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CN102634370B - Gasoline hydro-upgrading method - Google Patents

Gasoline hydro-upgrading method Download PDF

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CN102634370B
CN102634370B CN201110035565.XA CN201110035565A CN102634370B CN 102634370 B CN102634370 B CN 102634370B CN 201110035565 A CN201110035565 A CN 201110035565A CN 102634370 B CN102634370 B CN 102634370B
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gasoline
hydro
enters
hydrogen
desulfurization
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CN102634370A (en
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张学军
兰玲
许延
鞠雅娜
袁晓亮
侯远东
孙洪磊
钟海军
陈烈杭
吴平易
赵秦峰
马健波
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Petrochina Co Ltd
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Abstract

The invention relates to a method for gasoline hydrogenation modification; gasoline raw materials are firstly mixed with hydrogen and enter a catalytic distillation tower to remove diene, and then gasoline is cut into light and heavy gasoline components; the light gasoline coming out of the top of the catalytic distillation tower is directly used as a clean gasoline blending component, the heavy gasoline coming out of the bottom of the catalytic distillation tower firstly enters a hydro-upgrading reactor for aromatization, isomerization and other reactions, then enters a hydro-desulfurization reactor for supplementary refining, the material coming out of the hydro-desulfurization reactor is cooled and then enters a product separator for gas-liquid separation, the hydrogen coming out of the gas-liquid separator is recycled after desulfurization treatment, and the liquid phase product enters a desulfurization alcohol tower for further reducing the mercaptan content of the gasoline and then is mixed with the light gasoline to obtain a hydro-upgrading gasoline product; the method provided by the invention can not only greatly reduce the contents of sulfur and olefin in the gasoline, but also reduce the octane number loss brought by the modification process.

