CN1718688A - Hydrogenation modification method of faulty gasoline - Google Patents
Hydrogenation modification method of faulty gasoline Download PDFInfo
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- CN1718688A CN1718688A CN 200410020932 CN200410020932A CN1718688A CN 1718688 A CN1718688 A CN 1718688A CN 200410020932 CN200410020932 CN 200410020932 CN 200410020932 A CN200410020932 A CN 200410020932A CN 1718688 A CN1718688 A CN 1718688A
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- 238000005984 hydrogenation reaction Methods 0.000 title claims description 14
- 238000002715 modification method Methods 0.000 title claims description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 65
- 239000003054 catalyst Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 23
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001336 alkenes Chemical class 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 27
- 239000001257 hydrogen Substances 0.000 claims description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 8
- 238000006317 isomerization reaction Methods 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- 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 8
- 239000011148 porous material Substances 0.000 claims description 7
- 238000002407 reforming Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 150000001993 dienes Chemical class 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 239000012752 auxiliary agent Substances 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims description 2
- 150000004706 metal oxides Chemical class 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 18
- 239000005864 Sulphur Substances 0.000 description 17
- 238000004231 fluid catalytic cracking Methods 0.000 description 14
- 238000006477 desulfuration reaction Methods 0.000 description 13
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 12
- 230000023556 desulfurization Effects 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000000470 constituent Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000010523 cascade reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- DFHAXXVZCFXGOQ-UHFFFAOYSA-K trisodium phosphonoformate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)P([O-])([O-])=O DFHAXXVZCFXGOQ-UHFFFAOYSA-K 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A process for hydromodifying the poor-quality gasolinge(full-fraction FCC gasoline) features that under existence of H2 and in the condition that the temp is gradually raised, said gasoline is in contact with three catalysts to form 3 reaction regions. In the first low-temp region, the hydrorefining catalyst is used for removing biolefine. In the second higher-temp region, the modifying catalyst is used for increasing octane value and quality. In the third high-temp region, the selective hydrodesulfurizing catalyst is used for removing organic sulfide.
Description
Technical field
The present invention relates to a kind of method for modifying of inferior patrol, the hydrogenation modification method of inferior patrols such as particularly full cut FCC gasoline.
Background technology
The sustainable development of national economy has driven the fast development of automotive industry and transportation, and the objectionable impurities of motor vehicle exhaust has simultaneously become the maximum public hazards of urban air severe contamination.Along with the continuous enhancing of people's environmental consciousness, the human ball ecological environment of depending on for existence of protection, the cry of building blue sky is more and more high.Implement new motor vehicle exhaust pollutent control criterion, automobile and fuel production are all had higher requirement.For this reason, world many countries has proposed more and more higher standard to the quality of oil fuel, is not more than 50 μ g/g as the sulphur content of European IV vehicle exhaust standard-required European clean gasoline after 2005, and olefin(e) centent is 14v%～18v%; The sulphur content of U.S. U.S.EPA Tier2 standard code U.S.'s clean gasoline after 2006 is not more than 80 μ g/g, and olefin(e) centent is not more than 14v%.China from the petrol and diesel oil quality of main cities in 2005 with reference to European III class A fuel A standard (sulphur content ≯ 150 μ g/g, aromatic hydrocarbons ≯ 42.0v%, alkene ≯ 18.0v%) carry out.
FCC (fluid catalytic cracking) technology is the important source of gasoline, but FCC sulfur in gasoline and olefin(e) centent are higher, be respectively 500 μ g/g～2000 μ g/g and 40v%～55v%, but aromaticity content is lower, only is 10v%～25v%.Thereby the key of clean gasoline production is the FCC gasoline hydrodesulfurizationmethod, falls alkene.If adopt traditional hydrofining technology to carry out the FCC gasoline desulfur, fall alkene, the loss of octane number of product is bigger, and RON can lose 7～10 units, has also increased the hydrogen consumption simultaneously.
