CN102134508B - Oxidation desulfuration method based on modified MCM-41 anchored heteropolyacid catalyst - Google Patents
Oxidation desulfuration method based on modified MCM-41 anchored heteropolyacid catalyst Download PDFInfo
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- CN102134508B CN102134508B CN201110032894.9A CN201110032894A CN102134508B CN 102134508 B CN102134508 B CN 102134508B CN 201110032894 A CN201110032894 A CN 201110032894A CN 102134508 B CN102134508 B CN 102134508B
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- heteropolyacid
- grappling
- amine
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Abstract
The invention discloses an oxidation desulfuration method based on modified MCM-41 anchored heteropolyacid catalyst, adopting hydrogen peroxide as oxygenant and modified MCM-41 anchored heteropolyacid as catalyst. The method comprises the following steps: proportionally mixing oil with acetonitrile solvent, proportionally adding the mixture of the oxygenant and the catalyst at certain temperature and normal pressure, cooling to room temperature after reaction, naturally layering, obtaining desulphurized oil products at the upper layer of oil phase, separating the catalyst in the lower layer (namely the acetonitrile phase) through filtration, and recycling. Compared with the traditional process, the method has the advantages of low production process, high safety of operation under normal pressure, strong desulfuration capability, saving of oxygenant and low production cost, and achieves efficient, economic and environment-friendly production process.
Description
Technical field
The present invention relates to a kind of oxidation desulfurizing method based on Modified MCM-41 grappling heteropolyacid catalyst, belong to the deep processing of petroleum chemical industry oil product and green technology crossing domain.
Background technology
The SO that sour product forms in combustion processes
xbe one of presoma that in atmosphere, acid rain forms, it is cause buildings corrodibility destruction, plant and the infringement of crop big area and cause one of main arch-criminal of a series of environment and health problem.Relevant research shows, continuously and effectively reduce NO in vehicle exhaust
xetc. the quantity discharged of objectionable impurities, key is the sulphur content that will reduce in fuel oil, because sulfide can cause the poisoning actual effect of motor-vehicle tail-gas purifying device catalyzer.At present, strict restriction has been made to the sulphur content in fuel oil in countries in the world, and requires day by day harsh.European Union was down to 50ppm by diesel oil sulphur content by 350ppm in 2005, within 2009, was down to 10ppm; The standard that the U.S. carries out is now 15ppm; The standard that the standard that Uruguay carries out is now 50ppm, plans to be down to for 2012 10ppm.China, was down to 150ppm by white gasoline sulphur content by 500ppm in China in 31 days December in 2009.Face the increasingly strict of sulphur content of fuel oil standard, oxidative desulfurization techniques is high with its desulfuration efficiency, reaction conditions is gentle, invest the focus that the advantages such as running cost is low, technical process is simple become domestic and international research.
The oxygenant kind that oxidative desulfurization techniques relates to is more, take hydrogen peroxide as oxygenant is in dominant position.H
2o
2corrodibility is low, and byproduct of reaction is water and oxygen, has fundamentally eliminated the source of pollution of oxidising process, non-environmental-pollution.Heteropolyacid is as the novel catalytic material of a class, has to form simply, and structure determines, component is the advantage such as tunes easily, is subject to catalytic field investigators' extensive concern, is applied to the existing many research of deep oxidation desulfurization reports as catalyzer.Utilize the oxidative desulfurization techniques that acetonitrile is extraction agent, existing many deep research reports, but still have larger distance with actual requirement, exist catalyzer be soluble in acetonitrile mutually in, be difficult to recycle or have certain toxic, high in cost of production problem.In a word, existing sulfur removal technology exists catalyzer to be difficult to the problems such as recycling, oxidant consumption amount is large, security is difficult to guarantee, economic benefit is low, and this has also fundamentally limited industrial production application.Therefore, finding new catalytic material, explore new catalyzer curing technology, is the emphasis of current research work.
Summary of the invention
For above-mentioned prior art problem, the invention provides a kind of oxidation desulfurizing method based on Modified MCM-41 grappling heteropolyacid catalyst, there is the advantages such as catalyzer can directly be recycled, sweetening effectiveness is good.
The present invention is achieved by the following technical solutions:
An oxidation desulfurizing method based on Modified MCM-41 grappling heteropolyacid catalyst, comprises the following steps:
(1) get oxygenant H
2o
2with catalyst modification MCM-41 grappling heteropolyacid, pre-contact mixes 2～35min, standby.Wherein, the consumption of Modified MCM-41 grappling heteropolyacid is pending oil quality 0.25%～5%, H
2o
2consumption calculate in the following manner: the mole number with S in pending oil product is determined H
2o
2mole number, O/S mol ratio is (1～40): 1.
