CN106929098A - Method for hydro-upgrading poor catalytic gasoline - Google Patents
Method for hydro-upgrading poor catalytic gasoline Download PDFInfo
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- CN106929098A CN106929098A CN201511027275.5A CN201511027275A CN106929098A CN 106929098 A CN106929098 A CN 106929098A CN 201511027275 A CN201511027275 A CN 201511027275A CN 106929098 A CN106929098 A CN 106929098A
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- gasoline
- hydrogen
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- hydrogenation
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- 238000000034 method Methods 0.000 title claims abstract description 78
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 128
- 239000001257 hydrogen Substances 0.000 claims abstract description 128
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 76
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000001336 alkenes Chemical class 0.000 claims abstract description 33
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 25
- 239000011593 sulfur Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 15
- 239000007791 liquid phase Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims description 92
- 238000006477 desulfuration reaction Methods 0.000 claims description 40
- 230000023556 desulfurization Effects 0.000 claims description 38
- 150000002431 hydrogen Chemical class 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 29
- 239000005864 Sulphur Substances 0.000 claims description 18
- 239000002808 molecular sieve Substances 0.000 claims description 16
- 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 15
- 238000005194 fractionation Methods 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 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 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 241000269350 Anura Species 0.000 claims description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims description 2
- 229910052906 cristobalite Inorganic materials 0.000 claims description 2
- 229910052682 stishovite Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052905 tridymite Inorganic materials 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 31
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 18
- 238000005520 cutting process Methods 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 81
- 230000000052 comparative effect Effects 0.000 description 22
- 230000004048 modification Effects 0.000 description 18
- 238000012986 modification Methods 0.000 description 18
- 238000005899 aromatization reaction Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- 150000001993 dienes Chemical class 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 150000001335 aliphatic alkanes Chemical class 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000006317 isomerization reaction Methods 0.000 description 5
- 229930192474 thiophene Natural products 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 238000009874 alkali refining Methods 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 241000219782 Sesbania Species 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 238000002803 maceration Methods 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 238000006011 modification reaction Methods 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical class [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 230000011218 segmentation Effects 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 1
- 244000131522 Citrus pyriformis Species 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical class [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical class [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 235000016768 molybdenum Nutrition 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005732 thioetherification reaction Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for hydro-upgrading poor catalytic gasoline, which comprises the following steps of (1) mixing catalytic gasoline and hydrogen and feeding the mixture into a pre-hydrogenation reactor; (2) cutting the product obtained in the step (1) into light, medium and heavy gasoline components in a fractionating tower; (3) the light gasoline component coming out of the top of the fractionating tower is used as a modified gasoline blending component, and the middle gasoline component coming out of the lateral line and hydrogen are mixed, enter the first hydrodesulfurization reactor, react and then return to the fractionating tower; (4) mixing the heavy gasoline component and hydrogen from the bottom of the fractionating tower and allowing the mixture to enter a hydro-upgrading reactor for reaction; (5) the product of the step (4) enters a second hydrodesulfurization reactor for reaction; (6) and (5) cooling the product, then, introducing the product into a product separator for gas-liquid separation, recycling the hydrogen at the top, introducing the liquid phase at the bottom into a stabilizer for removing sulfur-containing gas, and mixing the liquid phase with light gasoline to obtain the modified gasoline product. The method of the invention greatly reduces the contents of olefin and sulfur, and simultaneously reduces the octane number loss in the catalytic gasoline hydro-upgrading.
Description
Technical field
The present invention relates to a kind of hydrogenation modification method of catalytically cracked gasoline inferior, for reducing catalytic gasoline
In sulphur and olefin(e) centent, reduce loss of octane number.
Background technology
China's haze weather occurs frequently in recent years, and the urban air-quality in the whole nation 70% is not up to standard, car tail
Gas pollutant emission is one of important sources of big and medium-sized cities haze, and quality of gasoline upgrading turns into reduction automobile
The important measures of exhaust pollutant discharge.More than 70% component is catalytic cracking vapour in China's motor petrol
Oil, the characteristics of it has sulphur and olefin(e) centent high, therefore the key of quality of gasoline upgrading is to reduce catalysis vapour
Sulphur and olefin(e) centent in oil；But alkene is the significant contributor of octane number, using conventional hydrogenation
Desulfurating and reducing olefinic hydrocarbon technology will significantly lose the octane number of gasoline.How catalytic gasoline both desulfurization, drop alkene are realized
Hydrocarbon, keeps the multiple target of octane number again, upgrades as China quality of gasoline in the urgent need to address great
Technical barrier.
Catalyzed gasoline hydrogenation desulfurization technology is mainly divided to two major classes both at home and abroad at present.One class is that selective hydrogenation takes off
Sulphur technology：By the improvement to technique and catalyst, suppress the alkene saturated activity of catalyst, in hydrogenation
Avoid alkene by excessive saturation while desulfurization, reduce the loss of octane number of hydrodesulfurization；It is another kind of
Technology is catalytic gasoline modification technology：Hydrodesulfurization uses conventional hydrogenation catalyst, then by isomery
The reaction such as change, aromatisation is processed hydrodesulfurization gasoline, improves the octane number of gasoline to make up hydrogenation
Loss of octane number in sweetening process.
ZL200410020932.9 discloses a kind of hydrogenation modification method of inferior patrol.The method is one
Plant the process of full cut catalyzed gasoline hydrogenation desulfurization Olefin decrease.Exist in hydrogen and temperature gradually rises
Under conditions of, contacted with three kinds of catalyst, form three reaction zones.First reaction zone temperature is relatively low, makes
With Hydrobon catalyst, the diolefin in main removing gasoline；Second, third reaction zone temperature is high,
Second reaction zone uses gasoline reforming catalyst, carries out including aromatisation, isomerization and benzene alkylation reaction
Modification reaction, improve gasoline octane number, improve product quality；3rd reaction zone is added using selectivity
Hydrogen desulphurization catalyst, removes organic sulfur compound in oil to greatest extent.The method is fed using full cut, pungent
The loss of alkane value is larger.
