CN100523143C - Method for desulfurizing and reducing olefine for gasoline - Google Patents
Method for desulfurizing and reducing olefine for gasoline Download PDFInfo
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- CN100523143C CN100523143C CNB2004100963195A CN200410096319A CN100523143C CN 100523143 C CN100523143 C CN 100523143C CN B2004100963195 A CNB2004100963195 A CN B2004100963195A CN 200410096319 A CN200410096319 A CN 200410096319A CN 100523143 C CN100523143 C CN 100523143C
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Abstract
The process of desulifurizing gasoline and reducing olefin content includes contacting gasoline material with hydrogen and hydrogen isomerization catalyst for hydrogen desulfurizing, saturating olefin, isomerizing olefin and cracking olefin; contacting the reaction effluent with selectively hydrogen desulfurizing catalyst; and separating hydrogen desulfurizing produced oil to obtain light olefin and gasoline fractions; and circulating the hydrogen-rich gas. The said process can produce high quality gasoline with low sulfur and olefin content and lowest octane number loss.
Description
Technical field
The invention belongs in the method that has refining hydrocarbon ils under the situation of hydrogen, more particularly, is that olefins process falls in the hydrogenating desulfurization that belongs to a kind of gasoline fraction.
Background technology
Along with the continuous enhancing of people to environmental consciousness, the discharging of hazardous and noxious substances will be strictly controlled in the vehicle exhaust, and therefore the oil quality as motor spirit requires more and more tighter.For this reason, various countries have all proposed very harsh restriction index to motor spirit specification such as oxygen level, vapour pressure, benzene content, aromatic hydrocarbons total content, boiling point, olefin(e) centent and sulphur content etc., to reduce emission of harmful substances.Contrast China motor spirit new standard can find that the subject matter of China's quality of gasoline is sulphur content and olefin(e) centent height.The major cause of sulfur in gasoline and olefin(e) centent superelevation is because the ratio of catalytic cracking (FCC) gasoline in gasoline pool is too high.In China, FCC gasoline is main blend component in the gasoline mediation pond, accounts for more than 80%.FCC content of sulfur in gasoline height, olefin(e) centent height, and the raw material of processing along with FCC develops to the heaviness direction, will cause sulphur content and olefin(e) centent in the FCC gasoline further to increase.Therefore reduce FCC sulfur in gasoline and olefin(e) centent and be the main path of sulphur and olefin(e) centent in the control motor spirit.
US5411658 discloses elder generation with behind the FCC gasoline hydrofinishing, directly enters second section, carries out a kind of method of handling FCC gasoline of octane value recovering process.Traditional Hydrobon catalyst is adopted in this patent hydrofining, and the octane value recovering process adopts the beta-zeolite molecular sieve catalyst.This patent provides a kind of thinking of the FCC of solution quality of gasoline.Higher (light FCC gasoline final boiling point is 246 ℃ but this method is used the stock oil final boiling point; Heavy FCC gasoline final boiling point is 296 ℃), hydrofining section temperature of reaction too high (reaching 370 ℃).
US5599439 discloses a kind of technology of handling heavy FCC gasoline.First section is carried out hydrofining earlier, it is saturated to remove impurity such as sulphur, nitrogen and alkene, pass through again intermediate section from, directly loop back first section (one is anti-) through the gas of isolating behind the impurity such as hydrogen sulfide, ammonia, intermediates oil enters second section (two is anti-), carries out the octane value recovering process.No longer mend new hydrogen for second section.The octane value recovering section adopts flowing bed reactor.First section temperature of reaction of this invention is 260～427 ℃, and second section temperature of reaction is 315～427 ℃, and working pressure is in 790～1825Kpa scope.Otherwise this technology has increased by a separator at one, two, increases facility investment, and working pressure is low excessively simultaneously, is unfavorable for the long-term operation of catalyzer.
US5399258 discloses a kind of method of handling heavy FCC gasoline.First section through hydrogenation desulfurization and denitrogenation, hydrogenation of olefins saturated after, it is two anti-that the intermediate product that obtains directly enters, and carries out the octane value recovering reaction.One anti-temperature of reaction is 347～410 ℃, maintains an equal level with two anti-temperature of reaction.Because an anti-temperature of reaction is too high, causes final product to produce a large amount of mercaptan sulfurs, temperature is high more, and the amount of the mercaptan sulfur of generation is big more.