(2) under normal temperature and pressure conditions, by pending oil product, according to volume ratio, be 1 with acetonitrile: the ratio of (0.5～3) is mixed, control 40～70 ℃ of temperature of reaction, add the oxygenant that makes in step (1) and the mixture of catalyzer, under magnetic agitation condition, react 2～5h.
(3) separation of reaction mixture: after above-mentioned reaction completes, be cooled to room temperature, reaction mixture natural layering, the upper oil phase separating is desulfurization oil product.Lower floor's acetonitrile is filtered mutually can be separated with desulfurization product by catalyzer, and catalyzer can directly reuse.
Described Modified MCM-41 grappling heteropolyacid catalyst obtains by following preparation method:
(1) preparation of amino modified MCM-41: the γ-aminopropyl triethoxysilane of the dehydrated alcohol of the MCM-41 of 1.0～8.0g, 30～250mL and 5～15g is placed in to reaction vessel (500mL there-necked flask), at N
2under protection, under 50～90 ℃ of water-bath return stirring conditions, react 8～20h, suction filtration, obtains white solid; The dehydrated alcohol of take carries out Soxhlet extraction to white solid as solvent, 80～180 ℃ of temperature, and extraction time 2～6h, finally by the dry 1～5h of infrared dryer, makes MCM-41/amine.
(2) MCM-41/amine/HPW
12o
40preparation: the MCM-41/amine of 3.0～6.0g is dropped in the deionized water of 20～100mL to stirring at room 0.5～4h; Then the heteropolyacid of 2.0～8.0g is dissolved in 30～90mL deionized water, is mixed with solvent, be added drop-wise in above-mentioned MCM-41/amine suspension liquid, under room temperature, after vigorous stirring 8～20h, suction filtration, obtains white solid.Infrared dryer is dried 1～5h, makes MCM-41/amine/HPW
12o
40, be Modified MCM-41 grappling heteropolyacid.
Heteropolyacid in described step (2) has XY
12o
40or XY
12-nz
no
40type anion structure, such as, HPW
12o
40, H
4pMo
11v
1o
40, H
5pMo
10v
2o
40or H
6pM0
9v
3o
40.
Described pending oil product comprises the work in-process oil in crude oil, oil fuel and crude oil refining process.
Principle of the present invention is: take hydrogen peroxide as oxygenant, Modified MCM-41 grappling heteropolyacid is catalyzer, acetonitrile is extraction agent, first, the sulfocompounds such as the thionaphthene in oil product, dibenzothiophene automatically transfer to acetonitrile mutually in, through catalyzed oxidation, generate corresponding sulfone or sulfoxide type material, along with the extraction equilibrium that carries out reacting is broken, more organic sulfide is transferred to the acetonitrile middle participation catalytic oxidation that continues mutually; Reaction product sulfone (or sulfoxide) belongs to polar material and is soluble in acetonitrile, continue to remain in acetonitrile mutually in, thereby reach desulfurizing oil object.
The oxidation desulfurizing method used catalyst preparation method who the present invention is based on Modified MCM-41 grappling heteropolyacid catalyst is simple, high and the good stability of catalytic activity, catalyzer is easy to reclaim and recycling, and whole process desulfuration efficiency is high, simple and the less investment of processing unit, is easy to industrialization promotion.
The invention has the beneficial effects as follows: synthesis modification MCM-41 grappling heteropolyacid novel material of the present invention, using it as catalyzer, utilizes the catalyzed oxidation principle that combines with extracting and separating to remove the sulfocompound in oil product.Compare with independent use oxygenant, desulfuration efficiency obviously improves, and Reaction time shorten has effectively been controlled the decomposition of hydrogen peroxide, has reduced the consumption of hydrogen peroxide, reduces production costs.Meanwhile, the present invention's Modified MCM-41 grappling used heteropolyacid catalyst recoverable, has significant economy.In a word, method of the present invention is compared with traditional technology, advantages such as having that production technique is simple, atmospheric operation is safe, sweetening power is strong, save oxygenant usage quantity, catalyzer recoverable, production cost are low is the production technique of a kind of efficient, economy, environmental protection.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but it should be noted that the present invention is not limited to following embodiment, do not departing under the prerequisite of aim of the present invention, and all changes are implemented to be all included in protection scope of the present invention.