ZL200410060574.4 discloses a kind of inferior patrol hydrogenation modifying process.Its technical process
It is：Feed gasoline is cut into light fraction and heavy distillat, wherein heavy distillat elder generation and hydrogen at 60~90 DEG C
Mixing, then with Hydrobon catalyst haptoreaction, reacted effluent again with aromatization modification be catalyzed
Agent contact carries out aromatization modification reaction, obtains high-octane rating low-sulphur oil cut；Heavy petrol after modification
Cut is mixed with light fraction or through the pretreated light fraction of removal of mercaptans again, obtains final product product gasoline.This
Patent needs that, using the method for alkali refining removal of mercaptans, the discharge of the disagreeableness alkaline residue of environment can be caused.
ZL200910080111.7 discloses a kind of adding for the ultra-deep desulfurization-recovery octane number of inferior patrol
Hydrogen method for modifying：By distillation gasoline inferior complete be cut into gently, heavy distillat, light petrol is taken off two with selectivity
Alkene catalyst and desulfurization-hydro carbons highly branched chain hydroisomerization catalyst contact；Heavy petrol is set to be reacted in first paragraph
Area contacts with catalyst for selectively hydrodesulfurizing, then in second segment reaction zone and supplement desulfurization-hydro carbons list
Branched chain isomer/aromatization catalyst contact；Light, the mixing of heavy distillat gasoline after by treatment, obtain cleaning vapour
Oil product.Light petrol after this patent is only fractionated to inferior patrol carries out de- diene treatment, and heavy petrol evaporates
Contain compared with homodiene hydrocarbon in point, the quick coking of catalyst for selectively hydrodesulfurizing, influence operation week can be caused
Phase.
ZL 201110035512.8 discloses a kind of method of inferior gasoline upgrading.The method is first to complete
Distillation gasoline carries out the de- diene treatment of selectivity, then its be cut into gently, in, weigh three components, light vapour
Directly as clean gasoline blend component, middle gasoline component is introduced into hydro-upgrading reactor and carries out aromatization oil
Change, isomerization etc. are reacted, and are then mixed into hydrodesulphurisatioreactors reactors with heavy petrol.The method of the present invention
Sulphur, olefin(e) centent in gasoline can be greatly reduced, reduces the octane number brought in upgrading processes and damages
Lose, but the bad gasoline higher for treatment thiophene content, loss of octane number during V gasoline of producing country
It is larger；Because directly being cut to gasoline after pre- hydrogenation using the patented method, to ensure light petrol sulphur
Content meets the mediation of state V and requires, need to control very low light petrol ratio (less than 25m%), as far as possible will
Thiophene is switched in heavy petrol, causes middle gasoline proportionality, olefin(e) centent to rise；Due to hydro-upgrading unit drop
After heavy petrol mixes with heavy petrol after alkene limited extent, therefore modification, its sulfur content, olefin(e) centent are equal
It is higher, deep hydrodesulfurizationof need to be carried out during V gasoline of producing country, cause loss of octane number big.
US 5413698 discloses the process that a kind of two-stage method produces low sulfur clean gasoline, first will
FCC gasoline cutting fractionation, heavy petrol first passes through hydrodesulfurization, hydro-upgrading is then carried out again and recovers pungent
Alkane value, the heavy petrol hydro-upgrading product for obtaining reconciles with light petrol product again.Although the technology can give birth to
Product meets the clean gasoline of the sulphur index request of Europe IV, while can recover hydrodesulfurization by hydro-upgrading causing
Loss of octane number, but the difficult clean gasoline for meeting production Europe V sulphur index requests.
The content of the invention
It is a primary object of the present invention to provide a kind of method of gasoline hydrogenation modification inferior, to overcome
Octane number reduction is more during gasoline upgrading in the prior art, and reformulated gasoline alkene and sulfur content are higher
Defect.
The object of the present invention is achieved like this, a kind of method of gasoline hydrogenation modification inferior, the party
Method is comprised the following steps：
(1) enter pre-hydrogenator after catalytic gasoline mixes with hydrogen, exist in catalyst for pre-hydrogenation
Under reacted, reaction condition is：1.0~3.0Mpa of hydrogen partial pressure, 100~260 DEG C of reaction temperature,
2.0~8.0h of volume space velocity-1, 10~200v/v of hydrogen to oil volume ratio；
(2) step (1) product enters in fractionating column, in 0.5~1.0Mpa of tower top pressure, enters material temperature
90~130 DEG C of degree, 70~110 DEG C of tower top temperature, cut at 190~230 DEG C of column bottom temperature it is light,
In, heavy gasoline components；
(3) from fractionator overhead light petrol component out directly as reformulated gasoline blend component, from
Enter the first hydrodesulphurisatioreactors reactors after fractionating column side line middle gasoline component out and hydrogen mixing, light
Reacted in the presence of degree Hydrobon catalyst, reaction condition is：1.0~3.0Mpa of hydrogen partial pressure,
200~300 DEG C of reaction temperature, 2.0~5.0h of volume space velocity-1, 200~400v/v of hydrogen to oil volume ratio,
Middle gasoline hydrodesulfurizationmethod product is returned again in fractionating column；
(4) from after fractionation column bottom heavy gasoline components out and hydrogen mixing into hydro-upgrading reaction
Device, is reacted in the presence of catalyst for hydro-upgrading, and reaction condition is：Hydrogen dividing potential drop 1.0~
3.0Mpa, 320~450 DEG C of reaction temperature, 1.0~3.0h of volume space velocity-1, hydrogen to oil volume ratio 250~
500v/v；
(5) product of step (4) enters the second hydrodesulphurisatioreactors reactors, is urged in selective hydrodesulfurization
Reacted in the presence of agent, reaction condition is：1.0~3.0Mpa of hydrogen dividing potential drop, reaction temperature 220~
350 DEG C, 2.0~5.0h of volume space velocity-1, 250~500v/v of hydrogen to oil volume ratio；
(6) after the cooling of step (5) product, gas-liquid separation is carried out into product separator, product is separated
Device top hydrogen out is recycled after being processed through desulphurization of recycle hydrogen tower into circulating hydrogen compressor, product
Separator bottom liquid-phase product enters stabilizer, in 0.7~1.2Mpa of tower top pressure, feeding temperature
140~200 DEG C, 120~180 DEG C of tower top temperature is removed under the conditions of 180~240 DEG C of column bottom temperature and contained
Sulphur gas, reformulated gasoline product is mixed to get with light petrol.
