CN1834207A - Catalyzed oxidation desulfuration process of petroleum products - Google Patents
Catalyzed oxidation desulfuration process of petroleum products Download PDFInfo
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- CN1834207A CN1834207A CNA2005100556210A CN200510055621A CN1834207A CN 1834207 A CN1834207 A CN 1834207A CN A2005100556210 A CNA2005100556210 A CN A2005100556210A CN 200510055621 A CN200510055621 A CN 200510055621A CN 1834207 A CN1834207 A CN 1834207A
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- desulfurization
- petroleum products
- sulphur content
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Abstract
This invention discloses a catalytic oxidative desulfurization method for petroleum products. In the method, oxidant, catalyst and solvent are added in the petroleum products for desulfurization. The catalyst is oxyacid salt of Mn, Sb, W, Ce, Sn, Mo, V or Cr. The catalyst as well as reaction conditions are only effective to organic sulfur and nitrogen compounds while have no effect on unsaturated hydrocarbons such as olefins and aromatic hydrocarbons. After the desulfurization method, the content of sulfur in the petroleum products can be less than 15 mg/L, while the octane number of the petroleum products is not changed. The desulfurization method is simple, and has such advantages as mild reaction conditions and high desulfurization efficiency, thus has wide potential applications.
Description
Technical field
The present invention relates to the method for petroleum oxidation desulfurization, particularly relate to the catalytic oxidation desulfurization method of petroleum products.
Background technology
With oil, Sweet natural gas is in the serial oil production (gasoline, diesel oil, kerosene etc.) of raw material, the existing of sulphur, nitrogen compound (content tens～10000ppm) is ubiquity, to the application of oil product and further processing all produced great negative impact.When oil product acts as a fuel, produce SO
xAnd NO
x, cause topsoil and acid rain phenomenon, cause serial irreversible disasters such as soil acidification, so each developed country formulated the strategy of sustainable development for this reason one after another, the SO of fuel emission
xAnd NO
xLimited as the major control object, to implement new fuel oil standard in 06 year as the U.S., wherein sulphur content requires to be reduced to below the 30mg/L from present 50mg/L, and European standard is also strict day by day, requires member state to reach the standard of fuel of 15mg/L in the past in 06 year.In addition; as organic chemical industry's basic raw material, also deep processing exerts an influence the sulfur impurity in the oil production to oil product, mainly is that organosulfur all has strong effect to catalyzer such as most precious metal, transition metal, metal oxides; catalyzer is seriously poisoned, influence large-scale production.Therefore, how low-cost, high-level efficiency and sulphur, the nitrogen eliminated cleanly in the oil product are the key subjects that the refinery field needs to be resolved hurrily always.
At present the hydrogenation catalyst desulfurization technology of widespread usage is a proven technique comparatively in the world, and its principle is to utilize selectivity of catalyst, separates with oil product thereby under high temperature, condition of high voltage organosulfur is reduced to inorganic hydrogen sulfide, reaches the desulfurization purpose.This technology has extraordinary effect when handling high-sulfur oil product (sulphur content several thousand ppm are to ppm up to ten thousand) to hundreds of ppm oil product on a large scale, at this moment, and all comparatively economical rationality of its hydrogen consumption and hydrogenation selectivity.But the oil product for low sulfur content is handled, as sulphur in the low-sulphur oil is removed, also there is huge difficulty, when to the further desulfurization of oil product of the about 100ppm of sulfur-bearing, need higher hydrogen pressure and high temperature of reaction, and selectivity of catalyst reduces greatly, quite a few hydrogen consumption is being wasted in the addition of unsaturated hydrocarbons, but also having reduced the octane value of gasoline, running cost and equipment cost are multiplied.
In the world from having carried out another kind of desulfurization notion---oxidation sweetening at the end of last century successively, principle is to utilize oxygenant that organosulfur is oxidized to sulfone and sulfoxide, rely on sulfone compound and the huge difference of oil product polar then, sulphur is separated from oil product by means such as extraction, rectifying, absorption.
