CN102994148B - Deep desulfurization method for gasoline - Google Patents
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- CN102994148B CN102994148B CN201110273454.2A CN201110273454A CN102994148B CN 102994148 B CN102994148 B CN 102994148B CN 201110273454 A CN201110273454 A CN 201110273454A CN 102994148 B CN102994148 B CN 102994148B
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- 239000003502 gasoline Substances 0.000 title claims abstract description 98
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 52
- 230000023556 desulfurization Effects 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 34
- 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 23
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 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
- 239000000203 mixture Substances 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
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- 229930192474 thiophene Natural products 0.000 claims abstract description 8
- 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
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 150000004767 nitrides Chemical class 0.000 abstract description 2
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical compound S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 abstract 1
- 238000007710 freezing Methods 0.000 abstract 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 150000005673 monoalkenes 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 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000012827 research and development 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
- 239000012141 concentrate Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 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
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 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
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification 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 deep desulfurization of gasoline, which comprises the following steps: mixing a gasoline raw material and hydrogen, feeding the mixture into a pre-hydrogenation reactor, and hydrogenating dialkene in the 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, the composition of countries in the world to motor spirit proposes stricter restriction, to reduce the discharge of objectionable impurities.Beijing has carried out motor spirit Beijing provincial standard DB11/238-2007 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 how reducing catalytic gasoline improves the key of China's motor spirit quality.
Catalyzed gasoline hydrogenation desulfurization technology mainly divides two large classes both at home and abroad at present.One class is selective hydrodesulfurization technology: by catalyst modification, suppress the olefin saturated of catalyzer active, avoid alkene by too much saturated, reduce the loss of octane number of hydrogenation process while hydrogenating desulfurization.Another kind of technology is catalytic gasoline modification technology: hydrogenating desulfurization uses conventional hydrogenation catalyst, then by isomerization, aromizing, cracking reaction, hydrogenating desulfurization gasoline is processed, improve the octane value of gasoline to make up the loss of octane number in hydrodesulfurization process.
In catalytically cracked gasoline, in component, the octane value of alkene is higher, is 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 heavy petrol section, and cut is heavier, and sulphur content is higher.In order to reduce the loss of octane number in catalyzed gasoline hydrogenation desulfurization process, according to sulphur, the alkene characteristic distributions in cat naphtha, hydrogenating desulfurization technology mostly have selected the mode of the cutting of catalytic gasoline weight, petroleum naphtha alkaline purification, heavy petrol hydrogenation.For producing country IV gasoline, select suitable cut point, after control alkali, the sulphur content of petroleum naphtha is within 0.0050% (m/m), then by hydrotreatment, the sulphur content of heavy petrol is also controlled, within 0.0050% (m/m), to make the sulphur content after weight gasoline blending reach the requirement of state IV gasoline.
Along with improving constantly of gasoline standard can make originally just not high petroleum naphtha yield reduce further, cause that the quantity of the heavy petrol entering hydrogenation unit increases, olefin(e) centent in heavy petrol increases, the loss of octane number that hydrogenating desulfurization brings increases, and the necessity being reduced hydrodesulfurization process loss of octane number by weight fractionation operation is greatly reduced.Therefore the yield adopting some technique means to improve petroleum naphtha reduces the important research direction that the treatment capacity of heavy petrol and severity are catalyzed gasoline hydrogenation desulfurizations.
CN1319644A relates to the method by sulfur-bearing raw material production low-sulphur oil.This method comprises at least one step a to diolefine and acetylene compound selective hydrogenation; The gasoline obtained from step a is separated into the step b of three cuts by least one; Unsaturated sulfocompound decomposes or the step C of hydrogenation by least one; And at least one is by least one middle runnings desulfurization and denitrogenation, carry out the steps d of catalytic reforming subsequently.
