CN100513524C - Method for producing low-sulfur diesel-oil by oxidation desulfurization - Google Patents
Method for producing low-sulfur diesel-oil by oxidation desulfurization Download PDFInfo
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- CN100513524C CN100513524C CNB2005100458684A CN200510045868A CN100513524C CN 100513524 C CN100513524 C CN 100513524C CN B2005100458684 A CNB2005100458684 A CN B2005100458684A CN 200510045868 A CN200510045868 A CN 200510045868A CN 100513524 C CN100513524 C CN 100513524C
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Abstract
This invention discloses an oxidizing and desulfurizing method for fraction oil including that the fraction oil and hydrogen peroxide are reacted in a multi-stage reactor where low level organic acid catalyst exists, the product in each stage reactor is separated in oil-water phase, the water phase product is recovered after the organic acid is removed and the oil phase product is taken as the feed of the next stage reactor, apart from the raw material oil from the above stage, the feed of each stage is added with organic acid and hydrogen peroxide, different reacting stages are determined according to the needs on sulfur by a product and its content and the fraction oil from the last stage is taken as the low sulfur product directly after being dehydrated, which leaves out the process of solvent extraction or adsorption to the oil phase products after the oxidizing reaction.
Description
Technical field
The present invention relates to a kind of fraction oil oxidation desulfurizing method, particularly the method for producing clean fuel with sulfur-containing diesel cut oxidation sweetening.
Background technology
Organosulfur compound in the oil fuel is a kind of objectionable impurities.The burning back generates SO
xCause forming acid rain, cause to the pollution of environment with to the infringement of human health.For vehicle fuel, SO then
xTo the NO particularly of HC, CO in the vehicle exhaust
xWith the discharging of PM obvious facilitation is arranged, thereby cause the increase of pollutant effulent.SO
xAlso can corrode engine, reduce the life-span of engine.In view of the harm of sulphur in the vehicle fuel oil, strict more diesel oil standard has all been issued in world many countries and area in succession.Face strict petrol and diesel oil sulphur content restriction and the market great demand to the low-sulfur clean diesel, countries in the world are devoted to develop various desulfurization of fuel oil technology one after another.
The traditional method of producing the low-sulfur clean fuel is hydrogenating desulfurization.Along with the increase of the hydrogenation degree of depth, last a spot of sulphur removes difficulty and sharply rises, thereby causes desulphurization cost to increase considerably.In order to address these problems, non-hydrogenating desulfurization approach is all being explored by many companies, and oxidation sweetening is one of numerous solutions.
Sulfocompound in the diesel oil mainly is an organosulfur compound, is many with thiophene and derivative thereof.Because carbon-carbon bond is close with carbon-sulfur bond polarity, so organosulfur compound is soluble in the diesel oil.One or two Sauerstoffatom is linked on the sulphur atom of sulfocompound by oxidation, just can be increased its polarity and it is increased in aqueous phase solubleness, reduce in the solubleness of oil phase, thereby reach and the isolating purpose of hydro carbons.The oxidation sweetening process of liquid oil plant can be divided into for three steps usually: the oxidizing reaction of (1) sulfocompound changes into the stronger sulfone of polarity, sulfoxide class S-contained substance with the sulfocompound in the distillate; (2) sepn process after the oxidizing reaction is carried out extraction treatment with the distillate after the oxidation with extraction agent, except that remaining a small amount of sulfone in deoiling, obtains low-sulfur fuel after the separation and is rich in the sulfide extraction solvent; (3) be rich in the regeneration of the solvent of sulfur oxide.In this operate continuously process, crucial oxidation at sulfide.Most of sulfocompounds are easy to oxidized dose (as H
2O
2) institute's oxidation.Following reaction can take place in the senior mercaptan under the effect of catalyzer in the liquid fuel, thioether etc.:
Thiophene-type sulfide oxidizing reaction formula is as follows:
The thiophene that alkyl replaces can take place and oxidizing reaction like the thiophene-based, the thionaphthene that alkyl replaces, the oxidizing reaction of dibenzothiophene then respectively with thionaphthene, the oxidation of dibenzothiophene is similar.
