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CN1782034A - Method for simultanesusly reducing sulfur and olefine content in gasoline - Google Patents

Method for simultanesusly reducing sulfur and olefine content in gasoline Download PDF

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CN1782034A
CN1782034A CN 200410096318 CN200410096318A CN1782034A CN 1782034 A CN1782034 A CN 1782034A CN 200410096318 CN200410096318 CN 200410096318 CN 200410096318 A CN200410096318 A CN 200410096318A CN 1782034 A CN1782034 A CN 1782034A
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gasoline
olefin
hydrogen
molecular sieve
sulfur
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CN100344733C (en
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习远兵
屈锦华
胡云剑
戴立顺
卫剑
李明丰
石亚华
聂红
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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Abstract

一种同时降低汽油硫、烯烃含量的方法,汽油原料、氢气与加氢异构催化剂接触,进行加氢脱硫、烯烃饱和、烯烃异构、烯烃裂化反应,分离加氢生成油得到轻烃和汽油馏分,富氢气体循环使用;所述汽油馏分与吸附催化剂接触,进行吸附脱硫后得到低硫、烯烃含量的汽油产品。该方法生产出硫、烯烃含量均满足《世界燃油规范》III类汽油指标规格的优质汽油,同时保证汽油的辛烷值损失最小。A method for simultaneously reducing gasoline sulfur and olefin content. Gasoline raw materials and hydrogen are contacted with a hydroisomerization catalyst to perform hydrodesulfurization, olefin saturation, olefin isomerization, and olefin cracking reactions, and separate hydrogenation to generate oil to obtain light hydrocarbons and gasoline. Fraction, hydrogen-rich gas is recycled; the gasoline fraction is contacted with an adsorption catalyst, and after adsorption and desulfurization, a gasoline product with low sulfur and olefin content is obtained. The method produces high-quality gasoline whose sulfur and olefin contents meet the Class III gasoline index specifications of the "World Fuel Specifications", while ensuring the minimum loss of the octane number of the gasoline.

Description

A kind of method that reduces gasoline sulfur, olefin(e) centent simultaneously
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 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, 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 VIB or VIII family and the optional group vib non-precious metal catalyst that loads on the molecular sieve carrier, described VIII family base metal be 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 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, ZS-01, gac or one or more mixture wherein.
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.
Embodiment 1
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.
Embodiment 2
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
Comparative Examples Embodiment 1 Embodiment 2
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 (5)

1、一种同时降低汽油硫、烯烃含量的方法,其特征在于该方法包括:1. A method for simultaneously reducing gasoline sulfur and olefin content, characterized in that the method comprises: (1)、汽油原料、氢气与加氢异构催化剂接触,进行加氢脱硫、烯烃饱和、烯烃异构、烯烃裂化反应,分离加氢生成油得到轻烃和汽油馏分,富氢气体循环使用;(1) Gasoline raw materials and hydrogen are contacted with hydroisomerization catalysts for hydrodesulfurization, olefin saturation, olefin isomerization, and olefin cracking reactions, and hydrogenated oil is separated to obtain light hydrocarbons and gasoline fractions, and the hydrogen-rich gas is recycled; (2)、步骤(1)所述汽油馏分与吸附催化剂接触,进行吸附脱硫后得到低硫、烯烃含量的汽油产品。(2) The gasoline fraction described in step (1) is contacted with an adsorption catalyst to obtain a gasoline product with low sulfur content and olefin content after adsorption desulfurization. 2、按照权利要求1的方法,其特征在于所述的汽油原料选自催化裂化汽油、催化裂解汽油、直馏汽油、焦化汽油、裂解汽油、热裂化汽油或其中一种以上的混合物。2. The method according to claim 1, characterized in that the gasoline raw material is selected from catalytic cracking gasoline, catalytic cracking gasoline, straight-run gasoline, coker gasoline, pyrolysis gasoline, thermal cracking gasoline or a mixture of more than one of them. 3、按照权利要求1的方法,其特征在于步骤(1)工艺条件为:氢分压1.0~4.0MPa,反应温度200~460℃,液时空速0.5~4.0h-1,氢油比100~1000v/v;步骤(2)工艺条件为:反应压力0.1~1.0MPa,反应温度40~400℃,液时空速1.0~10.0h-13. The method according to claim 1, characterized in that the process conditions of step (1) are: hydrogen partial pressure 1.0-4.0MPa, reaction temperature 200-460°C, liquid hourly space velocity 0.5-4.0h -1 , hydrogen-oil ratio 100- 1000v/v; the process conditions of step (2) are: reaction pressure 0.1-1.0MPa, reaction temperature 40-400°C, liquid hourly space velocity 1.0-10.0h -1 . 4、按照权利要求1的方法,其特征在于步骤(1)所述的加氢异构催化剂是负载在分子筛载体上的VIB或VIII族和任选的VIB族非贵金属催化剂,所述的VIII族非贵金属选自镍或/钴,所述的VIB族非贵金属选自钼或/和钨,所述分子筛选自八面沸石、Beta分子筛、ZSM-5分子筛、SAPO-11或其中一种以上的混合物。4. The method according to claim 1, characterized in that the hydroisomerization catalyst described in step (1) is VIB or VIII group and optional VIB group non-noble metal catalyst supported on a molecular sieve carrier, and the VIII group The non-noble metal is selected from nickel or/cobalt, the VIB group non-noble metal is selected from molybdenum or/and tungsten, and the molecular sieve is selected from faujasite, Beta molecular sieve, ZSM-5 molecular sieve, SAPO-11 or one or more of them mixture. 5、按照权利要求1的方法,其特征在于步骤(2)所述的吸附催化剂是负载在分子筛载体上的过渡金属催化剂,所述的过渡金属为钴和任选的镍或/和钼,所述分子筛选自NaY、ZSM-5、γ-Al2O3、ZS-01、活性炭或其中的一种或一种以上的混合物。5, according to the method for claim 1, it is characterized in that the described adsorption catalyst of step (2) is the transition metal catalyst supported on the molecular sieve carrier, and described transition metal is cobalt and optional nickel or/and molybdenum, so The above-mentioned molecules are screened from NaY, ZSM-5, γ-Al 2 O 3 , ZS-01, activated carbon or one or more mixtures thereof.
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Cited By (13)