CN1316485A discloses a kind of gasoline modified method.First section is carried out olefin isomerization, carries out olefin hydrogenation at second section then.First section dress be olefin isomerization catalyst, second section dress be olefin hydrogenation catalyst.This patent is only carried out olefin isomerization for first section, simultaneously other impurity such as sulphur is not proposed treatment process.
Summary of the invention
The purpose of present technique invention is exactly on the basis of existing technology, proposes a kind of method of desulfurizing and reducing olefine for gasoline, satisfies the premium of GB GB 17930-1999 to produce sulphur and olefin(e) centent.
Method provided by the invention comprises:
Gasoline stocks, hydrogen contact with hydroisomerization catalyst, carry out that hydrogenating desulfurization, alkene are saturated, olefin isomerization, cracking of olefins reaction, reaction effluent contacts with catalyst for selectively hydrodesulfurizing, separates hydrogenating desulfurization generation oil and obtains lighter hydrocarbons and gasoline fraction, and hydrogen-rich gas recycles.
The present invention produces the premium that sulphur, olefin(e) centent all satisfy GB GB 17930-1999, guarantees the loss of octane number minimum of gasoline simultaneously.
Description of drawings
Accompanying drawing is the method synoptic diagram of desulfurizing and reducing olefine for gasoline provided by the invention.
Embodiment
Method provided by the invention is so concrete enforcement:
Gasoline stocks enters the fixed bed hydrogenation isomerizing reactor and contacts with hydroisomerization catalyst after feedstock pump boosts, the intermediate product that obtains behind the serial reactions such as, olefin isomerization saturated through desulfurization, alkene, cracking of olefins enters the selective hydrodesulfurization reactor, contact with catalyst for selectively hydrodesulfurizing, the outlet effluent of selective hydrodesulfurization reactor mainly comprises the H that removes in the hydrogenation process
2S, NH
3And the treated oil after the hydrotreatment.This outlet effluent enters high-pressure separator in proper order, stabilizer tower obtains gasoline products.The isolated hydrogen rich stream of high score mixes by recycle compressor with new hydrogen delivers to hydrotreating reactor.
The used gasoline stocks of the present invention is selected from FCC gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline or more than one mixture wherein.This gasoline stocks has high sulphur, olefin(e) centent.
In the technology of the present invention, raw material must be handled through two steps: the first step, sulfur-bearing olefine contained gasoline cut obtains intermediates through isomerization, cracking.Second step, the further hydrofining of intermediates.Desulfurization, denitrification reaction and part olefin saturation mainly take place in this process.Raw material of the present invention is applicable to the gasoline fraction oil of high-sulfur high olefin content, and the quality index of stock oil character such as olefin(e) centent, sulphur content, boiling range scope etc. and product is largely depended in the technological operation handiness.Stock oil character is different, different to product requirement, flexibly the selection operation processing condition.
Method the first step processing condition of the present invention are: hydrogen dividing potential drop 1.0～4.0MPa, 200～460 ℃ of temperature of reaction, liquid hourly space velocity 0.5～6.0h
-1, hydrogen-oil ratio 100～1000v/v; The second step process condition is: hydrogen dividing potential drop 1.0～4.0MPa, 100～400 ℃ of temperature of reaction, liquid hourly space velocity 0.5～6.0h
-1, hydrogen-oil ratio 100～1000v/v.
The described hydroisomerization catalyst of the first step is to load on group vib base metal on the molecular sieve carrier or/and VIII family non-precious metal catalyst, described VIII family base metal is selected from nickel or cobalt, described group vib base metal is selected from molybdenum or/and tungsten, described molecular screening is from faujusite, Beta molecular sieve, ZSM-5 molecular sieve, SAPO-11 or more than one mixture wherein, and carrier is an aluminum oxide.
The catalyst for selectively hydrodesulfurizing in second step is group vib base metal and the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports, described group vib base metal is selected from molybdenum or/and tungsten, and described VIII family base metal is selected from nickel or/and cobalt.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.
Accompanying drawing is the method synoptic diagram of desulfurizing and reducing olefine for gasoline provided by the invention.
