CN102337151A - Preparation method of ultra-low-sulfur diesel oil - Google Patents
Preparation method of ultra-low-sulfur diesel oil Download PDFInfo
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- CN102337151A CN102337151A CN2010102387398A CN201010238739A CN102337151A CN 102337151 A CN102337151 A CN 102337151A CN 2010102387398 A CN2010102387398 A CN 2010102387398A CN 201010238739 A CN201010238739 A CN 201010238739A CN 102337151 A CN102337151 A CN 102337151A
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Abstract
The invention relates to a preparation method of ultra-low-sulfur diesel oil. The method comprises steps that: (1) under a common pressure, hydrorefined diesel oil is mixed with an amphipathic sandwich catalyst containing noble metals; the system is heated to a reaction temperature lower than 100 DEG C, and the catalyst is dissolved by stirring; and air or oxygen is delivered into the system; (2) when it is detected that organic sulfides in the diesel oil are completely converted into sulfone and/or sulfoxide, the reaction is stopped; (3) the temperature is cooled to room temperature, and precipitated catalyst is separated and recovered; (4) sulfone and/or sulfoxide in the obtained oxidized diesel oil is extracted by using an extractant, such that the ultra-low-sulfur diesel oil is obtained. With the method, sulfides which are extremely difficult to remove in hydrorefined diesel oil, such as 4,6-dimethyl dibenzothiophene and derivatives thereof, can be effectively removed. The adopted catalyst has strong catalytic activity and selectivity upon organic sulfides. According to the invention, diesel oil is directly adopted as a solvent, and air or oxygen is adopted as an oxidant, such that the technology is environment-friendly. Compared to a system with hydrogen peroxide as an oxidant, the operation cost is greatly reduced.
Description
Technical field
The present invention relates to a kind of diesel oil carried out the method for oxidation sweetening, relating more specifically to a kind of is the method for oxidant production ultra-low-sulphur diesel with oxygen or air.
Background technology
The fuel oil ultra-deep desulfurization has become an important environmental research problem being badly in need of solution in the world wide.Sulfide in the fuel oil can not only make the three-way catalyst of engine tail gas purification system produce irreversible poisoning through the oxysulfide (SOX) that engine combustion produces; And be discharged into airborne SOX and can cause acid rain, or the main contributor of particle swimmer in the atmosphere.Along with the enhancing gradually of human environmental consciousness in recent years, in order to reduce environmental pollution, the government regulations of world many countries all requires to produce and use more eco-friendly super low sulfur fuel oil.With diesel oil is example; The U.S. is 2000-5000ppm from the sulphur content standard of the eighties execution in latter stage; Promoting the use of the sulphur content standard since 1993 is the automobile-used clean diesel of 500ppm; Stipulate in the new environmental legislation that EPA (US EPA) formulates that the U.S. carried out new diesel oil standard in 2006, and the sulphur content of diesel oil is reduced to below the 15ppm.Europe from 2000ppm in 1993 drop to 2008 be lower than 10ppm (Europe V standard).China has implemented sulphur content on January 1st, 2002 and has been not more than 2000ppm derv fuel oil standard, also has sizable gap apart from developed country.After 1 day June in 2008, China has carried out sulphur content and has been not more than the diesel oil standard (being equivalent to Europe IV standard) of 50ppm in big cities such as Beijing, Shanghai, and will after 2011, diesel oil sulphur index will walk with world's pace.
The desired fuel oil sulphur content of environmental legislation become more and more lower in, most countries is but continuing to increase the demand of fuel oil in the world.Hydrogenating desulfurization can effectively remove mercaptan, thioether, disulphide, thiophene and verivate thereof and dibenzothiophene.Yet this method is difficult to remove 4, and the 6-dimethyl Dibenzothiophene (4,6-DMDBT) and verivate, thereby make the ultra-deep desulfurization of the diesel oil very difficulty that becomes.Want the sulphur in the diesel oil to be taken off to the super low sulfur level with the method for hydrogenating desulfurization; Must under harsh more operational condition, carry out,, increase working pressure as improving temperature of reaction; Use higher hydrogen-oil ratio etc., this certainly will increase facility investment expense and process cost greatly.Therefore, a kind of method that under gentle more condition, realizes Ultra-deep Desulfurization of Diesel Fuels of necessary exploitation is like absorption, extraction, oxidation and biological desulphurization etc.Wherein, oxidation and extraction (or absorption) combination sulfur method is considered to one of the most promising method because of potential advantages such as its operational condition are gentle, process cost is low.