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 tower, produces at least one C5 lighting end, for C6 or C6-C7 of aromatic hydrocarbon product or C6-C8 middle runnings, for C7+, C8+ or C9+ last running of gasoline products; C) at least one hydrogenating desulfurization of middle runnings and the 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, to produce the lighting end that directly can be used as low-sulphur oil, and C11+ or the C12+ last running of sulphur compound is rich in, to be used 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 comprising catalytic cracking catalytic gasoline, primary fractionator, single cut alkylation reactor, the device of the composition of separation column again of two cut alkylation reactor and mixture, 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 fraction section, then the mixture that intermediate boiling fraction adds high boiling fraction with low boiler cut is added two alkylation reactors respectively, alkylated reaction is carried out under the effect of acid catalyst, distill mixing with a certain amount of diesel oil and add separation column again after the mixing of the product of two reactors again, fractionator overhead extraction sweet gasoline again, tower reactor extraction sulfur-containing diesel.
Summary of the invention
The object 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 that gasoline stocks and hydrogen are mixed into pre-hydrogenator by the diene hydrogenation in catalytic gasoline; Pre-hydrogenation products enters a water wash column and washes, deviate from the partial alkaline nitride in gasoline, then a catalytic distillation tower is entered, under the effect of catalytic distillation tower top alkene thiophene alkylation catalyzer, make the part thiophene-type sulfide in gasoline increase weight, gasoline is cut into petroleum naphtha, heavy petrol, solar oil three components simultaneously; Heavy gasoline components enters selective hydrodesulfurization reactor and carries out deep desulfuration.Be mixed to get the gasoline products of deep desulfuration with petroleum naphtha after desulfurization product removes the hydrogen sulfide generated in reaction; Solar oil at the bottom of tower as the raw material of hydrogenating desulfurization, also can be done 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 gasoline significantly, reduces the loss of octane number that deep desulfurization process is brought simultaneously.
The reaction conditions of above-mentioned pre-hydrogenator is: hydrogen dividing potential drop 1.0 ~ 4.0Mpa, temperature of reaction 120 ~ 260 DEG C, volume space velocity 2.0 ~ 8.0h
-1, hydrogen to oil volume ratio 10 ~ 200.The GHC-31 catalyst series that catalyst for pre-hydrogenation can adopt Petroleum Chemical Engineering Institute of CNPC to research and develop, also the catalyzer of the same type that market can be bought can be used, the carrier of such catalyzer is generally 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 content is 10% ~ 60%, and specific surface area of catalyst is 100 ~ 300m
2/ g, pore volume is 0.20 ~ 0.60ml/g.
The operational condition of above-mentioned catalytic distillation tower is: tower top pressure 0.3 ~ 2.0Mpa, feeding temperature 120 ~ 250 DEG C, tower top temperature 80 ~ 200 DEG C, column bottom temperature 200 ~ 280 DEG C; 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 prioritizing selection 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, temperature of reaction 200 ~ 350 DEG C, 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 active metal is selected from one or more in VIB or VIIIB, and metal oxide content is 10% ~ 30%, and specific surface area of catalyst is 100 ~ 300m
2/ g, pore volume is 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 adding the weightening finish step of thiophene-type sulfide, the yield of petroleum naphtha can increase substantially, and sulphur content significantly declines, 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 have employed catalytic distillation technology, eliminate the fractionation process again of alkylate, significantly can reduce investment and the process cost of device.
3, the relative pure alkylating desulfurization technology such as CN101225327A, in the method, alkylating desulfurization technology is as the supplementary means of hydrogenating desulfurization technology, and object improves the yield of petroleum naphtha, reduces treatment capacity and the severity of heavy petrol hydrodesulfurization unit.Due to mainly based on selective hydrodesulfurization technology, the degree of depth of catalytic gasoline desulfurization has a very significant increase.
4, as the raw material of hydrogenating desulfurization, also can make low-coagulation diesel oil blend component from the solar oil at the bottom of catalytic distillation tower, the benefit done like this to improve the diesel and gasoline ratio of refinery, also contribute to refinery's high added value winter low-coagulation diesel oil production.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of gasoline deep hydrodesulphurization method provided by the present invention.