The most frequently used way of oxidation sweetening is to use peroxide oxidation.U.S. Pat P 5310479 proposes to remove the sulfocompound in the crude oil with formic acid-hydrogen peroxide oxidation system.The nearly phase Tian Zhefu of Ji university of Japan (petro-technology (day), 2000, (6): 43-46) oxidation sweetening that also hydrogen peroxide-carboxylic acid (formic acid) system is used for diesel oil has been done number of research projects.
Alkis S.Rappas has proposed a scheme that adopts hydrogen peroxide and formic acid to cooperate low amounts of organic sulfur in the oxidation removal diesel oil in U.S. Pat P 6402940.(patent requires to form series by 2-3 reactor in describing to be characterized in that serial continuous-stirring reactor is sent into stock oil in formic acid-hydrogen peroxide-water mixing back, do not have oil water separation process between each reactor), oil phase and containing after the formic acid aqueous phase separation is handled respectively in the reaction product.The formic acid water that contains the partial oxidation products sulfone with remove flashing tower after hot gas oil mixes, the water of telling from cat head goes distillation tower to reclaim formic acid to utilize, contain the defocusing of gas oil or the accent pitch of sulfone.The oil phase of telling in the reaction product goes flash distillation to remove water and formic acid that part is carried secretly after heating, and cooling back alkali cleaning (adding calcium oxide) is to remove residual formic acid again.The oil phase of telling behind the solid alkaline residue removes oxidation products sulfone in the oil phase with solvent extraction, and residual sulfone removes with alumina adsorption again.Thereby the shortcoming of this scheme one is to remove the alkaline residue that residual acid in the oil phase will produce contaminate environment with alkali cleaning, and the latter's harmless treatment needs higher cost; The 2nd, remove oil phase behind the residual acid and will desolvate extraction and alumina adsorption removing the sulfocompound in the oil phase, and solvent extraction and alumina adsorption make whole sweetening process cost increase more.
Summary of the invention
At the deficiencies in the prior art, the present invention proposes a kind of oxidation desulfurizing method of sulfur-containing liquid oil plant, by the sepn process of oxidation sweetening and sulfocompound, obtains doctor negative clean fuel products.
The contriver finds by process and interpretation of result to sulfur-containing liquid oil plant such as diesel oil distillate oxidation sweetening, sour distillate oil is carried out in the process of oxidation sweetening with hydrogen peroxide and organo-peroxide, sulfocompound be oxidized to behind sulfone and the sulfoxide in oil phase and aqueous phase be dissolved with certain allocation proportion.Because the polarity of sulfone is bigger than sulfoxide, thus sulfone the content of sulfoxide in oil phase is more in that the content of aqueous phase is more.In addition, from the angle of chemical equilibrium, the oxidation products in the reaction system has restraining effect to further oxidizing reaction.When one timing of oxygenant consumption, if tell oxidation products from system, then total desulfurization degree has remarkable increase.The contriver finds that also then the sulphur content in the oil phase can reduce significantly if take out of after making a large amount of selective oxidation of sulfur containing compounds in particular from the solvent phase (as formic acid and water) of oxidation system.If the sulphur in the oil phase is taken out of by solvent phase in a large number, residual sulfur is sloughed in extraction or alumina adsorption is sloughed the residual sulfur process then can to save the solvent (usually with methyl alcohol etc.) of reaction back oil phase.No matter and be that solvent extraction or alumina adsorption all make the process cost of oxidation sweetening increase more.
At above-mentioned result of study, the concrete scheme of sour distillate oil oxidation desulfurizing method of the present invention is as follows:
The distillate of sulfur-bearing is in the presence of peroxide oxidant and catalyzer, in 2～6 stage reactors, carry out oxidation desulfur reaction, material behind every order reaction is after profit is separated, water is concentrated distillation recovering liquid acid catalyst, oil phase is as the stock oil of next stage reaction, stock oil all enters reactor as raw material jointly with peroxidation thing, liquid catalyst during every order reaction, and the product that last step reflects oil phase after profit is separated directly goes out device as low sulfur product.
Reacted material carries out after profit is separated, and water goes tripping device to tell the sulfone that liquid catalyst and reaction generate, and liquid catalyst recycles after reclaiming; Oil phase enters the further oxidation sweetening of next stage reactor, and the oil phase that last step reflects obtains low-sulfur cleaning oil plant after washing and dehydration.The isolated water of first step reaction product is sent to the bath water of the oil phase that reflects as last step.