In recent years, selective oxidation desulfurization (ODS) has caused people's great attention with its gentle operational condition and low investment, low cost.USP 6; 160; 193 disclose a kind of fractional oil desulfurizing method: with selective oxidation becomes sulphur and nitrogen oxides to increase its polarity with nitrogenous compound, these contain oxysulfide, contain oxynitride to reach the purpose of desulfurization removing nitric with the immiscible SX of hydro carbons in a kind of and the distillate again with the sulfur-bearing in the distillate in elder generation.The strong oxidizer that this patent is used is that strongly-acid oxygenant such as peroxyboric acid, persulfuric acid and temperature of reaction are higher, thereby must cause the generation of a large amount of side reactions with this method processing diesel oil, is unfavorable for the raising of diesel quality; The strongly-acid oxygenant has the very strong corrodibility of corrosion to equipment simultaneously, and is also unfriendly to environment.
USP 6,274,785 pairs of above-mentioned patents have been done improvement, have changed highly acid strong oxidizer into peroxy acetic acid.Since the peroxy acetic acid oxidation capacity a little less than, thereby temperature of reaction is higher, side reaction is more, the amount of the hydrogen peroxide of producing peroxy acetic acid simultaneously and being consumed is also bigger, is unfavorable for reducing running cost.
USP 6; 402,940 disclose a kind of fractional oil desulfurizing method: with sulfurous fuels oil 50～130 ℃ with oxygenant/extraction agent (a small amount of hydrogen peroxide, a large amount of formic acid and be lower than the mixing solutions that 25% water is formed) mixing solutions reaction after; After the fractionate aqueous solutions; Remove a small amount of residue formic acid and water in deoiling through distillation, use quicklime dry again, with the oil that obtains through one alumina adsorbant is housed the adsorption column sulfone or and the sulfoxide that fall with the not extraction that removes in deoiling.This sulfur removal technology is owing to use a large amount of formic acid, thereby unfriendly to environment; Simultaneously service temperature is higher, and side reaction is more, and this not only consumes a large amount of hydrogen peroxide, increases running cost, and is unfavorable for the raising (like colourity etc.) of oil quality.
What above-mentioned three parts of patents adopted is water oil two-phase system, and speed of response is slower, normally adopts the raising temperature of reaction to improve speed of response.
Also have and adopt other method to improve speed of response, like USP 6,402; 939 and 6; 500,219 disclose a kind of desulfurization of fuel oil method: oil and alkyl peroxide (or hydrogen peroxide), tensio-active agent, metal catalyst (like tungstate etc.) are mixed, under 75 ℃ of temperature; The container that fills this mixing solutions is inserted in the ultra-sonic generator; Organic sulfide in the oil is oxidized to sulfone or/and sulfoxide, again with polarity extracting agent with sulfone or/and sulfoxide from oil, extract, thereby reach the purpose of desulfurization.Although this patent utilization UW, tensio-active agent and catalyzer have been accelerated speed of response; But temperature of reaction still higher (＞70 ℃), this not only can't be avoided many side reactions, consumes a large amount of hydrogen peroxide; Increase running cost, but also to diesel quality influential (like colourity etc.); Not mentioned tensio-active agent and the catalyzer of how reclaiming of this patent simultaneously.