US4397739 has proposed at first gasoline rectifying to be become light constituent and heavy constituent before hydrotreatment, heavy constituent is carried out the method for specific hydrogenating desulfurization again.The give chapter and verse difference of gasoline boiling point of patent US4131537 becomes several fractions with gasoline rectifying, three kinds of cuts preferably, and then under different condition, carry out desulfurization respectively.Above-mentioned technology can be by lighter fraction caustic wash desulfuration and heavy fractioning hydrogenation desulfurization, the purpose of reach and fall alkene, falling sulphur can avoid again that the light olefin hydrogenation is saturated to cause too much loss of octane number.Also there is deficiency in above-mentioned technology, and that is exactly to reduce more for a long time at product requirement alkene, still can not avoid the too much loss of octane value, generates substandard product, and the hydrogenation saturation of olefins also can increase the hydrogen consumption greatly.
CN1316485A, US5865988 etc. have proposed a kind of technology of gasoline being carried out modification by isomerizing hydrogenation, and this technology comprises two sections cascade reactions, and first section is carried out olefin isomerization, carries out hydrogenation reaction at second section then.First section dress be olefin isomerization catalyst, second section dress be olefin hydrogenation catalyst, this two-stage catalytic agent can be respectively charged into two reactors, or in the same reactor of packing into.Because isomerization reaction needs to carry out under the temperature more higher than hydrogenation reaction, therefore, carry out carrying out behind the isomerization reaction flow arrangement of hydrogenation reaction earlier, Btu utilization is unreasonable, and the hydrogenator temperature in is wayward, also has the bigger shortcoming of hydrogen consumption simultaneously.EP0537372A1 two-step approach modified gasoline, the first step select hydrogenation to remove high unsaturated hydrocarbons such as alkynes in the gasoline, diolefine, and second step carried out isomerization to the alkene in the gasoline and handles.The desulfurizing function of this flow process is relatively poor, and is inapplicable for the gasoline that sulphur content is higher.If follow-up increase hydrodesulfurisationstep step, because common Hydrobon catalyst needs (general below 300 ℃) operation at a lower temperature, and the temperature higher (general about 400 ℃) of upgradings such as isomerization reaction, therefore must increase an independently reactor, facility investment and process cost all can significantly increase, and can make the alkene in the product further saturated, reduce the octane value of gasoline products, increase the hydrogen consumption.
Summary of the invention
At the deficiencies in the prior art, the present invention propose a kind of turndown ratio greatly, organic sulfide removal thing, running is stable, flow process simple, investment is low, alkene falls in full cut FCC gasoline hydrodesulfurizationmethod that the catalyst runs cycle is long production method to greatest extent.
Olefins process falls in inferior patrol hydrogenating desulfurization of the present invention, and bad gasoline such as full cut FCC gasoline in the presence of hydrogen, are contacted with three kinds of different catalysts, forms three reaction zones.Contact with Hydrobon catalyst at first at a lower temperature and form first reaction zone, mainly remove the diolefin in the gasoline; Reaction effluent contacts formation second reaction zone with modifying catalyst under comparatively high temps then, comprises reactions such as aromizing, isomerization and benzene alkylation, improves the octane value of gasoline; The final reaction effluent forms the 3rd reaction zone with catalyst for selectively hydrodesulfurizing under comparatively high temps, remove wherein organic sulfide and part alkene to greatest extent, guarantees the octane value that loss is minimum.
The operational condition of above-mentioned first reaction zone is: hydrogen dividing potential drop 1.5～6.0 MPas, volume space velocity 0.5～8.0 hour
-1, 160～220 ℃ of temperature of reaction, hydrogen to oil volume ratio 200～1200.The first reaction zone catalyzer is selected conventional Hydrobon catalyst for use.