The method flow of desulfurizing and reducing olefine for gasoline provided by the invention is described in detail as follows:
Gasoline stocks is through pipeline 1 incoming stock pump 2, raw material after boosting through pipeline 3 with after hydrogen stream from pipeline 26 mixes, after pipeline 4 enters interchanger 5 and the reactor 14 outlet effluent heat exchange from pipeline 15, again after pipeline 6 enters interchanger 7 and the reactor 11 effluent heat exchange from pipeline 12, again after pipeline 8 enters process furnace 9 preheatings, enter fixed bed hydrogenation isomerizing reactor 11 through pipeline 10, by contacting with the hydroisomerisation catalysts bed, make alkane, alkene generation isomerization, cracking reaction, remove the part sulphur in the raw material simultaneously, after impurity such as nitrogen and part hydrogenation of olefins are saturated, the outlet effluent of reactor 11 is after pipeline 12 enters interchanger 7 and mixture heat exchange from the raw material of pipeline 6 and hydrogen, enter selective hydrodesulfurization reactor 14 through pipeline 13, contact further desulfurization with catalyst for selectively hydrodesulfurizing, denitrogenation and part hydrogenation of olefins are saturated.The outlet effluent of reactor 14 is after pipeline 15 enters interchanger 5 and mixture heat exchange from the raw material of pipeline 4 and hydrogen, enter high-pressure separator 17 through pipeline 16, in high-pressure separator 17, be divided into two bursts of logistics, wherein one is a hydrogen rich stream, wherein be mainly hydrogen, comprise partial vulcanization hydrogen, ammonia and lighter hydrocarbons simultaneously.This hydrogen rich stream is after pipeline 22 enters recycle compressor 23 compressions, through pipeline 24 with mix from the additional fresh hydrogen of pipeline 25 after, loop back reactor 11 through pipeline 26, pipeline 4, interchanger 5, pipeline 6, interchanger 7, pipeline 8, process furnace 9, pipeline 10 successively.Another burst logistics of high-pressure separator 17 then enters follow-up stable system 19 through pipeline 18, the logistics of coming out from stable system 19 bottoms is the gasoline products behind the hydrogenation, this product is drawn through pipeline 21, and the logistics of coming out from stable system 19 tops is lighter hydrocarbons, and these lighter hydrocarbons are drawn through pipeline 20.
The present invention is directed to China's content of olefin in gasoline height (can up to 55v%), aromaticity content low (＜20v%), characteristics that final boiling point is low, successively raw material is carried out hydroisomerizing, selective hydrodesulfurization, produce sulphur, olefin(e) centent and all satisfy the premium (sulphur, olefin(e) centent are respectively less than 800ppm, 35v%) of GB GB 17930-1999, guarantee the loss of octane number minimum of gasoline simultaneously, anti-knock index (RON+MON)/2 loss generally is lower than 2 units.The present invention is not limited to handle domestic gasoline stocks, also can handle the gasoline stocks of external similarity.
The following examples will give further instruction to present method, but therefore not limit present method.
The used hydroisomerization catalyst and the trade names of catalyst for selectively hydrodesulfurizing are respectively RIDOS-1 and RSDS-1 among the embodiment, and these two kinds of catalyzer are produced by Sinopec Group's Chang Ling oil-refining chemical head factory catalyst plant.
Comparative Examples
The used raw material A of this Comparative Examples is a FCC gasoline, and its character is as shown in table 1.Raw material A is through conventional hydrotreatment, and its processing condition and product property are as shown in table 2.As can be seen from Table 2, when olefin(e) centent was 29.0v% in the gasoline products, anti-knock index lost up to 3.3 units.
Embodiment 1
The used raw material A of the used raw material of present embodiment and Comparative Examples is identical.Raw material A contacts with the RSDS-1 catalyzer with RIDOS-1 successively, carries out hydroisomerizing, selective hydrodesulfurization respectively, and its processing condition and product property are as shown in table 2.As can be seen from Table 2, produce the premium product that sulphur, olefin(e) centent all satisfy GB GB 17930-1999, when olefin(e) centent was 30.1v% in this gasoline products, the anti-knock index loss only was 1.3 units.
The used raw material B of present embodiment is a FCC gasoline, and its character is as shown in table 1.Raw material B contacts with the RSDS-1 catalyzer with RIDOS-1 successively, carries out hydroisomerizing, selective hydrodesulfurization respectively, and its processing condition and product property are as shown in table 2.As can be seen from Table 2, produce the premium product that sulphur, olefin(e) centent all satisfy GB GB 17930-1999.Content of olefin in gasoline drops to 34.9v% from 46.4v%, and the anti-knock index loss only is 1.5 units.