On application prospect, oxidative desulfurization techniques is gentle, green oxidation technology, compare with high temperature, the high-pressure hydrogenation sulfur removal technology of present widespread use, have the gentle service advantages under the normal temperature and pressure, can reduce facility investment significantly, reduce equipment loss, reduce unnecessary hydrogenation of unsaturated hydrocarbons side reaction, technical process also shortens dramatically and simplifies.Therefore, international academic community and oil refining industry all also give great concern to oxidation sweetening under the mild conditions, and the consistent oxidation sweetening of admitting highly selective will be the mainstream technology of subduing oil product sulphur from now on, and each state has all accelerated fundamental research and applied research.As the Valero energy company of the U.S. at the bring into operation diesel fuel desulfurization demonstration unit of 50 barrels/day in a cover of the refinery of Krotz Springs, test the advanced technologies (ASR) of the oxidation sweetening of UniPure company invention first, utilize organo-peroxide with the organic sulfide oxidation, separate with sulfoxide with the sulfone of extraction agent then, wish to be less than the desulfurization target of 5ppm the polarity grow.Sulph Co. then adopts the ultrasound oxidation technology desulfurization technology, and Aida company utilizes formic acid+H
2O
2Oxidation technology, Petro Star company also utilizes oxidation/extraction process (CED) oil product to be carried out the continuous processing technique of oxidation sweetening.Japan Energy center (PEC) even the target of oxidation sweetening fixed on the production that can be used for fuel cell gasoline that is lower than 5ppm.But because the polytropy and the complicacy of oil product composition, the oxidative desulfurization techniques limitation of reporting and declaring pilot scale at present is very big, the most outstanding is the means that most of oxidizing procesies do not have the applied catalysis oxidation, but be based upon on the basis of organic peroxide acid oxidizing reaction, therefore, have some defectives: need in the organic acidity medium, to react, and the intensive polar solvent extracting; Owing to use H
2O
2The phase-splitting problem that exists makes and uses H
2O
2Oxidation sweetening efficient is very low; Because the organic peroxide acid selectivity is low, often causes the unsaturated hydrocarbons over oxidation again with the organo-peroxide oxidation, destroy oil quality, aftertreatment is also very complicated; Because a large amount of uses of strongly-acid and polarity oxygenant and extractant cause the sticking collection of colloid oxidation occluding device in equipment corrosion and the oil product, the operation difficulty, desulfurization processing cost height is about about 120 yuan/ton.
Summary of the invention
The method that the purpose of this invention is to provide a kind of catalytic oxidation desulfurization of petroleum products.
The method of petroleum products catalytic oxidation desulfurization provided by the present invention, be in petroleum products, to add oxygenant to carry out desulphurization reaction, wherein, also be added with desulfurization catalyst and solvent in the petroleum products, described desulfurization catalyst contains the metal oxygen-containing hydrochlorate, and described metal is Mn, Sb, W, Ce, Sn, Mo, V and Cr.
Wherein, common solvent is N-Methyl pyrrolidone, acetone, methyl halide, halo ethane, vinyl halides, methyl alcohol, ethanol, Virahol or second eyeball etc.; The ammonium salt that described metal oxygen-containing hydrochlorate is metal oxygen-containing acid, monovalence metallic cation salt.
Described desulfurization catalyst also includes the carrier of band amino or quaternary ammonium group, and described carrier is ion exchange resin, tensio-active agent and dyestuff, on these carriers institute electrically charged just in time can in the negative charge of metal M oxygen acid root, make catalyst molecule become electric neutrality.Ion exchange resin commonly used has the strong basic ion exchange resin that contains quaternary ammonium group; Tensio-active agent commonly used is Dodecyl trimethyl ammonium chloride, hexadecyl benzyltrimethylammonium bromide etc.; Dyestuff commonly used is rhodamine, Victoria Green WPB etc.The mol ratio of carrier and described metal oxygen-containing hydrochlorate is 0-1000: 1.
