CN102994148A - Deep desulfurization method for gasoline - Google Patents
Deep desulfurization method for gasoline Download PDFInfo
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- CN102994148A CN102994148A CN2011102734542A CN201110273454A CN102994148A CN 102994148 A CN102994148 A CN 102994148A CN 2011102734542 A CN2011102734542 A CN 2011102734542A CN 201110273454 A CN201110273454 A CN 201110273454A CN 102994148 A CN102994148 A CN 102994148A
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- 239000003502 gasoline Substances 0.000 title claims abstract description 97
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 51
- 230000023556 desulfurization Effects 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000003197 catalytic effect Effects 0.000 claims abstract description 38
- 238000004821 distillation Methods 0.000 claims abstract description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 25
- 239000001257 hydrogen Substances 0.000 claims abstract description 25
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 22
- 150000001336 alkenes Chemical class 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000029936 alkylation Effects 0.000 claims abstract description 12
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 12
- 239000002283 diesel fuel Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229930192474 thiophene Natural products 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims description 25
- 239000003208 petroleum Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- 238000005345 coagulation Methods 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 229910044991 metal oxide Inorganic materials 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000004523 catalytic cracking Methods 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 18
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 8
- 239000011593 sulfur Substances 0.000 abstract description 8
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical compound S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 abstract 1
- 230000003009 desulfurizing effect Effects 0.000 abstract 1
- 238000007710 freezing Methods 0.000 abstract 1
- 150000005673 monoalkenes Chemical class 0.000 abstract 1
- 150000004767 nitrides Chemical class 0.000 abstract 1
- 239000005864 Sulphur Substances 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 11
- 238000003889 chemical engineering Methods 0.000 description 7
- 230000009183 running Effects 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000012827 research and development Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000002152 alkylating effect Effects 0.000 description 3
- 238000005194 fractionation Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- -1 acetylene compound Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
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- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 150000003016 phosphoric acids Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000001833 catalytic reforming Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 239000012535 impurity Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
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- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
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Abstract
The invention relates to a method for deeply desulfurizing gasoline, wherein a gasoline raw material and hydrogen are mixed and enter a pre-hydrogenation reactor to hydrogenate dialkene in catalytic gasoline into mono-olefin; the pre-hydrogenation product enters a water washing tower for water washing to remove partial alkaline nitride in the gasoline, then enters a catalytic distillation tower, weight of partial thiophene sulfide in the gasoline is increased under the action of an olefin thiophene alkylation catalyst on the upper part of the catalytic distillation tower, and the gasoline is cut into three components of light gasoline, heavy gasoline and light diesel oil; the heavy gasoline component enters a selective hydrodesulfurization reactor for deep desulfurization, and a desulfurization product is mixed with light gasoline after hydrogen sulfide generated in the reaction is removed to obtain a deep-desulfurization gasoline product; the light diesel oil at the tower bottom is used as the raw material for hydrodesulfurization, or is used as a low-freezing point diesel oil blending component for blending and leaving the factory; the method of the invention can greatly reduce the sulfur content in the gasoline and simultaneously reduce the octane number loss caused by the deep desulfurization process.
Description
Technical field
The present invention relates to the method for the secondary processing of gasoline deep desulfurations such as a kind of method of deep desulfurization of gasoline, 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 discharging of objectionable impurities.Beijing has carried out the provincial standard DB11/238-2007 of motor spirit Beijing on January 1st, 2008, and the standard code 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, the 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%.The ratio of catalytically cracked gasoline has accounted for more than 80% in China's motor spirit, is alkene and sulfide main source in the gasoline.Therefore, the sulphur content that how to reduce catalytic gasoline is to improve the key of China's motor spirit quality.
The catalyzed gasoline hydrogenation desulfurization technology is mainly divided two large classes both at home and abroad at present.One class is the selective hydrodesulfurization technology: by to 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 the 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 remedy the loss of octane number in the hydrodesulfurization process.
In the catalytically cracked gasoline in the component octane value of alkene higher, be the important component part of gasoline octane rating.Alkene mainly concentrates on the petroleum naphtha section of catalytic gasoline, and cut is lighter, and olefin(e) centent is higher.Sulphur mainly concentrates on the heavy petrol section, and cut is heavier, and sulphur content is higher.In order to reduce the loss of octane number in the catalyzed gasoline hydrogenation desulfurization process, according to sulphur, the alkene characteristic distributions in cat naphtha, the hydrogenating desulfurization technology has mostly been selected the mode of catalytic gasoline weight cutting, petroleum naphtha alkaline purification, heavy petrol hydrogenation.Take producing country IV gasoline as example, select suitable cut point, the sulphur content of petroleum naphtha is in 0.0050% (m/m) behind the control alkali, then also be controlled in 0.0050% (m/m) by the sulphur content of hydrotreatment with heavy petrol, the sulphur content after weight gasoline is in harmonious proportion reaches the requirement of state IV gasoline.