The method of gasoline hydrogenation modification inferior of the present invention, wherein, the catalyst for pre-hydrogenation
Carrier is preferably the mixture of aluminum oxide, silica or both, and active component is preferably the VIth B, the VIIIth
One or more in race, based on catalyst weight 100%, active component oxide content is preferably
10~30%, balance of carrier.
The method of gasoline hydrogenation modification inferior of the present invention, wherein, the catalyst for pre-hydrogenation
Specific surface area is preferably 100~300m2/ g, pore volume is preferably 0.2~0.6ml/g.
The method of gasoline hydrogenation modification inferior of the present invention, wherein, the mild hydrogenation desulfurization
Catalyst carrier is preferably the mixture of aluminum oxide and hydrogen type molecular sieve, active component be preferably the VIth B,
One or more in VIIIth race, the molecular sieve be preferably HZSM-5, HMCM-22, H β and
One or more in HY, the molecular sieve preferably accounts for the 10~60% of catalyst weight, active component
Oxide preferably accounts for the 5~15% of catalyst weight.
The method of gasoline hydrogenation modification inferior of the present invention, wherein, the mild hydrogenation desulfurization
Specific surface area of catalyst is preferably 200~400m2/ g, pore volume is preferably 0.4~0.8ml/g.
The method of gasoline hydrogenation modification inferior of the present invention, wherein, the hydro-upgrading catalysis
Agent carrier is preferably the compound of aluminum oxide and molecular sieve, and active component is preferably in the VIth B, the VIIIth race
One or more, the molecular sieve be preferably one kind in ZSM-5, Beta, SAPO molecular sieve or
Several, in terms of catalyst weight 100%, the molecular sieve content is preferably 60~90%, the activity
Component oxide content is preferably 1~10%.
The method of gasoline hydrogenation modification inferior of the present invention, wherein, the hydro-upgrading catalysis
Agent specific surface area is preferably 200~500m2/ g, pore volume is preferably 0.2~0.5ml/g.
The method of gasoline hydrogenation modification inferior of the present invention, these, it is preferred to, the choosing
Selecting property Hydrobon catalyst is with Al2O3、SiO2、TiO2And ZrO2In one or more be carrier,
With P2O5、K2One or more in O and MgO are auxiliary agent, and active component is in VI B races, VIII race
One or more, based on catalyst weight 100%, active component oxide accounts for 6~20%, auxiliary agent
Account for 1~15%, balance of carrier；The catalyst for selectively hydrodesulfurizing specific surface area is 170~270
m2/ g, pore volume is 0.3~0.6ml/g.
The method of gasoline hydrogenation modification inferior of the present invention, these, it is preferred to, it is described to urge
Change gasoline be catalytically cracked gasoline, sulfur content be less than or equal to 1000mg/kg, olefin(e) centent be less than or
Equal to 45v%.
Beneficial effects of the present invention：
1st, using the pre- hydrogenation technique of full distillation gasoline, the diene content in gasoline is reduced, and significantly drop
Mercaptans content in low light petrol, instead of alkali refining removal of mercaptans operation, it is to avoid the disagreeableness alkali of environment
The discharge of slag, diene content is reduced in heavy petrol, significantly extends the fortune of Hydrobon catalyst
Line period；
2nd, employ be cut into after the pre- hydrogenation technique of full cut it is light, in, the component of heavy petrol three, middle gasoline
The flow that fractionating column cuts again is returned again to after component hydrodesulfurization, the flow can be greatly reduced middle gasoline group
Segmentation sulfur content, therefore relative to the flow directly cut after full cut in advance hydrogenation, light vapour can be improved
Oily cutting ratio, reduces heavy petrol alkene and sulfur content, and it is pungent that reduction heavy petrol hydrodesulfurization is caused
Alkane value is lost, and is specially adapted to process thiophene content bad gasoline high；
3rd, using the flow of " desulfurization of heavy petrol first hydro-upgrading back end hydrogenation ", relative to " heavy petrol elder generation
The flow of hydrodesulfurization back end hydrogenation modification ", the olefin(e) centent of heavy petrol hydro-upgrading unit feed is high, energy
Enough ensure gasoline aromatization rate high, reduce loss of octane number；Due to catalyst for hydro-upgrading with plus
Hydrogen desulfurizing function, therefore heavy petrol experienced first slight desulfurization, then deep desulfuration relay sweetening process,
It is also beneficial to reduce loss of octane number.
Brief description of the drawings
Fig. 1 is the flow chart of institute's poor quality gasoline hydrogenation method for modifying of the invention.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is with technical solution of the present invention as preceding
Put and implemented, give detailed implementation method and process, but protection scope of the present invention is not limited to
Following embodiments, the experimental technique of unreceipted actual conditions in the following example, generally according to conventional strip
Part.
The method of gasoline hydrogenation inferior modification of the invention is：Catalytic gasoline and hydrogen are mixed into pre-
Hydrogenation reactor removes alkadienes；Pre- hydrogenation products into fractionating column by gasoline be cut into gently, in, weight vapour
Oily three components；From tower top light petrol component out directly as clean gasoline blend component, from fractionation
The middle gasoline component of tower lateral line withdrawal function is introduced into the first hydrodesulphurisatioreactors reactors, and to carry out mild hydrogenation desulfurization anti-
Should, product returns again to fractionating column to be continued to cut；It is introduced into from fractionation column base heavy gasoline components out and is added
Hydrogen reforming reactor carries out the reaction such as mild hydrogenation desulfurization and aromatisation, isomerization, heavy petrol hydrogenation products
Entering back into the second hydrodesulphurisatioreactors reactors carries out deep hydrodesulfurizationof reaction；From the second hydrodesulphurisatioreactors reactors
After material cooling out, gas-liquid separation is carried out into product separator；From gas-liquid separator hydrogen out
Gas is used through desulfurization process Posterior circle, liquid-phase product enter stabilizer remove after lighter hydrocarbons and hydrogen sulfide with light vapour
Oil is mixed to get final reformulated gasoline product.