The operational condition of second reaction zone is: hydrogen dividing potential drop 1.5～6.0 MPas, volume space velocity 0.5～8.0 hour
-1, 380～480 ℃ of temperature of reaction, hydrogen to oil volume ratio 200～1200.Second reaction zone uses the metal oxide content of gasoline reforming catalyst to be 1.0w%～10.0w%, and molecular sieve content is 50.0w%～90.0w%; Surplus is a binding agent.Metal is selected from one or more in zinc, iron, manganese, nickel, cobalt, molybdenum, tungsten, magnesium, calcium, the barium etc., one or more in preferably magnesium, zinc and the nickel.Molecular sieve is the hydrogen type molecular sieve of the little grain fineness number of grain fineness number in 20nm～800nm scope, as among HZSM-5, HL, HBeta, HM, HMCM-41, HSAPO-5, HSAPO-11, HSAPO-31 or the HSAPO-41 etc. one or more, particularly HZSM-5 and/or HBeta.The specific surface area of catalyzer is 300m
2/ g～600m
2/ g, pore volume are 0.15ml/g～0.55ml/g.
The operational condition of the 3rd reaction zone is: hydrogen dividing potential drop 1.5～6.0 MPas, volume space velocity 20.0～60.0 hours
-1, be preferably 30.0～50.0 hours
-1, 380～480 ℃ of temperature of reaction, hydrogen to oil volume ratio 200～1200.The 3rd reaction zone uses catalyst for selectively hydrodesulfurizing: catalyzer is carrier with aluminum oxide, is reactive metal with Mo and Co, is auxiliary agent with P and K, and wherein catalyzer contains MoO
37.0-18.0w% is preferably 10.0-16.0w%, is preferably 10.0-15.0w%, and CoO1.0-6.0w% is preferably 2.0-5.0w%, is preferably 2.0-4.0w%.Catalyzer pore volume 0.3-1.3ml/g, specific surface area 150-300m
2/ g, Co/Mo atomic ratio 0.1-1.0 is preferably 0.2-0.8, is preferably 0.25-0.72, contains potassium 0.2-10.2w%, is preferably 0.5-5.0w%, is preferably 1.0-3.0w%, and P/K atomic ratio 0.1-10.0 is preferably 0.8-5.0, is preferably 1.0-2.0.The second reaction zone catalyzer and the 3rd reaction zone catalyzer can be seated in the reactor simultaneously.
Compared with prior art, the inventive method has the following advantages:
(1) can be processed as the premium product by the inferior full cut FCC gasoline that sulphur, olefin(e) centent is higher, as can be with the olefin(e) centent of full cut FCC gasoline and sulphur content respectively by being reduced to olefin(e) centent＜18 (v) %, sulphur content＜50 μ g/g,＜2.0 units of (R+M)/2 loss about 50v%, 1500 μ g/g.
(2) technology is simple, stable operation.Can adopt two, three reactors in series flow processs, the centre does not need separating device.
(3) Btu utilization is abundant, easy handling.Previous reaction zone is a strong exothermal reaction, and the temperature of reaction of latter two reaction zone needs to raise, and therefore can make full use of exothermic heat of reaction.The 3rd reaction zone effluent and reaction raw materials heat exchange can reach the required temperature of first reaction zone, do not need to establish in addition heating installation.
(4) compare with other technology, deep desulfuration is carried out in the logistics that enters the 3rd reaction zone.Select the suitable selective desulfurization catalyst of performance for use, with the gasoline upgrading reacting phase with temperature condition under, adopt higher air speed, can under situation about reaching, make the saturation exponent of alkene lower, help improving the product loss of octane number than high desulfurization rate, the hydrogen consumption is few simultaneously, and running expense is low.
Embodiment
Employed raw material is full cut FCC gasoline among the present invention, wherein olefin(e) centent and sulphur content ≯ 50v%, ≯ 1500 μ g/g.(v) %, sulphur content＜150 μ g/g, anti-knock index (R+M)/2 lose＜2.0 units to generate oily olefin(e) centent＜18.Alkene, sulphur content can reach European III, IV class A fuel A standard.
