CN100352893C - Cut-fracted oil oxidation desulfurizing method - Google Patents
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Abstract
The present invention discloses an oxidative desulfurization process for distillate oil, which comprises the step: distillate oil raw materials and hydrogen peroxide reacts in a high-efficiency mass transfer reactor, such as an impact flow reactor, with an internal turbulent flow strengthening member under the condition that low-grade organic acid catalysts exist. Reactants in the high-efficiency mass transfer reactor can be thoroughly and uniformly mixed in a short time and rapidly react due to the effective collision of molecules. Thus, the reaction efficiency can be obviously improved, and the reaction condition is moderate when an identical desulfurizing result is obtained as compared with a conventional stirring type reactor. Compared with the existing oxidative desulfurization technique for distillate oil, the process can treat raw materials with high sulfur content and low quality to obtain low-sulfur fuel.
Description
Technical field
The present invention relates to a kind of fraction oil oxidation desulfurizing method, particularly the method for producing clean fuel with sour distillate oil 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 thiophenes 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 three parts: 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 sulfide 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 similar.
For traditional hydrogenation (HDS) process, sulphur content is low more, and the desulfurization difficulty is big more.This mainly is because thereby the dibenzothiophene compounds that has alkyl to replace exists due to the sterically hindered inaccessible activity of such catalysts center.And during oxidation sweetening because the aromaticity of thiphene ring is destroyed, the influence of substituent electronic effect is better than space steric effect, thus dibenzothiophene compounds that alkyl replaces is arranged than the easier sulfone that is oxidized to of thiophene-based, and substituting group is many more, electronic effect is strong more, easy more removing.Therefore, adopt the deep desulfuration of the easier realization oil plant of oxidation desulfuration process.
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 also 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.Being characterized in will formic acid-hydrogen peroxide-water mixes the back and send into serial continuous-stirring reactor (patent requires to form series by 2-3 reactor in describing) with stock oil, in the reaction product oil phase with contain processing respectively after the formic acid aqueous phase separation.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.The shortcoming one of this scheme is to adopt serial continuous-stirring reactor mass-transfer efficiency lower (it is fast to need the serial reaction device could satisfy hydrogen peroxide-diesel oxidation desulfurizing speed of response, thereby the requirement very high) to mixing efficiency, the 2nd, thus the residual acid that removes in the oil phase will produce contaminate environment and harmless treatment needs the alkaline residue of higher cost with alkali cleaning, the 3rd, to dissolve sulfone with hot gas oil when acid separates with sulfone, thereby contain sulfone coking charging or mixing asphalt component what the gas oil of high value had become low value.
Teh Fu Yen etc. have proposed to adopt the oxidative desulfurization techniques of ultrasound reactor respectively in United States Patent (USP) 6500219 with Rudolf W. Gunerman in United States Patent (USP) 6402939.Used oxygenant can be a hydrogen peroxide, also can be other superoxide that contains the R-O-O-H structure.Benefit with ultrasound reactor is the mass transfer that has increased oxygenant water and sulfur-bearing oil phase, has improved dispersion efficiency, and reaction is easier to be carried out thereby make.Use ultrasonic wave to need Special Equipment, and have certain unsafe factor aspect operation and the environmental protection.
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 fraction oil oxidation desulfurizing, sour distillate oil is carried out in the process of oxidation sweetening with hydrogen peroxide and organo-peroxide, sulfocompound preferentially is oxidized to sulfone and sulfoxide, along with the carrying out of reaction, other components in the distillate such as nitrogenous compound and polycyclic aromatic hydrocarbons, colloid precursor etc. then further are oxidized to corresponding oxygenatedchemicals.In existing sour distillate oil oxidation sweetening process because oxygenant and S-contained substance are in not jljl mutually in (water and oil phase) usually, disperse with contact very inabundant, if so control certain desulfurization degree, need the certain reaction time usually.Need to control the certain reaction time just, above-mentioned undesirable side reaction then may take place in a large number, consequently under the situation of the identical desulfurization degree of maintenance, the consumption of oxygenant increases, oil quality changes, the oil product yield decreases, and the reaction times is grown or needs and operate under higher temperature.