Embodiment
Processing method of the present invention is: enter pre-hydrogenator by after gasoline stocks and hydrogen mixing, the GHC-31 catalyst series of Petroleum Chemical Engineering Institute of CNPC research and development is loaded, at hydrogen dividing potential drop 1.0 ~ 4.0Mpa, temperature of reaction 150 ~ 260 DEG C, volume space velocity 2.0 ~ 8.0h in pre-hydrogenator
-1, carry out hydrogenation reaction under hydrogen-oil ratio 10 ~ 200 condition, the diene in catalytic gasoline is saturated to monoolefine.Pre-hydrogenation products enters catalytic distillation tower after 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 in gasoline increase weight, gasoline is divided into petroleum naphtha, heavy petrol, solar oil three components simultaneously.The condition of catalytic distillation tower is tower top pressure 0.3 ~ 2.0Mpa, feeding temperature 120 ~ 250 DEG C, tower top temperature 80 ~ 200 DEG C, column bottom temperature 200 ~ 280 DEG C.Hydrodesulphurisatioreactors reactors is entered after catalytic distillation tower heavy petrol out mixes with hydrogen, the GHC-11 optional series Hydrobon catalyst of Petroleum Chemical Engineering Institute of CNPC is loaded, at hydrogen dividing potential drop 1.0 ~ 4.0Mpa, temperature of reaction 200 ~ 350 DEG C, volume space velocity 2.0 ~ 8.0h in hydrodesulphurisatioreactors reactors
-1, the sulphur content reduced under hydrogen to oil volume ratio 100 ~ 500 condition in gasoline, avoid olefins hydrogenation as far as possible simultaneously.Hydrogenating desulfurization product is mixed to get deep desulfuration gasoline products with petroleum naphtha after removing the lighter hydrocarbons and hydrogen sulfide dissolved in gasoline.Solar oil at the bottom of tower as the raw material of hydrogenating desulfurization, also can make 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
With a kind of catalytically cracked gasoline A for raw material, its character is as shown in table 1.The GHC-31 catalyst series of Petroleum Chemical Engineering Institute of CNPC research and development is loaded in pre-hydrogenator, catalytic gasoline is first at hydrogen dividing potential drop 2.4Mpa, temperature 150 DEG C, air speed 4.0, weighted BMO spaces is carried out under the condition of hydrogen-oil ratio 10: 1, then water wash column washing dealkalize nitrogen is entered, enter catalytic distillation tower afterwards, 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 in gasoline increase weight, be divided into petroleum naphtha simultaneously, heavy petrol, solar oil three components.The operational condition of catalytic distillation tower is: tower top pressure 0.8MPa, feeding temperature 150 DEG C, tower top temperature 110 DEG C, column bottom temperature 220 DEG C.From catalytic distillation tower out heavy petrol, solar oil and hydrogen mixing after enter hydrodesulphurisatioreactors reactors, in hydrodesulphurisatioreactors reactors, load the GHC-11 optional series Hydrobon catalyst of Petroleum Chemical Engineering Institute of CNPC, under hydrogen dividing potential drop 1.8MPa, air speed 4.0, temperature of reaction 265 DEG C, hydrogen-oil ratio 200: 1 condition, carry out hydrogenating desulfurization.After hydrogenating desulfurization product removes the hydrogen sulfide of dissolving, be mixed to get deep desulfuration gasoline products with petroleum naphtha.As can be seen from Table 1, after aforesaid method process, content of sulfur in gasoline drops to 15ppm from 310ppm, desulfurization degree 95.2%, and olefin(e) centent drops to 25.2% from 28.6%, and octane value (RON) loses 1.0 units.
