CN100344733C - Method for simultanesusly reducing sulfur and olefine content in gasoline - Google Patents
Method for simultanesusly reducing sulfur and olefine content in gasoline Download PDFInfo
- Publication number
- CN100344733C CN100344733C CNB2004100963180A CN200410096318A CN100344733C CN 100344733 C CN100344733 C CN 100344733C CN B2004100963180 A CNB2004100963180 A CN B2004100963180A CN 200410096318 A CN200410096318 A CN 200410096318A CN 100344733 C CN100344733 C CN 100344733C
- Authority
- CN
- China
- Prior art keywords
- gasoline
- olefin
- reaction
- catalyst
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a method for simultaneously reducing the sulfur content and the olefinic content of gasoline. Gasoline raw materials and hydrogen gas contact a hydroisomerizing catalyst to carry out hydrodesulfurization reaction, olefin saturating reaction, olefin isomerization reaction and olefin cracking reaction. Hydrogenated oil is separated to obtain a light hydrocarbon and a gasoline fraction, and hydrogen rich gas is circularly used. The gasoline fraction is in contact with an adsorptive catalyst, and a gasoline product with low sulfur content and low olefinic content is obtained after adsorption desulfurization is carried out. The method can produce the good quality gasoline, the olefinic content and the olefinic content of which satisfy the index specification of the third class gasoline of 'World Fuel Specification', and meanwhile, the minimal loss of the octane value of the gasoline is ensured.
Description
Technical field
The invention belongs in the method that has refining hydrocarbon ils under the situation of hydrogen, more particularly, is to belong to a kind of method that reduces gasoline fraction sulphur, olefin(e) centent.
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.
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.
US6184176 discloses a kind of sorbent material production method that is used to handle FCC gasoline, and the sorbent material of producing with this method carries out adsorption desulfurize to FCC gasoline, sulfur in gasoline can be reduced to very low-level, but olefin(e) centent does not almost reduce.
WO98/53030 discloses a kind of method of the FCC of processing gasoline.First section is carried out reactions such as cracking, aromizing, alkylation with catalytically cracked gasoline under an acidic catalyst effect, then intermediate product is entered second section and carry out reactions such as hydrogenating desulfurization, denitrogenation, alkene be saturated under the Hydrobon catalyst effect.Because the aromatization of alkene and naphthenic hydrocarbon and the alkylating of aromatic hydrocarbons and alkene make that aromaticity content increases in the product.
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 that reduces gasoline sulfur, olefin(e) centent simultaneously, to produce all premiums of satisfied " world's fuel oil standard " III class gasoline index specification of sulphur, olefin(e) centent.
Method provided by the invention comprises:
(1), gasoline stocks, hydrogen contact with hydroisomerization catalyst, carries out that hydrogenating desulfurization, alkene are saturated, olefin isomerization, cracking of olefins reaction, separates hydrogenated oil and obtain lighter hydrocarbons and gasoline fraction, hydrogen-rich gas recycles;
(2), the described gasoline fraction of step (1) contacts with adsorptive catalyst, carries out obtaining behind the adsorption desulfurize gasoline products of low-sulfur, olefin(e) centent.
The present invention produces the premium that sulphur, olefin(e) centent all satisfy " world's fuel oil standard " III class gasoline index specification, guarantees the loss of octane number minimum of gasoline simultaneously.
Description of drawings
Accompanying drawing is the method synoptic diagram that reduces gasoline sulfur, olefin(e) centent simultaneously provided by the invention.
Embodiment
Method provided by the invention is so concrete enforcement:
Gasoline stocks enters the fixed bed hydrogenation isomerizing reactor after feedstock pump boosts, contact with hydroisomerization catalyst, enter high-pressure separator behind the serial reactions such as, olefin isomerization saturated, cracking of olefins, mix with new hydrogen from the isolated hydrogen rich stream of high-pressure separator and deliver to hydroisomerization reactor by recycle compressor and circulate through hydrogenating desulfurization, alkene.The liquid phase intermediate product that obtains from high-pressure separator enters stabilizer tower, and the stabilizer tower bottom stream enters the adsorption desulfurize reactor, contacts with adsorptive catalyst to carry out adsorption desulfurize, and adsorption desulfurize reactor outlet effluent obtains the gasoline products of low-sulfur, olefin(e) centent.
The used gasoline stocks of the present invention is selected from one or more the mixture in FCC gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline and the pressure gasoline.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, second step, the further adsorption desulfurize of intermediates.Raw material of the present invention is applicable to the gasoline fraction oil of high-sulfur high olefin content, and according to the variation of the quality index of stock oil character such as olefin(e) centent, sulphur content, boiling range scope etc. and product, the present invention has certain flexibility of operation.