Description

A kind of method of gasoline hydrogenation modifying
Technical field
The present invention relates to a kind of method of the secondary processing of gasoline hydro-upgradings such as hydrogenation modification method of inferior patrol, particularly catalytically cracked gasoline.
Background technology
In recent years, be protection of the environment, countries in the world have proposed stricter restriction to the composition of motor spirit, to reduce the discharge of objectionable impurities.Beijing has carried out the provincial standard DB11/238-2007 of motor spirit Beijing on January 1st, 2008, and standard regulation vehicle gasoline and sulfur content in vehicle gasoline is not more than 0.005% (m/m), and olefin(e) centent is not more than 30%.Estimate that Beijing will implement state V standard in 2012, regulation vehicle gasoline and sulfur content in vehicle gasoline is not more than 0.001% (m/m), and olefin(e) centent is not more than 25%.In China's motor spirit, the ratio of catalytically cracked gasoline has accounted for more than 80%, is alkene and sulfide main source in gasoline.Therefore the sulphur content that, how to reduce catalytic gasoline is to improve the key of China's motor spirit quality.
Catalyzed gasoline hydrogenation desulfurization technology is mainly divided two large classes both at home and abroad at present.One class is selective hydrodesulfurization technology: by catalyst modification, suppress the olefin saturated activity of catalyzer, avoid alkene by too much saturated in hydrogenating desulfurization, reduce the loss of octane number of hydrogenation process.Another kind of technology is catalytic gasoline modification technology: conventional hydrogenation catalyst is used in hydrogenating desulfurization, then by isomerization, aromizing, cracking reaction, hydrogenating desulfurization gasoline is processed, improved the octane value of gasoline to make up the loss of octane number in hydrodesulfurization process.
ZL200410020932 patent discloses a kind of hydrogenation modification method of inferior patrol.The method is the processing method that alkene falls in a kind of full cut FCC gasoline hydrodesulfurizationmethod.Under the condition that hydrogen exists and temperature raises gradually, contact with three kinds of catalyzer, form three reaction zones.The first reaction zone temperature is lower, uses Hydrobon catalyst, mainly removes the diolefin in gasoline; Second, third reaction zone temperature is high, and gasoline reforming catalyst is used in second reaction zone, comprises the upgrading reaction of aromizing, isomerization and benzene alkylation reaction, improves the octane value of gasoline, improves quality product; Catalyst for selectively hydrodesulfurizing is used in the 3rd reaction zone, removes to greatest extent organic sulfide in oil.It is charging that the method adopts full cut catalytic gasoline, and loss of octane number is larger.
ZL200410060574 patent discloses a kind of inferior patrol hydrogenation modifying process.Its technological process is: feed gasoline is cut into lighting end and last running at 60~90 ℃, wherein last running elder generation and hydrogen mix, again with Hydrobon catalyst contact reacts, reacted effluent contacts and carries out aromatization modification reaction with aromatization modification catalyzer again, obtains high-octane rating low-sulphur oil cut; Heavy naphtha after upgrading mixes with lighting end or through the pretreated lighting end of mercaptan removal again, obtains product gasoline.This patent need to adopt the method for soda finishing mercaptan removal, can cause the discharge of the disagreeableness alkaline residue of environment.
ZL200510090501 patent discloses a kind of method of gasoline hydrogenation modifying.Gasoline stocks is cut into light gasoline fraction and heavy naphtha, and light gasoline fraction removes mercaptan wherein through alkali cleaning refining desulfurization alcohol; Heavy gasoline cut contacts with catalyst for hydro-upgrading together and carries out hydrogenating desulfurization and hydro-upgrading reaction with hydrogen, and described catalyst for hydro-upgrading is a kind of catalyzer by zeolite and alumina composite shaping carrier load non-noble metal components.The method is used a kind of catalyst for hydro-upgrading, and the functions such as isomerization, cracking, desulfurization, denitrogenation, olefin saturated complete on same catalyzer.This patent also needs to adopt the method for soda finishing mercaptan removal, can cause the discharge of the disagreeableness alkaline residue of environment.
ZL200410102818 patent discloses a kind of gasoline modifying method.Comprise the following steps: a) under isomerisation of olefin processing condition, gasoline fraction oil is contacted with olefin skeletal isomerization catalyzer; B), under hydrodesulfurization condition, step reaction effluent a) is contacted with Hydrobon catalyst.This method mainly adopts the method for isomerization upgrading, and liquid product yield is lower.
US5411658 discloses a kind of method of gasoline upgrading, and the method, by after catalytic gasoline hydrofining, directly enters second segment reactor and carries out octane value recovering.This patent hydrofining adopts traditional Hydrobon catalyst, and loss of octane number is larger.
Summary of the invention
The object of the invention is to provide on the basis of existing technology a kind of method of inferior patrol hydro-upgrading.
