CN100532505C - Method for catalyzing oxygenizing desulfurizing straight-run gasoline - Google Patents
Method for catalyzing oxygenizing desulfurizing straight-run gasoline Download PDFInfo
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- CN100532505C CN100532505C CNB2006100219404A CN200610021940A CN100532505C CN 100532505 C CN100532505 C CN 100532505C CN B2006100219404 A CNB2006100219404 A CN B2006100219404A CN 200610021940 A CN200610021940 A CN 200610021940A CN 100532505 C CN100532505 C CN 100532505C
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Abstract
The invention discloses a catalyzing oxidizing desulfurizing method of straight gasoline, which comprises the following steps: (1) allocating nitrogen oxide and gasoline with bulk rate at 10:1-36:1 in the reactor; (2) aerating oxygen; stirring; reacting under 20-50 deg.c for 30-90 min; (3) blending active carclazyte/oxidized gasoline with weight rate at 0.5-5% to distill; or distilling the oxidized gasoline; blending active carclazyte/oxidized gasoline with weight rate at 0.5-5%; adsorbing; filtering to obtain the product.
Description
Technical field
The present invention relates to a kind of gasoline desulfating method, particularly relate to the method that removes the sulfocompound in the straight-run spirit.
Background technology
Along with the continuous enhancing of people's environmental consciousness, the pollution that vehicle exhaust brought more and more becomes the focus that people pay close attention to.The specification of motor spirit index such as oxygen level, vapour pressure, benzene content, aromatic hydrocarbons total content, boiling point, olefin(e) centent and sulphur content are more and more stricter, especially sulphur content.Using Exhaust Gas Catalytic Converter for Automobiles is to reduce the optimal path of automobile exhaust pollution thing quantity discharged, and the sulphur content in still high performance tail gas convertor the needs high-quality oil fuel, particularly gasoline has remarkable influence to the performance of exhaust catalytic converter.For this reason, the requirement of 30～150 μ g/g is reduced to the sulphur content in the gasoline in propositions such as the U.S., Europe, Canada.And China is as developing country, in the production technology of oil fuel with require all to remain in a certain distance with western developed country on the standard: on July 1st, 2005 rose, China's petrol and diesel oil begin to carry out suitable Europe II emission standard be in the petrol and diesel oil sulphur content less than 500 μ g/g, and Beijing from July 1st, 2005 just carry out suitable Europe III emission standards be sulphur content the gasoline less than 150 μ g/g, it is that the petrol and diesel oil sulphur content is less than 50ppm that some main cities such as Beijing, the left and right sides in 2010, Shanghai will be carried out Europe IV emission standard.Therefore, the desulfurization situation of China's oil refining industry is very urgent.
By the complexity of sulphur content and desulfurization, can be the gasoline blend component three classes.The first kind comprises reformate, alkylate oil, the very low blend component of isomerization wet goods sulphur content; Second class is light virgin naphtha, although contain a certain amount of sulphur, olefin(e) centent is low, can carry out with traditional hydrofining technology; The 3rd class is FCC gasoline, coker gasoline etc., particularly FCC gasoline, and not only sulphur content height (account in the gasoline total sulfur 85～95%) also contains a large amount of alkene.
The gasoline desulfur technology of exploitation mainly contains two classes both at home and abroad at present, and the one, full hydrogen addition technology, in the time of desulfurization, alkene is all saturated; The 2nd, the selective hydrodesulfurization technology, in the time of desulfurization, the alkene fractional saturation.