The weight ratio that the effect dosage of desulfurization catalyst generally can be controlled at petroleum products is 1: in the scope of 10-100000.
When application the present invention carried out desulphurization reaction, oxygenant commonly used had H
2O
2, KClO
3, NaOCl or K
2S
2O
8Deng; Temperature of reaction is 25-150 ℃.
The metal oxygen-containing hydrochlorate that can be used as catalyzer use of the present invention is sylvite, sodium salt and the ammonium salt of metal oxygen-containing acid, also can be double salt, as potassium permanganate, sodium antimonate, sodium wolframate, ammonium cerous sulfate, sodium stannate, ammonium molybdate and ammonium vanadate etc., it uses form can be solid-state, solution.
The present invention uses a metalloid oxysalt as catalyst H
2O
2, then sulphur, oxynitride are separated from oil product the organosulfur in the oil product, nitrogen high-selectivity oxidation etc. water miscible oxygenant, thereby reach the purpose of desulfurizing oil.Such catalyzer can be effectively with H
2O
2Be converted into and have unique singlet oxygen that optionally distributes according to a certain percentage (
1O
2) and metal peroxides
This two classes intermediate oxidation attitude has organosulfur, nitrogen compound is had very high oxidation selectivity, but the oil soluble difference of the two is huge, singlet oxygen (
1O
2) easier in oil phase earlier and the organosulfur in the oil product, the addition of nitrogen priority, form the peroxide adducts of temporary stable state.Because temporarily the polarity of stable state adducts strengthens, easily and another part polarity bigger
Near the oxygen shift reaction also further takes place, generate sulfone compound, and
Itself be converted into as-reduced metal hydrochlorate polarity and further become big, be transferred to water then and continue and H
2O
2Reaction, after organosulfur, nitrogen reacted completely, catalytic cycle stopped.In the full cycle process, be with R-S
δ+-O-O
δ+(order of R-N → O), R-OOH, unsaturated hydrocarbons, stable hydrocarbon with
React, therefore, in the course of whole oxidation sweetening, may affected unsaturated hydrocarbons in the oil product be subjected to corresponding protection, can as hydrogenating desulfurization, peracid oxidation sweetening, not be easy to oxidizedly, therefore have very unique selectivity.After reaction finished, oxysulfides such as the sulfone class that is generated can make itself and oil product, separated from solvent by operations such as simple fractionation (rectifying), extraction and absorption, reach the target of desulfurizing oil.
Catalyzer that the present invention is selected and reaction conditions are to the not influence of unsaturated hydrocarbons such as alkene, aromatic hydrocarbons, only to organosulfur, nitrogen compound effect, have very high selectivity and oxidation efficiency, sulfur content in oil products is reached＜low-sulfur and the super low sulfur standard of 15mg/L; The octane value of the oil product that the process desulphurization reaction is handled does not reduce, and oil quality is not had influence.The inventive method is simple, the reaction conditions gentleness, and the desulfurization degree height is with a wide range of applications.
Description of drawings
Fig. 1 is the variation diagram of sulfur content in oil products with the reaction times.
Embodiment
Choose reinforcing yin essence ion exchange resin (the Amberlite IRA of the U.S. Aldrich reagent company 900 types) 10g of the band quaternary amines of commercially available vinylbenzene/divinyl benzene copolymer, after the washing pre-treatment, join in the reaction vessel, stir down, slowly add potassium permanganate (KMnO
4, quality 60mg) and the aqueous solution carries out the load bonding, till the no red-purple, filters then in the aqueous solution, and is standby.