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 0.5～4.0h
-1, hydrogen-oil ratio 100～1000v/v; The second step process condition is: reaction pressure 0.1～1.0MPa, 40～400 ℃ of temperature of reaction, liquid hourly space velocity 1.0～10.0h
-1
The hydroisomerization catalyst of the first step is VIII family base metal and the optional group vib non-precious metal catalyst that loads on the molecular sieve carrier, described VIII family base metal is selected from nickel or/and cobalt, described group vib base metal is selected from molybdenum or/and tungsten, one or more the mixture of described molecular screening in faujusite, Beta molecular sieve, ZSM-5 molecular sieve and SAPO-11, carrier is an aluminum oxide.
The adsorptive catalyst in second step is the transition-metal catalyst that loads on the molecular sieve carrier, and described transition metal is cobalt and optional nickel or/and molybdenum, and wherein cobalt is necessary component, nickel or/and molybdenum for selecting component; Described molecular screening is from NaY, ZSM-5, γ-Al
2O
3, one or more the mixture in ZS-01 and the gac.
Below in conjunction with accompanying drawing method provided by the present invention is further detailed.
Accompanying drawing is the method synoptic diagram that reduces gasoline sulfur, olefin(e) centent simultaneously 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 17 mixes, after pipeline 4 enters interchanger 5 and the reactor 9 outlet effluent heat exchange from pipeline 10, again after pipeline 6 enters process furnace 7 preheatings, enter fixed bed hydrogenation isomerizing reactor 9 through pipeline 8, 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 9 is after pipeline 10 enters interchanger 5 and mixture heat exchange from the raw material of pipeline 4 and hydrogen, enter high-pressure separator 12 through pipeline 11, in high-pressure separator 12, be divided into two bursts of logistics, wherein one is a hydrogen rich stream, wherein be mainly hydrogen, comprise partial vulcanization hydrogen simultaneously, ammonia and lighter hydrocarbons.This hydrogen rich stream after pipeline 13 enters recycle compressor 14 compression, through pipeline 15 with mix from the additional fresh hydrogen of pipeline 16 after, loop back reactor 9 through pipeline 17, pipeline 4, interchanger 5, pipeline 6, process furnace 7, pipeline 8 successively.Another burst logistics of high-pressure separator 12 then enters follow-up stable system 19 through pipeline 18, and the logistics of coming out from stable system 19 tops is lighter hydrocarbons, and these lighter hydrocarbons are drawn through pipeline 20.The logistics of coming out from stable system 19 bottoms enters adsorption desulfurize reactor 22 through pipeline 21, and gasoline products is drawn through pipeline 23.
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, adsorption desulfurize, produce all premiums (sulphur, olefin(e) centent are respectively less than 30ppm, 10v%) of satisfied " world's fuel oil standard " III class gasoline index specification of sulphur, olefin(e) centent, guarantee the loss of octane number minimum of gasoline simultaneously, general 2 units of anti-knock index (RON+MON)/2 loss.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.
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 10.0v% in the gasoline products, anti-knock index lost up to 8.9 units.
The used raw material A of the used raw material of present embodiment and Comparative Examples is identical.Raw material A successively with catalyzer RIDOS-1 and sorbent material (wherein sorbent material is carrier with ZS-01, carrying metal Co).Hydroisomerizing, adsorption desulfurize are carried out in contact 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 " world's fuel oil standard " III class gasoline index specification, sulphur content is 9ppm in the product, desulfurization degree is greater than 99.0m%, olefin(e) centent drops to 9.5v% from 38.7v%, and the anti-knock index loss only is 1.8 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 sorbent material (sorbent used with embodiment 1 in the present embodiment) with catalyzer RIDOS-1 successively, carries out hydroisomerizing, adsorption desulfurize 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 " world's fuel oil standard " III class gasoline index specification, sulphur content is less than 10ppm in the product, desulfurization degree is greater than 99.0m%, olefin(e) centent drops to 9.2v% from 38.6v%, and the anti-knock index loss only is 1.7 units.