The disclosed catalytic distillation sulfur removal technology of CN1189183A enters a catalytic distillation tower with whole petroleum naphthas, kerosene, diesel oil, make the light gasoline fraction of high olefin content, low sulfur content also contact Hydrobon catalyst, increase the saturated chance of this part hydrogenation of olefins like this, can cause bigger loss of octane number.US5,597,476 disclosed catalytic distillation sulfur removal technologies comprise two catalytic distillation towers.In first tower, under the effect of catalyzer, make mercaptan and diolefine reaction generation high boiling substance in the light gasoline fraction enter last running, obtain the C of low thioalcohol content from cat head
5Or C
5, C
6Cut is simultaneously remaining diolefin hydrogenate; Last running enters second catalytic distillation tower, adopts common Hydrobon catalyst to carry out hydrogenating desulfurization.Adopt two catalytic distillation tower catalyst loadings loaded down with trivial details.Because the porosity of catalytic distillation catalyst filling zone is littler than general distillation tower, promptly turndown ratio is little, can not adjust treatment capacity or the desulfurization degree and the loss of octane number amount of two towers neatly.Ke Ming, Fan Zhiming etc. are at " NO
2Oxidation style removes the organosulfur compound in the Sweet natural gas winterization gasoline " in (University of Petroleum's journal (natural science edition), 1996,20 (4)) research point out: under the normal temperature and pressure, logical NO
2Gas reacts 40min in the Sweet natural gas winterization gasoline of sulfur-bearing 0.28%, make that mercaptan and thioether are oxidized to alkylsulphonic acid and inferior alum in the oil, removes with acid-alkali washing again, and last mercaptan removal rate can reach 100%, and desulfurization degree can reach 70%.But the final desulfurization degree of treated oil is on the low side and technological process will be used strong acid and strong base so have corrosion and wastewater treatment, also has remaining NO
xThe exhaust gas discharging problem.The disclosed selective hydrogenation desulfurization process of CN02129039.3 is cut into light gasoline fraction, heavy naphtha with gasoline stocks; Heavy naphtha contacts with Hydrobon catalyst together with hydrogen, carry out the selective hydrodesulfurization reaction, after reaction effluent is isolated gas phase through high-pressure separator, remaining liquid phase is mixed back repeated hydrogenation mercaptan-eliminating catalyst with new hydrogen and is contacted, and effluent once enters high-pressure separator, stabilizer tower obtains qualified product; Returning hydrotreating reactor from the isolated hydrogen rich stream of high-pressure separator after recycle compressor boosts recycles owing to sulphur content the raw materials used oil is not more than 1500ppm, hydrogenating desulfurization hydrogen dividing potential drop 1.0～3.2MPa, 200～320 ℃ of temperature of reaction, thereby still have hydro condition and harsh relatively operational condition.
So the non-hydrogenating desulfurization technology of gasoline is subjected to more attention gradually, and has obtained very big development.Wherein, the gasoline oxidation desulfurization technology is the focus of studying both at home and abroad.Compare with traditional hydrogenating desulfurization technology, it has the following advantages:
(1) deep desulfuration; The reaction conditions gentleness, temperature＜100 ℃, atmospheric operation, process cost is low;
(2) need not hydrogen source, pressure-resistant equipment and Claus desulfurizer, technical process is simple, and facility investment is extremely low;
(3) oxidative desulfurization techniques also can be used for denitrogenation;
(4) energy-conservation, low CO
2The environment-protective process of discharging;
(5) the desulfurization matter effect of coming unstuck in addition when not losing octane value, oil stability can also improve.
Summary of the invention
The object of the present invention is to provide a kind of method of catalyzing oxygenizing desulfurizing straight-run gasoline, this method has overcome hydrogenating desulfurization cost height in the prior art, non-Hydrobon catalyst and oxidant cost problem and aftertreatment problem thereof, this method catalyzer raw material is easy to get, and cost is low and can recycle non-exhaust emission; Operation is simple and feasible in the processing of oxidation of gasoline, can guarantee the quality and the yield of the gasoline products of gasoline oxidation desulfuration purification technology.This method can also be used for the desulfurization of sulfur-containing gas condensate oil simultaneously.