At above-mentioned result of study, the concrete scheme of sour distillate oil oxidation sweetening of the present invention is as follows:
The distillate of sulfur-bearing carries out oxidation desulfur reaction in the efficient mass transfer reactor in the presence of peroxide oxidant and catalyzer, reacted material carries out profit and is separated.Wherein thereby the efficient mass transfer reactor is to contain the reactor that the inner member that can increase the liquid turbulence is strengthened heat and mass transfer between liquid, comprises that impact flow reactor, static mixer formula reactor, Multiple Combination static mixer reactor or other have the forms such as reactor of efficient mass transfer inner member.
Reacted material carries out after profit is separated, and water goes tripping device to tell sulfone, water that liquid catalyst and reaction generate, and the former recycles after reclaiming; Oil phase with dissolved sulfone in the methyl alcohol equal solvent extraction oil phase, obtains low-sulfur cleaning oil plant after water elution removes remaining acid, extraction reuses after reclaiming with solvent.
Sour distillate oil is 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 of H or C4-5, is preferably hydrogen peroxide.Catalyzer comprises liquid organic acid, and organic acid is generally 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 static mixer reactor, Multiple Combination static mixer reactor etc. also can be other various reactors that have the efficient mass transfer inner member.
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.The oxidation sweetening process of sour distillate oil is mass transfer control when reacting in the popular response device, because mass-transfer efficiency is lower in the popular response device, oxidation desulfur reaction speed is slower, just need relatively large oxygenant or long time or higher temperature of reaction when reaching certain desulfurization degree, and these conditions have certain promoter action to side reaction, so side reaction is more.This has increased running cost on the one hand, product yield is descended, and quality product also may be under some influence.For polycyclic aromatic hydrocarbons, the more distillate of colloid precursor content, its influence is more outstanding.The inventive method is by efficient mass transfer reaction device forms such as employing impact flow reactors, improve mass-transfer efficiency greatly, make mass transfer process not become the controlling factor of oxidation desulfur reaction process, improved speed of response greatly, so under the condition of identical desulfurization transformation efficiency, the inventive method can adopt lower temperature of reaction or than short reaction times or less oxygenant consumption, side reaction is simultaneously effectively suppressed, and quality product and yield all can improve.
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
The concrete technical process of the inventive method is as follows: the reaction raw materials after pre-mixing (stock oil, oxygenant, catalyzer) enters the reactor 2 of high mass transfer efficiency 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.To the remaining catalyzer of water washing device flush away (if use organic acid, then be washed till acidity and meet the product specification requirement), the water that washing is told goes catalyst recovery through pipeline 12 to oil phase after the separation via pipeline 9.Oil phase after washing is removed a small amount of sulfone compound of dissolved in the oil phase through pipeline 13 extraction tower 14 that desolvates.The extraction liquid that is rich in sulfone compound reclaims solvent and sulfones through pipeline 15 recovery tower 16 that desolvates, and solvent loops back extraction tower by pipeline 17, and sulfone compound then comes along the sulfone utilization through pipeline 18 and the sulfone that obtains from catalyst recovery tower 6.The low-sulfur that extraction tower comes out or do not have sulfur diesel and then go out device via pipeline 19.
Hydrocarbon oil containing surphur 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.Reacted material carries out oil-aqueous phase separation earlier, and the water disacidify reclaims and recycling; Oil phase obtains low-sulfur or sweet oil product through solvent extraction again after the washing depickling, the extraction agent that is rich in the sulfone class then recycles and reuses; The sulfone compound of telling is processed into tensio-active agent or does him and use.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: 20～150 ℃ of temperature of reaction better are 40～120 ℃; Liquid hourly space velocity 1～60h
-1, better be 2～50h
-1, 3～20h preferably
-1During periodical operation: 20～150 ℃ 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.Catalyzer also can add a small amount of other decentralized oxide catalyst, makes 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.
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 distillate.
Described extraction agent can be the inorganic or organism of various polarity, as water and/or alcohol etc., the C of pure useable linear or collateralization
1～C
10Alkanol, C
5～C
8Cycloalkanol and C
7～C
12In the aryl alcohol one or more, particularly C
1～C
6Alkyl alcohol, preferred cheapest methyl alcohol.The extraction agent consumption is 30～300% of an oil product weight during extraction, better is 60～150%.
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.
Comparative example 1～3
Get 400 gram diesel oil (comparative example 1: Medium diesel oil, urge bavin: straight bavin=1: 1.5, sulfur-bearing 1600 μ g/g; Comparative example 2: Middle East hydrogenated diesel oil, sulfur-bearing 650 μ g/g; Comparative example 3: catalytic diesel oil, sulfur-bearing 3000 μ g/g) in the conventional stirred autoclave of packing into, agitator speed is 900 rev/mins, is warming up to 90 ℃ of constant temperature, adds industrial hydrogen peroxide (30wt%) and the industrial formic acid (85wt%) that mixes while stirring 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.Oil phase goes out sulfone compound with the methanol extraction of oil product weight 70%, and then surveys sulphur content.Analytical data sees Table 1.