Raw materials usedly see Table 1.The commercial Hydrobon catalyst FH-98 that first reaction zone uses Wenzhou Hua Hua group company to produce, character sees Table 2-1.Second reaction zone uses gasoline reforming catalyst, and character sees Table 2-3.Gasoline modified catalyst can adopt ordinary method preparation, as: with little grain fineness number hydrogen type molecular sieve and binding agent according to required mixed, moulding, 10 hours, 520 ℃ following roastings of 120 ℃ of dryings 5 hours.Use the solution impregnation of metal ion then, 120 ℃ of dry down 10 hours, 480 ℃ roastings 6 hours.Use water vapor 450 ℃ of following hydrothermal treatment consists 10 hours at last, obtain final catalyzer.The 3rd reaction zone uses selects Hydrobon catalyst, and character sees Table 2-2.Second reaction zone and the 3rd reaction zone catalyzer are contained in the reactor.
Table 1, stock oil character
| Project | FCC gasoline stocks 1 | FCC gasoline stocks 2 | FCC gasoline stocks 3 |
| The boiling range scope, ℃ | 35～191 | 34～168 | 35～182 |
| Fluorescent method composition/v% | |||
| Stable hydrocarbon | 35.1 | 31.7 | 32.1 |
| Alkene | 41.3 | 54.2 | 56.3 |
| Aromatic hydrocarbons | 23.6 | 14.1 | 11.6 |
| Sulphur, μ g/g | 730 | 1600 | 230 |
| Nitrogen, μ g/g | 47 | 53 | 40 |
| Diolefin, gI/100g | 1.67 | 2.54 | 2.60 |
| RON | 93.0 | 92.2 | 90.6 |
| MON | 80.6 | 80.4 | 76.8 |
| (R+M)/2 | 86.8 | 86.3 | 83.7 |
The composition and the character of table 2-1, FH-98 hydrogenation catalyst
| Catalyzer | FH-98 |
| Chemical constitution, w% | |
| WO 3 | 20.2 |
| MoO 3 | 9.3 |
| NiO | 4.2 |
| Pore volume, ml/g | 0.30 |
| Specific surface area, m 2/g | 140 |
Table 2-2, selective desulfurization catalyst are formed and character
| Project | DS-A | DS-B | DS-C |
| MoO 3，w％ | 8.1 | 11.9 | 15.8 |
| CoO，w％ | 2.5 | 3.2 | 4.0 |
| The Co/Mo atomic ratio | 0.59 | 0.52 | 0.49 |
| P，w％ | 1.7 | 1.6 | 1.8 |
| K 2O，w％ | 2.6 | 2.5 | 2.7 |
| The P/K atomic ratio | 1.0 | 1.0 | 1.0 |
| Pore volume, ml/g | 0.49 | 0.47 | 0.45 |
| Specific surface area, m 2/g | 205 | 200 | 199 |
Table 2-3, gasoline reforming catalyst are formed and character
| Project | MQ-A | MQ-B | MQ-C |
| Form and content w% | NiO 1.5％ MgO 0.25％ | NiO 3.0％ MgO 0.5％ | NiO 6.0％ MgO 1.0％ ZnO 0.50％ |
| Crystal grain 70～150nm SiO 2/Al 2O 3The Hbeta of mol ratio 33 (A) is 60% | Crystal grain 100～500nm SiO 2/Al 2O 3The HZSM-5 of mol ratio 27 (B) is 70% | A：35％ B：40％ | |
| Al 2O 3Surplus | Al 2O 3Surplus | Al 2O 3Surplus | |
| Specific surface area, m 2/g | 505 | 335 | 397 |
| Pore volume, ml/g | 0.40 | 0.23 | 0.33 |
Embodiment 1～3
The processing condition of embodiment 1～3 are listed in the table 3, and treated gasoline character is listed in the table 4.