Table 1
| Raw material A | Raw material B | |
| Density (20 ℃), g/cm 3 | 0.7252 | 0.7242 |
| Sulphur content, ppm | 1400 | 628 |
| Olefin(e) centent, v% | 38.7 | 46.4 |
| Boiling range, ℃ | ||
| Initial boiling point | 34 | 42 |
| 10％ | 52 | 51 |
| 50％ | 94 | 101 |
| Final boiling point | 186 | 194 |
| Anti-knock index | 86.5 | 84.5 |
Table 2
| Comparative Examples | Embodiment 1 | |
|
| Processing condition | |||
| The hydrogen dividing potential drop, MPa | 3.2 | 3.2 | 3.2 |
| Temperature of reaction, ℃ | 190 | ||
| Hydroisomerizing | - | 340 | 340 |
| Selective hydrodesulfurization | - | 240 | 240 |
| Liquid hourly space velocity, h -1 | |||
| Hydroisomerizing | - | 2.0 | 2.0 |
| Selective hydrodesulfurization | - | 4.0 | 4.0 |
| Hydrogen-oil ratio, Nm 3/m 3 | 500 | 500 | |
| Product property | |||
| Density (20 ℃), g/cm 3 | 0.7077 | 0.7315 | 0.7222 |
| Sulphur content, ppm | - | 350 | 140 |
| Olefin(e) centent, v% | 29.0 | 30.1 | 34.9 |
| Anti-knock index | 3.3 | 1.3 | 1.5 |
Claims (4)
1, a kind of method of desulfurizing and reducing olefine for gasoline, it is characterized in that gasoline stocks, hydrogen contacts with hydroisomerization catalyst, carry out hydrogenating desulfurization, alkene is saturated, olefin isomerization and cracking of olefins reaction, reaction effluent contacts with catalyst for selectively hydrodesulfurizing, separate hydrogenating desulfurization generation oil and obtain lighter hydrocarbons and gasoline fraction, hydrogen-rich gas recycles, described hydroisomerization catalyst is to load on group vib base metal on the molecular sieve carrier or/and VIII family non-precious metal catalyst, described VIII family base metal is selected from nickel or cobalt, described group vib base metal is selected from molybdenum or/and tungsten, described molecular screening is from faujusite, the Beta molecular sieve, the ZSM-5 molecular sieve, SAPO-11 or more than one mixture wherein, described catalyst for selectively hydrodesulfurizing is group vib base metal and the VIII family non-precious metal catalyst that loads on unformed aluminum oxide or the silica-alumina supports, described group vib base metal is selected from molybdenum or/and tungsten, and described VIII family base metal is selected from nickel or/and cobalt.
2,, it is characterized in that described gasoline stocks is selected from catalytically cracked gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline, pressure gasoline or more than one mixture wherein according to the method for claim 1.
3,, it is characterized in that described gasoline stocks is a catalytic cracking gasoline according to the method for claim 1.
4,, it is characterized in that the processing condition that gasoline stocks, hydrogen contact with hydroisomerization catalyst are: hydrogen dividing potential drop 1.0～4.0MPa, 200～460 ℃ of temperature of reaction, liquid hourly space velocity 0.5～6.0h according to the method for claim 1
-1, hydrogen-oil ratio 100～1000v/v; The processing condition that the reaction effluent that gasoline stocks, hydrogen contact with hydroisomerization catalyst contacts with catalyst for selectively hydrodesulfurizing again are: hydrogen dividing potential drop 1.0～4.0MPa, 100～400 ℃ of temperature of reaction, liquid hourly space velocity 0.5～6.0h
-1, hydrogen-oil ratio 100～1000v/v.
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| CNB2004100963195A CN100523143C (en) | 2004-11-30 | 2004-11-30 | Method for desulfurizing and reducing olefine for gasoline |
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| CNB2004100963195A CN100523143C (en) | 2004-11-30 | 2004-11-30 | Method for desulfurizing and reducing olefine for gasoline |
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| CN100523143C true CN100523143C (en) | 2009-08-05 |
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