Sour distillate oil can be the natural oil cut, particularly diesel oil distillate of sulfur-bearing, also can be other distillate that needs desulfurization, as adopting artificial petroleum cut that methods such as gelatin liquefaction, shale retorting obtain etc.
Peroxide oxidant is to have the R-O-O-H structure, and R is the tertiary alkyl peroxide of H or C4-5, is preferably hydrogen peroxide.Catalyzer is the catalyzer that comprises liquid organic acid, and wherein organic acid is formic acid or acetate.
The actual conditions of reaction process can be selected to determine in the common process condition according to raw material properties and quality product requirement.
The inventive method can be selected existing efficient mass transfer reactor according to concrete processing condition, as various impact flow reactors, the various tank reactors that have stirring, the static mixer reactor, Multiple Combination static mixer reactor etc., also can be other various reactors that have the efficient mass transfer inner member, also can be fixed-bed reactor.
The present invention is by the reaction process of further investigation sour distillate oil oxidation sweetening, and the pests occurrence rule at sour distillate oil oxidation sweetening process main reaction and side reaction proposes above-mentioned oxidation sweetening process.Because the present invention has adopted the plural serial stage reaction that oxidation depth is significantly improved, a large amount of sulfocompounds are told from aqueous phase after oxidation, sulphur in the oil phase just can meet the sulphur content requirement of product without solvent extraction or absorption, thereby saved the solvent extraction or the alumina adsorption of oil phase after the oxidation, shortened Production Flow Chart, production cost is reduced significantly.
Because technological process of the present invention all has the water that an oily-water seperating equipment will be rich in the selective oxidation of sulfur containing compounds in particular product to tell behind every stage reactor, and every stage reactor inlet all replenishes new oxygenant and liquid catalyst, makes the chemical reaction environment more help the carrying out of oxidizing reaction.
Because the present invention adopts reaction of high order, reaction order can determine according to production requirement.Make that employing desulfurization production decision of the present invention is more flexible, can adapt to the raw material of different sulphur contents, also can adapt to the products scheme of different sulfur-bearing requirements.
Description of drawings
Fig. 1 is an oxidation desulfuration process schematic flow sheet of the present invention.
Fig. 2 is a kind of impact flow reactor structural representation that oxidation sweetening process of the present invention is used.81 guide shells wherein, 82 propeller, 83 impingement regions, 84 opening for feeds, 85 discharge ports.
Embodiment
Now be example illustrates the inventive method with reference to Fig. 1 concrete technical process with the two-stage reaction: the reaction raw materials after pre-mixing (stock oil, oxygenant, catalyzer) enters reactor 2 via pipeline 1.Enter liquid liquid separator 4 with different product requirement reaction after products under the reaction conditions of regulation via pipeline 3 by different material.Water after the separation removes the recovery tower 6 of organic acid catalyst and sulfone via pipeline 5, and the organic acid catalyst of recovery mixes with stock oil and oxygenant via pipeline 7.Oil phase after the separation arrives second stage reactor 10 via pipeline 9.Oxygenant and liquid catalyst then respectively pipeline 12 and 11 enter reactor 10.The reaction after product enters secondary liquid liquid separator 14 via pipeline 13.Water after the separation removes the recovery tower 6 of organic acid catalyst and sulfone via pipeline 15.The oil phase that comes out from secondary liquid liquid separator 14 anhydrates via pipeline 16 and washes removing residual trace acid, the low-sulfur after the dehydration or do not have sulfur diesel and then go out device via pipeline 18.Acid-bearing wastewater removes the recovery tower 6 of organic acid catalyst and sulfone through pipeline 19; The cleaning water that recovery tower 6 steams is got back to the recycle of diesel oil water washing device through pipeline 17.
According to the different needs of raw material and quality product, also can carry out reaction of high order.The reactor effluent of every order reaction oil phase after profit is separated mixes laggard next stage reactor with the oxygenant and the liquid catalyst that replenish, carries out profit after the reaction again and is separated.