Table 3, each embodiment processing condition
| Processing condition | Example 1 | Example 2 | Example 3 | ||||||
| Stock oil | Stock oil 1 | Stock oil 2 | Stock oil 3 | ||||||
| Reaction zone | One district | Two districts | Three districts | One district | Two districts | Three districts | One district | Two districts | Three districts |
| Catalyzer | FH-98 | QG-A | DS-A | FH-98 | QG-B | DS-B | FH-98 | QG-C | DS-C |
| Temperature of reaction/℃ | 180 | 415 | 415 | 190 | 415 | 415 | 180 | 425 | 425 |
| Reaction pressure/Mpa | 3.2 | 3.2 | 3.2 | 2.7 | 2.7 | 2.7 | 3.2 | 3.2 | 3.2 |
| The volume of hydrogen oil ratio | 600 | 600 | 600 | 600 | 600 | 600 | 600 | 600 | 600 |
| Volume space velocity/h -1 | 6.0 | 2.0 | 40.0 | 6.0 | 2.0 | 30.0 | 6.0 | 2.0 | 45.0 |
Table 4 embodiment 1～3 treated gasoline character
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| The boiling range scope, ℃ | 45～197 | 33～175 | 45～188 |
| Fluorescent method composition/v% | |||
| Stable hydrocarbon | 65.2 | 65.2 | 69.4 |
| Alkene | 4.2 | 5.4 | 5.8 |
| Aromatic hydrocarbons | 30.6 | 29.4 | 24.8 |
| Sulphur, μ g/g | 50 | 90 | 28 |
| Nitrogen, μ g/g | 13 | 18 | 12 |
| Diolefin, gI/100g | 0.01 | 0.02 | 0.01 |
| RON/Δ | 90.0/-3.0 | 89.6/-2.6 | 88.2/-2.4 |
| MON/Δ | 80.0/-0.6 | 80.0/-0.4 | 76.4/-0.4 |
| (R+M)/2/Δ | 85.0/-1.8 | 84.8/-1.5 | 82.3/-1.4 |
| C 5 +Liquid is received, m% | 95.62 | 95.56 | 93.84 |
| The hydrogen consumption, m% | 0.18 | 0.34 | 0.28 |
Comparative example 1
Press the operational condition of embodiment 1, the 3rd reaction zone all uses the modifying catalyst identical with second reaction zone, and other condition is identical, and reaction result sees Table 5.Data use selective desulfurization catalyst that product is played tangible effect to reducing sulphur content as can be seen from table, and (R+M)/2 loss is less than 2 units.
Table 5 the 3rd reaction zone does not use the reaction result of selective desulfurization catalyst
| Project | Embodiment 1 | The 3rd reaction zone uses modifying catalyst |
| The boiling range scope, ℃ | 45～197 | 43～197 |
| Fluorescent method composition/v% | ||
| Stable hydrocarbon | 65.2 | 60.5 |
| Alkene | 4.2 | 8.4 |
| Aromatic hydrocarbons | 30.6 | 31.1 |
| Sulphur, μ g/g | 50 | 230 |
| Nitrogen, μ g/g | 13 | 27 |
| Diolefin, gI/100g | 0.01 | 0.06 |
| RON/Δ | 90.0/-3.0 | 90.8/-2.2 |
| MON/Δ | 80.0/-0.6 | 80.4/-0.2 |
| (R+M)/2/Δ | 85.0/-1.8 | 85.6/-1.2 |
| C 5 +Liquid receipts/m% | 95.62 | 97.68 |
| Hydrogen consumption/m% | 0.18 | 0.12 |
Comparative example 2
Press the operational condition of embodiment 1, the 3rd reaction zone uses common Hydrobon catalyst FH-98, and other condition is identical, and reaction result sees Table continuous 5.Data use selective desulfurization catalyst that product is played tangible effect to reducing sulphur content as can be seen from table, and (R+M)/2 loss is less than 2 units, and the hydrogen consumption is low.