(octane value is 90.1 (RON) to add sulphur content and be the commercial gasoline 30ml of 102mg/L in the 250ml stainless steel reactor, sulphur content 120mg/L), according to adding desulfurization catalyst than 0.05% amount, add ethanol 50ml then with quality of gasoline, after the mixing, add H
2O
2(30%) 1.5ml, confined reaction is kept 75 ℃ of temperature of reaction, and with the gasoline that do not add catalyzer in contrast, and content of sulfur in gasoline is with the variation in reaction times as shown in Figure 1.The result shows that content of sulfur in gasoline drops to 21.6mg/L from initial 102mg/L, and the important quality index of oil product such as octane value, boiling range, colloid, copper corrosion and water-soluble soda acid do not descend or variation, are 90.07 (RON) as octane value, sulphur content 23mg/L.
Get commercial cationic surfactant Dodecyl trimethyl ammonium chloride 0.1g, be dissolved in 2.5mlH
2O
2(30%) in, (octane value is 90.1 (RON) with this solution and 50ml feed gasoline, sulphur content 120mg/L) mixes, add 80ml ethanol, mix the back and add sodium wolframate 15mg, in stainless steel cauldron, be warming up to 80 ℃ of reactions 30 minutes, after isolating the second alcohol and water, measure and handle back oil quality and sulphur content, the result is 90.07 (RON) for octane value, sulphur content 23mg/L.
Get commercially available cationic dyestuff rhodamine B and O.05g be dissolved in the 50ml second eyeball and after 50g gasoline (octane value 93.2 (RON), sulphur content 79mg/L) mixes, add ammonium cerous sulfate 0.05g, mix the back and add Virahol 50ml, stir and also add 5mlH
2O
2, in stainless steel cauldron, be warming up to 80 ℃ of reactions 30 minutes, isolate Virahol and water after, measure to handle back oil quality and sulphur content, octane value is 93.3 (RON) as a result, sulphur content 16.2mg/L.
Get 0.75mg ammonium vanadate and 5ml H
2O
2(30%) mixed dissolution, (octane value is 93.2 (RON) to join 75g gasoline, sulphur content 79mg/L) and 75ml methanol mixed solution, 25 ℃ are reacted 1h down in stainless steel cauldron, after isolating Virahol and water, measure and handle back oil quality and sulphur content, octane value is 93.1 (RON) as a result, sulphur content 33.2mg/L.
Get reinforcing yin essence ion exchange resin (the homemade D701 type) 1g of the band quaternary amines of commercially available vinylbenzene/divinyl benzene copolymer, the sodium antimonate solution that adds 20ml 1mM, behind the stirring reaction 20min, the elimination aqueous solution, (octane value is 90.1 (RON) with solid resin and 50ml gasoline, sulphur content 120mg/L) and 75ml 1, the 2-ethylene dichloride mixes, and stirs also to add 5ml H
2O
2(30%), in stainless steel cauldron, be warming up to 80 ℃ of reactions 20 minutes, isolate Virahol and water after, measure to handle back oil quality and sulphur content, octane value is 90.0 (RON) as a result, sulphur content 52.7mg/L.
Get reinforcing yin essence ion exchange resin (the homemade D701 type) 1g of the band quaternary amines of commercially available vinylbenzene/divinyl benzene copolymer, the ammonium molybdate solution that adds 20ml 1mM, behind the stirring reaction 20min, the elimination aqueous solution, (octane value is 89.0 (RON) with solid resin and 50ml gasoline, sulphur content 125.0mg/L) and 75ml ethanol mix, stir and also add 3ml 10%KClO
3The aqueous solution is warming up to 75 ℃ of reactions 20 minutes in stainless steel cauldron, isolate Virahol and water after, measure to handle back oil quality and sulphur content, octane value is 89.2 (RON) as a result, sulphur content 21.9mg/L.