Technological process of the invention can also be expressed as：Enter pre-add hydrogen after gasoline stocks and hydrogen are mixed
Reactor, 1.0~3.0Mpa of hydrogen dividing potential drop, 100~260 DEG C of reaction temperature, volume space velocity 2.0~
8.0h-1, contacted with catalyst for pre-hydrogenation under the conditions of 10~200v/v of hydrogen to oil volume ratio be hydrogenated with it is anti-
Should, it is into monoolefine and anti-by diene thioetherification by the diene selective saturation of easy green coke in catalytic gasoline
Low boiling mercaptan in light petrol should be transferred in heavy petrol.Pre- hydrogenation products enter back into fractionating column, in tower
0.5~1.0Mpa of pressure on top surface, 90~130 DEG C of feeding temperature, 70~110 DEG C of tower top temperature, bottom of towe temperature
Degree 190~230 DEG C under the conditions of by gasoline be divided into gently, in, heavy constituent；After middle gasoline mixes with hydrogen
Into the first hydrodesulphurisatioreactors reactors, 1.0~3.0Mpa of hydrogen dividing potential drop, reaction temperature 200~
300 DEG C, 2.0~5.0h of volume space velocity-1, under 200~400v/v of hydrogen to oil volume ratio with mild hydrogenation desulfurization
Catalyst contact carries out mild hydrogenation desulphurization reaction, and middle gasoline hydrogenation product returns again to fractionating column charging；From
Fractionation column base heavy petrol out is introduced into hydro-upgrading reactor after mixing with hydrogen, in hydrogen dividing potential drop
1.0~3.0Mpa, 320~450 DEG C of reaction temperature, 1.0~3.0h of volume space velocity-1, hydrogen to oil volume ratio
Contacted with catalyst for hydro-upgrading under the conditions of 250~500v/v, hydrodesulfurization, aromatisation and isomery occur
Change reaction, while with the reaction such as a small amount of alkene saturation.Hydro-upgrading product enters back into the second hydrogenation
Desulfurization reactor, in 1.0~3.0Mpa of hydrogen dividing potential drop, 220~350 DEG C of reaction temperature, volume space velocity
2.0~5.0h-1, contacted with catalyst for selectively hydrodesulfurizing under the conditions of 250~500v/v of hydrogen to oil volume ratio
Deep hydrodesulfurizationof reaction is carried out, after the cooling of hydrodesulfurization product, is separated into promoting the circulation of qi into product separator
Liquid is separated.Used by desulfurization process Posterior circle from gas-liquid separator hydrogen out, liquid-phase product enters
Product stabilizer, in 0.7~1.2Mpa of tower top pressure, 140~200 DEG C of feeding temperature, tower top temperature
120~180 DEG C, lighter hydrocarbons and the vulcanization dissolved in gasoline are removed under the conditions of 180~240 DEG C of column bottom temperature
Hydrogen, is finally mixed to get reformulated gasoline product with light petrol.
Wherein, under the above-mentioned reaction condition of the first hydrodesulphurisatioreactors reactors, gasoline component in catalytic gasoline
In 30~50% sulfur-containing compounds will be hydrogenated removing, while the removal efficiency of thiophene be more than 60%, alkene
Saturation factor is less than 10%；The light petrol component come from fractionating column ejection can be directly entered products pot conduct
Clean gasoline blend component, it is also possible to through Etherification of Light FCC Gasoline cell processing, after lifting light petrol octane number again
As clean gasoline blend component；Initially entered from Fractionator Bottom heavy gasoline components out and hydrogen mixing
Hydro-upgrading reactor, contacts with catalyst for hydro-upgrading, carry out mild hydrogenation desulfurization and olefin isomerization
Aromatization, by heavy gasoline components sulfur content hydrogenation and removing 20~50%；From hydro-upgrading reactor
Heavy petrol hydrogenation products out enter back into the second hydrodesulphurisatioreactors reactors, are catalyzed with selective hydrodesulfurization
Agent is contacted, by sulfur content hydrogenation and removing to less than 50mg/kg (gasoline standard of state IV) or less than 10
Mg/kg (state V and above gasoline standard).
The present invention is applied to the hydro-upgrading of catalytically cracked gasoline inferior, and gasoline upgrading technique of the invention is adopted
With full distillation gasoline pre-process then by fractionating column by catalytic gasoline be separated into gently, in, weigh three groups
Point, fractionating column is returned after middle gasoline mild hydrogenation desulfurization, heavy petrol is using first hydro-upgrading and then is hydrogenated with de-
The technological process of sulphur.
When the inventive method production sulfur content is less than IV gasoline blend component of 50mg/kg states, organon is pungent
The loss of alkane value is less than 1.0 units；When production sulfur content is less than V gasoline blend component of 15mg/kg states,
Research octane number (RON) loss is less than 2.0 units；The yield of blend gasoline product is all higher than 99.0w%.
Each catalyst used in following comparative example, embodiment is identical, and specific preparation process is exemplified below：
(1) catalyst for pre-hydrogenation：Industrial alumina powder 100g is taken, 50g water is added, mediated, extruded
Shaping, 120 DEG C of drying, 500 DEG C are calcined 4 hours, then are calcined 4 hours at 900 DEG C, obtain catalyst
Carrier.By stirring and dissolving in 14g ammonium molybdates addition 45g water, 75g nickel nitrates, 12g lemons are added
Acid, stirring and dissolving is made catalyst activity metal impregnation liquid.Catalyst carrier is added into above-mentioned maceration extract
In, taken out after being impregnated 3 hours under normal temperature, it is aged 12 hours, then 120 DEG C of drying, 500 DEG C of roastings
4 hours, finished catalyst A (referring to ZL201210367401.1, being not limited to the method) is obtained.