Not high petroleum naphtha yield further reduces along with improving constantly of gasoline standard just can make originally, cause the quantity increase of the heavy petrol that enters hydrogenation unit, the olefin(e) centent in the heavy petrol to increase, the loss of octane number that hydrogenating desulfurization brings increases, so that greatly reduce by the necessity of weight fractionation operation minimizing hydrodesulfurization process loss of octane number.Therefore the yield that adopts some technique means to improve petroleum naphtha reduces the treatment capacity of heavy petrol and the important research direction that severity is catalyzed gasoline hydrogenation desulfurization.
CN1319644A relates to the method by sulfur-bearing raw material production low-sulphur oil.This method comprises that at least one is to the step a of diolefine and acetylene compound selective hydrogenation; At least one will be separated into from the gasoline that step a obtains the step b of three cuts; At least one is with the step C of unsaturated sulfocompound decomposition or hydrogenation; And at least one is with at least a middle runnings desulfurization and denitrogenation, carries out subsequently the steps d of catalytic reforming.
CN101265421A relates to a kind of sulfur method of hydrocarbon fractions from steam cracking effluents, comprising: a) at least one material choice hydrotreating stage; B) effluent of fractionation stage a in one or more distillation towers produces at least a C5 lighting end, is used for C6 or C6-C7 or the C6-C8 middle runnings of aromatic hydrocarbon product, is used for C7+, C8+ or the C9+ last running of gasoline products; C) at least one hydrogenating desulfurization of middle runnings and deep hydrogenation stage; D) at least one alkylation stage of C7+, C8+ or C9+ last running; E) at least one distillation stage of stage d effluent, with produce can be directly as the lighting end of low-sulphur oil, and C11+ or the C12+ last running of being rich in sulphur compound are with as middle runnings or oil fuel.
CN101225327A relates to a kind of hydrocarbon recombinant alkylating desulfurization method of catalytically cracked gasoline.The method adopts the pretreater that comprises the catalytic cracking catalytic gasoline, primary fractionator, single cut alkylation reactor, the device that the again separation column of two cut alkylation reactors and mixture forms, implement the desulfurization of catalytically cracked gasoline, it is characterized in that comprising following process: with primary fractionator catalytically cracked gasoline is divided into three cut sections, then the mid-boiling point cut is added respectively two alkylation reactors with the mixture that low boiler cut adds high boiling fraction, under the effect of acid catalyst, carry out alkylated reaction, mixing and add again separation column with a certain amount of diesel oil after the product mixing with two reactors again distills, fractionator overhead extraction sweet gasoline again, tower reactor extraction sulfur-containing diesel.
Summary of the invention
The objective of the invention is the deficiency for existing deep desulfurization of gasoline method, the method for a kind of deep desulfurization of gasoline of proposition.
The method of deep desulfurization of gasoline of the present invention: it is monoolefine with the diene hydrogenation in the catalytic gasoline that gasoline stocks and hydrogen are mixed into pre-hydrogenator; Pre-hydrogenation products enters a water wash column and washes, deviate from the part basic nitrogen compound in the gasoline, then enter a catalytic distillation tower, under the effect of catalytic distillation tower top alkene thiophene alkylation catalyzer, make the part thiophene-type sulfide weightening finish in the gasoline, simultaneously gasoline is cut into petroleum naphtha, heavy petrol, three components of solar oil; The heavy petrol component enters the selective hydrodesulfurization reactor and carries out deep desulfuration.Desulfurization product removes the gasoline products that is mixed to get deep desulfuration behind the hydrogen sulfide that generates in the reaction with petroleum naphtha; Solar oil at the bottom of the tower can be used as the raw material of hydrogenating desulfurization, also can do the mediation of low-coagulation diesel oil blend component and dispatch from the factory.Method of the present invention can reduce the sulphur content in the gasoline significantly, reduces simultaneously the loss of octane number that deep desulfurization process is brought.