A kind of method of catalyzing oxygenizing desulfurizing straight-run gasoline may further comprise the steps successively:
1. with catalyzer oxynitride NO
xWith the volume ratio of gasoline be that 10:1～36:1 joins reactor;
2. aerating oxygen, and stirring under 20～50 ℃, carries out catalytic oxidation 30～90min, emits oxidation of gasoline and treats further processing, and catalyzer and remnant oxygen recycle;
3. oxidation of gasoline is handled by following any one method, promptly obtains refining straight-run spirit:
(1) the oxidation of gasoline treatment process one: the distillation oxidation of gasoline promptly obtains refining straight-run spirit;
(2) the oxidation of gasoline treatment process two: than the amount that is 0.5%～5% atlapulgite is mixed with oxidation of gasoline and distill by the massfraction of atlapulgite/oxidation of gasoline, promptly obtain refining straight-run spirit;
(3) the oxidation of gasoline treatment process three: the distillation oxidation of gasoline, and the massfraction by atlapulgite/oxidation of gasoline mixes atlapulgite than the amount that is 0.5%～5% with oxidation of gasoline again, and absorption is also filtered, and promptly obtains refining straight-run spirit;
(4) the oxidation of gasoline treatment process four: oxidation of gasoline is coalescent, distillation promptly obtains refining straight-run spirit;
(5) the oxidation of gasoline treatment process five: be that 0.05～～0.3 amount is mixed distillation with vacuum residuum with oxidation of gasoline by vacuum residuum/oxidation of gasoline volume ratio, promptly obtain refining straight-run spirit.Rich sulfur resid can be made fuel oil or remove hydrogenation unit;
(6) the oxidation of gasoline treatment process six: be that 0.05～～0.3 amount is mixed distillation with long residuum with oxidation of gasoline by long residuum/oxidation of gasoline volume ratio, promptly obtain refining straight-run spirit.Rich sulfur resid can be made fuel oil or remove hydrogenation unit;
(7) the oxidation of gasoline treatment process seven: be that 0.05～～0.3 amount is mixed distillation with catalytic slurry with oxidation of gasoline by catalytic slurry/oxidation of gasoline volume ratio, promptly obtain refining straight-run spirit.Rich sulphur slurry oil can be made fuel oil or go hydrotreatment;
(8) the oxidation of gasoline treatment process eight: by the volume ratio of composite extraction agent/oxidation of gasoline is that 0.01～0.08 amount is mixed extraction agent with oxidation of gasoline, leave standstill phase-splitting, obtain oil phase (go up phase) and extraction agent (mutually following), will go up phase and distill again and promptly obtain treated gasoline.Extraction agent is for recycling.Consisting of of composite extraction agent wherein: 20～50 weight %NaOH+5～20 weight %CH
3OH+30～75 weight % water.
Be that the consumption of 10:1～36:1 adds reactor, preferred volume ratio 16:1～36:1 with catalyzer and gasoline by catalyzer/gasoline volume ratio among the present invention.As oxygenant,, carry out catalytic oxidation 30～90min, preferred 40～80min under preferred 30～50 ℃ of temperature with oxygen at 20～50 ℃.Present method catalyst n O
xMainly be NO and NO
2, adopt oxygen excessive, guaranteed NO in the catalyzer
2Content, strengthened the catalyzed oxidation effect.Its chemical equation is:
2NO↑+O
2↑＝2NO
2↑
Handle oxidation of gasoline with any one method in oxidation of gasoline treatment process one～oxidation of gasoline treatment process eight, can obtain treated gasoline.
Compared with prior art, the invention provides a kind of novel method of desulfurization from high sulfur-bearing straight-run spirit, with the tail gas NO of nitric acid industry
xFor oxide catalyst, oxygen are oxygenant, catalyzer and oxygenant are all cheap and easy to get, and the catalyzed oxidation effect is obvious, and catalyzer and remaining oxygenant can recycle, and be simple to operate, continuous, and do not have sulfur-containing waste water and exhaust gas emission.The desulfurization degree of gasoline is reached as high as more than 96%, and the content of sulfur in gasoline after the desulfurization reaches Europe III class gasoline quality standard (＜150 μ g/g).