(2) mild hydrogenation desulphurization catalyst：Take industrial boehmite powder 84g, H beta-molecular sieve
40g, plus sesbania powder 4g, nitric acid 3.5g, water 105g, kneading, extrusion molding, 120 DEG C of drying,
500 DEG C are calcined 4 hours, obtain catalyst carrier.Stirred during 10g ammonium molybdates are added into 55g water, plus
Enter 6g phosphoric acid, 5g cobalt nitrates, 5g nickel nitrates, stirring and dissolving is made catalyst activity metal impregnation
Liquid.Using above-mentioned metallic solution impregnated catalyst support, it is aged 6 hours, then 120 DEG C of drying,
500 DEG C are calcined 4 hours, and finished catalyst B (being not limited to the method) is obtained.
(3) catalyst for hydro-upgrading：HZSM-5 molecular sieves 150g, alumina powder 40g are taken, plus
150ml concentration for 3g/100ml dilute nitric acid solution, mediate, extrusion molding, 120 DEG C drying,
500 DEG C are calcined 4 hours, obtain catalyst carrier.Take above-mentioned carrier 100g be put into 200ml molybdenums, nickel,
In the solution of lanthanum, solution concentration is MoO3 10g/100ml、NiO 3.5g/100ml、La2O3
1.6g/100ml, impregnates 2 hours under normal temperature, by 120 DEG C of drying of catalyst, 500 DEG C of roastings after separation of solid and liquid
Burn 4 hours, finished catalyst C is obtained and (referring to ZL200410074059.1, is not limited to the party
Method).
(4) catalyst for selectively hydrodesulfurizing：Take ZrO obtained in 50g2-Al2O3Powder, adds
10g kaliophilites, 1.25g sesbania powders, 30ml water, kneading, extrusion molding, 120 DEG C of drying, 550 DEG C
Roasting 4 hours, obtains catalyst carrier.Weigh 13g cobalt nitrates, 15g ammonium molybdates EDTA, dilute
Ammoniacal liquor complexing dissolving, adds 10g ammonium dihydrogen phosphates, 15g magnesium nitrates, and stirring and dissolving is made catalysis
Agent active metal maceration extract.Using above-mentioned metallic solution impregnated catalyst support, 4 hours are aged, then
120 DEG C of drying, 450 DEG C are calcined 4 hours, be obtained finished catalyst D (referring to
ZL201010252648.X, is not limited to the method).
Comparative example 1
With a kind of catalytically cracked gasoline as raw material, its property is shown in Table the catalytic gasoline 1 listed by 1.Catalysis vapour
It is oily first in hydrogen dividing potential drop 2.2Mpa, 110 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:1
Under the conditions of pre-processed using A catalyst, subsequently into fractionating column cut into gently, heavy petrol two
Component, fractionation column pressure on top surface 0.7Mpa, 120 DEG C of feeding temperature, 80 DEG C of tower top temperature, bottom of towe temperature
205 DEG C of degree, heavy naphtha accounts for the 65% of raw material.Heavy petrol is mixed into hydro-upgrading with hydrogen first
Reactor is in hydrogen dividing potential drop 2.0MPa, 370 DEG C of reaction temperature, volume space velocity 1.22h-1, hydrogen to oil volume ratio
250:Hydro-upgrading is carried out using C catalyst under 1 reaction condition, subsequently into hydrodesulphurisatioreactors reactors
In hydrogen dividing potential drop 1.8MPa, 255 DEG C of reaction temperature, volume space velocity 2.44h-1, hydrogen to oil volume ratio 250:1
Under the conditions of carry out hydrodesulfurization using D catalyst, carry out gas-liquid into product separator after product cooling
Separate, product separator top hydrogen out compresses after recycle hydrogen sulphur tower desulfurization process into recycle hydrogen
Machine is recycled, and product separator bottom liquid phases product enters stabilizer, in tower top pressure 0.85Mpa,
155 DEG C of feeding temperature, 145 DEG C of tower top temperature removes sulfurous gas under the conditions of 215 DEG C of column bottom temperature,
Clean gasoline product is mixed to get with light petrol component.Process conditions and generation oil nature are shown in Table 2.From table
2 can be seen that product sulfur content for 41mg/kg, desulfurization degree 89.3%, and olefin(e) centent is under 41.0%
26.0% is dropped to, octane number (RON) loses 1.2 units.
Comparative example 2
The feedstock oil that comparative example 2 is used is identical with comparative example 1.Catalytic gasoline is first in hydrogen dividing potential drop
2.2Mpa, 120 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:A is used under the conditions of 1
Catalyst is pre-processed, subsequently into fractionating column cut into gently, two components of heavy petrol, fractionation column
Pressure on top surface 0.7Mpa, 115 DEG C of feeding temperature, 70 DEG C of tower top temperature, 200 DEG C of column bottom temperature, weight vapour
Oil distillate accounts for the 80% of raw material.Heavy petrol is mixed into hydro-upgrading reactor in hydrogen point with hydrogen first
Pressure 2.0MPa, 380 DEG C of reaction temperature, volume space velocity 1.5h-1, hydrogen to oil volume ratio 300:1 reaction bar
Hydro-upgrading is carried out using C catalyst under part, subsequently into hydrodesulphurisatioreactors reactors in hydrogen dividing potential drop
1.8MPa, 275 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 300:Used under the conditions of 1
D catalyst carries out hydrodesulfurization, and gas-liquid separation, product point are carried out into product separator after product cooling
From device top, hydrogen out is recycled after recycle hydrogen sulphur tower desulfurization process into circulating hydrogen compressor,
Product separator bottom liquid phases product enters stabilizer, in tower top pressure 0.88Mpa, feeding temperature
150 DEG C, 140 DEG C of tower top temperature removes sulfurous gas, with light petrol under the conditions of 210 DEG C of column bottom temperature
Component is mixed to get clean gasoline product.Process conditions and generation oil nature are shown in Table 2.Can from table 2
Go out, product sulfur content be 11mg/kg, desulfurization degree 97.1%, olefin(e) centent drops to from 41v%
22.3v%, octane number (RON) loses 2.2 units.