Continuous table 5 the 3rd reaction zone does not use the reaction result of selective desulfurization catalyst
| Project | Embodiment 1 | The 3rd reaction zone uses FH-98 |
| The boiling range scope, ℃ | 45～197 | 43～197 |
| Fluorescent method composition/v% | ||
| Stable hydrocarbon | 65.2 | 69.0 |
| Alkene | 4.2 | 1.2 |
| Aromatic hydrocarbons | 30.6 | 29.8 |
| Sulphur, μ g/g | 50 | 34 |
| Nitrogen, μ g/g | 13 | 10 |
| Diolefin, gI/100g | 0.01 | 0 |
| RON/Δ | 90.0/-3.0 | 87.8/-5.2 |
| MON/Δ | 80.0/-0.6 | 78.4/-2.2 |
| (R+M)/2/Δ | 85.0/-1.8 | 83.1/-3.7 |
| C 5 +Liquid is received, m% | 95.62 | 94.42 |
| The hydrogen consumption, m% | 0.18 | 0.27 |
Claims (10)
1, a kind of hydrogenation modification method of inferior patrol is characterized in that with the inferior patrol being raw material, in the presence of hydrogen, contacts with three kinds of catalyzer, forms three reaction zones; Contact with Hydrobon catalyst at first at a lower temperature and form first reaction zone, mainly remove the diolefin in the gasoline; Reaction effluent contacts formation second reaction zone with modifying catalyst under comparatively high temps then, comprises one or more upgradings reactions in aromizing, isomerization and the benzene alkylation reaction, improves the octane value of gasoline; The final reaction effluent contacts with catalyst for selectively hydrodesulfurizing and forms the 3rd reaction zone, removes wherein organic sulfide and part alkene to greatest extent.
2, in accordance with the method for claim 1, the operational condition that it is characterized in that first reaction zone is: hydrogen dividing potential drop 1.5～6.0 MPas, volume space velocity 0.5～8.0 hour
-1, 160～220 ℃ of temperature of reaction, hydrogen to oil volume ratio 200～1200; The first reaction zone catalyzer is a Hydrobon catalyst.
3, in accordance with the method for claim 1, the operational condition that it is characterized in that described second reaction zone is: hydrogen dividing potential drop 1.5～6.0 MPas, volume space velocity 0.5～8.0 hour
-1, 380～480 ℃ of temperature of reaction, hydrogen to oil volume ratio 200～1200; Second reaction zone uses gasoline reforming catalyst.
4, in accordance with the method for claim 1, the operational condition that it is characterized in that described the 3rd reaction zone is: hydrogen dividing potential drop 1.5～6.0 MPas, volume space velocity 10.0～50.0 hours
-1, 380～480 ℃ of temperature of reaction, hydrogen to oil volume ratio 200～1200; The 3rd reaction zone uses catalyst for selectively hydrodesulfurizing; The second reaction zone catalyzer and the 3rd reaction zone catalyst loading are in a reactor.
5, in accordance with the method for claim 3, the metal oxide content that it is characterized in that described gasoline reforming catalyst is 1.0w%～10.0w%, and molecular sieve content is 50.0w%～90.0w%; Surplus is a binding agent; Metal is selected from one or more in zinc, iron, manganese, nickel, cobalt, molybdenum, tungsten, magnesium, calcium, the barium etc., and molecular sieve is the hydrogen type molecular sieve of the little grain fineness number of grain fineness number in 20nm～800nm scope; The specific surface area of catalyzer is 300m
2/ g～600m
2/ g, pore volume are 0.15ml/g～0.55ml/g.
6, in accordance with the method for claim 8, the metal component that it is characterized in that described gasoline reforming catalyst is selected from one or more in magnesium, zinc and the nickel.
