2g are from controlling catalyst, in 60 ℃ of constant temperature stirring reaction 60min, reaction finishes postcooling to room temperature, isolating the solid catalyst recovery set uses, standing demix then, the upper strata obtains the desulfurized diesel oil that sulphur content is 183.7 μ g/g by analysis, desulfurization degree is 89.2%, and the oil product yield is 98.9%.
Three, sum up:
By embodiment 1 and embodiment 2 as seen, be oxygenant with the aqueous hydrogen peroxide solution, with WO
3/ ZrO
2Solid super-strong acid is a catalyzer, and with N, dinethylformamide is an extraction agent, carries out the reaction of oxidation-extraction coupled diesel deep desulfurization under the power ultrasonic strengthening effect, and diesel fuel desulfurization rate and oil product yield all are higher than 98%.
Claims (9)
1. oxidation-extraction coupled deep desulfurization method for diesel is characterized by and may further comprise the steps:
1) the zirconium hydroxide carrier is pulverized fine ground back and immersed in the steeping fluid that ammonium metatungstate aqueous solution constitutes, described steeping fluid is placed carry out ultrasonic facilitating impregnation in the ultrasonic generator, dipping boils off moisture after finishing, drying, and make WO through high-temperature roasting
3/ ZrO
2Solid super acid catalyst;
2) in sulfur-containing diesel, add aqueous hydrogen peroxide solution, extraction solvent and WO
3/ ZrO
2Solid super acid catalyst carries out catalytic oxidation desulfurization reaction under the power ultrasonic effect, reaction finishes postcooling to room temperature, the Separation and Recovery solid catalyst, and standing demix then, the upper strata then be a desulfurized diesel oil, lower floor recycles after regenerating.
2. method according to claim 1, the volumetric molar concentration that it is characterized in that the ammonium metatungstate aqueous solution described in the step 1) is 0.015～0.025M.
3. method according to claim 1 is characterized in that the zirconium hydroxide carrier described in the step 1) accounts for 20～40% of steeping fluid weight.
4. method according to claim 1 is characterized in that the maturing temperature described in the step 1) is 750～900 ℃.
5. method according to claim 1 is characterized in that step 2) described in the weight percent concentration of aqueous hydrogen peroxide solution be 30%～35%, aqueous hydrogen peroxide solution accounts for 10～25% of sulfur-containing diesel weight.
6. method according to claim 1 is characterized in that step 2) described in extraction solvent be N, dinethylformamide, N, the volume ratio of dinethylformamide and sulfur-containing diesel is 2: 1～1: 2.
7. method according to claim 1 is characterized in that step 2) described in WO
3/ ZrO
2Solid super acid catalyst accounts for 1～5% of sulfur-containing diesel weight.
8. method according to claim 1 is characterized in that step 2) described in the temperature of catalytic oxidation desulfurization reaction be 40～80 ℃, the time is 30～70min.
9. method according to claim 1 is characterized in that step 2) described in the ultrasonic frequency of power ultrasonic effect be 50～70kHz, ultrasonic power is 350～450W.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851529A (en) * | 2010-06-24 | 2010-10-06 | 东北石油大学 | Deep desulphurization method for oil by catalytic oxidation of potassium ferrate serving as oxidant with solid super acid |
| CN102660678A (en) * | 2012-05-17 | 2012-09-12 | 四川大学 | Method for selectively separating iron from hydrochloric acid solution containing ferrous chloride |
| CN102757811A (en) * | 2011-04-26 | 2012-10-31 | 中国石油化工股份有限公司 | Diesel oil oxidative desulphurization method |
| CN103450931A (en) * | 2013-09-06 | 2013-12-18 | 余国贤 | Ultrasonic oxidation-extraction and deep desulfurization method for diesel oil |
| CN105219425A (en) * | 2015-11-09 | 2016-01-06 | 扬州大学 | A kind of method of catalytic oxidative desulfurization Sulfur content in Fuel Oil compound |
| CN108467746A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | The method of sulfide in molecular sieve catalytic oxidation removal oil product |
| 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 |
| CN109534956A (en) * | 2018-11-21 | 2019-03-29 | 黄山科宏生物香料股份有限公司 | A kind of biomass methanol sulfur method |
| US20190314757A1 (en) * | 2018-04-13 | 2019-10-17 | Jiangnan Environmental Protection Group Inc. | Oxidization of ammonia desulfurization solution |
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2009
- 2009-11-30 CN CN200910232076A patent/CN101717659A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851529A (en) * | 2010-06-24 | 2010-10-06 | 东北石油大学 | Deep desulphurization method for oil by catalytic oxidation of potassium ferrate serving as oxidant with solid super acid |
| CN102757811A (en) * | 2011-04-26 | 2012-10-31 | 中国石油化工股份有限公司 | Diesel oil oxidative desulphurization method |
| CN102757811B (en) * | 2011-04-26 | 2014-10-15 | 中国石油化工股份有限公司 | Diesel oil oxidative desulphurization method |
| CN102660678A (en) * | 2012-05-17 | 2012-09-12 | 四川大学 | Method for selectively separating iron from hydrochloric acid solution containing ferrous chloride |
| CN103450931A (en) * | 2013-09-06 | 2013-12-18 | 余国贤 | Ultrasonic oxidation-extraction and deep desulfurization method for diesel oil |
| CN105219425A (en) * | 2015-11-09 | 2016-01-06 | 扬州大学 | A kind of method of catalytic oxidative desulfurization Sulfur content in Fuel Oil compound |
| CN108467746A (en) * | 2017-02-23 | 2018-08-31 | 中国石油化工股份有限公司 | The method of sulfide in molecular sieve catalytic oxidation removal oil product |
| US20190314757A1 (en) * | 2018-04-13 | 2019-10-17 | Jiangnan Environmental Protection Group Inc. | Oxidization of ammonia desulfurization solution |
| US11027234B2 (en) * | 2018-04-13 | 2021-06-08 | Jiangnan Environmental Protection Group Inc. | Oxidization of ammonia desulfurization solution |
| 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 |
| CN109534956A (en) * | 2018-11-21 | 2019-03-29 | 黄山科宏生物香料股份有限公司 | A kind of biomass methanol sulfur method |
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Application publication date: 20100602 |