Sour distillate oil oxidation desulfurizing method of the present invention comprises following content: with sour distillate oil (as sulfur-containing diesel) is raw material, carries out oxidation desulfur reaction in the presence of superoxide and organic acid catalyst.The reactor with high mass transfer efficiency is adopted in reaction, can operate continuously, also can adopt batch operation.Reaction conditions can be adjusted in following ranges according to stock oil character with to the requirement of processed oil quality, and during operate continuously: 10～150 ℃ of temperature of reaction better are 40～120 ℃; Liquid hourly space velocity 1～the 60h of each reactor
-1, better be 2～50h
-1, 3～20h preferably
-1During periodical operation: 10～150 ℃ of temperature of reaction better are 40～120 ℃; 0.02～1.0 hour reaction times better was 2 minutes～30 minutes; Reaction pressure is higher than normal pressure, but only requires that usually can keep material gets final product for liquid phase under temperature of reaction.
Catalyst system therefor can also add a small amount of other decentralized oxide catalyst except that rudimentary organic acid, make cocatalyst, preferably water soluble metal salts etc. as water-soluble or finely divided property oxide catalyst.If use these cocatalysts, then these trace catalysts usually and sulfone compound one trip out device.The organic acid catalyst consumption is 5～40 times (moles) of oxygenant consumption.
If the employing fixed-bed reactor then can be adorned the solid catalyst of containing metal oxide compound or metal-salt in the reactor, also can adorn other has katalysis to oxidizing reaction solid catalyst.
Described hydrocarbon oil containing surphur can be the diesel oil (sulphur content 50～1500 μ g/g) of hydrotreatment, also can be sulfur-bearing or high-sulfur diesel component (sulphur content 500～7000 μ g/g) without hydrotreatment, can be straight-run diesel oil, also can be secondary processing diesel oil or Medium diesel oil component.Can be that oil is the various distillates that raw material obtains, also can be the distillate that obtains by gelatin liquefaction or other synthetic.Optimal stock oil is the various distillates of sulphur content less than 2000 μ g/g.
Described peroxide oxidant is preferably hydrogen peroxide.As use hydrogen peroxide, then its weight concentration is generally 20%～90%, better is 30%～60%.The oxygenant add-on is generally 1～10 times of theoretical requirement, better is 1～5 times.Theoretical requirement is to be the chemical requirement of respective substance with the selective oxidation of sulfur containing compounds in particular in the charging.
The present invention is described in further detail below in conjunction with embodiment; following examples are not limiting the scope of the invention; those skilled in the art is in conjunction with specification sheets of the present invention and can do suitable expansion in full, and these expansions all should be protection scope of the present invention.
Embodiment 1～3
Get 400 gram diesel oil (embodiment 1: Medium diesel oil, urge bavin: straight bavin=1:1.5, sulfur-bearing 1600 μ g/g; Embodiment 2: Middle East hydrogenated diesel oil, sulfur-bearing 650 μ g/g; Embodiment 3: catalytic diesel oil, sulfur-bearing 3000 μ g/g) in the stirred autoclave of packing into, warming while stirring to 90 ℃ constant temperature adds industrial hydrogen peroxide (30wt%) and the industrial formic acid (85wt%) that mixes continuously.The total add-on of hydrogen peroxide is 3 times of the chemical need amount of whole sulphur when all being converted into sulfone, and the formic acid add-on is 20 times (mol ratios) of hydrogen peroxide add-on.React cooling after 10 minutes,, survey sulphur content in the oil phase water and separation of oil.Analytical data sees Table 1.
Embodiment 4～6
Embodiment 1～3 is separated the back stock oil as second stage oxidizing reaction of oil phase dehydration that obtains carry out secondary reaction, other condition and example 1～3 are together.Reaction finishes the back profit and is separated, and oil phase is surveyed sulphur content, the results are shown in table 1.
Embodiment 7～9
Embodiment 4～6 is separated the back stock oil as third stage oxidizing reaction of oil phase dehydration that obtains react for the third time, other condition and example 1～3 are together.Reaction finishes the back profit and is separated, and oil phase is surveyed sulphur content, and the result also lists in table 1.The oxidation sweetening experimental result shows, through oxidation repeatedly with separate after the sulphur content of diesel oil obtained significant reduction.
Comparative example 1～3
Press the process of embodiment 1～3, adopt three tandem reactors (centre does not have oil water separation process), operational condition is identical with embodiment 1～9, and reaction result is listed in the table 1.As can be seen, adopt the middle separating process of reactor to obtain beyond thought effect.