The reaction conditions of above-mentioned pre-hydrogenator is: hydrogen dividing potential drop 1.0～4.0Mpa, 120～260 ℃ of temperature of reaction, volume space velocity 2.0～8.0h
-1, hydrogen to oil volume ratio 10～200.Catalyst for pre-hydrogenation can adopt the GHC-31 catalyst series of Petroleum Chemical Engineering Institute of CNPC research and development, also can use the catalyzer of the same type that to buy on the market, the carrier of such catalyzer is generally the mixture of aluminum oxide, silicon oxide or aluminum oxide and silicon oxide, reactive metal is selected from one or more among VIB or the VIIIB, metal oxide content is 10%～60%, and specific surface area of catalyst is 100～300m
2/ g, pore volume are 0.20～0.60ml/g.
The operational condition of above-mentioned catalytic distillation tower is: tower top pressure 0.3～2.0Mpa, 120～250 ℃ of feeding temperatures, 80～200 ℃ of tower top temperatures, 200～280 ℃ of column bottom temperatures; The catalyzer of catalytic distillation tower filling is generally molecular sieve an acidic catalyst, sulfonate resin class catalyzer, solid phosphoric acid class catalyzer etc., wherein preferentially selects molecular sieve catalyst or solid phosphoric acid class catalyzer;
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, and reactive metal is selected from one or more among VIB or the VIIIB, and metal oxide content is 10%～30%, and specific surface area of catalyst is 100～300m
2/ g, pore volume are 0.20～0.80ml/g.
Compared with prior art, deep desulfurization of gasoline method provided by the invention mainly contains following advantage:
1, relative patent CN1319644A etc., owing to increased the weightening finish step of thiophene-type sulfide, the yield of petroleum naphtha can increase substantially, sulphur content significantly descends, and can reduce treatment capacity and the severity of heavy petrol hydrogenation unit.Reduce the loss of octane number of deep hydrodesulfurizationof process.
2, relative CN101265421A etc., owing to adopted catalytic distillation technology, saved the again fractionation process of alkylate, investment and process cost that can the decrease device.
3, the relative pure alkylating desulfurization technology such as CN101225327A, in the method, the alkylating desulfurization technology is as the supplementary means of hydrogenating desulfurization technology, and purpose is to improve the yield of petroleum naphtha, reduces treatment capacity and the severity of heavy petrol hydrodesulfurization unit.Because mainly based on the selective hydrodesulfurization technology, the degree of depth of catalytic gasoline desulfurization has a very significant increase.
4, can be used as the raw material of hydrogenating desulfurization from the solar oil at the bottom of the catalytic distillation tower, also can make the low-coagulation diesel oil blend component, the benefit of doing like this is to improve the diesel and gasoline ratio of refinery, also help refinery's high added value winter low-coagulation diesel oil production.
Description of drawings
Fig. 1 is the synoptic diagram of gasoline deep hydrodesulphurization method provided by the present invention.
Embodiment
Processing method of the present invention is: will enter pre-hydrogenator after gasoline stocks and the hydrogen mixing, the GHC-31 catalyst series of Petroleum Chemical Engineering Institute of filling CNPC research and development in the pre-hydrogenator is at hydrogen dividing potential drop 1.0～4.0Mpa, 150～260 ℃ of temperature of reaction, volume space velocity 2.0～8.0h
-1, carry out hydrogenation reaction under hydrogen-oil ratio 10～200 conditions, the diene in the catalytic gasoline is saturated to monoolefine.Pre-hydrogenation products enters catalytic distillation tower after the water wash column washing, the GHC-41 series alkene thiophene alkylation catalyzer of catalytic distillation tower top filling Petroleum Chemical Engineering Institute research and development, under the effect of alkene thiophene alkylation catalyzer, make the part thiophene-type sulfide weightening finish in the gasoline, simultaneously gasoline is divided into petroleum naphtha, heavy petrol, three components of solar oil.The condition of catalytic distillation tower is tower top pressure 0.3～2.0Mpa, 120～250 ℃ of feeding temperatures, 80～200 ℃ of tower top temperatures, 200～280 ℃ of column bottom temperatures.From catalytic distillation tower heavy petrol out with enter hydrodesulphurisatioreactors reactors after hydrogen mixes, the GHC-11 series catalyst for selectively hydrodesulfurizing of Petroleum Chemical Engineering Institute of filling CNPC in hydrodesulphurisatioreactors reactors is at hydrogen dividing potential drop 1.0～4.0Mpa, 200～350 ℃ of temperature of reaction, volume space velocity 2.0～8.0h
-1, reduce the sulphur content in the gasoline under hydrogen to oil volume ratio 100～500 conditions, avoid as far as possible olefins hydrogenation simultaneously.Be mixed to get the deep desulfuration gasoline products with petroleum naphtha behind the lighter hydrocarbons that the hydrogenating desulfurization product dissolves and the hydrogen sulfide in removing gasoline.Solar oil at the bottom of the tower can be used as the raw material of hydrogenating desulfurization, also can make the low-coagulation diesel oil blend component.