Embodiment
The present invention is further illustrated below by example.The analytical procedure that test is adopted:
Adopt the sulphur content in the GB/T380-88 petroleum products sulphur content determination method mensuration gasoline, the desulfurization degree method of calculation are: desulfurization degree=(1-treated gasoline sulphur content/stock oil sulphur content) * 100%
Example 1
Press catalyzer and gasoline by volume for 16:1, in the sulphur content that Northwest Sichuan Gas Field of Southwest Oil and Gas Field Branch, PCL provides is the straight-run spirit of 3009 μ g/g, feed 320ml NO
x, make oxygenant with oxygen, react 50min down at 20 ℃, reaction finishes to pour out oxidation of gasoline, and catalyst recirculation is used.Adopt thickened oil treatment process one to handle oxidation of gasoline, obtain refining straight-run spirit, sulphur content is 261 μ g/g, and desulfurization degree reaches 91.33%.
Example 2
Press catalyzer and gasoline by volume for 26:1, the sulphur content that provides in gas ore deposit, northwest, PetroChina Company Limited. Southwest Oil branch office river is to feed 520ml NO in the straight-run spirit of 3009 μ g/g
x, make oxygenant with oxygen, react 50min down at 20 ℃, reaction finishes to pour out oxidation of gasoline, and catalyst recirculation is used.Adopt the thickened oil treatment process to manage oxidation of gasoline everywhere, obtain refining straight-run spirit, obtain refining straight-run spirit, sulphur content is 177 μ g/g, and desulfurization degree reaches 94.12%.
Example 3
Press catalyzer and gasoline by volume for 32:1, the sulphur content that provides in gas ore deposit, northwest, PetroChina Company Limited. Southwest Oil branch office river is to feed 640ml NO in the straight-run spirit of 3009 μ g/g
x, make oxygenant with oxygen, react 50min down at 20 ℃, reaction finishes to pour out oxidation of gasoline, and catalyst recirculation is used.Adopt the oxidation of gasoline treatment process to manage oxidation of gasoline everywhere, obtain refining straight-run spirit, sulphur content is 177 μ g/g, and desulfurization degree reaches 94.12%.
Example 4
Press catalyzer and gasoline by volume for 26:1, the sulphur content that provides in gas ore deposit, northwest, PetroChina Company Limited. Southwest Oil branch office river is to feed 520ml NO in the straight-run spirit of 3009 μ g/g
x, make oxygenant with oxygen, react 40min down at 20 ℃, reaction finishes to pour out oxidation of gasoline, and catalyst recirculation is used.Adopt the thickened oil treatment process to manage oxidation of gasoline everywhere, obtain refining straight-run spirit, sulphur content is 178 μ g/g, and desulfurization degree reaches 94.08%.
Example 5
Press catalyzer and gasoline by volume for 26:1, the sulphur content that provides in gas ore deposit, northwest, PetroChina Company Limited. Southwest Oil branch office river is to feed 520ml NO in the straight-run spirit of 3009 μ g/g
x, make oxygenant with oxygen, react 40min down at 20 ℃, reaction finishes to pour out oxidation of gasoline, and catalyst recirculation is used.Adopt thickened oil treatment process one to handle oxidation of gasoline, obtain refining straight-run spirit, sulphur content is 353 μ g/g, and desulfurization degree reaches 88.27%.
Example 6
Press catalyzer and gasoline by volume for 26:1, the sulphur content that provides in gas ore deposit, northwest, PetroChina Company Limited. Southwest Oil branch office river is to feed 520ml NO in the straight-run spirit of 3009 μ g/g
x, make oxygenant with oxygen, react 40min down at 30 ℃, reaction finishes to pour out oxidation of gasoline, and catalyst recirculation is used.Adopt thickened oil treatment process two to handle oxidation of gasoline, obtain refining straight-run spirit, sulphur content is 174 μ g/g, and desulfurization degree reaches 94.22%.