Embodiment 1～3
This example proof adopts the conversion unit of high mass transfer efficiency can obviously improve desulfuration efficiency.Experimentation and experimental raw just are reflected in the identical impact flow reactor with Fig. 2 structure and carry out with comparative example 1～3, adopt two propeller, and the propeller rotating speed is 900 rev/mins, batch operation, and temperature of reaction is reduced to 70 ℃.The reaction raw materials oil of example 1～3 is then corresponding with comparative example 1～3 respectively.The analysis of sulfur content data of reaction product are also listed in table 1.
The test-results of table 1 example 1～3 and comparative example 1～3
| Example | Product oil sulfur-bearing, before the extraction, μ g/g | Product oil sulfur-bearing, after the extraction, μ g/g |
| Comparative example 1 comparative example 2 comparative examples 3 examples 1 example 2 examples 3 | 914 279 1800 840 208 1600 | 480 45 960 428 28 810 |
Obviously, under same materials and other reaction conditions when identical, adopt the higher impact flow reactor of mass-transfer efficiency can obviously improve the desulfurization degree of oxidizing reaction, and temperature of reaction can also reduce greatly.
Embodiment 6
Embodiment 6 presses embodiment 1 process, and temperature of reaction is 65 ℃, and the reaction times is 8 minutes, and the actual gum content of final product is 90mg/100ml, and the product actual gum content is 105mg/100ml in the comparative example 1.Other of embodiment 6 the results are shown in Table 2.As seen under same reaction conditions, when reaching close desulfurization degree, the quality that obtains product with impact flow reactor is better, and temperature of reaction is lower.
Table 2 example 4～6 test-results
| Example | Product oil sulfur-bearing, after the extraction, μ g/g |
| Comparative example 1 example 4 examples 5 examples 6 | 480 460 450 440 |
With reference to the accompanying drawing process description.Sulphur content 1600 μ g/g urge bavin-straight bavin mixing raw material and hydrogen peroxide, formic acid catalyzer to pump into carrying out oxidizing reaction in the continous way impact flow reactor.The reaction after product obtains low-sulfur diesel-oil after separation and extraction, formic acid loops back reactor, and the methanol extraction agent loops back extraction tower after reclaiming.Be reflected at 80 ℃ and a little more than carrying out air speed 8h under the normal pressure
-1, other reaction conditions is: H
2O
2Add-on is 2 times (example 7-1) that institute's sulphur content all changes into the sulfone chemical requirement in the diesel oil, 3 times (example 7-2) and 4 times (example 7-3), and H
2O
2In oxidation is to account for 2.5% in the body, formic acid and H
2O
2The mol ratio of add-on is 20.Reaction product through separate and extraction after in the diesel oil sulphur content test result see Table 3.
With reference to the accompanying drawing process description.The hydrogenated diesel oil of sulphur content 650 μ g/g is a raw material, and raw material and hydrogen peroxide, formic acid catalyzer pump into and carry out oxidizing reaction in the continous way impact flow reactor.The reaction after product obtains low-sulfur diesel-oil after separation and extraction, formic acid loops back reactor, and the methanol extraction agent loops back extraction tower after reclaiming.Be reflected at 110 ℃ and a little more than carrying out air speed 30h under the normal pressure
-1, other reaction conditions is: H
2O
2Add-on is institute's sulphur content all changes into the sulfone chemical requirement in the diesel oil 2 times, formic acid and H
2O
2The mol ratio of add-on is 30.Reaction product through separate and extraction after in the diesel oil sulphur content test result see Table 3.
With reference to the accompanying drawing process description.The hydrogenated diesel oil of sulphur content 650 μ g/g is a raw material, and raw material and hydrogen peroxide, formic acid catalyzer pump into and carry out oxidizing reaction in the continous way impact flow reactor.The reaction after product obtains low-sulfur diesel-oil after separation and extraction, formic acid loops back reactor, and the methanol extraction agent loops back extraction tower after reclaiming.Be reflected at 40 ℃ and a little more than carrying out air speed 3h under the normal pressure
-1, other reaction conditions is: H
2O
2Add-on is institute's sulphur content all changes into the sulfone chemical requirement in the diesel oil 6 times, formic acid and H
2O
2The mol ratio of add-on is 10.Reaction product through separate and extraction after in the diesel oil sulphur content test result see Table 3.