Gasoline stocks mix with hydrogen first enter a catalytic distillation tower remove diolefine and by gasoline cut into gently, two components of heavy petrol.From catalytic distillation column overhead petroleum naphtha out, directly as clean gasoline blend component, from heavy petrol out at the bottom of tower and hydrogen mix, be introduced into a hydro-upgrading reactor, and then enter a hydrodesulphurisatioreactors reactors and carry out post-refining.From hydrodesulphurisatioreactors reactors material is out cooling, enters product separator and carry out gas-liquid separation.From gas-liquid separator hydrogen out, after desulfurization is processed, recycle, liquid-phase product enters after mercaptan removal tower reduces the mercaptans content in gasoline and is mixed to get reformulated gasoline product with petroleum naphtha.
The reaction conditions of above-mentioned catalytic distillation tower is: tower top pressure 0.5~2.0Mpa, 120~180 ℃ of feeding temperatures, 60~120 ℃ of tower top temperatures, 160~220 ℃ of column bottom temperatures, hydrogen to oil volume ratio 10~200.The support of the catalyst of catalytic distillation tower filling is the mixture of aluminum oxide, silicon oxide or aluminum oxide and silicon oxide, active metal is selected from one or more in VIB or VIIIB, metal oxide weight is 10%~70%, specific surface area of catalyst is 100~300m2/g, and pore volume is 0.20~0.60ml/g.
The reaction conditions of above-mentioned hydro-upgrading reactor is: hydrogen dividing potential drop 1.0~4.0Mpa, 280~450 ℃ of temperature of reaction, volume space velocity 1.0~4.0h -1, hydrogen to oil volume ratio 100~600.Catalyst for hydro-upgrading carrier is ZSM-5, Beta, SAPO molecular sieve or its mixture, by catalyst weight 100%, molecular sieve weight is 60%~90%, and metal oxide weight is 1%~10%, active metal is selected from one or more in VIB or VIIIB, and surplus is binding agent.Specific surface area of catalyst is 200~500m 2/ g, pore volume is 0.20~0.50ml/g.
The reaction conditions of above-mentioned hydrodesulphurisatioreactors reactors is: hydrogen dividing potential drop 1.0~4.0Mpa, 200~350 ℃ of temperature of reaction, volume space velocity 2.0~8.0h -1, hydrogen to oil volume ratio 100~600.Hydrodesulfurization catalyst support is the mixture of aluminum oxide, silicon oxide or aluminum oxide and silicon oxide, active metal is selected from one or more in VIB or VIIIB, by catalyst weight 100%, metal oxide weight is 10%~30%, and specific surface area of catalyst is 100~300m 2/ g, pore volume is 0.20~0.80ml/g.
The reaction conditions of above-mentioned mercaptan removal tower is: hydrogen dividing potential drop 0.5~2.0Mpa, feeding temperature 200-300 ℃, tower top temperature 180-280 ℃, column bottom temperature 250-350 ℃, hydrogen to oil volume ratio 5~50.Mercaptan-eliminating catalyst is aluminum oxide, silicon oxide or its mixture or without hydrogen exchange na-pretreated zeolite.
Gasoline hydrogenation modifying process provided by the invention mainly contains following advantage:
1, the flow process that the present invention adopts, not only reduced the olefin(e) centent in gasoline, also significantly reduce the mercaptans content in gasoline, substituted soda finishing mercaptan removal operation in patent ZL200410060574, ZL200510090501, avoided the discharge of the disagreeableness alkaline residue of environment.
2, the present invention mainly adopts aromatization modification technology, the isomerization modification technology that patent ZL200410102818 adopts relatively, and loss of octane number is little, and liquid is received high.
3, the present invention has adopted the flow process of first upgrading back end hydrogenation, and with respect to the flow process of upgrading after the first hydrogenation of the employings such as patent ZL200410060574, product aromatization rate is high, and loss of octane number is little.
4, the refining catalyst for selectively hydrodesulfurizing that adopts after the present invention, for the Hydrobon catalyst of patent ZL200510090501, US5411658 use, the loss of octane number that hydrogenation process is brought is less.
Accompanying drawing explanation
Fig. 1 is the principle flow chart of gasoline hydrogenation modifying method provided by the present invention.
Embodiment
Technical process of the present invention is: will after gasoline stocks and hydrogen mixing, enter a catalytic distillation tower, under tower top pressure 0.5~2.0Mpa, 120~180 ℃ of feeding temperatures, 60~120 ℃ of tower top temperatures, 160~220 ℃ of column bottom temperatures, hydrogen to oil volume ratio 10~200 conditions, carry out hydrogenation reaction, by the diene in catalytic gasoline saturated and by gasoline be divided into light, weigh two components.Heavy petrol enters hydro-upgrading reactor after mixing with hydrogen, at hydrogen dividing potential drop 1.0~4.0Mpa, 280~450 ℃ of temperature of reaction, volume space velocity 1.0~4.0h -1, under hydrogen to oil volume ratio 100~500 conditions, there is aromizing, isomerization reaction, follow the reactions such as desulfurization, olefin saturated simultaneously.By hydro-upgrading, olefin(e) centent, sulphur content in gasoline significantly reduce.Then hydro-upgrading reaction product enters hydrodesulphurisatioreactors reactors and carries out post-refining, at hydrogen dividing potential drop 1.0~4.0Mpa, 200~350 ℃ of temperature of reaction, volume space velocity 2.0~8.0h -1, under hydrogen to oil volume ratio 100~500 conditions, further reduce olefin(e) centent and sulfide content in gasoline.After hydrogenating desulfurization product is cooling, enters product separator separation and carry out gas-liquid separation.From gas-liquid separator hydrogen out, after processing, desulfurization recycles, liquid-phase product enters mercaptan removal tower, after hydrogen dividing potential drop 0.5~2.0Mpa, feeding temperature 200-300 ℃, tower top temperature 180-280 ℃, column bottom temperature 250-350 ℃ reaction conditions first remove the mercaptan in gasoline with fractionator overhead out petroleum naphtha be mixed to get reformulated gasoline product.