The test-results of table 1 example 1～9 and comparative example 1～3
| Example | The stock oil sulfur-bearing, μ g/g | Product oil sulfur-bearing, μ g/g |
| Example 1 | 1600 | 914 |
| Example 2 | 650 | 279 |
| Example 3 | 3000 | 1800 |
| Example 4 | 495 | |
| Example 5 | 121 | |
| Example 6 | 1080 | |
| Example 7 | 295 | |
| Example 8 | 50 | |
| Example 9 | 639 | |
| Comparative example 1 | 1600 | 835 |
| Comparative example 2 | 650 | 254 |
| Comparative example 3 | 3000 | 1680 |
| Comparative example 4 | 1600 | 420 |
| Comparative example 5 | 650 | 35 |
| Comparative example 6 | 3000 | 580 |
Comparative example 4～6
Identical with embodiment 1～3, but the reaction times increased to 30 minutes, carry out oily water separation then, oil phase is with the methanol extraction of one times of its weight four times, the diesel oil (methyl alcohol also dissolves a small amount of diesel oil in the dissolving sulfone compound) that reclaims extraction agent and carry secretly with the distillation mode.The results are shown in Table 1.Adopt the maximum deficiency of this mode to be operating process energy consumption height, under the close situation of desulfurization degree, energy consumption is 2～5 times of the inventive method.Show that through predesigne the energy consumption of comparative example 4 is 3 times of embodiment 7, the energy consumption of comparative example 5 is 2 times of embodiment 8, and the energy consumption of comparative example 6 is 4 times of embodiment 9.
Embodiment 10
With reference to the accompanying drawing process description.The Medium diesel oil raw material of sulphur content 1600 μ g/g and hydrogen peroxide, formic acid pump in the continous way impact flow reactor (as Fig. 2 structure, adopt two propeller, the propeller rotating speed is 900 rev/mins) and carry out oxidizing reaction.The water of reaction product after separating is via pipeline 5 formic acid removal recovery towers 6, and the organic acid catalyst of recovery mixes with stock oil and oxygenant via pipeline 7.Oil phase after the separation arrives second stage reactor 10 via pipeline 9.Oxygenant and liquid catalyst then respectively pipeline 12 and 11 enter reactor 10.The reaction after product enters secondary liquid liquid separator 14 via pipeline 13.Water after the separation is via pipeline 15 formic acid removal recovery towers 6.The oil phase that comes out from secondary liquid liquid separator 14 anhydrates via pipeline 16 and washes to remove residual trace acid, and the low-sulfur diesel-oil after the dehydration then goes out device via pipeline 18.Acid-bearing wastewater removes the recovery tower 6 of organic acid catalyst and sulfone through pipeline 19; The cleaning water that recovery tower 6 steams is got back to the recycle of diesel oil water washing device through pipeline 17.Be reflected at 50 ℃ and a little more than carrying out under the normal pressure, each reactor residence time 5 minutes, other reaction conditions is: H
2O
2Add-on is institute's sulphur content all changes into the sulfone chemical requirement in the diesel oil 5 times, formic acid and H
2O
2The mol ratio of add-on is 10.The diesel oil sulphur content of (operational condition is identical with first order reaction) is reduced to 494 μ g/g after secondary oxidation reaction and dehydration.
Embodiment 11
Identical with embodiment 10, but increase A reactor.The hydrogenated diesel oil of sulphur content 650 μ g/g is a raw material, and raw material and hydrogen peroxide, formic acid pump into and carries out oxidizing reaction in the continous way fixed-bed reactor.Solid oxide catalyst is housed in the reactor.The reaction after product through separate and extraction after obtain low-sulfur diesel-oil, formic acid loops back reactor, is reflected at 80 ℃ and a little more than carrying out under the normal pressure, the air speed of single reactor is 5h
-1, other reaction conditions is: every order reaction H
2O
2Add-on is institute's sulphur content all changes into the sulfone chemical requirement in the diesel oil 4 times, formic acid and H
2O
2The mol ratio of add-on is 10.Reaction product after separating in the diesel oil sulphur content be 48 μ g/g.