Table 1
| Raw material A | Raw material B | |
| Density (20 ℃), g/cm 3 | 0.7252 | 0.7100 |
| Sulphur content, ppm | 1400 | 1400 |
| Olefin(e) centent, v% | 38.7 | 38.6 |
| Boiling range, ℃ | ||
| Initial boiling point | 34 | 34 |
| 10％ | 52 | 44 |
| 50％ | 94 | 84 |
| Final boiling point | 186 | 196 |
| Anti-knock index | 86.5 | 85.0 |
Table 2
| | Embodiment | 1 | | |
| Processing condition | ||||
| Hydroisomerizing | ||||
| The hydrogen dividing potential drop, MPa | 3.2 | 3.2 | 3.2 | |
| Temperature of reaction, ℃ | 230 | 370 | 370 | |
| Liquid hourly space velocity, h -1 | 2.0 | 2.0 | 2.0 | |
| Hydrogen-oil ratio, Nm 3/m 3 | 500 | 500 | 500 | |
| Adsorption desulfurize | ||||
| Reaction pressure, MPa | - | 0.2 | 0.2 | |
| Temperature of reaction, ℃ | - | 370 | 370 | |
| Liquid hourly space velocity, h -1 | - | 8.0 | 8.0 | |
| Product property | ||||
| Density (20 ℃), g/cm 3 | 0.7200 | 0.7286 | 0.7135 | |
| Sulphur content, ppm | - | 9 | ＜10 | |
| Olefin(e) centent, v% | 10.0 | 9.5 | 9.4 | |
| The anti-knock index loss | 8.9 | 1.8 | 1.7 | |
| Desulfurization degree, m% | - | ＞99.0 | ＞99.0 |
Claims (3)
1, a kind of method that reduces gasoline sulfur, olefin(e) centent simultaneously is characterized in that this method comprises:
(1), gasoline stocks, hydrogen contact with hydroisomerization catalyst, carries out that hydrogenating desulfurization, alkene are saturated, olefin isomerization, cracking of olefins reaction, separates hydrogenated oil and obtain lighter hydrocarbons and gasoline fraction, hydrogen-rich gas recycles; Described hydroisomerization catalyst is VIII family base metal and the optional group vib non-precious metal catalyst that loads on the molecular sieve carrier, described VIII family base metal is selected from nickel or/and cobalt, described group vib base metal is selected from molybdenum or/and tungsten, one or more the mixture of described molecular screening in faujusite, Beta molecular sieve, ZSM-5 molecular sieve and SAPO-11;
(2), the described gasoline fraction of step (1) contacts with adsorptive catalyst, carry out obtaining behind the adsorption desulfurize gasoline products of low-sulfur, olefin(e) centent, described adsorptive catalyst is the transition-metal catalyst that loads on the molecular sieve carrier, described transition metal is cobalt and optional nickel or/and molybdenum, and described molecular screening is from NaY, ZSM-5, γ-Al
2O
3, one or more the mixture in ZS-01 and the gac.
2,, it is characterized in that described gasoline stocks is selected from one or more the mixture in catalytically cracked gasoline, catalytic cracking gasoline, straight-run spirit, coker gasoline, pyrolysis gasoline and the pressure gasoline according to the method for claim 1.
3,, it is characterized in that step (1) processing condition are: hydrogen dividing potential drop 1.0～4.0MPa, 200～460 ℃ of temperature of reaction, liquid hourly space velocity 0.5～4.0h according to the method for claim 1
-1, hydrogen-oil ratio 100～1000v/v; Step (2) processing condition are: reaction pressure 0.1～1.0MPa, 40～400 ℃ of temperature of reaction, liquid hourly space velocity 1.0～10.0h
-1
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100963180A CN100344733C (en) | 2004-11-30 | 2004-11-30 | Method for simultanesusly reducing sulfur and olefine content in gasoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100963180A CN100344733C (en) | 2004-11-30 | 2004-11-30 | Method for simultanesusly reducing sulfur and olefine content in gasoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1782034A CN1782034A (en) | 2006-06-07 |
| CN100344733C true CN100344733C (en) | 2007-10-24 |
Family
ID=36772658
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004100963180A Active CN100344733C (en) | 2004-11-30 | 2004-11-30 | Method for simultanesusly reducing sulfur and olefine content in gasoline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100344733C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113126B (en) * | 2006-07-26 | 2010-05-12 | 李莉 | Olefin-containing lighter hydrocarbons catalytic hydrogenation method |
| CN101134914B (en) * | 2006-08-31 | 2012-02-15 | 中国石油化工股份有限公司 | Catalytic hydroprocessing adsorbing desulfurization for hydrocarbon oil in fixed bed reactor |
| CN101173191B (en) * | 2006-11-01 | 2010-12-01 | 中国石油化工股份有限公司 | Method for producing lubricating oil basic oil |
| CN101492609B (en) * | 2008-01-23 | 2012-09-12 | 中国石油化工股份有限公司 | Method for deep desulfurization olefin hydrocarbon reduction of gasoline |