The present invention is applicable to the hydro-upgrading of inferior patrol, is mainly used in the hydro-upgrading of the secondary processing of gasoline such as catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline and pressure gasoline.
Gasoline upgrading technique of the present invention, is characterized in that adopting full distillation gasoline pre-treatment, then light, heavy petrol is separated, heavy petrol adopts the technical process of first hydro-upgrading back end hydrogenation desulfurization.
Comparative example
Take a kind of catalytically cracked gasoline as raw material, and its character is as shown in table 1.First catalytic gasoline enters catalytic distillation tower, under tower top pressure 0.75Mpa, 145 ℃ of feeding temperatures, 90 ℃ of tower top temperatures, 205 ℃ of conditions of column bottom temperature, reacts, and is cut into two components of weight gasoline simultaneously, and heavy naphtha accounts for 65% of raw material.First heavy petrol be mixed into hydrodesulphurisatioreactors reactors with hydrogen, under hydrogen dividing potential drop 1.8MPa, 252 ℃ of conditions, carries out hydrogenating desulfurization.Then enter hydro-upgrading reactor and carry out hydro-upgrading under the reaction conditions of 385 ℃ of hydrogen dividing potential drop 2.0MPa, temperature of reaction.Hydro-upgrading product is mixed to get clean gasoline product with petroleum naphtha after stabilizer tower is stable.Processing condition and generation oil nature are in Table 2.As can be seen from Table 2, product sulphur content is 66ppm, desulfurization degree 81.5%, and olefin(e) centent drops to 27.8%, octane value (RON) loss 1.1Ge unit from 48.5%.
Embodiment 1
The stock oil that embodiment 1 is used is identical with comparative example.First catalytic gasoline enters catalytic distillation tower, under tower top pressure 0.75Mpa, 145 ℃ of feeding temperatures, 90 ℃ of tower top temperatures, 205 ℃ of conditions of column bottom temperature, reacts, and is cut into two components of weight gasoline simultaneously, and heavy naphtha accounts for 65% of raw material.First heavy petrol be mixed into hydro-upgrading reactor with hydrogen, under the reaction conditions of 385 ℃ of hydrogen dividing potential drop 2.0MPa, temperature of reaction, carries out hydro-upgrading, then enters hydrodesulphurisatioreactors reactors and carry out hydrogenating desulfurization under hydrogen dividing potential drop 1.8MPa, 252 ℃ of conditions.After desulfurization, then product enters mercaptan removal tower, under hydrogen dividing potential drop 1.8Mpa, 300 ℃ of feeding temperatures, 260 ℃ of tower top temperatures, 350 ℃ of column bottom temperatures, hydrogen to oil volume ratio 50 conditions, further reduce after the mercaptans content of gasoline with fractionator overhead out petroleum naphtha be mixed to get reformulated gasoline product.Processing condition and generation oil nature are in Table 2.As can be seen from Table 2, product sulphur content is 45ppm, desulfurization degree 87.4%, and olefin(e) centent drops to 29.5%, octane value (RON) loss 0.5Ge unit from 48.5%.
Embodiment 2
The stock oil that embodiment 2 is used is identical with comparative example.First catalytic gasoline enters catalytic distillation tower and reacts under tower top pressure 0.75Mpa, 145 ℃ of feeding temperatures, 90 ℃ of tower top temperatures, 205 ℃ of conditions of column bottom temperature, is cut into two components of weight gasoline simultaneously, and heavy naphtha accounts for 65% of raw material.First heavy petrol be mixed into hydro-upgrading reactor with hydrogen, under the reaction conditions of 385 ℃ of hydrogen dividing potential drop 2.0MPa, temperature of reaction, carries out hydro-upgrading, then enters hydrodesulphurisatioreactors reactors and carry out hydrogenating desulfurization under hydrogen dividing potential drop 1.8MPa, 265 ℃ of conditions.Product introduction mercaptan removal tower after desulfurization, under hydrogen dividing potential drop 1.8Mpa, 300 ℃ of feeding temperatures, 260 ℃ of tower top temperatures, 350 ℃ of column bottom temperatures, hydrogen to oil volume ratio 50 conditions, further reduce after the mercaptans content of gasoline with fractionator overhead out petroleum naphtha be mixed to get reformulated gasoline product.Processing condition and generation oil nature are in Table 2.As can be seen from Table 2, in product, sulphur content is 20ppm, desulfurization degree 94.4%, and olefin(e) centent drops to 28.1%, octane value (RON) loss 1.1Ge unit from 48.5%.
Table 1
Material name Catalytic gasoline
Density (20 ℃), g/cm 3 0.721
Sulphur, ppm 356
Olefin(e) centent, volume % 48.5
Boiling range, ℃
Initial boiling point 36
10% 52
50% 96
Do 197
Octane value (RON) 92
Table 2
Comparative example 1 Embodiment 1 Embodiment 2
Processing condition
Catalytic distillation tower tower top pressure, MPa 0.75 0.75 0.75
Catalytic distillation tower feeding temperature, ℃ 145 145 145
Catalytic distillation tower tower top temperature, ℃ 90 90 90
Catalytic distillation tower column bottom temperature, ℃ 205 205 205
Pre-hydrogenation temperature, ℃ 160 160 90
Hydro-upgrading pressure, MPa 2.0 2.0 205
Hydro-upgrading temperature, ℃ 385 385 385
Hydrogenating desulfurization pressure, MPa 1.8 1.8 1.8
Hydrogenating desulfurization temperature, ℃ 252 252 265
Mercaptan removal column overhead pressure, MPa 1.8 1.8
Mercaptan removal tower feeding temperature, ℃ 300 300
Mercaptan removal column overhead temperature, ℃ 260 260
Mercaptan removal tower column bottom temperature, ℃ 350 350
Product property
Density, (20 ℃), g/cm 3 0.713 0.715 0.712
Sulphur content, ppm 66 45 20
Olefin(e) centent, volume % 27.8 29.5 28.1
Octane value (RON) 90.9 91.5 90.9
Loss of octane number 1.1 0.5 1.1
Desulfurization degree % 81.5 87.4 94.4