USP 5; 958; 224 also disclose a kind of with hydrotreatment and oxidation depth desulfurization combination process: with the oil fuel and a peroxide metal complex oxygenant effect of hydrotreatment; Organic sulfide in the oil fuel is oxidized to sulfone or/and sulfoxide, again through one sorbent material is housed adsorption column with the sulfone in the oil or/and sulfoxide absorption remove.Because the employed catalyzer of this method is one to be insoluble to the solid adsorbent of oil fuel, can only be dissolved in the chloro-hydrocarbons (like methylene dichloride), because it is chloro-hydrocarbons toxicity is big, unfriendly to environment.
Chinese patent (application number) 03107599.1,200510073771.4,200610001376.X disclose three kinds of methods for Ultra-deep Desulfurization of Diesel Fuels, be with hydrofining diesel oil with consist of three kinds of parental type catalyzer Q
3[XM
12O
40], Q
3[XM
nO
q] and Q
+[MW
xO
y]
-After the mixture of forming with aqueous hydrogen peroxide solution fully stirred, under gentle relatively reaction conditions (temperature of reaction≤60 ℃, normal pressure), the organic sulfide that will be present in the diesel oil was converted into sulfone or/and sulfoxide promptly obtains oxidated diesel oil.The oxidated diesel oil that will obtain after will handling again is through a kind of polar solvent; Optionally remove wherein most of sulfone or and sulfoxide; To remove at last most of sulfone or with the diesel oil of sulfoxide through the adsorption column of sorbent material is housed, to obtain a sulphur content be 0ppm or be lower than 10ppm.Because these above-mentioned three kinds of catalyzer can only be oxygenant with the hydrogen peroxide, handle sulfur-containing diesel, although the consumption of hydrogen peroxide is near measuring ratio, it consumes a big chunk that still accounts for process cost, has great room for improvement, remains further to be improved.
It is just at the early-stage at present with the atmospheric oxygen to be that oxygenant carries out the research of oxidation sweetening in the world, but because its cheapness, and advantages such as green have become the focus of catalytic field research.With oxygen or air is that oxygenant substitutes hydrogen peroxide, because cost is low, advantages such as Green Chemistry are the targets that chemist and scientific worker pursue always, but use it for the desulfurization of oil fuel, and present report also seldom.
Summary of the invention
The object of the present invention is to provide a kind of is oxygenant with oxygen or air, the method for the ultra-low-sulphur diesel of preparation sulphur content＜50ppm.
Be the realization above-mentioned purpose, preparation method provided by the invention, key step is:
A) reaction pressure is a normal pressure, and 80 ℃≤T of temperature of reaction≤110 ℃ is with hydrofining diesel oil and catalyzer Q
xNa
y[A
zB
mC
19O
68] mix, treat catalyst dissolution after, bubbling air or oxygen are oxygenant;
B) detect that organic sulfide in the diesel oil is converted into sulfone fully or/and behind the sulfoxide, stopped reaction; Cool the temperature to room temperature, the catalyzer that Separation and Recovery is separated out obtains oxidated diesel oil;
C) oxidated diesel oil that obtains is through washing, after the drying, or/and sulfoxide, can obtain the ultra-low-sulphur diesel of sulphur content＜50ppm with the sulfone in the extraction agent extraction diesel oil;
Among the above-mentioned preparation method, the used hydrofined oil of step a refers to the diesel oil that sulphur content is 100ppm to 600ppm, and preferred sulphur content is lower than the refined diesel oil of 500ppm.
Catalyzer Q
xNa
y[A
zB
mC
19O
68] in Q refer to quaternary ammonium salt, quaternary ammonium salt cationic is one of following or its arbitrary combination: [(C
18H
37) (75%)+(C
16H
33) (25%)]
2N
+(CH
3)
2, (C
8H
17)
4N
+, (C
12H
25)
4N
+, (C
16H
33)
4N
+, (π-C
5H
5N
+C
16H
33), (C
18H
37)
2N
+(CH
3)
2, the carbon chain lengths that has a group at least in the preferred quaternary ammonium salt is more than or equal to 8 carbon atoms, and preferred carbonatoms is that the quaternary ammonium salt of 16,18 alkyl is or/and its combination preferably consists of (C
18H
37)
3N
+CH
3Quaternary ammonium salt; X+y=11;
Catalyzer Q
xNa
y[A
zB
mC
19O
68] in A be meant noble ruthenium, palladium, platinum, ruthenium preferably, z=1 or 2;
Catalyzer Q
xNa
y[A
zB
mC
19O
68] in B be meant metallic zinc, m=2-5;
Catalyzer Q
xNa
y[A
zB
mC
19O
68] in C be meant tungsten.