Comparative example 3
The feedstock oil that comparative example 3 is used is identical with comparative example 1.Catalytic gasoline is first in hydrogen dividing potential drop
2.2Mpa, 120 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:A is used under the conditions of 1
Catalyst is pre-processed, subsequently into fractionating column cut into gently, in, three components of heavy petrol, fractionation
Column overhead pressure 0.7Mpa, 118 DEG C of feeding temperature, 75 DEG C of tower top temperature, 202 DEG C of column bottom temperature,
Middle gasoline fraction accounts for the 50% of raw material, and heavy naphtha accounts for the 20% of raw material.Middle gasoline is first and hydrogen
The first hydrodesulphurisatioreactors reactors are mixed into, in hydrogen dividing potential drop 2.2MPa, 230 DEG C of reaction temperature, volume
Air speed 3.13h-1, hydrogen to oil volume ratio 300:Hydrodesulfurization is carried out using B catalyst under 1 reaction condition,
Product returns again to fractionating column charging；Heavy petrol is mixed into hydrodesulphurisatioreactors reactors in hydrogen point with hydrogen first
Pressure 1.8MPa, 250 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 300:Make under the conditions of 1
Hydrodesulfurization is carried out with D catalyst, subsequently into hydro-upgrading reactor in hydrogen dividing potential drop 2.0MPa, anti-
Answer 380 DEG C of temperature, volume space velocity 1.5h-1, hydrogen to oil volume ratio 300:Urged using C under 1 reaction condition
Agent carries out hydro-upgrading, and gas-liquid separation, product separator are carried out into product separator after product cooling
Top hydrogen out is recycled after recycle hydrogen sulphur tower desulfurization process into circulating hydrogen compressor, product
Separator bottom liquid-phase product enters stabilizer, in tower top pressure 0.88Mpa, 153 DEG C of feeding temperature,
143 DEG C of tower top temperature, sulfurous gas is removed under the conditions of 212 DEG C of column bottom temperature, is mixed with light petrol component
Obtain clean gasoline product.Process conditions and generation oil nature are shown in Table 2.From table 2 it can be seen that product
Sulfur content is 10mg/kg, and desulfurization degree 97.4%, olefin(e) centent drops to 24v%, octane from 41v%
Value (RON) loses 1.8 units.
Embodiment 1
The feedstock oil that embodiment 1 is used is identical with comparative example 1.Catalytic gasoline is first in hydrogen dividing potential drop
2.2Mpa, 110 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:A is used under the conditions of 1
Catalyst is pre-processed, subsequently into fractionating column cut into gently, in, three components of heavy petrol, fractionation
Column overhead pressure 0.7Mpa, 122 DEG C of feeding temperature, 85 DEG C of tower top temperature, 210 DEG C of column bottom temperature,
Middle gasoline fraction accounts for the 40% of raw material, and heavy naphtha accounts for the 20% of raw material.Middle gasoline is first and hydrogen
The first hydrodesulphurisatioreactors reactors are mixed into, in hydrogen dividing potential drop 2.2MPa, 220 DEG C of reaction temperature, volume
Air speed 2.5h-1, hydrogen to oil volume ratio 250:Hydrodesulfurization is carried out using B catalyst under 1 reaction condition,
Product returns again to fractionating column charging；Heavy petrol is mixed into hydro-upgrading reactor in hydrogen point with hydrogen first
Pressure 2.0MPa, 370 DEG C of reaction temperature, volume space velocity 1.22h-1, hydrogen to oil volume ratio 250:1 reaction
Under the conditions of carry out hydro-upgrading using C catalyst, subsequently into hydrodesulphurisatioreactors reactors in hydrogen dividing potential drop
1.8MPa, 235 DEG C of reaction temperature, volume space velocity 2.44h-1, hydrogen to oil volume ratio 250:Make under the conditions of 1
Hydrodesulfurization is carried out with D catalyst, gas-liquid separation is carried out into product separator after product cooling, produced
Product separator top hydrogen out enters circulating hydrogen compressor circulation after recycle hydrogen sulphur tower desulfurization process and makes
With product separator bottom liquid phases product enters stabilizer, in tower top pressure 0.87Mpa, feeding temperature
158 DEG C, 146 DEG C of tower top temperature removes sulfurous gas, with light petrol under the conditions of 218 DEG C of column bottom temperature
Component is mixed to get clean gasoline product.Process conditions and generation oil nature are shown in Table 2.Can from table 2
Go out, product sulfur content be 40mg/kg, desulfurization degree 89.5%, olefin(e) centent drops to from 41v%
27.8v%, octane number (RON) loses 0.4 unit.
Embodiment 2
The feedstock oil that embodiment 2 is used is identical with comparative example 2.Catalytic gasoline is first in hydrogen dividing potential drop
2.2Mpa, 120 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:A is used under the conditions of 1
Catalyst is pre-processed, subsequently into fractionating column cut into gently, in, three components of heavy petrol, fractionation
Column overhead pressure 0.7Mpa, 118 DEG C of feeding temperature, 75 DEG C of tower top temperature, 202 DEG C of column bottom temperature,
Middle gasoline fraction accounts for the 50% of raw material, and heavy naphtha accounts for the 20% of raw material.Middle gasoline is first and hydrogen
The first hydrodesulphurisatioreactors reactors are mixed into, in hydrogen dividing potential drop 2.2MPa, 230 DEG C of reaction temperature, volume
Air speed 3.13h-1, hydrogen to oil volume ratio 300:Hydrodesulfurization is carried out using B catalyst under 1 reaction condition,
Product returns again to fractionating column charging；Heavy petrol is mixed into hydro-upgrading reactor in hydrogen point with hydrogen first
Pressure 2.0MPa, 380 DEG C of reaction temperature, volume space velocity 1.5h-1, hydrogen to oil volume ratio 300:1 reaction bar
Hydro-upgrading is carried out using C catalyst under part, subsequently into hydrodesulphurisatioreactors reactors in hydrogen dividing potential drop
1.8MPa, 255 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 300:Used under the conditions of 1
D catalyst carries out hydrodesulfurization, and gas-liquid separation, product point are carried out into product separator after product cooling
From device top, hydrogen out is recycled after recycle hydrogen sulphur tower desulfurization process into circulating hydrogen compressor,
Product separator bottom liquid phases product enters stabilizer, in tower top pressure 0.88Mpa, feeding temperature
153 DEG C, 143 DEG C of tower top temperature removes sulfurous gas, with light petrol under the conditions of 212 DEG C of column bottom temperature
Component is mixed to get clean gasoline product.Process conditions and generation oil nature are shown in Table 2.Can from table 2
Go out, product sulfur content be 10mg/kg, desulfurization degree 97.4%, olefin(e) centent drops to from 41v%
26.5v%, octane number (RON) loses 1.0 units.
Embodiment 3
The feedstock oil that embodiment 3 is used is shown in Table the catalytic gasoline 2 listed by 1.Catalytic gasoline is first in hydrogen dividing potential drop
2.2Mpa, 120 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:A is used under the conditions of 1
Catalyst is pre-processed, subsequently into fractionating column cut into gently, in, three components of heavy petrol, fractionation
Column overhead pressure 0.7Mpa, 116 DEG C of feeding temperature, 73 DEG C of tower top temperature, 203 DEG C of column bottom temperature,
Middle gasoline fraction accounts for the 47% of raw material, and heavy naphtha accounts for the 21% of raw material.Middle gasoline is first and hydrogen
The first hydrodesulphurisatioreactors reactors are mixed into, in hydrogen dividing potential drop 2.2MPa, 240 DEG C of reaction temperature, volume
Air speed 3.0h-1, hydrogen to oil volume ratio 300:Hydrodesulfurization is carried out using B catalyst under 1 reaction condition,
Product returns again to fractionating column charging；Heavy petrol is mixed into hydro-upgrading reactor in hydrogen point with hydrogen first
Pressure 2.0MPa, 380 DEG C of reaction temperature, volume space velocity 1.5h-1, hydrogen to oil volume ratio 300:1 reaction bar
Hydro-upgrading is carried out using C catalyst under part, subsequently into hydrodesulphurisatioreactors reactors in hydrogen dividing potential drop
1.8MPa, 265 DEG C of reaction temperature, volume space velocity 2.5h-1, hydrogen to oil volume ratio 300:Used under the conditions of 1
D catalyst carries out hydrodesulfurization, and gas-liquid separation, product point are carried out into product separator after product cooling
From device top, hydrogen out is recycled after recycle hydrogen sulphur tower desulfurization process into circulating hydrogen compressor,
Product separator bottom liquid phases product enters stabilizer, in tower top pressure 0.87Mpa, feeding temperature
151 DEG C, 142 DEG C of tower top temperature removes sulfurous gas, with light petrol under the conditions of 210 DEG C of column bottom temperature
Component is mixed to get clean gasoline product.Process conditions and generation oil nature are shown in Table 2.Can from table 2
Go out, product sulfur content be 12mg/kg, desulfurization degree 98.0%, olefin(e) centent drops to from 40v%
25v%, octane number (RON) loses 1.2 units.
Table 1
Table 2
Comparative result when comparative example 1 is IV gasoline products of producing country with embodiment 1, comparative example 2 and reality
Comparative result when applying example 2 for V gasoline products of producing country.Differ primarily in that embodiments of the invention
1st, embodiment 2 contains " middle gasoline extraction, mild hydrogenation desulfurization " processing unit, and comparative example
1st, comparative example 2 does not have.Be can be seen that for treatment sulfur content 382mg/kg, alkene by the result of table 2
The catalytic gasoline of 41.0v%, under the desulfurization degree of IV scheme of state 89.5%, embodiment 1 is compared with the octane of comparative example 1
Value loses 0.8 unit less；Under the identical desulfurization degree of V scheme of state 97.4%, embodiment 2 is compared with comparative example
2 octane numbers lose 1.2 units less；
Comparative result when comparative example 3 is V gasoline products of producing country with embodiment 2.Differ primarily in that
The flow of the use of embodiments of the invention 2 " desulfurization of heavy petrol first hydro-upgrading back end hydrogenation ", and comparative example
3 flows for using " heavy petrol elder generation hydrodesulfurization back end hydrogenation is modified ".Be can be seen that by the result of table 2
Under the identical desulfurization degree of V scheme of state 97.4%, embodiment 2 loses 0.8 list less compared with the octane number of comparative example 3
Position；Additionally, being urged using the another kind of the inventive method treatment sulfur content 695mg/kg, alkene 40v%
Change gasoline, under 98.3% desulfurization degree, alkene reduction 15v%, octane number only loses 1.2 units.
Beneficial effects of the present invention：
1st, using the pre- hydrogenation technique of full distillation gasoline, the diene content in gasoline is reduced, and significantly drop
Mercaptans content in low light petrol, instead of alkali refining removal of mercaptans operation, it is to avoid the disagreeableness alkali of environment
The discharge of slag, diene content is reduced in heavy petrol, significantly extends the fortune of Hydrobon catalyst
Line period；
2nd, employ be cut into after the pre- hydrogenation technique of full cut it is light, in, the component of heavy petrol three, middle gasoline
The flow that fractionating column cuts again is returned again to after component hydrodesulfurization, the flow can be greatly reduced middle gasoline group
Segmentation sulfur content, therefore relative to the flow directly cut after full cut in advance hydrogenation, light vapour can be improved
Oily cutting ratio, reduces heavy petrol alkene and sulfur content, and it is pungent that reduction heavy petrol hydrodesulfurization is caused
Alkane value is lost, and is specially adapted to process thiophene content bad gasoline high；
3rd, using the flow of " desulfurization of heavy petrol first hydro-upgrading back end hydrogenation ", relative to " heavy petrol elder generation
The flow of hydrodesulfurization back end hydrogenation modification ", the olefin(e) centent of heavy petrol reforming unit charging is high, Neng Goubao
Card gasoline aromatization rate high, reduces loss of octane number；Because catalyst for hydro-upgrading is de- with hydrogenation
Sulfur functional, therefore heavy petrol experienced first slight desulfurization, then deep desulfuration relay sweetening process, also have
Beneficial to reduction loss of octane number.
Certainly, the present invention can also have other various embodiments, without departing substantially from spiritual and its essence of the invention
In the case of, those of ordinary skill in the art can make various corresponding changes and deformation according to the present invention,
But these corresponding changes and deformation should all belong to the protection domain of the claims in the present invention.