Claims (1)

1. a method for gasoline hydrogenation modifying, is characterized in that:
First catalytic gasoline enters catalytic distillation tower, under tower top pressure 0.75Mpa, 145 ℃ of feeding temperatures, 90 ℃ of tower top temperatures, 205 ℃ of conditions of column bottom temperature, reacts, and is cut into two components of weight gasoline simultaneously, and heavy naphtha accounts for 65% of raw material; First heavy petrol be mixed into hydro-upgrading reactor with hydrogen, under the reaction conditions of 385 ℃ of hydrogen dividing potential drop 2.0MPa, temperature of reaction, carries out hydro-upgrading, then enters hydrodesulphurisatioreactors reactors and carry out hydrogenating desulfurization under hydrogen dividing potential drop 1.8MPa, 252 ℃ of conditions; After desulfurization, then product enters mercaptan removal tower, under hydrogen dividing potential drop 1.8Mpa, 300 ℃ of feeding temperatures, 260 ℃ of tower top temperatures, 350 ℃ of column bottom temperatures, hydrogen to oil volume ratio 50 conditions, further reduce after the mercaptans content of gasoline with fractionator overhead out petroleum naphtha be mixed to get reformulated gasoline product; Product sulphur content is 45ppm, desulfurization degree 87.4%, and olefin(e) centent drops to 29.5% from 48.5%, and octane value RON loses 0.5Ge unit;
The character of described catalytic gasoline is: 20 ℃ of density 0.721g/cm 3, S35 6ppm, olefin(e) centent 48.5v%, 36 ℃ of initial boiling points, 10% heats up in a steamer a little 52 ℃, and 50% heats up in a steamer a little 96 ℃, does 197 ℃, and octane value RON is 92.
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CN105733672A (en) * 2014-12-11 2016-07-06 中国石油天然气股份有限公司 Combined production method of ultra-low sulfur gasoline
SG11201903082QA (en) * 2016-10-21 2019-05-30 China Petroleum & Chem Corp Process for treating gasoline

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CN1718688A (en) * 2004-07-06 2006-01-11 中国石油化工股份有限公司 Hydrogenation modification method of faulty gasoline
CN101307254A (en) * 2007-05-18 2008-11-19 中国石油化工股份有限公司 Process for producing cleaning gasoline from poor-quality gasoline
CN101845322A (en) * 2010-05-12 2010-09-29 中国石油天然气股份有限公司 Production method for reducing sulfur and olefin content in gasoline

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EP0949314B1 (en) * 1998-03-20 2006-06-14 China Petrochemical Corporation Hydrodesulfurisation of hydrocarbon oils
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CN1718688A (en) * 2004-07-06 2006-01-11 中国石油化工股份有限公司 Hydrogenation modification method of faulty gasoline
CN101307254A (en) * 2007-05-18 2008-11-19 中国石油化工股份有限公司 Process for producing cleaning gasoline from poor-quality gasoline
CN101845322A (en) * 2010-05-12 2010-09-29 中国石油天然气股份有限公司 Production method for reducing sulfur and olefin content in gasoline

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