Separation method among the step b refers to filtration, spinning or/and its combination, preferred spinning.
Used extraction agent refers to methyl alcohol, ethanol, formic acid, acetate, N-Methyl pyrrolidone (NMP), N among the step c; N-dimethyl-formyl ammonium (DMF), acetonitrile are or/and its combination; Preferred N-Methyl pyrrolidone (NMP), N, N-dimethyl-formyl ammonium (DMF), acetonitrile are or/and its combination.
Technological process of the present invention both can remove the extremely difficult sulfide that removes in the hydrofining diesel oil effectively as 4; 6-dimethyl Dibenzothiophene and verivate thereof; Used catalyzer not only has extremely strong catalytic activity and selectivity to organic sulfide; And with diesel oil (reactant) directly as solvent, air does not have other by products, thereby this technological process is friendly more to environment.
Specifically, compared with prior art, ultra-low-sulphur diesel preparation method of the present invention and technology have the following advantages:
1, with the molecular oxygen being oxygenant, under mild conditions, carrying out the oxidation sweetening of diesel oil, is a kind of green, inexpensive method, is a ultra-deep desulfurization technology that has DEVELOPMENT PROSPECT.
2, to sulfide particularly in the diesel oil difficult remove 4,6-dimethyl Dibenzothiophene and verivate thereof have the selective oxidation ability, can realize the low-temperature atmosphere-pressure oxidation, running cost can reduce greatly.
3, can the sulphur content in the hydrofining diesel oil be reduced to super low sulfur level (sulphur content＜50ppm).
Embodiment
In order to further specify the present invention, enumerate following examples, but it does not limit the defined invention scope of each accessory claim.
The present invention can be used for low-sulfur diesel-oil (preparation method of sulphur content＜50ppm), form by following operating process: (one) with hydrofining diesel oil with consist of Q
xNa
y[A
zB
mC
19O
68] catalyst mixture fully stir after, (temperature of reaction 80oC≤T≤110 ℃ under gentle relatively reaction conditions., normal pressure), be oxygenant with oxygen or air, the organic sulfide that will be present in the diesel oil is converted into sulfone or/and sulfoxide promptly obtains oxidated diesel oil.(2) through filtering with Q
xNa
y[A
zB
mC
19O
68] catalyzer separates from oxidated diesel oil, behind water, absolute ethyl alcohol thorough washing, reclaims this Q
xNa
y[A
zB
mC
19O
68] catalyzer.(3) utilize sulfone or/and the polarity difference of other hydrocarbon molecules in sulfoxide and the diesel oil; The oxidated diesel oil that obtains is after treatment passed through a kind of polar solvent; Optionally remove wherein most of sulfone or/and sulfoxide, obtain the ultra-low-sulphur diesel of a kind of sulphur content＜50ppm.
The preparation method of desulfurized diesel oil of the present invention and technology can be used for a concrete unit process: at normal temperatures and pressures, with the aforementioned catalyst mix of hydrofining diesel oil, under vigorous stirring, treat catalyst dissolution after, bubbling air or add oxygen.Organic sulfide in detecting diesel oil is converted into sulfone fully or/and behind the sulfoxide, stopped reaction.After cooling the temperature to room temperature, the catalyzer that Separation and Recovery is separated out.With the oxidated diesel oil that obtains with the sulfone in the extraction agent extraction diesel oil or/and sulfoxide.