| CN103666559B (en) * | 2012-09-05 | 2016-03-23 | 中国科学院大连化学物理研究所 | A kind of FCC gasoline ultra-deep desulfurization combined method |
| CN103834439B (en) * | 2012-11-23 | 2015-09-30 | 中国海洋石油总公司 | A kind of method of deep hydrodesulfurizationof |
| CN103834438B (en) * | 2012-11-23 | 2015-09-30 | 中国海洋石油总公司 | A kind of processing method of hydrogenating desulfurization |
| CN105435836B (en) * | 2014-08-29 | 2018-07-31 | 中国石油化工股份有限公司 | A kind of hydrocracking catalyst and its preparation and application |
| CN104388118B (en) * | 2014-11-24 | 2017-01-04 | 湖南省馨盛能源开发有限责任公司 | The technological process of producing diesel by coal tar |
| US9683183B2 (en) | 2015-02-04 | 2017-06-20 | China University of Petroleum—Beijing | Method for deep desulfurization of gasoline |
| WO2016123861A1 (en) * | 2015-02-04 | 2016-08-11 | 中国石油大学(北京) | Method for upgrading catalytic cracking gasoline |
| WO2016123860A1 (en) * | 2015-02-04 | 2016-08-11 | 中国石油大学(北京) | Gasoline deep desulfurization method |
| CN108865261A (en) * | 2018-07-20 | 2018-11-23 | 北京欧美中科学技术研究院 | A kind of deep gasoline desulfurization device adopting |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399258A (en) * | 1991-08-15 | 1995-03-21 | Mobil Oil Corporation | Hydrocarbon upgrading process |
| US6184176B1 (en) * | 1999-08-25 | 2001-02-06 | Phillips Petroleum Company | Process for the production of a sulfur sorbent |
| CN1465666A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Method of heavily desulfurating and reducing olefinic hydrocarbon for gasoline |
-
2004
- 2004-11-30 CN CNB2004100963180A patent/CN100344733C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5399258A (en) * | 1991-08-15 | 1995-03-21 | Mobil Oil Corporation | Hydrocarbon upgrading process |
| US6184176B1 (en) * | 1999-08-25 | 2001-02-06 | Phillips Petroleum Company | Process for the production of a sulfur sorbent |
| CN1465666A (en) * | 2002-06-27 | 2004-01-07 | 中国石油化工股份有限公司 | Method of heavily desulfurating and reducing olefinic hydrocarbon for gasoline |
Non-Patent Citations (1)
| Title |
|---|
| "生产低硫低烯烃汽油的RIDOS技术" 李大东，等，中国工程科学，第vol.6卷第no.4期 2004 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1782034A (en) | 2006-06-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1224679C (en) | Method for producing low sulfur gasoline | |
| Song | An overview of new approaches to deep desulfurization for ultra-clean gasoline, diesel fuel and jet fuel | |
| CN103627435B (en) | FCC gasoline is to the selective hydrodesulfurization lower than 10 PPM sulphur | |
| CN101368111B (en) | Hydrogenation modification method for catalytically cracked gasoline | |
| CN102311795A (en) | Hydrogenation method for producing high-octane gasoline components by diesel oil raw material | |
| CN100344733C (en) | Method for simultanesusly reducing sulfur and olefine content in gasoline | |
| CN1896192A (en) | Two-way combined process of wax-oil hydrogenation treatment and catalytic cracking | |
| CN1171976C (en) | Combined hydrogenation method of producing diesel oil with high cetane number and low solidifying point | |
| CN1912063A (en) | Method of producing catalytic reforming raw material | |
| CN102041086A (en) | Selective hydrodesulfurization method for high-sulfur high-olefin catalytic gasoline | |
| CN1208436C (en) | Method of heavily desulfurating and reducing olefinic hydrocarbon for gasoline | |
| CN109988650B (en) | Hydrogenation modification and hydrofining combined method for poor diesel oil | |
| CN1912062A (en) | Hydrogenation method for producing catalytic reforming raw material | |
| CN1224675C (en) | Method for producing sweet gasoline | |
| CN1234815C (en) | Method of gasoline desulfurization | |
| CN109988643B (en) | Hydrogenation modification and hydrofining combined process for poor diesel oil | |
| CN109988645B (en) | Hydrogenation modification and hydrofining combined process for inferior diesel oil | |
| CN104560165A (en) | Method for reducing content of sulphur in gasoline | |
| CN1261544C (en) | Medium pressure hydrogenation method for maximumly producing high quality diesel fuel | |
| CN102199448A (en) | Process method for reducing olefins by hydrogen desulfurization of catalytic gasoline | |
| CN109988635B (en) | Hydrotreatment and hydrocracking combined process | |
| CN109988625B (en) | Hydrofining and hydrocracking combined process | |
| CN1313576C (en) | Process for hydrogenating treatment of foulty gasoline | |
| CN1313575C (en) | Process for hydrogenating modifying faulty gasoline | |
| CN1727448A (en) | Method for rectifying qualities of fractions of diesel oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |