CN106929098B - Method for hydro-upgrading poor catalytic gasoline - Google Patents
Method for hydro-upgrading poor catalytic gasoline Download PDFInfo
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- CN106929098B CN106929098B CN201511027275.5A CN201511027275A CN106929098B CN 106929098 B CN106929098 B CN 106929098B CN 201511027275 A CN201511027275 A CN 201511027275A CN 106929098 B CN106929098 B CN 106929098B
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- 238000000034 method Methods 0.000 title claims abstract description 71
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 26
- 239000001257 hydrogen Substances 0.000 claims abstract description 133
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 133
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 128
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 65
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 37
- 150000001336 alkenes Chemical class 0.000 claims abstract description 35
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 26
- 239000011593 sulfur Substances 0.000 claims abstract description 26
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000007791 liquid phase Substances 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000007789 gas Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 96
- 238000006477 desulfuration reaction Methods 0.000 claims description 35
- 230000023556 desulfurization Effects 0.000 claims description 34
- 230000004048 modification Effects 0.000 claims description 26
- 238000012986 modification Methods 0.000 claims description 26
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- 238000005194 fractionation Methods 0.000 claims description 16
- 239000002808 molecular sieve Substances 0.000 claims description 14
- 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 13
- 150000002431 hydrogen Chemical class 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 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
- 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
- 150000002927 oxygen compounds Chemical class 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 34
- 239000003381 stabilizer Substances 0.000 abstract description 9
- 238000005520 cutting process Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 80
- 230000000052 comparative effect Effects 0.000 description 21
- 239000005864 Sulphur Substances 0.000 description 17
- 239000002994 raw material Substances 0.000 description 12
- 238000005899 aromatization reaction Methods 0.000 description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 150000001993 dienes Chemical class 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 238000006317 isomerization reaction Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000004519 manufacturing process 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
- 238000004821 distillation Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 230000001404 mediated effect Effects 0.000 description 4
- 238000002715 modification method Methods 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
- 238000009874 alkali refining Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 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
- 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
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000004615 ingredient Substances 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
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002407 reforming Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 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
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 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
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical class C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical class [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 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
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 239000002010 green coke Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 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
- 238000002386 leaching Methods 0.000 description 1
- 238000002803 maceration Methods 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
- 239000000463 material Substances 0.000 description 1
- 238000006011 modification reaction Methods 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005732 thioetherification reaction 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 in catalytic gasoline sulphur and
Olefin(e) centent reduces 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, automobile exhaust pollution object row
Put be big and medium-sized cities haze one of important sources, quality of gasoline upgrading, which becomes, reduces important arranging for automobile exhaust pollution object discharge
It applies.70% or more component is catalytically cracked gasoline in China's motor petrol, has the characteristics that sulphur and olefin(e) centent are high, therefore vapour
The key of oil quality upgrading is the sulphur and olefin(e) centent reduced in catalytic gasoline；But alkene is the main contributions of octane number
Person will substantially lose the octane number of gasoline using conventional hydrodesulfurization Olefin decrease technology.How to realize catalytic gasoline both desulfurization,
Olefin decrease, and the multiple target of octane number is kept, become China's quality of gasoline and upgrades significant technology issues in the urgent need to address.
Catalyzed gasoline hydrogenation desulfurization technology mainly divides two major classes both at home and abroad at present.One kind is selective hydrodesulfurization technology：
By the improvement to technique and catalyst, inhibits the alkene saturated activity of catalyst, alkene quilt is avoided while hydrodesulfurization
Excessive saturation, reduces the loss of octane number of hydrodesulfurization；Another kind of technology is catalytic gasoline modification technology：Hydrodesulfurization makes
With conventional hydrogenation catalyst, then hydrodesulfurization gasoline is handled by the reaction such as isomerization, aromatisation, improves gasoline
Octane number is to make up the loss of octane number in hydrodesulfurization.
ZL200410020932.9 discloses a kind of hydrogenation modification method of inferior patrol.This method is that a kind of full fraction is urged
Change the process of gasoline hydrodesulfurizationmethod Olefin decrease.Under conditions of hydrogen exists and temperature gradually rises, with three kinds of catalyst
Contact forms three reaction zones.First reaction zone temperature is relatively low, using Hydrobon catalyst, main pair removed in gasoline
Alkene；Second, third reaction zone temperature is high, and second reaction zone uses gasoline reforming catalyst, carries out including aromatisation, isomerization
Modification with benzene alkylation reaction is reacted, and the octane number of gasoline is improved, and improves product quality；Third reaction zone is added using selectivity
Hydrogen desulphurization catalyst, organic sulfur compound during removing is oily to greatest extent.This method is fed using full fraction, and loss of octane number is larger.
ZL200410060574.4 discloses a kind of inferior patrol hydrogenation modifying process.Its technical process is：By raw material vapour
Oil is cut into light fraction and heavy distillat at 60~90 DEG C, and wherein heavy distillat is first mixed with hydrogen, then is connect with Hydrobon catalyst
Reaction is touched, the effluent after reaction is contacted with aromatization modification catalyst again carries out aromatization modification reaction, obtains high-octane rating
Low-sulphur oil fraction；Heavy naphtha after modification is mixed with light fraction or through the pretreated light fraction of removal of mercaptans again,
Up to product gasoline.This patent needs the method using alkali refining removal of mercaptans, can cause the discharge of the disagreeableness alkaline residue of environment.
ZL200910080111.7 discloses a kind of hydro-upgrading side of the ultra-deep desulfurization of inferior patrol-recovery octane number
Method：Full distillation gasoline inferior is cut into light, heavy distillat, keeps light petrol and the de- diene catalyst of selectivity and desulfurization-hydro carbons more
Branch hydroisomerization catalyst contacts；Heavy petrol is set to be contacted with catalyst for selectively hydrodesulfurizing in first segment reaction zone, then
It is contacted with supplement desulfurization-hydro carbons list branched chain isomer/aromatization catalyst in second segment reaction zone；Treated by general gently, heavy distillat vapour
Oil mixing, obtains clean gasoline product.This patent only carries out de- diene to the light petrol after inferior patrol fractionation and handles, and weight vapour
Containing compared with homodiene hydrocarbon in oil distillate, the quick coking of catalyst for selectively hydrodesulfurizing can be caused, influence the cycle of operation.
ZL 201110035512.8 discloses a kind of method of inferior gasoline upgrading.This method is first to full distillation gasoline
Carry out the de- diene processing of selectivity, then its be cut into it is light, in, weigh three components, light petrol reconciles directly as clean gasoline
Component, middle gasoline component are introduced into hydro-upgrading reactor and carry out the reactions such as aromatisation, isomerization, be then mixed into heavy petrol
Enter hydrodesulphurisatioreactors reactors.Sulphur, olefin(e) centent in gasoline can be greatly reduced in the method for the present invention, reduce upgrading processes
In the loss of octane number that brings, but for handling the higher bad gasoline of thiophene content, octane number when V gasoline of producing country
It loses larger；Because directly being cut to gasoline after pre-add hydrogen using the patented method, to ensure that light petrol sulfur content meets
State V, which reconciles, to be required, and need to be controlled very low light petrol ratio (being less than 25m%), thiophene is switched in heavy petrol as possible, in causing
Gasoline proportionality, olefin(e) centent rise；Due to hydro-upgrading unit Olefin decrease limited extent, heavy petrol and heavy petrol after modification
After mixing, sulfur content, olefin(e) centent are higher, and when V gasoline of producing country need to carry out deep hydrodesulfurizationof, and octane number is caused to damage
It loses big.
US 5413698 discloses a kind of process of two-stage method production low sulfur clean gasoline, first cuts FCC gasoline
Fractionation is cut, heavy petrol first passes through hydrodesulfurization, then carries out hydro-upgrading again and restores octane number, obtained heavy petrol hydro-upgrading
Product reconciles with light petrol product again.Although the technology can produce the clean gasoline for meeting IV sulphur index request of Europe, lead to simultaneously
Loss of octane number caused by hydrodesulfurization, but the difficult clean gasoline for meeting production Europe V sulphur index requests can be restored by crossing hydro-upgrading.
Invention content
The main purpose of the present invention is to provide a kind of methods of gasoline hydrogenation modification inferior, to overcome the prior art
Octane number reduces more, reformulated gasoline alkene and the higher defect of sulfur content during middle gasoline upgrading.
The object of the present invention is achieved like this, it is a kind of poor quality gasoline hydrogenation modification method, this method include with
Lower step：
(1) enter pre-hydrogenator after catalytic gasoline is mixed with hydrogen, reacted in the presence of catalyst for pre-hydrogenation,
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, hydrogen oil volume
Than 10~200v/v；
(2) step (1) product enters in fractionating column, in 0.5~1.0Mpa of tower top pressure, 90~130 DEG C of feeding temperature, tower
Push up 70~110 DEG C of temperature, cut at 190~230 DEG C of column bottom temperature it is light, in, heavy gasoline components；
(3) the light petrol component being ejected from fractionation column is directly as reformulated gasoline blend component, from fractionating column side line
Middle gasoline component and hydrogen out enters the first hydrodesulphurisatioreactors reactors after mixing, in the presence of mild hydrogenation desulphurization catalyst
It is reacted, 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 returns again in fractionating column；
(4) enter hydro-upgrading reactor after heavy gasoline components and the hydrogen mixing come out from fractionation column bottom, add hydrogen
It is reacted in the presence of modifying catalyst, reaction condition is：1.0~3.0Mpa of hydrogen partial pressure, 320~450 DEG C of reaction temperature, volume
1.0~3.0h of air speed-1, 250~500v/v of hydrogen to oil volume ratio；
(5) product of step (4) enter the second hydrodesulphurisatioreactors reactors, in the presence of catalyst for selectively hydrodesulfurizing into
Row reaction, reaction condition are：1.0~3.0Mpa of hydrogen partial pressure, 220~350 DEG C of reaction temperature, 2.0~5.0h of volume space velocity-1, hydrogen
Oil volume is than 250~500v/v；
(6) after the cooling of step (5) product, gas-liquid separation is carried out into product separator, is come out at the top of product separator
Hydrogen enters circulating hydrogen compressor after the processing of desulphurization of recycle hydrogen tower and recycles, and product separator bottom liquid phases product enters steady
Tower is determined, in 0.7~1.2Mpa of tower top pressure, 140~200 DEG C of feeding temperature, 120~180 DEG C of tower top temperature, column bottom temperature 180
Sulfurous gas is removed under the conditions of~240 DEG C, reformulated gasoline product is mixed to get with light petrol.
The method of poor quality gasoline hydrogenation modification of the present invention, wherein the catalyst for pre-hydrogenation carrier is preferred
For the mixture of aluminium oxide, silica or both, active component is preferably one or more of the VIth B, the VIIIth race, by catalysis
Agent weight 100% is counted, and active component oxide content is preferably 10~30%, and surplus is carrier.
The method of poor quality gasoline hydrogenation modification of the present invention, wherein the catalyst for pre-hydrogenation specific surface area
Preferably 100~300m2/ g, it is preferably 0.2~0.6ml/g that hole, which holds,.
The method of poor quality gasoline hydrogenation modification of the present invention, wherein the mild hydrogenation desulphurization catalyst carries
Body is preferably the mixture of aluminium oxide and hydrogen type molecular sieve, and active component is preferably one or more of the VIth B, the VIIIth race,
The molecular sieve is preferably one or more of HZSM-5, HMCM-22, H β and HY, and the molecular sieve preferably accounts for catalyst weight
The 10~60% of amount, active component oxide preferably accounts for the 5~15% of catalyst weight.
The method of poor quality gasoline hydrogenation modification of the present invention, wherein the mild hydrogenation desulphurization catalyst ratio
Surface area is preferably 200~400m2/ g, it is preferably 0.4~0.8ml/g that hole, which holds,.
The method of poor quality gasoline hydrogenation modification of the present invention, wherein the catalyst for hydro-upgrading carrier is excellent
It is selected as aluminium oxide and the compound of molecular sieve, active component is preferably one or more of the VIth B, the VIIIth race, the molecule
Sieve is preferably one or more of ZSM-5, Beta, SAPO molecular sieve, and in terms of catalyst weight 100%, the molecular sieve contains
Amount preferably 60~90%, the active component oxide content is preferably 1~10%.
The method of poor quality gasoline hydrogenation modification of the present invention, wherein the catalyst for hydro-upgrading specific surface
Product is preferably 200~500m2/ g, it is preferably 0.2~0.5ml/g that hole, which holds,.
The method of poor quality gasoline hydrogenation modification of the present invention, wherein preferably, the selective hydrogenation is de-
Sulfur catalyst is with Al2O3、SiO2、TiO2And ZrO2One or more of be carrier, with P2O5、K2One kind or several in O and MgO
Kind is auxiliary agent, and active component is one or more of VI B races, VIII race, based on catalyst weight 100%, active component oxidation
Object accounts for 6~20%, and auxiliary agent accounts for 1~15%, and surplus is carrier；The catalyst for selectively hydrodesulfurizing specific surface area be 170~
270m20.3~0.6ml/g of/g, Kong Rongwei.
The method of poor quality gasoline hydrogenation modification of the present invention, wherein preferably, the catalytic gasoline is to urge
Change cracking gasoline, sulfur content is less than or equal to 1000mg/kg, and olefin(e) centent is less than or equal to 45v%.
Beneficial effects of the present invention：
1, using the pre- hydrogenation technique of full distillation gasoline, the diene content in gasoline is reduced, and be greatly reduced in light petrol
Mercaptans content avoid the discharge of the disagreeableness alkaline residue of environment instead of alkali refining removal of mercaptans process, alkadienes in heavy petrol
Content is reduced, and substantially extends the cycle of operation of Hydrobon catalyst；
2, use be cut into after the pre- hydrogenation technique of full fraction it is light, in, three component of heavy petrol, middle gasoline component hydrodesulfurization
The flow that fractionating column is cut again is returned again to afterwards, which can be greatly reduced middle gasoline component section sulfur content, therefore relative to complete
The flow directly cut after fraction pre-add hydrogen can be improved light petrol cutting ratio, reduce heavy petrol alkene and sulfur content, subtract
Loss of octane number caused by few heavy petrol hydrodesulfurization is specially adapted to the high bad gasoline of processing thiophene content；
3, using the flow of " the hydro-upgrading back end hydrogenation desulfurization of heavy petrol elder generation ", relative to " after the hydrodesulfurization of heavy petrol elder generation plus
The olefin(e) centent of the flow of hydrogen modification ", heavy petrol hydro-upgrading unit feed is high, can ensure the high aromatization rate of gasoline, subtract
Few loss of octane number；Since catalyst for hydro-upgrading is with hydrodesulfurization function, heavy petrol experienced first slight desulfurization,
The relay sweetening process of deep desulfuration again is also beneficial to reduce loss of octane number.
Description of the drawings
Fig. 1 is the flow chart of institute's poor quality gasoline hydrogenation method for modifying of the invention.
Specific implementation mode
It elaborates below to the embodiment of the present invention：The present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and process, but protection scope of the present invention is not limited to following embodiments, following implementation
Test method without specific conditions in example, usually according to normal condition.
The present invention gasoline hydrogenation inferior modification method be：Catalytic gasoline and hydrogen are mixed into pre-hydrotreating reaction
Device removes alkadienes；Pre- hydrogenation products enter fractionating column by gasoline be cut into it is light, in, three components of heavy petrol；It is come out from tower top
Light petrol component directly as clean gasoline blend component, from the middle gasoline component of fractionating column lateral line withdrawal function be introduced into first plus
Hydrogen desulfurization reactor carries out mild hydrogenation desulphurization reaction, and product, which returns again to fractionating column, to be continued to cut；It is come out from fractionation column base
Heavy gasoline components are introduced into hydro-upgrading reactor and carry out the reactions such as mild hydrogenation desulfurization and aromatisation, isomerization, and heavy petrol adds
Hydrogen product enters back into the second hydrodesulphurisatioreactors reactors and carries out deep hydrodesulfurizationof reaction；It is come out from the second hydrodesulphurisatioreactors reactors
After material cooling, gas-liquid separation is carried out into product separator；The hydrogen come out from gas-liquid separator recycles after desulfurization process
It uses, liquid-phase product enters after stabilizer removing lighter hydrocarbons and hydrogen sulfide is mixed to get final reformulated gasoline product with light petrol.