Embodiment 1: catalyzer synthetic
(1) preparation of amino modified MCM-41: 1.0MCM-41,50mL dehydrated alcohol and 1.5g γ-aminopropyl triethoxysilane are placed in to 100mL there-necked flask.At N
2under protection, under 70 ℃ of water-bath return stirring conditions, react 12h, suction filtration, obtains white solid.The dehydrated alcohol of take carries out Soxhlet extraction to above-mentioned white solid as solvent, 180 ℃ of temperature, and extraction time 4h, finally by the dry 1h of infrared dryer, makes MCM-41/amine.
(2) MCM-41/amine/PW
12o
40preparation: 3.5g MCM-41/amine is dissolved in 40mL deionized water to stirring at room 1h.By 4.0g HPW
12o
40be dissolved in 20mL deionized water, be mixed with solvent, be added drop-wise in above-mentioned MCM-41/amine solution, under room temperature, after vigorous stirring 12h, suction filtration, obtains white solid.Infrared dryer is dried 3.5h, makes MCM-41/amine/PW
12o
40, standby.
Embodiment 2: catalyzer synthetic
Outside lower difference, the other the same as in Example 1: by changing heteropolyacid (H used
3pW
12o
40, H
3pMo
12o
40, H
4siW
12o
40, H
4pMo
11v
1o
40, H
5pMo
10v
2o
40and H
6pMo
9v
3o
40), synthetic Modified MCM-41 grappling heteropoly compound has 6 kinds, respectively: MCM-41/amine/PW
12o
40, MCM-41/amine/PMo
12o
40, MCM-41/amine/SiW
12o
40, MCM-41/amine/PMo
11v
1o
40, MCM-41/amine/PMo
10v
2o
40, MCM-41/amine/PMo
9v
3o
40.
Embodiment 3: the simulated system of dibenzothiophene (DBT)-octane
The more difficult dibenzothiophene removing (DBT) in hydrogenating desulfurization of take is representative, and a certain amount of DBT is dissolved in to 60ml octane, is mixed with the simulated system that sulphur content is 500ppm, adds 60ml acetonitrile, and magnetic agitation is heated to 60 ℃.Press O/S (mol ratio)=10 and calculate H
2o
2add-on, by 1% octane Mass Calculation MCM-41/amine/PW
12o
40catalyzer add-on, by H
2o
2with MCM-41/amine/PW
12o
40pre-contact reacts 10min, after join above-mentioned simulated system, after reaction 240min, in octane, the transformation efficiency of DBT reaches 72.97%.
Embodiment 4: the simulated system of dibenzothiophene (DBT)-octane
The more difficult dibenzothiophene removing (DBT) in hydrogenating desulfurization of take is representative, and a certain amount of DBT is dissolved in to 60ml octane, is mixed with the simulated system that sulphur content is 500ppm, adds 60ml acetonitrile, and magnetic agitation is heated to 40 ℃.Press O/S (mol ratio)=15 and calculate H
2o
2add-on, by 1% octane Mass Calculation MCM-41/amine/PW
12o
40catalyzer add-on, by H
2o
2with MCM-41/amine/PW
12o
40pre-contact reacts 10min, after join above-mentioned simulated system, after reaction 180min, in octane, the transformation efficiency of DBT reaches 82.95%.
Embodiment 5: the simulated system of dibenzothiophene (DBT)-octane
The more difficult dibenzothiophene removing (DBT) in hydrogenating desulfurization of take is representative, and a certain amount of DBT is dissolved in to 60ml octane, is mixed with the simulated system that sulphur content is 500ppm, adds 60ml acetonitrile, and magnetic agitation is heated to 60 ℃.Press O/S (mol ratio)=15 and calculate H
2o
2add-on, by 0.5% octane Mass Calculation MCM-41/amine/PW
12o
40catalyzer add-on, by H
2o
2with MCM-41/amine/PW
12o
40pre-contact reacts 10min, after join above-mentioned simulated system, after reaction 240min, in octane, the transformation efficiency of DBT reaches 85.54%.