Embodiment 1
Preparation of catalysts.As an illustrative examples, with sandwich-like heteropolyacid Na
11[WZnRu
2(OH) (H
2O) (ZnW
9O
34)
2] 42H
2(compound method is seen document R.Neumann and A.M.Khenkin to O; Inorganic Chemistry, 1995,34; 5753.) 6.1g (1mmol) is dissolved in the 50ml deionized water; Other gets distearyl dimethyl ammonium chloride 6.5g (11mmol) and is dissolved in the 40ml absolute ethyl alcohol, and heating is dissolved it fully slightly, and it is splashed into Na slowly
11[WZnRu
2(OH) (H
2O) (ZnW
9O
34)
2] 42H
2In the aqueous solution of O, vigorous stirring is filtered the white precipitate that obtains simultaneously, washing, and under the vacuum condition, 60 ℃ of dry 24h promptly get catalyzer [(C
18H
37)
2N (CH
3)
2]
11[WZnRu
2(OH) (H
2O) (ZnW
9O
34)
2], be called catalyst A.
Embodiment 2
In the oxidation reaction process of a standard, 4,6 dimethyl Dibenzothiophene 212mg (1mmol) are dissolved in the 25ml model diesel oil (perhydronaphthalene).Bath temperature is raised to 60 ℃, adds catalyzer [(C
18H
37)
2N (CH
3)
2]
11[WZnRu
2(OH) (H
2O) (ZnW
9O
34)
2] 44.2mg (0.005mmol), Bubbling method aerating oxygen, induction stirring.React 6 hours (h) and take out sample, and put into refrigerator with stopped reaction.The situation of oxidation is detected in centrifugal back with FPD (GC-FPD).Measure sulphur content with Microcoulomb instrument.The results are shown in Table 1 in desulfurization.
Embodiment 3
(1) get the 25ml sulphur content be the hydrofining diesel oil of 300ppm in the 150ml triangular flask, at room temperature add 0.1g catalyst A (grinding the back), Bubbling method feeds pure oxygen, vigorous stirring 10h; (2) catalyzer is reclaimed in above-mentioned processing diesel oil spinning; (3) with diesel oil after the oxidation with 25ml composite extractant extraction (by several kinds of extraction agent groups with form), separate lower floor's composite extractant, the re-extract secondary.The diesel oil that obtains is measured sulphur content with microcoulometry, and the result lists in the table 1.
Embodiment 4
With embodiment 3, just oxygenant is used air.
Embodiment 5
With embodiment 3, just extraction agent is with N-N-methyl-2-2-pyrrolidone N-(NMP).
Embodiment 6
With embodiment 3, just extraction agent is used ethanol.
Embodiment 7
With embodiment 3, just extraction agent is with DMSO 99.8MIN. (DMSO).
Embodiment 8
With embodiment 1, just the sandwich-like heteropolyacid is got Na
12[WZnPt
2(OH) (H
2O) (ZnW
9O
34)
2] 42H
2O (compound method is with reference to Claude M.Tourn é, Gilbert F.Tourn é, and Frans Zonnevijlle, J.Chem.Soc., Dalton Trans., 1991, (1), 143-155), quaternary ammonium salt is got (C
12H
25) N (CH
3)
3Cl obtains catalyzer [(C
12H
25) N (CH
3)
3]
11[WZnPt
2(OH) (H
2O) (ZnW
9O
34)
2], be called catalyst B.
Embodiment 9
With embodiment 2, only be to use catalyst B.
Embodiment 10
With embodiment 3, only be to use catalyst B.
Embodiment 11.
With embodiment 1, just the sandwich-like heteropolyacid is got Na
12[WZnPd
2(OH) (H
2O) (ZnW
9O
34)
2] 42H
2O (compound method is with reference to Claude M.Tourn é, Gilbert F.Tourn é, and Frans Zonnevijlle, J.Chem.Soc., Dalton Trans., 1991, (1), 143-155), quaternary ammonium salt is got (C
18H
37) N (CH
3)
3Cl obtains catalyzer [(C
18H
37) N (CH
3)
3]
11[WZnPt
2(OH) (H
2O) (ZnW
9O
34)
2], be called catalyzer C.
Embodiment 12
With embodiment 2, only be to use catalyzer C.