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CN101113126B (en) * 2006-07-26 2010-05-12 李莉 Olefin-containing lighter hydrocarbons catalytic hydrogenation method
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
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
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
CN103666559A (en) * 2012-09-05 2014-03-26 中国科学院大连化学物理研究所 Super deep desulfurization combined method for FCC (fluid catalytic cracking) gasoline
CN103834439A (en) * 2012-11-23 2014-06-04 中国海洋石油总公司 Deep hydrodesulfurization method
CN103834438A (en) * 2012-11-23 2014-06-04 中国海洋石油总公司 Hydrodesulfurization process method
CN104388118A (en) * 2014-11-24 2015-03-04 湖南省馨盛能源开发有限责任公司 Process flow for preparing diesel by using coal tar
CN105435836A (en) * 2014-08-29 2016-03-30 中国石油化工股份有限公司 Hydrocracking catalyst, and preparation method and application thereof
WO2016123860A1 (en) * 2015-02-04 2016-08-11 中国石油大学(北京) Gasoline deep desulfurization method
WO2016123861A1 (en) * 2015-02-04 2016-08-11 中国石油大学(北京) Method for upgrading catalytic cracking gasoline
US9683183B2 (en) 2015-02-04 2017-06-20 China University of Petroleum—Beijing Method for deep desulfurization of gasoline
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

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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
CN1208436C (en) * 2002-06-27 2005-06-29 中国石油化工股份有限公司 Method of heavily desulfurating and reducing olefinic hydrocarbon for gasoline

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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
CN103666559A (en) * 2012-09-05 2014-03-26 中国科学院大连化学物理研究所 Super deep desulfurization combined method for FCC (fluid catalytic cracking) 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
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
CN103834438A (en) * 2012-11-23 2014-06-04 中国海洋石油总公司 Hydrodesulfurization process method
CN103834439A (en) * 2012-11-23 2014-06-04 中国海洋石油总公司 Deep hydrodesulfurization method
CN105435836A (en) * 2014-08-29 2016-03-30 中国石油化工股份有限公司 Hydrocracking catalyst, and preparation method and application thereof
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
CN104388118A (en) * 2014-11-24 2015-03-04 湖南省馨盛能源开发有限责任公司 Process flow for preparing diesel by using coal tar
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
WO2016123860A1 (en) * 2015-02-04 2016-08-11 中国石油大学(北京) Gasoline deep desulfurization method
WO2016123861A1 (en) * 2015-02-04 2016-08-11 中国石油大学(北京) Method for upgrading catalytic cracking gasoline
US9683183B2 (en) 2015-02-04 2017-06-20 China University of Petroleum—Beijing Method for deep desulfurization of gasoline
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

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