The technological process of the present invention can also be expressed as：Enter pre-hydrogenator after gasoline stocks and hydrogen are mixed,
In 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/ of hydrogen to oil volume ratio
It is contacted with catalyst for pre-hydrogenation under the conditions of v and carries out hydrogenation reaction, the diene selective of easy green coke in catalytic gasoline is saturated into list
Alkene, and low boiling point mercaptan in light petrol is transferred in heavy petrol by diene thioetherification reaction.Pre- hydrogenation products enter back into
Fractionating column, in 0.5~1.0Mpa of tower top pressure, 90~130 DEG C of feeding temperature, 70~110 DEG C of tower top temperature, column bottom temperature 190
Under the conditions of~230 DEG C by gasoline be divided into it is light, in, heavy constituent；Middle gasoline enters the first hydrodesulfurization reaction after being mixed with hydrogen
Device, in 1.0~3.0Mpa of hydrogen partial pressure, 200~300 DEG C of reaction temperature, 2.0~5.0h of volume space velocity-1, hydrogen to oil volume ratio 200~
Mild hydrogenation desulphurization reaction is carried out with mild hydrogenation hydrodesulfurization catalyst under 400v/v, middle gasoline hydrogenation product returns again to fractionation
Tower is fed；From fractionation column base come out heavy petrol mixed with hydrogen after be introduced into hydro-upgrading reactor, hydrogen partial pressure 1.0~
3.0Mpa, 320~450 DEG C of reaction temperature, 1.0~3.0h of volume space velocity-1, under the conditions of 250~500v/v of hydrogen to oil volume ratio with plus
Hydrogen modifying catalyst contacts, and hydrodesulfurization, aromatisation and isomerization reaction occurs, while with reactions such as a small amount of alkene saturations.
Hydro-upgrading reaction product enters back into the second hydrodesulphurisatioreactors reactors, in 1.0~3.0Mpa of hydrogen partial pressure, reaction temperature 220~350
DEG C, 2.0~5.0h of volume space velocity-1, contacted with catalyst for selectively hydrodesulfurizing under the conditions of 250~500v/v of hydrogen to oil volume ratio into
Row deep hydrodesulfurizationof reacts, and after the cooling of hydrodesulfurization product, is detached into product separator and carries out gas-liquid separation.From gas-liquid point
From device come out hydrogen recycled after desulfurization process, liquid-phase product enters product stabilizer, tower top pressure 0.7~
Gasoline is removed under the conditions of 1.2Mpa, 140~200 DEG C of feeding temperature, 120~180 DEG C of tower top temperature, 180~240 DEG C of column bottom temperature
The lighter hydrocarbons and hydrogen sulfide of middle dissolving, are finally mixed to get reformulated gasoline product with light petrol.
Wherein, under the above-mentioned reaction condition of the first hydrodesulphurisatioreactors reactors, in catalytic gasoline 30 in gasoline component~
50% sulfur-containing compound will be hydrogenated removing, while the removal efficiency of thiophene is more than 60%, and alkene saturation factor is less than 10%；From fractionation
The light petrol component that tower top comes out can be directly entered products pot as clean gasoline blend component, can also be through Etherification of Light FCC Gasoline
Cell processing is re-used as clean gasoline blend component after promoting light petrol octane number；The heavy gasoline components come out from Fractionator Bottom
Hydro-upgrading reactor is initially entered with hydrogen mixing, is contacted with catalyst for hydro-upgrading, carries out mild hydrogenation desulfurization and alkene
Isomery aromatization, by heavy gasoline components sulfur content hydrogenation and removing 20~50%；The heavy vapour come out from hydro-upgrading reactor
Oily hydrogenation products enter back into the second hydrodesulphurisatioreactors reactors, are contacted with catalyst for selectively hydrodesulfurizing, and sulfur content plus hydrogen are taken off
Remove to less than 50mg/kg (IV gasoline standard of state) or be less than 10mg/kg (state V and the above gasoline standard).
The present invention is suitable for the hydro-upgrading of catalytically cracked gasoline inferior, and gasoline upgrading technique of the invention uses full fraction
Gasoline pretreatment then by fractionating column by catalytic gasoline be separated into it is light, in, weigh three components, after middle gasoline mild hydrogenation desulfurization
Fractionating column is returned to, heavy petrol is using first hydro-upgrading and then the technological process of hydrodesulfurization.
When the method for the present invention produces sulfur content less than IV gasoline blend component of 50mg/kg states, research octane number (RON) loss is small
In 1.0 units；When producing sulfur content less than V gasoline blend component of 15mg/kg states, research octane number (RON) loss is less than 2.0
Unit；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, is mediated, extrusion molding, 120 DEG C of drying,
500 DEG C roast 4 hours, then are roasted 4 hours at 900 DEG C, obtain catalyst carrier.It is molten by being stirred in 14g ammonium molybdates addition 45g water
Solution, adds 75g nickel nitrates, 12g citric acids, catalyst activity metal impregnation liquid is made in stirring and dissolving.By catalyst carrier plus
Entering in above-mentioned maceration extract, taken out after being impregnated 3 hours under room temperature, is aged 12 hours, then 120 DEG C of drying, 500 DEG C roast 4 hours,
Finished catalyst A (referring to ZL201210367401.1, being not limited to this method) is made.
(2) mild hydrogenation desulphurization catalyst：Industrial boehmite powder 84g, H beta-molecular sieve 40g is taken, sesbania powder 4g, nitre are added
Sour 3.5g, water 105g are mediated, extrusion molding, and 120 DEG C of drying, 500 DEG C roast 4 hours, obtain catalyst carrier.By 10g molybdic acids
Ammonium is added in 55g water and stirs, and 6g phosphoric acid, 5g cobalt nitrates, 5g nickel nitrates is added, and the leaching of catalyst activity metal is made in stirring and dissolving
Stain liquid.Using above-mentioned metallic solution impregnated catalyst support, it is aged 6 hours, then 120 DEG C of drying, 500 DEG C roast 4 hours, system
Obtain finished catalyst B (being not limited to this method).
(3) catalyst for hydro-upgrading：HZSM-5 molecular sieves 150g, alumina powder 40g are taken, a concentration of 3g/ of 150ml are added
The dilute nitric acid solution of 100ml is mediated, extrusion molding, and 120 DEG C of drying, 500 DEG C roast 4 hours, obtain catalyst carrier.It takes
It states carrier 100g to be put into the solution of 200ml molybdenums, nickel, lanthanum, solution concentration MoO3 10g/100ml、NiO 3.5g/100ml、
La2O31.6g/100ml impregnates 2 hours under room temperature, and by 120 DEG C of drying of catalyst after separation of solid and liquid, 500 DEG C roast 4 hours, system
Obtain finished catalyst C (referring to ZL200410074059.1, being not limited to this method).
(4) catalyst for selectively hydrodesulfurizing：Take ZrO made from 50g2-Al2O310g kaliophilites, 1.25g is added in powder
Sesbania powder, 30ml water are mediated, extrusion molding, and 120 DEG C of drying, 550 DEG C roast 4 hours, obtain catalyst carrier.Weigh 13g nitre
Sour cobalt, 15g ammonium molybdates EDTA, weak aqua ammonia complexing dissolving, add 10g ammonium dihydrogen phosphates, 15g magnesium nitrates, stirring and dissolving, system
At catalyst activity metal impregnation liquid.Using above-mentioned metallic solution impregnated catalyst support, it is aged 4 hours, then 120 DEG C of bakings
Dry, 450 DEG C roast 4 hours, and finished catalyst D (referring to ZL201010252648.X, being not limited to this method) is made.
Comparative example 1
Using a kind of catalytically cracked gasoline as raw material, property is shown in Table the catalytic gasoline 1 listed by 1.Catalytic gasoline is first in hydrogen point
Press 2.2Mpa, 110 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:Located in advance using A catalyst under the conditions of 1
Reason cuts into light, two components of heavy petrol subsequently into fractionating column, fractionation column pressure on top surface 0.7Mpa, 120 DEG C of feeding temperature,
80 DEG C of tower top temperature, 205 DEG C of column bottom temperature, heavy naphtha accounts for the 65% of raw material.Heavy petrol is mixed into hydrogen first to be added
Hydrogen reforming reactor is in hydrogen partial 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 using C catalyst carry out hydro-upgrading, subsequently into hydrodesulphurisatioreactors reactors in hydrogen partial pressure 1.8MPa, reaction temperature
255 DEG C, volume space velocity 2.44h-1, hydrogen to oil volume ratio 250:Hydrodesulfurization is carried out using D catalyst under the conditions of 1, after product cooling
Gas-liquid separation is carried out into product separator, the hydrogen come out at the top of product separator enters after recycle hydrogen sulphur tower desulfurization process
Circulating hydrogen compressor recycles, and product separator bottom liquid phases product enters stabilizer, in tower top pressure 0.85Mpa, charging
155 DEG C of temperature, 145 DEG C of tower top temperature remove sulfurous gas under the conditions of 215 DEG C of column bottom temperature, are mixed to get with light petrol component
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 41mg/kg, desulfurization
Rate 89.3%, olefin(e) centent drop to 26.0% from 41.0%, and octane number (RON) loses 1.2 units.
Comparative example 2
The feedstock oil that comparative example 2 uses is identical as comparative example 1.Catalytic gasoline is first in hydrogen partial pressure 2.2Mpa, reaction temperature 120
DEG C, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:It is pre-processed using A catalyst under the conditions of 1, is cut subsequently into fractionating column
At light, 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, column bottom temperature
200 DEG C, heavy naphtha accounts for the 80% of raw material.Heavy petrol is mixed into hydro-upgrading reactor in hydrogen partial pressure with hydrogen first
2.0MPa, 380 DEG C of reaction temperature, volume space velocity 1.5h-1, hydrogen to oil volume ratio 300:It is carried out using C catalyst under 1 reaction condition
Hydro-upgrading, subsequently into hydrodesulphurisatioreactors reactors in hydrogen partial pressure 1.8MPa, 275 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen
Oil volume is than 300:Hydrodesulfurization is carried out using D catalyst under the conditions of 1, entering product separator after product cooling carries out gas-liquid point
From the hydrogen at the top of product separator out enters circulating hydrogen compressor after recycle hydrogen sulphur tower desulfurization process and recycles, production
Product separator bottom liquid-phase product enters stabilizer, in tower top pressure 0.88Mpa, 150 DEG C of feeding temperature, and 140 DEG C of tower top temperature,
Sulfurous gas is removed under the conditions of 210 DEG C of column bottom temperature, clean gasoline product is mixed to get with light petrol component.Process conditions and life
It is shown in Table 2 at oil nature.From table 2 it can be seen that product sulfur content is 11mg/kg, desulfurization degree 97.1%, olefin(e) centent is from 41v%
Drop to 22.3v%, octane number (RON) loses 2.2 units.
Comparative example 3
The feedstock oil that comparative example 3 uses is identical as comparative example 1.Catalytic gasoline is first in hydrogen partial pressure 2.2Mpa, reaction temperature 120
DEG C, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:It is pre-processed using A catalyst under the conditions of 1, is cut subsequently into fractionating column
At it is light, in, three components of heavy petrol, fractionation column pressure on top surface 0.7Mpa, 118 DEG C of feeding temperature, 75 DEG C of tower top temperature, bottom of tower temperature
202 DEG C of degree, middle gasoline fraction accounts for the 50% of raw material, and heavy naphtha accounts for the 20% of raw material.Middle gasoline is mixed into hydrogen first
Enter the first hydrodesulphurisatioreactors reactors, in hydrogen partial pressure 2.2MPa, 230 DEG C of reaction temperature, volume space velocity 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 first and hydrogen
Gas is mixed into hydrodesulphurisatioreactors reactors in hydrogen partial pressure 1.8MPa, 250 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio
300:Hydrodesulfurization is carried out using D catalyst under the conditions of 1, subsequently into hydro-upgrading reactor in hydrogen partial pressure 2.0MPa, reaction
380 DEG C of temperature, volume space velocity 1.5h-1, hydrogen to oil volume ratio 300:Under 1 reaction condition hydro-upgrading, production are carried out using C catalyst
Enter product separator after product cooling and carry out gas-liquid separation, the hydrogen at the top of product separator out through recycle hydrogen sulphur tower desulfurization at
Enter circulating hydrogen compressor after reason to recycle, product separator bottom liquid phases product enters stabilizer, in tower top pressure
0.88Mpa, 153 DEG C of feeding temperature, 143 DEG C of tower top temperature remove sulfurous gas under the conditions of 212 DEG C of column bottom temperature, with light petrol
Component is mixed to get 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, desulfurization degree 97.4%, olefin(e) centent drop to 24v% from 41v%, and octane number (RON) loses 1.8 units.
Embodiment 1
The feedstock oil that embodiment 1 uses is identical as comparative example 1.Catalytic gasoline is first in hydrogen partial pressure 2.2Mpa, reaction temperature 110
DEG C, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:It is pre-processed using A catalyst under the conditions of 1, is cut subsequently into fractionating column
At it is light, in, three components of heavy petrol, fractionation column pressure on top surface 0.7Mpa, 122 DEG C of feeding temperature, 85 DEG C of tower top temperature, bottom of tower temperature
210 DEG C of degree, middle gasoline fraction accounts for the 40% of raw material, and heavy naphtha accounts for the 20% of raw material.Middle gasoline is mixed into hydrogen first
Enter the first hydrodesulphurisatioreactors reactors, in hydrogen partial pressure 2.2MPa, 220 DEG C of reaction temperature, volume space velocity 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 first and hydrogen
Gas is mixed into hydro-upgrading reactor in hydrogen partial pressure 2.0MPa, 370 DEG C of reaction temperature, volume space velocity 1.22h-1, hydrogen oil volume
Than 250:Hydro-upgrading is carried out using C catalyst under 1 reaction condition, subsequently into hydrodesulphurisatioreactors reactors in hydrogen partial pressure
1.8MPa, 235 DEG C of reaction temperature, volume space velocity 2.44h-1, hydrogen to oil volume ratio 250:It is carried out plus hydrogen using D catalyst under the conditions of 1
Desulfurization enters product separator and carries out gas-liquid separation after product cooling, the hydrogen come out at the top of product separator is through recycle hydrogen sulphur
Enter circulating hydrogen compressor after tower desulfurization process to recycle, product separator bottom liquid phases product enters stabilizer, in tower top
Pressure 0.87Mpa, 158 DEG C of feeding temperature, 146 DEG C of tower top temperature remove sulfurous gas under the conditions of 218 DEG C of column bottom temperature, and light
Gasoline component is mixed to get clean gasoline product.Process conditions and generation oil nature are shown in Table 2.From table 2 it can be seen that product sulphur contains
It is 40mg/kg to measure, desulfurization degree 89.5%, and olefin(e) centent drops to 27.8v% from 41v%, and octane number (RON) loses 0.4 list
Position.
Embodiment 2
The feedstock oil that embodiment 2 uses is identical as comparative example 2.Catalytic gasoline is first in hydrogen partial pressure 2.2Mpa, reaction temperature 120
DEG C, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:It is pre-processed using A catalyst under the conditions of 1, is cut subsequently into fractionating column
At it is light, in, three components of heavy petrol, fractionation column pressure on top surface 0.7Mpa, 118 DEG C of feeding temperature, 75 DEG C of tower top temperature, bottom of tower temperature
202 DEG C of degree, middle gasoline fraction accounts for the 50% of raw material, and heavy naphtha accounts for the 20% of raw material.Middle gasoline is mixed into hydrogen first
Enter the first hydrodesulphurisatioreactors reactors, in hydrogen partial pressure 2.2MPa, 230 DEG C of reaction temperature, volume space velocity 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 first and hydrogen
Gas is mixed into hydro-upgrading reactor in hydrogen partial pressure 2.0MPa, 380 DEG C of reaction temperature, volume space velocity 1.5h-1, hydrogen to oil volume ratio
300:Hydro-upgrading is carried out using C catalyst under 1 reaction condition, subsequently into hydrodesulphurisatioreactors reactors in hydrogen partial pressure
1.8MPa, 255 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 300:It is carried out using D catalyst under the conditions of 1 plus hydrogen is de-
Sulphur enters product separator and carries out gas-liquid separation after product cooling, the hydrogen come out at the top of product separator is through recycle hydrogen sulphur tower
Enter circulating hydrogen compressor after desulfurization process to recycle, product separator bottom liquid phases product enters stabilizer, in tower top pressure
Power 0.88Mpa, 153 DEG C of feeding temperature, 143 DEG C of tower top temperature remove sulfurous gas under the conditions of 212 DEG C of column bottom temperature, with light vapour
Oil ingredient is mixed to get 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
For 10mg/kg, desulfurization degree 97.4%, olefin(e) centent drops to 26.5v% from 41v%, and octane number (RON) loses 1.0 units.
Embodiment 3
The feedstock oil that embodiment 3 uses is shown in Table the catalytic gasoline 2 listed by 1.Catalytic gasoline is first in hydrogen partial pressure 2.2Mpa, reaction
120 DEG C of temperature, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10:Pre-processed using A catalyst under the conditions of 1, subsequently into point
Evaporate tower cut into it is light, in, three components of heavy petrol, fractionation column pressure on top surface 0.7Mpa, 116 DEG C of feeding temperature, tower top temperature 73
DEG C, 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
Gas is mixed into the first hydrodesulphurisatioreactors reactors, in hydrogen partial pressure 2.2MPa, 240 DEG C of reaction temperature, volume space velocity 3.0h-1, hydrogen 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 first
First and hydrogen is mixed into hydro-upgrading reactor in hydrogen partial pressure 2.0MPa, 380 DEG C of reaction temperature, volume space velocity 1.5h-1, hydrogen oil
Volume ratio 300:Hydro-upgrading is carried out using C catalyst under 1 reaction condition, subsequently into hydrodesulphurisatioreactors reactors in hydrogen partial pressure
1.8MPa, 265 DEG C of reaction temperature, volume space velocity 2.5h-1, hydrogen to oil volume ratio 300:It is carried out using D catalyst under the conditions of 1 plus hydrogen is de-
Sulphur enters product separator and carries out gas-liquid separation after product cooling, the hydrogen come out at the top of product separator is through recycle hydrogen sulphur tower
Enter circulating hydrogen compressor after desulfurization process to recycle, product separator bottom liquid phases product enters stabilizer, in tower top pressure
Power 0.87Mpa, 151 DEG C of feeding temperature, 142 DEG C of tower top temperature remove sulfurous gas under the conditions of 210 DEG C of column bottom temperature, with light vapour
Oil ingredient is mixed to get 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
For 12mg/kg, desulfurization degree 98.0%, olefin(e) centent drops to 25v% from 40v%, and octane number (RON) loses 1.2 units.
Table 1
Table 2
Comparative result when comparative example 1 and embodiment 1 are IV gasoline products of producing country, comparative example 2 are production with embodiment 2
Comparative result when V gasoline products of state.The main distinction is that the embodiment of the present invention 1, embodiment 2 contain " middle gasoline pumping
Go out, mild hydrogenation desulfurization " processing unit, and comparative example 1, comparative example 2 do not have.Processing sulphur is contained it can be seen from 2 result of table
The catalytic gasoline of 382mg/kg, alkene 41.0v% are measured, under IV scheme of state, 89.5% desulfurization degree, embodiment 1 is pungent compared with comparative example 1
Alkane value loses 0.8 unit less；Under V scheme of state, 97.4% identical desulfurization degree, embodiment 2 is lost less compared with 2 octane number of comparative example
1.2 units；
Comparative result when comparative example 3 and embodiment 2 are V gasoline products of producing country.The main distinction is the reality of the present invention
Flow of the example 2 using " the hydro-upgrading back end hydrogenation desulfurization of heavy petrol elder generation " is applied, and comparative example 3 is using " after the hydrodesulfurization of heavy petrol elder generation
The flow of hydro-upgrading ".It can be seen from 2 result of table under V scheme of state, 97.4% identical desulfurization degree, embodiment 2 relatively compares
3 octane number of example loses 0.8 unit less；In addition, using the method for the present invention processing sulfur content 695mg/kg, alkene 40v% it is another
A kind of catalytic gasoline, under 98.3% desulfurization degree, alkene reduces 15v%, and octane number only loses 1.2 units.
Beneficial effects of the present invention：
1, using the pre- hydrogenation technique of full distillation gasoline, the diene content in gasoline is reduced, and be greatly reduced in light petrol
Mercaptans content avoid the discharge of the disagreeableness alkaline residue of environment instead of alkali refining removal of mercaptans process, alkadienes in heavy petrol
Content is reduced, and substantially extends the cycle of operation of Hydrobon catalyst；
2, use be cut into after the pre- hydrogenation technique of full fraction it is light, in, three component of heavy petrol, middle gasoline component hydrodesulfurization
The flow that fractionating column is cut again is returned again to afterwards, which can be greatly reduced middle gasoline component section sulfur content, therefore relative to complete
The flow directly cut after fraction pre-add hydrogen can be improved light petrol cutting ratio, reduce heavy petrol alkene and sulfur content, subtract
Loss of octane number caused by few heavy petrol hydrodesulfurization is specially adapted to the high bad gasoline of processing thiophene content；
3, using the flow of " the hydro-upgrading back end hydrogenation desulfurization of heavy petrol elder generation ", relative to " after the hydrodesulfurization of heavy petrol elder generation plus
The olefin(e) centent of the flow of hydrogen modification ", the charging of heavy petrol reforming unit is high, can ensure the high aromatization rate of gasoline, reduces pungent
Alkane value is lost；Since catalyst for hydro-upgrading is with hydrodesulfurization function, heavy petrol experienced first slight desulfurization, then deep
The relay sweetening process for spending desulfurization is also beneficial to reduce loss of octane number.