Embodiment 6: the simulated system of dibenzothiophene (DBT)-octane
The more difficult dibenzothiophene removing (DBT) in hydrogenating desulfurization of take is representative, and a certain amount of DBT is dissolved in to 60ml octane, is mixed with the simulated system that sulphur content is 500ppm, adds 60ml acetonitrile, and magnetic agitation is heated to 60 ℃.Press O/S (mol ratio)=15 and calculate H
2o
2add-on, by 0.5% octane Mass Calculation MCM-41/amine/PMo
11v
1o
40catalyzer add-on, by H
2o
2with MCM-41/amine/PMo
11v
1o
40pre-contact reacts 10min, after join above-mentioned simulated system, after reaction 240min, in octane, the transformation efficiency of DBT reaches 72.51%.
Embodiment 7: the simulated system of dibenzothiophene (DBT)-octane
The more difficult dibenzothiophene removing (DBT) in hydrogenating desulfurization of take is representative, and a certain amount of DBT is dissolved in to 60ml octane, is mixed with the simulated system that sulphur content is 500ppm, adds 60ml acetonitrile, and magnetic agitation is heated to 60 ℃.Press O/S (mol ratio)=15 and calculate H
2o
2add-on, by 0.5% octane Mass Calculation MCM-41/amine/PW
12o
40catalyzer add-on, by H
2o
2with MCM-41/amine/PW
12o
40pre-contact reacts 5min, after join above-mentioned simulated system, after reaction 240min, in octane, the transformation efficiency of DBT reaches 96.83%.
Claims (3)
1. the oxidation desulfurizing method based on Modified MCM-41 grappling heteropolyacid catalyst, is characterized in that, comprises the following steps:
(1) get oxygenant H
2o
2with catalyst modification MCM-41 grappling heteropolyacid, pre-contact mixes 2～35min, standby; Wherein, the consumption of Modified MCM-41 grappling heteropolyacid is pending oil quality 0.25%～5%, H
2o
2consumption calculate in the following manner: the mole number with S in pending oil product is determined H
2o
2mole number, O/S mol ratio is (1～40): 1;
(2) under normal temperature and pressure conditions, by pending oil product, according to volume ratio, be 1:(0.5～3 with acetonitrile) ratio mix, control 40～70 ℃ of temperature of reaction, add the oxygenant that makes in step (1) and the mixture of catalyzer, under agitation condition, react 2～5h;
(3) separation of reaction mixture: after above-mentioned reaction completes, be cooled to room temperature, reaction mixture natural layering, the upper oil phase separating is desulfurization oil product;
Described Modified MCM-41 grappling heteropolyacid catalyst obtains by following preparation method:
(1) preparation of amino modified MCM-41: the γ-aminopropyl triethoxysilane of the dehydrated alcohol of the MCM-41 of 1.0～8.0g, 30～250mL and 5～15g is placed in to reaction vessel, at N
2under protection, under 50～90 ℃ of water-bath backflows and agitation condition, react 8～20h, suction filtration, obtains white solid; The dehydrated alcohol of take carries out Soxhlet extraction to white solid as solvent, 80～180 ℃ of temperature, and extraction time 2～6h, finally by infrared drying 1～5h, makes MCM-41/amine;
(2) MCM-41/amine/HPW
12o
40preparation: the MCM-41/amine of 3.0～6.0g is joined in the deionized water of 20～100mL to stirring at room 0.5～4h; Then the heteropolyacid of 2.0～8.0g be dissolved in 30～90mL deionized water to wiring solution-forming and be added drop-wise in above-mentioned MCM-41/amine suspension liquid, under room temperature, after vigorous stirring 8～20h, suction filtration, obtains white solid, infrared dryer is dried 1～5h, makes MCM-41/amine/HPW
12o
40, be Modified MCM-41 grappling heteropolyacid catalyst.
2. a kind of oxidation desulfurizing method based on Modified MCM-41 grappling heteropolyacid catalyst according to claim 1, is characterized in that: described heteropolyacid is H
3pW
12o
40, H
3pMo
12o
40, H
4siW
12o
40, H
4pMo
11v
1o
40, H
5pMo
10v
2o
40or H
6pMo
9v
3o
40in any.
3. a kind of oxidation desulfurizing method based on Modified MCM-41 grappling heteropolyacid catalyst according to claim 1, is characterized in that: described pending oil product comprises the work in-process oil in crude oil, oil fuel and crude oil refining process.
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| CN109225332A (en) * | 2018-08-24 | 2019-01-18 | 中国石油大学(华东) | A kind of preparation method for Desulphurization of fuels catalyst |
| CN109201105B (en) * | 2018-08-24 | 2021-12-07 | 山东法恩泰科技工程有限公司 | Preparation method of deep desulfurization catalyst |
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