Example 7
Press catalyzer and gasoline by volume for 26:1, the sulphur content that provides in gas ore deposit, northwest, PetroChina Company Limited. Southwest Oil branch office river is to feed 520ml NO in the straight-run spirit of 3009 μ g/g
x, make oxygenant with oxygen, react 40min down at 30 ℃, reaction finishes to pour out oxidation of gasoline, and catalyst recirculation is used.Adopt thickened oil treatment process three to handle oxidation of gasoline, obtain refining straight-run spirit, sulphur content is 174 μ g/g, and desulfurization degree reaches 94.22%.
Example 8
Press catalyzer and gasoline by volume for 26:1, the sulphur content that provides in gas ore deposit, northwest, PetroChina Company Limited. Southwest Oil branch office river is to feed 520ml NO in the straight-run spirit of 3009 μ g/g
x, make oxygenant with oxygen, react 40min down at 30 ℃, reaction finishes to pour out oxidation of gasoline, and catalyst recirculation is used.Adopt thickened oil treatment process five to handle oxidation of gasoline, obtain refining straight-run spirit, sulphur content is 165 μ g/g, and desulfurization degree reaches 94.52%.
Example 9
Press catalyzer and gasoline by volume for 26:1, the sulphur content that provides in gas ore deposit, northwest, PetroChina Company Limited. Southwest Oil branch office river is to feed 520ml NO in the straight-run spirit of 3009 μ g/g
x, make oxygenant with oxygen, react 40min down at 30 ℃, reaction finishes to pour out oxidation of gasoline, and catalyst recirculation is used.Adopt thickened oil treatment process six to handle oxidation of gasoline, obtain refining straight-run spirit, sulphur content is 125 μ g/g, and desulfurization degree reaches 95.85%.
Example 10
Press catalyzer and gasoline by volume for 26:1, the sulphur content that provides in gas ore deposit, northwest, PetroChina Company Limited. Southwest Oil branch office river is to feed 520ml NO in the straight-run spirit of 3009 μ g/g
x, make oxygenant with oxygen, react 40min down at 30 ℃, reaction finishes to pour out oxidation of gasoline, and catalyst recirculation is used.Adopt thickened oil treatment process seven to handle oxidation of gasoline, obtain refining straight-run spirit, sulphur content is 148 μ g/g, and desulfurization degree reaches 95.08%.
Example 11
Press catalyzer and gasoline by volume for 26:1, the sulphur content that provides in gas ore deposit, northwest, PetroChina Company Limited. Southwest Oil branch office river is to feed 520ml NO in the straight-run spirit of 3009 μ g/g
x, make oxygenant with oxygen, react 40min down at 30 ℃, reaction finishes to pour out oxidation of gasoline, and catalyst recirculation is used.Adopt thickened oil treatment process eight to handle oxidation of gasoline, obtain refining straight-run spirit, sulphur content is 111 μ g/g, and desulfurization degree reaches 96.11%.
Claims (2)
- The method of 1 one kinds of catalyzing oxygenizing desulfurizing straight-run gasolines may further comprise the steps successively:(1) with catalyzer oxynitride NO xWith the volume ratio of gasoline be that 10:1～36:1 joins reactor;(2) aerating oxygen, and stir, under 20～50 ℃, carry out catalytic oxidation 30～90min, to emit oxidation of gasoline and treat further processing, catalyzer and remnant oxygen recycle;(3) atlapulgite is mixed with oxidation of gasoline than the amount that is 0.5%～5% by the massfraction of atlapulgite/oxidation of gasoline and distill, or after distilling oxidation of gasoline earlier, massfraction by atlapulgite/oxidation of gasoline mixes atlapulgite than the amount that is 0.5%～5% with oxidation of gasoline again, absorption is also filtered, and promptly obtains refining straight-run spirit.
- 2 the method for claim 1 is characterized in that, described (1) step catalyzer/gasoline volume ratio is 16:1～36:1, carry out catalytic oxidation 40～80min under 30～50 ℃.
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