Certainly, the present invention can also have other various embodiments, without deviating from the spirit and substance of the present invention, ripe
Various corresponding change and deformations, but these corresponding change and deformations can be made according to the present invention by knowing those skilled in the art
The protection domain of the claims in the present invention should all be belonged to.
Claims (9)
1. a kind of method of poor quality gasoline hydrogenation modification, which is characterized in that this approach includes the following steps：
(1) enter pre-hydrogenator after catalytic gasoline is mixed with hydrogen, reacted in the presence of catalyst for pre-hydrogenation, reacted
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, hydrogen to oil volume ratio 10
~200v/v；
(2) step (1) product enters in fractionating column, in 0.5~1.0Mpa of tower top pressure, 90~130 DEG C of feeding temperature, tower top temperature
70~110 DEG C of degree, cut at 190~230 DEG C of column bottom temperature it is light, in, heavy gasoline components；
(3) the light petrol component being ejected from fractionation column comes out directly as reformulated gasoline blend component from fractionating column side line
Middle gasoline component and hydrogen mixing after enter the first hydrodesulphurisatioreactors reactors, carried out in the presence of mild hydrogenation desulphurization catalyst
Reaction, reaction condition are：1.0~3.0Mpa of hydrogen partial pressure, 200~300 DEG C of reaction temperature, 2.0~5.0h of volume space velocity-1, hydrogen
Oil volume is returned again to than 200~400v/v, middle gasoline hydrodesulfurizationmethod product in fractionating column；
(4) enter hydro-upgrading reactor after heavy gasoline components and the hydrogen mixing come out from fractionation column bottom, in hydro-upgrading
It is reacted in the presence of catalyst, reaction condition is：1.0~3.0Mpa of hydrogen partial pressure, 320~450 DEG C of reaction temperature, volume space velocity
1.0~3.0h-1, 250~500v/v of hydrogen to oil volume ratio；
(5) product of step (4) enters the second hydrodesulphurisatioreactors reactors, is carried out in the presence of catalyst for selectively hydrodesulfurizing anti-
It answers, reaction condition is：1.0~3.0Mpa of hydrogen partial pressure, 220~350 DEG C of reaction temperature, 2.0~5.0h of volume space velocity-1, hydrogen oil body
250~500v/v of product ratio；And
(6) after the cooling of step (5) product, gas-liquid separation, the hydrogen come out at the top of product separator are carried out into product separator
Enter circulating hydrogen compressor after desulphurization of recycle hydrogen tower desulfurization process to recycle, product separator bottom liquid phases product enters steady
Tower is determined, in 0.7~1.2Mpa of tower top pressure, 140~200 DEG C of feeding temperature, 120~180 DEG C of tower top temperature, column bottom temperature 180
Sulfurous gas is removed under the conditions of~240 DEG C, reformulated gasoline product is mixed to get with light petrol.
2. the method for poor quality gasoline hydrogenation modification according to claim 1, which is characterized in that the pre- hydrogenation catalyst
Agent carrier is the mixture of aluminium oxide, silica or both, and active component is one or more of the VIth B, the VIIIth race, by urging
Agent weight 100% is counted, and active component oxide content is 10~30%, and surplus is carrier.
3. the method for poor quality gasoline hydrogenation modification according to claim 1, which is characterized in that the pre- hydrogenation catalyst
Agent specific surface area is 100~300m20.2~0.6ml/g of/g, Kong Rongwei.
4. the method for poor quality gasoline hydrogenation modification according to claim 1, which is characterized in that the mild hydrogenation is de-
Sulfur catalyst carrier is the mixture of aluminium oxide and hydrogen type molecular sieve, and active component is one kind or several in the VIth B, the VIIIth race
Kind, the molecular sieve is one or more of HZSM-5, HMCM-22, H β and HY, and the molecular sieve accounts for the 10 of catalyst weight
~60%, active component oxide accounts for the 5~15% of catalyst weight.
5. the method for poor quality gasoline hydrogenation modification according to claim 1, which is characterized in that the mild hydrogenation is de-
Sulfur catalyst specific surface area is 200~400m20.4~0.8ml/g of/g, Kong Rongwei.
6. the method for poor quality gasoline hydrogenation modification according to claim 1, which is characterized in that the hydro-upgrading is urged
Agent carrier is the compound of aluminium oxide and molecular sieve, and active component is the VIth B, one or more of the VIIIth race, described point
Son sieve is one or more of ZSM-5, Beta, SAPO molecular sieve, in terms of catalyst weight 100%, the molecular sieve content
It is 60~90%, the active component oxide content is 1~10%.
7. the method for poor quality gasoline hydrogenation modification according to claim 1, which is characterized in that the hydro-upgrading is urged
Agent specific surface area is 200~500m20.2~0.5ml/g of/g, Kong Rongwei.
8. the method for poor quality gasoline hydrogenation modification according to claim 1, which is characterized in that the selective hydrogenation
Desulphurization catalyst is with Al2O3、SiO2、TiO2And ZrO2One or more of be carrier, with P2O5、K2One kind in O and MgO or
Several is auxiliary agent, and active component is one or more of VI B races, VIII race, based on catalyst weight 100%, active component oxygen
Compound accounts for 6~20%, and auxiliary agent accounts for 1~15%, and surplus is carrier；The catalyst for selectively hydrodesulfurizing specific surface area is 170
~270m20.3~0.6ml/g of/g, Kong Rongwei.
9. the method for poor quality gasoline hydrogenation modification according to claim 1, which is characterized in that the catalytic gasoline is
Catalytically cracked gasoline, sulfur content are less than or equal to 1000mg/kg, and olefin(e) centent 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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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
|---|---|---|---|---|
| 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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