7, in accordance with the method for claim 8, the molecular sieve component that it is characterized in that described gasoline reforming catalyst is HZSM-5 and/or Hbeta.
8, in accordance with the method for claim 4, it is characterized in that described catalyst for selectively hydrodesulfurizing is carrier with the aluminum oxide, is reactive metal with Mo and Co, is auxiliary agent with P and K, and wherein catalyzer contains MoO
37.0-18.0w%, CoO1.0-6.0w%, Co/Mo atomic ratio 0.1-1.0 contains potassium 0.2-10.2w%, P/K atomic ratio 0.1-10.0, catalyzer pore volume 0.3-1.3ml/g, specific surface area 150-300m
2/ g.
9, in accordance with the method for claim 5, it is characterized in that described catalyzer contains MoO
3Be 10.0-16.0w%, CoO is 2.0-5.0w%, Co/Mo atomic ratio 0.2-0.8, and containing potassium is 0.5-5.0w%, the P/K atomic ratio is 0.8-5.0.
10, in accordance with the method for claim 5, it is characterized in that described catalyzer contains MoO
3Be 10.0-15.0w%, CoO is 2.0-4.0w%, and the Co/Mo atomic ratio is 0.25-0.72, and containing potassium is 1.0-3.0w%, and the P/K atomic ratio is 1.0-2.0.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508913B (en) * | 2009-03-19 | 2012-05-30 | 中国石油大学(北京) | Deep desulfurization-octane value recovery hydrogenation modification combined method for faulty full-distillation gasoline |
| CN101508911B (en) * | 2009-03-19 | 2012-07-18 | 中国石油大学(北京) | Hydrogenation modification method for faulty gasoline |
| CN102634370A (en) * | 2011-02-10 | 2012-08-15 | 中国石油天然气股份有限公司 | Gasoline hydro-upgrading method |
| US8597494B2 (en) | 2009-03-19 | 2013-12-03 | China University of Petroleum—Beijing (CUPB) | Method for producing ultra-clean gasoline |
| US8603324B2 (en) | 2009-03-19 | 2013-12-10 | China University of Petroleum—Bejing (CUPB) | Method for hydro-upgrading inferior gasoline via ultra-deep desulfurization and octane number recovery |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EA199900177A1 (en) * | 1996-08-01 | 1999-08-26 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | HYDRAULIC CLEANING METHOD |
| FR2757532B1 (en) * | 1996-12-20 | 1999-02-19 | Inst Francais Du Petrole | PROCESS FOR THE CONVERSION OF A GAS CUT TO PRODUCE FUEL WITH A HIGH INDEX OF CETANE, DESAROMATISED AND DESULPHURIZED |
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2004
- 2004-07-06 CN CNB2004100209329A patent/CN1294241C/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101508913B (en) * | 2009-03-19 | 2012-05-30 | 中国石油大学(北京) | Deep desulfurization-octane value recovery hydrogenation modification combined method for faulty full-distillation gasoline |
| CN101508911B (en) * | 2009-03-19 | 2012-07-18 | 中国石油大学(北京) | Hydrogenation modification method for faulty gasoline |
| US8597494B2 (en) | 2009-03-19 | 2013-12-03 | China University of Petroleum—Beijing (CUPB) | Method for producing ultra-clean gasoline |
| US8603324B2 (en) | 2009-03-19 | 2013-12-10 | China University of Petroleum—Bejing (CUPB) | Method for hydro-upgrading inferior gasoline via ultra-deep desulfurization and octane number recovery |
| CN102634370A (en) * | 2011-02-10 | 2012-08-15 | 中国石油天然气股份有限公司 | Gasoline hydro-upgrading method |
| CN102634370B (en) * | 2011-02-10 | 2014-08-06 | 中国石油天然气股份有限公司 | Gasoline hydro-upgrading method |
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