Embodiment 7, hexadecyl benzyltrimethylammonium bromide-positive sodium stannate catalytic gasoline desulfurization
Get tensio-active agent hexadecyl benzyltrimethylammonium bromide 0.05g and 5ml H
2O
2(30%) mixed dissolution, (octane value is 89.0 (RON) to join 50ml gasoline, sulphur content 125.0mg/L) and 75ml acetone mixing solutions, in stainless steel cauldron, be warming up to 80 ℃ of reactions 30 minutes after adding the positive sodium stannate of 50mg, after isolating acetone and water, measure and handle back oil quality and sulphur content, octane value is 88.6 (RON) as a result, sulphur content 62.4mg/L.
Embodiment 8, Victoria Green WPB-sodium antimonate catalytic gasoline desulfurization
Get commercially available cationic dyestuff Victoria Green WPB 0.05g and 5mlH
2O
2Mixed dissolution, (octane value is 90.1 (RON) to join 50ml gasoline, sulphur content 120mg/L) and in the trieline mixing solutions, in stainless steel cauldron, be warming up to 75 ℃ of reactions 20 minutes after adding the 50mg sodium antimonate, after isolating acetone and water, measure and handle back oil quality and sulphur content, octane value is 89.8 (RON) as a result, sulphur content 31.3mg/L.
Embodiment 9, the desulfurization of ammonium tungstate catalytic gasoline
Get 5g ammonium tungstate and 5ml 20% aqueous sodium hypochlorite solution mixed dissolution, (octane value is 90.1 (RON) to join 50g gasoline, sulphur content 120mg/L) and 75ml chloroform mixing solutions, in stainless steel cauldron, be warming up to 100 ℃ of reactions 30 minutes, after isolating chloroform and water, measure and handle back oil quality and sulphur content, octane value is 90.2 (RON) as a result, sulphur content 29.3mg/L.
Get 50mg ammonium molybdate and 5ml 10%K
2S
2O
8The water mixed dissolution, (octane value is 90.1 (RON) to join 50ml gasoline, sulphur content 120mg/L) and 75ml methanol mixed solution, in stainless steel cauldron, be warming up to 50 ℃ of reactions 30 minutes, after isolating Virahol and water, measure and handle back oil quality and sulphur content, octane value is 88.7 (RON) as a result, sulphur content 32.5mg/L.
Embodiment 11, rhodamine B-sodium wolframate catalytic gasoline desulfurization
Get 0.05g rhodamine B, 1.5g sodium wolframate and 5.5ml 30%H
2O
2Mixed dissolution, (octane value is 93.2 (RON) to join 50ml gasoline, sulphur content 79mg/L) and 75ml methanol mixed solution, in stainless steel cauldron, be warming up to 65 ℃ of reactions 45 minutes, after isolating the first alcohol and water, same process is handled once again, measures and handles back oil quality and sulphur content, octane value is 93.1 (RON) as a result, sulphur content 5.5mg/L.
Embodiment 12, Dodecyl trimethyl ammonium chloride-potassium bichromate catalytic gasoline desulfurization
Get 0.01g Dodecyl trimethyl ammonium chloride, 1.2g potassium bichromate and 5.5ml 30%H
2O
2Mixed dissolution, (octane value is 90.1 (RON) to join 50ml gasoline, sulphur content 120mg/L) and 10ml second eyeball mixing solutions, in stainless steel cauldron, be warming up to 150 ℃ of reactions 25 minutes, after isolating second eyeball and water, measure and handle back oil quality and sulphur content, octane value is 90.1 (RON) as a result, sulphur content 45.2mg/L.
Claims (9)
1, a kind of catalytic oxidation desulfurization method of petroleum products, be in petroleum products, to add oxygenant to carry out desulphurization reaction, it is characterized in that: also be added with desulfurization catalyst and solvent in the described petroleum products, described desulfurization catalyst contains the metal oxygen-containing hydrochlorate, and described metal is Mn, Sb, W, Ce, Sn, Mo, V or Cr.