Embodiment 12～14
Reaction process and condition are with example 10 (two-stage reactor), and reactor uses the straight pipe type static mixer as reactor.The diesel oil that reaction raw materials is crossed with hydrogenation, sulphur content 760 μ g/g.Every stage reactor superoxide add-on is 2 times (examples 12) of chemical requirement when institute's sulphur content all changes into sulfone in the diesel oil, 3 times (example 13) and 4 times (example 14).70 ℃ of temperature of reaction, air speed 50h-1 is premixed into the phospho-wolframic acid promotor of 5 μ g/g (in metal) before raw material advances reactor.Reaction product through separate and extraction after in the diesel oil sulphur content test result also list in table 3.Embodiment 12～13 uses hydrogen peroxide as oxidant, and embodiment 14 usefulness tertbutyl peroxides are made oxygenant.
The test-results of table 2 example 12～14
| Example | Raw material diesel oil | Stock oil sulphur content S, μ g/g | Product diesel oil sulphur content, μ g/g |
| Example 12 | Hydrogenated diesel oil | 760 | 295 |
| Example 13 | Hydrogenated diesel oil | 760 | 185 |
| Example 14 | Hydrogenated diesel oil | 760 | 120 |
Claims (8)
1, a kind of method of fraction oil oxidation desulfurizing, the distillate that it is characterized in that sulfur-bearing is in the presence of peroxide oxidant and catalyzer, in 2～6 stage reactors, carry out oxidation desulfur reaction, material behind every order reaction is after profit is separated, water is concentrated distillation recovering liquid acid catalyst, oil phase is as the stock oil of next stage reaction, stock oil all enters reactor as raw material jointly with superoxide, liquid catalyst during every order reaction, and the product that last step reflects oil phase after profit is separated directly goes out device as low sulfur product; Described peroxide oxidant structure is R-O-O-H, and wherein R is the tertiary alkyl of H or C4-5; Described liquid catalyst is the catalyzer that comprises liquid organic acid, and wherein organic acid is formic acid or acetate.
2, in accordance with the method for claim 1, it is characterized in that described reacted material carries out after profit is separated, water goes tripping device to tell the sulfone that liquid catalyst and reaction generate, and liquid catalyst recycles after reclaiming; Oil phase enters the further oxidation sweetening of next stage reactor, and the oil phase that last step reflects obtains low-sulfur cleaning oil plant after washing and dehydration.
3, in accordance with the method for claim 1, it is characterized in that reaction employing operate continuously or batch operation; During operate continuously: 10～150 ℃ of temperature of reaction, liquid hourly space velocity 1～60h
-1, during periodical operation: 10～150 ℃ of temperature of reaction, 0.02～1.0 hour reaction times.
When 4, in accordance with the method for claim 3, it is characterized in that operate continuously is adopted in reaction: 40～120 ℃ of temperature of reaction, liquid hourly space velocity 2～50h
-1, during periodical operation: 40～120 ℃ of temperature of reaction, 2 minutes～30 minutes reaction times.
5, in accordance with the method for claim 1, it is characterized in that described oxygenant add-on is 1～10 times of theoretical requirement.
6, in accordance with the method for claim 1, it is characterized in that described oxygenant add-on is 1～5 times of theoretical requirement.
7, in accordance with the method for claim 1, the mole dosage of the described catalyzer that it is characterized in that is 5～40 times of oxygenant consumption.
8, in accordance with the method for claim 1, it is characterized in that described staged reactor is that stirred-tank reactor, impact flow reactor, static mixer formula reactor, fixed-bed reactor or other have the reactor of efficient mass transfer inner member, or the combination of dissimilar reactors.
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| CN105087060A (en) * | 2015-09-21 | 2015-11-25 | 广西大学 | Method for applying insulin and cholic acid to coker diesel oil desulfurization |
| CN105112096B (en) * | 2015-09-21 | 2017-02-01 | 广西大学 | Method of applying insulin to coking diesel oil desulfurization |
| CN105948010A (en) * | 2016-04-27 | 2016-09-21 | 四川大学 | Impinging stream reinforced wet-process phosphoric acid extraction method and device |
| WO2022133768A1 (en) * | 2020-12-23 | 2022-06-30 | Solvay Sa | Desulfurization process |
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