Table 1 catalytic gasoline A and desulfurization product property analysis
Embodiment 2
With a kind of catalytically cracked gasoline B for raw material, its character is as shown in table 2.Catalytic gasoline first carries out weighted BMO spaces under the condition of hydrogen dividing potential drop 2.4Mpa, temperature 150 DEG C, air speed 4.0, hydrogen-oil ratio 10: 1, then water wash column washing dealkalize nitrogen is entered, enter catalytic distillation tower afterwards, under the effect of catalytic distillation tower top alkene thiophene alkylation catalyzer, make the part thiophene-type sulfide in gasoline increase weight, be divided into petroleum naphtha, heavy petrol, solar oil three components simultaneously.The operational condition of catalytic distillation tower is: tower top pressure 0.8MPa, feeding temperature 145 DEG C, tower top temperature 100 DEG C, column bottom temperature 210 DEG C.Mix laggard selectable hydrodesulphurisatioreactors reactors from catalytic distillation tower heavy petrol out and hydrogen, under hydrogen dividing potential drop 1.8MPa, air speed 4.0, temperature of reaction 275 DEG C, hydrogen-oil ratio 200: 1 condition, carry out hydrogenating desulfurization.After hydrogenating desulfurization product removes the hydrogen sulfide dissolved in gasoline, be mixed to get deep desulfuration gasoline products with petroleum naphtha.Solar oil at the bottom of tower can be used as the charging of diesel hydrotreating unit, also can be in harmonious proportion as low-coagulation diesel oil blend component and dispatch from the factory.As can be seen from Table 2, after aforesaid method process, content of sulfur in gasoline drops to 18ppm from 480ppm, desulfurization degree 96.2%, and olefin(e) centent drops to 29.2% from 33.8%, and octane value (RON) loses 1.2 units.
Table 2 catalytic gasoline B and desulfurization product property analysis
Claims (2)
1. a method for deep desulfurization of gasoline, is characterized in that:
(1) first gasoline stocks and hydrogen being mixed into pre-hydrogenator, is monoolefine by the diene hydrogenation in catalytic gasoline in the reactor; Reaction conditions is: hydrogen dividing potential drop 1.0 ~ 4.0Mpa, temperature of reaction 120 ~ 260 DEG C, volume space velocity 2.0 ~ 8.0h
-1, hydrogen to oil volume ratio 10 ~ 200; Catalyst for pre-hydrogenation carrier is the mixture of aluminum oxide, silicon oxide or aluminum oxide and silicon oxide, and active metal is selected from one or more in VIB, VIIIB, and metal oxide content is 10 ~ 60%, and specific surface area of catalyst is 100 ~ 300m
2/ g, pore volume is 0.20 ~ 0.60ml/g;
(2) pre-hydrogenation products enters catalytic distillation tower and carries out the reaction of alkene thiophene alkylation and gasoline is divided into petroleum naphtha, heavy petrol, solar oil three components simultaneously after water wash column washing; The operational condition of catalytic distillation tower is: tower top pressure 0.3 ~ 2.0Mpa, feeding temperature 120 ~ 250 DEG C, tower top temperature 80 ~ 200 DEG C, column bottom temperature 200 ~ 280 DEG C; 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 laggard selectable hydrodesulphurisatioreactors reactors; Reaction conditions is: hydrogen dividing potential drop 1.0 ~ 4.0Mpa, temperature of reaction 200 ~ 350 DEG C, 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 active metal is selected from one or more in VIB, VIIIB, and 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;
(4) remove from hydrodesulphurisatioreactors reactors material out the lighter hydrocarbons and hydrogen sulfide that dissolve gasoline, last and petroleum naphtha is mixed to get deep desulfuration gasoline products, the solar oil at the bottom of tower as hydrogenating desulfurization raw material or make low-coagulation diesel oil blend component.
2. according to the method for deep desulfurization of gasoline according to claim 1, it is characterized in that: described gasoline stocks is the mixing oil of one or more in catalytically cracked gasoline, catalytic cracking gasoline, coker gasoline and pressure gasoline.
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| 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 |
| 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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| 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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