The test-results of table 3 example 7～12
| Example | Raw material diesel oil | Stock oil sulphur content S, μ g/g | Product diesel oil sulphur content, μ g/g |
| Example 7-1 example 7-2 example 7-3 example 8 examples 9 examples 10 examples 11 examples 12 | Hydrogenated diesel oil hydrogenated diesel oil hydrogenated diesel oil hydrogenated diesel oil hydrogenated diesel oil hydrogenated diesel oil hydrogenated diesel oil hydrogenated diesel oil not not | 1600 1600 1600 650 650 760 760 760 | 680 420 330 45 15 100 70 45 |
Reaction process and condition are with example 7～9, 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.The superoxide add-on is 2 times (examples 10) of chemical requirement when institute's sulphur content all changes into sulfone in the diesel oil, 3 times (example 11) and 4 times (example 12).60 ℃ of temperature of reaction, air speed 50h
-1, before raw material advances reactor, be premixed into the phospho-wolframic acid promotor of 5 μ g/g (in metal).Reaction product through separate and extraction after in the diesel oil sulphur content test result also list in table 3.Embodiment 10～11 uses hydrogen peroxide as oxidant, and embodiment 12 usefulness tertbutyl peroxides are made oxygenant.
Claims (10)
1, a kind of method of fraction oil oxidation desulfurizing, the distillate that it is characterized in that sulfur-bearing are carried out oxidation desulfur reaction in the efficient mass transfer reactor in the presence of peroxide oxidant and catalyzer, reacted material carries out profit and is separated; Wherein thereby the efficient mass transfer reactor is to contain the reactor that the inner member that can increase the liquid turbulence is strengthened heat and mass transfer between liquid, comprises that impact flow reactor, static mixer formula reactor or other have the reactor of efficient mass transfer inner member.
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 sulfone, water that liquid catalyst and reaction generate, and liquid catalyst recycles after reclaiming; Oil phase with dissolved sulfone in the methyl alcohol equal solvent extraction oil phase, obtains low-sulfur cleaning oil plant after water elution removes remaining acid, extraction reuses after reclaiming with solvent.
3, in accordance with the method for claim 1, it is characterized in that described peroxide oxidant structure is R-O-OH, wherein R is the tertiary alkyl of H or C4-5.
4, in accordance with the method for claim 1, it is characterized in that described catalyzer is the catalyzer that comprises liquid organic acid, wherein organic acid is formic acid or acetate.
5, in accordance with the method for claim 1, it is characterized in that reaction employing operate continuously or batch operation; During operate continuously: 20～150 ℃ of temperature of reaction, liquid hourly space velocity 1～60h
-1, during periodical operation: 20～150 ℃ of temperature of reaction, 0.02～1.0 hour reaction times.
When 6, in accordance with the method for claim 5, 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.
7,, it is characterized in that described oxygenant add-on is 1～10 times of theoretical requirement according to claim 1 or 3 described methods.
8,, it is characterized in that described oxygenant add-on is 1～5 times of theoretical requirement according to claim 1 or 3 described methods.
9, according to claim 1 or 4 described methods, the mole dosage that it is characterized in that described catalyzer is 5～40 times of oxygenant mole dosage.
10, in accordance with the method for claim 2, it is characterized in that described extraction agent is water and/or alcohol.
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| CN103861544B (en) * | 2012-12-17 | 2016-07-27 | 中国石油化工股份有限公司 | A kind of impact flow reactor and application thereof |
| 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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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3901792A (en) * | 1972-05-22 | 1975-08-26 | Hydrocarbon Research Inc | Multi-zone method for demetallizing and desulfurizing crude oil or atmospheric residual oil |
| CN1510111A (en) * | 2002-12-26 | 2004-07-07 | 中国科学院大连化学物理研究所 | Hydrocarbon oil cryogenic desulfurizing method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3901792A (en) * | 1972-05-22 | 1975-08-26 | Hydrocarbon Research Inc | Multi-zone method for demetallizing and desulfurizing crude oil or atmospheric residual oil |
| CN1510111A (en) * | 2002-12-26 | 2004-07-07 | 中国科学院大连化学物理研究所 | Hydrocarbon oil cryogenic desulfurizing method |
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