The present invention is applicable to the deep hydrodesulfurizationof of gasoline, is mainly used in the deep hydrodesulfurizationof of the secondary processing of gasoline such as catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline and pressure gasoline.
Embodiment 1
Take a kind of catalytically cracked gasoline A as raw material, its character is as shown in table 1.The GHC-31 catalyst series of Petroleum Chemical Engineering Institute of filling CNPC research and development in the pre-hydrogenator, catalytic gasoline is first at hydrogen dividing potential drop 2.4Mpa, 150 ℃ of temperature, air speed 4.0, add hydrogen pretreatment under 10: 1 the condition of hydrogen-oil ratio, then enter water wash column washing dealkalize nitrogen, enter afterwards catalytic distillation tower, the GHC-41 series alkene thiophene alkylation catalyzer of catalytic distillation tower top filling Petroleum Chemical Engineering Institute research and development, under the effect of catalytic distillation tower top alkene thiophene alkylation catalyzer, make the part thiophene-type sulfide weightening finish in the gasoline, be divided into simultaneously petroleum naphtha, heavy petrol, three components of solar oil.The operational condition of catalytic distillation tower is: tower top pressure 0.8MPa, 150 ℃ of feeding temperatures, 110 ℃ of tower top temperatures, 220 ℃ of column bottom temperatures.After mixing, catalytic distillation tower heavy petrol, solar oil and hydrogen out enters hydrodesulphurisatioreactors reactors, the GHC-11 series catalyst for selectively hydrodesulfurizing of Petroleum Chemical Engineering Institute of filling CNPC condition under carries out hydrogenating desulfurization at hydrogen dividing potential drop 1.8MPa, air speed 4.0,265 ℃ of temperature of reaction, hydrogen-oil ratio at 200: 1 in hydrodesulphurisatioreactors reactors.After the hydrogenating desulfurization product removes the hydrogen sulfide of dissolving, be mixed to get the deep desulfuration gasoline products with petroleum naphtha.As can be seen from Table 1, after the aforesaid method processing, content of sulfur in gasoline drops to 15ppm from 310ppm, desulfurization degree 95.2%, and olefin(e) centent drops to 25.2%, 1.0 units of octane value (RON) loss from 28.6%.
Table 1 catalytic gasoline A and desulfurization product property analysis
Embodiment 2
Take a kind of catalytically cracked gasoline B as raw material, its character is as shown in table 2.Catalytic gasoline adds hydrogen pretreatment first under hydrogen dividing potential drop 2.4Mpa, 150 ℃ of temperature, air speed 4.0,10: 1 condition of hydrogen-oil ratio, then enter water wash column washing dealkalize nitrogen, enter afterwards catalytic distillation tower, under the effect of catalytic distillation tower top alkene thiophene alkylation catalyzer, make the part thiophene-type sulfide weightening finish in the gasoline, be divided into simultaneously petroleum naphtha, heavy petrol, three components of solar oil.The operational condition of catalytic distillation tower is: tower top pressure 0.8MPa, 145 ℃ of feeding temperatures, 100 ℃ of tower top temperatures, 210 ℃ of column bottom temperatures.Mix the laggard selectivity hydrodesulphurisatioreactors reactors that enters from catalytic distillation tower heavy petrol and hydrogen out, condition under carry out hydrogenating desulfurization at 200: 1 at hydrogen dividing potential drop 1.8MPa, air speed 4.0,275 ℃ of temperature of reaction, hydrogen-oil ratio.After the hydrogenating desulfurization product removes the hydrogen sulfide that dissolves in the gasoline, be mixed to get the deep desulfuration gasoline products with petroleum naphtha.Solar oil at the bottom of the tower can be used as the charging of diesel hydrotreating unit, also can be used as the mediation of low-coagulation diesel oil blend component and dispatches from the factory.As can be seen from Table 2, after the aforesaid method processing, content of sulfur in gasoline drops to 18ppm from 480ppm, desulfurization degree 96.2%, and olefin(e) centent drops to 29.2%, 1.2 units of octane value (RON) loss from 33.8%.