Claims (9)
1. a kind of method that gasoline hydrogenation inferior is modified, it is characterised in that the method includes following
Step：
(1) enter pre-hydrogenator after catalytic gasoline mixes with hydrogen, exist in catalyst for pre-hydrogenation
Under reacted, reaction condition is：1.0~3.0Mpa of hydrogen partial pressure, 100~260 DEG C of reaction temperature,
2.0~8.0h of volume space velocity-1, 10~200v/v of hydrogen to oil volume ratio；
(2) step (1) product enters in fractionating column, in 0.5~1.0Mpa of tower top pressure, enters material temperature
90~130 DEG C of degree, 70~110 DEG C of tower top temperature, cut at 190~230 DEG C of column bottom temperature it is light,
In, heavy gasoline components；
(3) from fractionator overhead light petrol component out directly as reformulated gasoline blend component, from
Enter the first hydrodesulphurisatioreactors reactors after fractionating column side line middle gasoline component out and hydrogen mixing, light
Reacted in the presence of degree Hydrobon catalyst, reaction condition is：1.0~3.0Mpa of hydrogen partial pressure,
200~300 DEG C of reaction temperature, 2.0~5.0h of volume space velocity-1, 200~400v/v of hydrogen to oil volume ratio,
Middle gasoline hydrodesulfurizationmethod product is returned again in fractionating column；
(4) from after fractionation column bottom heavy gasoline components out and hydrogen mixing into hydro-upgrading reaction
Device, is reacted in the presence of catalyst for hydro-upgrading, and reaction condition is：Hydrogen dividing potential drop 1.0~
3.0Mpa, 320~450 DEG C of reaction temperature, 1.0~3.0h of volume space velocity-1, hydrogen to oil volume ratio 250~
500v/v；
(5) product of step (4) enters the second hydrodesulphurisatioreactors reactors, is urged in selective hydrodesulfurization
Reacted in the presence of agent, reaction condition is：1.0~3.0Mpa of hydrogen dividing potential drop, reaction temperature 220~
350 DEG C, 2.0~5.0h of volume space velocity-1, 250~500v/v of hydrogen to oil volume ratio；And
(6) after the cooling of step (5) product, gas-liquid separation is carried out into product separator, product is separated
Device top hydrogen out is recycled after desulphurization of recycle hydrogen tower desulfurization process into circulating hydrogen compressor,
Product separator bottom liquid phases product enters stabilizer, in 0.7~1.2Mpa of tower top pressure, feeding temperature
140~200 DEG C, 120~180 DEG C of tower top temperature is removed under the conditions of 180~240 DEG C of column bottom temperature and contained
Sulphur gas, reformulated gasoline product is mixed to get with light petrol.
2. the method that gasoline hydrogenation inferior according to claim 1 is modified, its feature exists
In the catalyst for pre-hydrogenation carrier is the mixture of aluminum oxide, silica or both, and active component is
One or more in VIth B, the VIIIth race, based on catalyst weight 100%, active component oxide
Content is 10~30%, balance of carrier.
3. the method that gasoline hydrogenation inferior according to claim 1 is modified, its feature exists
In the catalyst for pre-hydrogenation specific surface area is 100~300m2/ g, pore volume is 0.2~0.6ml/g.
4. the method that gasoline hydrogenation inferior according to claim 1 is modified, its feature exists
In the mild hydrogenation desulfurization catalyst agent carrier is the mixture of aluminum oxide and hydrogen type molecular sieve, activearm
It is divided into one or more in the VIth B, the VIIIth race, the molecular sieve is HZSM-5, HMCM-
22nd, one or more in H β and HY, the molecular sieve accounts for the 10~60% of catalyst weight, living
Property component oxide accounts for the 5~15% of catalyst weight.
5. the method that gasoline hydrogenation inferior according to claim 1 is modified, its feature exists
In the mild hydrogenation desulphurization catalyst specific surface area is 200~400m2/ g, pore volume is 0.4~0.8
ml/g。
6. the method that gasoline hydrogenation inferior according to claim 1 is modified, its feature exists
In the compound that, the catalyst for hydro-upgrading carrier is aluminum oxide and molecular sieve, active component is the
One or more in VI B, the VIIIth race, the molecular sieve is ZSM-5, Beta, SAPO molecular sieve
In one or more, in terms of catalyst weight 100%, the molecular sieve content be 60~90%, institute
It is 1~10% to state active component oxide content.
7. the method that gasoline hydrogenation inferior according to claim 1 is modified, its feature exists
In the catalyst for hydro-upgrading specific surface area is 200~500m2/ g, pore volume is 0.2~0.5
ml/g。
8. the method that gasoline hydrogenation inferior according to claim 1 is modified, its feature exists
In the catalyst for selectively hydrodesulfurizing is with Al2O3、SiO2、TiO2And ZrO2In one kind or several
It is carrier to plant, with P2O5、K2One or more in O and MgO are auxiliary agent, and active component is VI B
One or more in race, VIII race, based on catalyst weight 100%, active component oxide accounts for 6~
20%, auxiliary agent accounts for 1~15%, balance of carrier；The catalyst for selectively hydrodesulfurizing specific surface area
It is 170~270m2/ g, pore volume is 0.3~0.6ml/g.
9. the method that gasoline hydrogenation inferior according to claim 1 is modified, its feature exists
In the catalytic gasoline is catalytically cracked gasoline, and sulfur content is less than or equal to 1000mg/kg, alkene
Content is less than or equal to 45v%.
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| CN201511027275.5A CN106929098B (en) | 2015-12-30 | 2015-12-30 | Method for hydro-upgrading poor catalytic gasoline |
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| CN1597864A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Process for hydrogenating treatment of foulty gasoline |
| CN103059955A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing clean gasoline from catalytic cracking gasoline |
| CN104673378A (en) * | 2015-02-04 | 2015-06-03 | 中国石油大学(北京) | Method for producing desulfurized gasoline |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1597864A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Process for hydrogenating treatment of foulty gasoline |
| CN103059955A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Method for producing clean gasoline from catalytic cracking gasoline |
| CN104673378A (en) * | 2015-02-04 | 2015-06-03 | 中国石油大学(北京) | Method for producing desulfurized gasoline |
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