Embodiment 13
With embodiment 3, only be to use catalyzer C.
Table 1. test-results
The diesel oil sulphur content of producing by the present invention all is lower than 50ppm, reached the clean diesel IV of the European countries (standard of sulphur content＜50ppm).
Claims (5)
1. the preparation method of a ultra-low-sulphur diesel, key step is following:
A) reaction pressure is a normal pressure, and 80 ℃≤T of temperature of reaction≤110 ℃ is with hydrofining diesel oil and amphiphilic sandwich-like catalyzer Q
xNa
y[A
zB
mC
19O
68] mix, treat catalyst dissolution after, bubbling air or oxygen are oxygenant;
B) detect that organic sulfide in the diesel oil is converted into sulfone fully or/and behind the sulfoxide, stopped reaction; Cool the temperature to room temperature, the catalyzer that Separation and Recovery is separated out obtains oxidated diesel oil;
C) oxidated diesel oil that obtains is through washing, after the drying, or/and sulfoxide, can obtain the ultra-low-sulphur diesel of sulphur content＜50ppm with the sulfone in the extraction agent extraction diesel oil;
Catalyzer Q
xNa
y[A
zB
mC
19O
68] in Q be meant quaternary ammonium salt cationic, x+y=11;
Catalyzer Q
xNa
y[A
zB
mC
19O
68] in A be meant noble ruthenium, palladium or platinum, z=1 or 2;
Catalyzer Q
xNa
y[A
zB
mC
19O
68] in B be meant metallic zinc, m=2-5;
Catalyzer Q
xNa
y[A
zB
mC
19O
68] in C be meant tungsten.
2. according to the described preparation method of claim 1, it is characterized in that: hydrofining diesel oil is meant that sulphur content is the refined diesel oil of 100ppm to 600ppm.
3. according to the described preparation method of claim 1, it is characterized in that: carbon chain lengths>=8 that have an alkyl in the quaternary ammonium salt cationic at least; Be preferably between 8 to 18, i.e. 8≤carbon chain lengths≤18.
4. according to claim 1 or 3 described preparing methods, it is characterized in that: quaternary ammonium salt cationic is one of following or its multiple arbitrary combination:
[(C
18H
37)(75mol％)+(C
16H
33)(25mol％)]
2N
+(CH
3)
2、(C
8H
17)
4N
+、(C
12H
25)
4N
+、(C
16H
33)
4N
+、(π-C
5H
5N
+C
16H
33)、(C
18H
37)
2N
+(CH
3)
2。
5. according to the described preparation method of claim 1, it is characterized in that: extraction agent is one of following or more than one arbitrary combination:
Methyl alcohol, formic acid, ethanol, acetate, DMSO 99.8MIN., two formyl ammoniums, acetonitrile, N-N-methyl-2-2-pyrrolidone N-.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1961061A (en) * | 2004-05-31 | 2007-05-09 | 新加坡科技研究局 | Novel process for removing sulfur from fuels |
| CN101003744A (en) * | 2006-01-19 | 2007-07-25 | 中国科学院大连化学物理研究所 | Method for preparing desulfurized diesel oil |
-
2010
- 2010-07-28 CN CN2010102387398A patent/CN102337151A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1961061A (en) * | 2004-05-31 | 2007-05-09 | 新加坡科技研究局 | Novel process for removing sulfur from fuels |
| CN101003744A (en) * | 2006-01-19 | 2007-07-25 | 中国科学院大连化学物理研究所 | Method for preparing desulfurized diesel oil |
Non-Patent Citations (1)
| Title |
|---|
| RONNY NEUMANN,ALEXANDER M.KHENKIN: "Noble Metal(RuⅢ,PdⅡ,PtⅡ)Substituted "sandwich" Type Polyoxometalates:Preparation,Characterization,and Catalytic Activity in Oxidation of Alkanes and Alkenes by Peroxides", 《INORG.CHEM》, 31 December 1995 (1995-12-31) * |
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Application publication date: 20120201 |