2, method according to claim 1 is characterized in that: described solvent is N-Methyl pyrrolidone, acetone, methyl halide, halo ethane, vinyl halides, methyl alcohol, ethanol, Virahol or second eyeball.
3, method according to claim 1 is characterized in that: ammonium salt that described metal oxygen-containing hydrochlorate is metal oxygen-containing acid or monovalence metallic cation salt.
4, method according to claim 1 is characterized in that: described desulfurization catalyst also includes the carrier of band amino or quaternary ammonium group, and described carrier is ion exchange resin, tensio-active agent or dyestuff.
5, according to claim 4, it is characterized in that: described ion exchange resin is the strong basic ion exchange resin that contains quaternary ammonium group; Described tensio-active agent is Dodecyl trimethyl ammonium chloride or hexadecyl benzyltrimethylammonium bromide; Described dyestuff is rhodamine or Victoria Green WPB.
6, method according to claim 4 is characterized in that: the mol ratio of described carrier and described metal oxygen-containing hydrochlorate is 0-1000: 1.
7, according to the arbitrary described method of claim 1-6, it is characterized in that: the weight ratio of described desulfurization catalyst and described petroleum products is 1: 10-100000.
8, according to the arbitrary described method of claim 1-6, it is characterized in that: described oxygenant is H
2O
2, KClO
3, NaOCl or K
2S
2O
8
9, according to the arbitrary described method of claim 1-6, it is characterized in that: the temperature of reaction of described desulphurization reaction is 25-150 ℃.
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| CN102337149A (en) * | 2010-07-20 | 2012-02-01 | 林欣栋 | Method for removing sulfide from liquid fossil fuels and continuous desulfurization device thereof |
| CN101381625B (en) * | 2008-10-28 | 2012-08-08 | 天津大学 | Method for removing sulfide from oil products with high aromatic hydrocarbon content |
| CN101734875B (en) * | 2009-12-28 | 2012-10-31 | 华北电力大学（保定） | Method for catalytic oxidation of calcium sulfite in desulphurization ash by dry method and semi-dry method |
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| CN104693357A (en) * | 2013-12-04 | 2015-06-10 | 中国科学院大连化学物理研究所 | An oxidation desulphurization method for C9 petroleum resin |
| CN105733654A (en) * | 2014-12-08 | 2016-07-06 | 中国科学院大连化学物理研究所 | Fuel oil oxidation treatment device for fuel oil desulphurization |
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| CN101734875B (en) * | 2009-12-28 | 2012-10-31 | 华北电力大学（保定） | Method for catalytic oxidation of calcium sulfite in desulphurization ash by dry method and semi-dry method |
| CN102337149A (en) * | 2010-07-20 | 2012-02-01 | 林欣栋 | Method for removing sulfide from liquid fossil fuels and continuous desulfurization device thereof |
| CN104693357A (en) * | 2013-12-04 | 2015-06-10 | 中国科学院大连化学物理研究所 | An oxidation desulphurization method for C9 petroleum resin |
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| CN104694152B (en) * | 2013-12-05 | 2016-04-06 | 中国科学院大连化学物理研究所 | The fuel oil oxidation treatment method of hydrogen peroxide-chlorine coupling |
| CN105733654A (en) * | 2014-12-08 | 2016-07-06 | 中国科学院大连化学物理研究所 | Fuel oil oxidation treatment device for fuel oil desulphurization |
| CN105733654B (en) * | 2014-12-08 | 2017-06-23 | 中国科学院大连化学物理研究所 | A kind of fuel oil oxidation treatment device for fuel desulfuration process |
| CN110624533A (en) * | 2019-10-11 | 2019-12-31 | 天津科技大学 | Preparation method of anchoring type catalyst and catalytic oxidation heavy oil desulfurization, denitrification, demetalization and deacidification method |
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| WO2022133768A1 (en) * | 2020-12-23 | 2022-06-30 | Solvay Sa | Desulfurization process |
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