Table 2 catalytic gasoline B and desulfurization product property analysis
Claims (2)
1. the method for a deep desulfurization of gasoline is characterized in that:
(1) first gasoline stocks and hydrogen being mixed into pre-hydrogenator, is monoolefine with the diene hydrogenation in the catalytic gasoline in reactor; Reaction conditions is: hydrogen dividing potential drop 1.0～4.0Mpa, 120～260 ℃ of temperature of reaction, volume space velocity 2.0～8.0h
-1, hydrogen to oil volume ratio 10～200; The catalyst for pre-hydrogenation carrier is the mixture of aluminum oxide, silicon oxide or aluminum oxide and silicon oxide, and reactive metal is selected from one or more among VIB, the VIIIB, and metal oxide content is 10～60%, and specific surface area of catalyst is 100～300m
2/ g, pore volume are 0.20～0.60ml/g;
(2) pre-hydrogenation products enters catalytic distillation tower after through the water wash column washing and carries out the reaction of alkene thiophene alkylation and simultaneously gasoline is divided into petroleum naphtha, heavy petrol, three components of solar oil; The operational condition of catalytic distillation tower is: tower top pressure 0.3～2.0Mpa, 120～250 ℃ of feeding temperatures, 80～200 ℃ of tower top temperatures, 200～280 ℃ of column bottom temperatures; The catalyzer of catalytic distillation tower filling is molecular sieve an acidic catalyst, sulfonate resin class catalyzer or solid phosphoric acid catalyst;
(3) heavy naphtha and hydrogen mix the laggard selectivity hydrodesulphurisatioreactors reactors that enters; Reaction conditions 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; Catalyzer by weight 100%, carrier is the mixture of aluminum oxide, silicon oxide or aluminum oxide and silicon oxide, and reactive metal is selected from one or more among VIB, the VIIIB, and metal oxide weight is 10～30%, and specific surface area of catalyst is 100～300m
2/ g, pore volume are 0.20～0.80ml/g;
(4) remove lighter hydrocarbons and the hydrogen sulfide that dissolves the gasoline from hydrodesulphurisatioreactors reactors material out, last and petroleum naphtha is mixed to get the deep desulfuration gasoline products, and the solar oil at the bottom of the tower is as the raw material of hydrogenating desulfurization or make the low-coagulation diesel oil blend component.
2. according to the method for deep desulfurization of gasoline claimed in claim 1, it is characterized in that: described gasoline stocks is one or more the mixing oil in catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline and the pressure gasoline.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892948A (en) * | 2020-06-15 | 2020-11-06 | 新疆寰球工程公司 | Processing method for hydrogenation and octane number loss reduction of catalytically cracked gasoline |
| CN112143523A (en) * | 2019-06-27 | 2020-12-29 | 中国石油化工股份有限公司 | Pretreatment method of alkylated gasoline raw material |
| CN114763493A (en) * | 2021-01-13 | 2022-07-19 | 中国石油化工股份有限公司 | Method and system for producing gasoline blend oil by using carbon five raffinate oil |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1769388A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Hydrogenation and quality improvement method for reducing sulfur and olefin content of inferior gasoline |
| CN101597510A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | Catalytic distillation method for gasoline alkylation desulfurization |
| CN102041086A (en) * | 2011-01-17 | 2011-05-04 | 江苏佳誉信实业有限公司 | Selective hydrodesulfurization method for high-sulfur high-olefin catalytic gasoline |
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| CN1769388A (en) * | 2004-10-29 | 2006-05-10 | 中国石油化工股份有限公司 | Hydrogenation and quality improvement method for reducing sulfur and olefin content of inferior gasoline |
| CN101597510A (en) * | 2008-06-04 | 2009-12-09 | 中国石油天然气股份有限公司 | Catalytic distillation method for gasoline alkylation desulfurization |
| CN102041086A (en) * | 2011-01-17 | 2011-05-04 | 江苏佳誉信实业有限公司 | Selective hydrodesulfurization method for high-sulfur high-olefin catalytic gasoline |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112143523A (en) * | 2019-06-27 | 2020-12-29 | 中国石油化工股份有限公司 | Pretreatment method of alkylated gasoline raw material |
| CN112143523B (en) * | 2019-06-27 | 2024-06-11 | 中国石油化工股份有限公司 | Pretreatment method of alkylation gasoline raw material |
| CN111892948A (en) * | 2020-06-15 | 2020-11-06 | 新疆寰球工程公司 | Processing method for hydrogenation and octane number loss reduction of catalytically cracked gasoline |
| CN114763493A (en) * | 2021-01-13 | 2022-07-19 | 中国石油化工股份有限公司 | Method and system for producing gasoline blend oil by using carbon five raffinate oil |
| CN114763493B (en) * | 2021-01-13 | 2024-01-12 | 中国石油化工股份有限公司 | Method and system for producing gasoline blend oil by using carbon five raffinate oil |
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