CN101092575A - Method for producing diesel oil with low sulphur and low arene - Google Patents
Method for producing diesel oil with low sulphur and low arene Download PDFInfo
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- CN101092575A CN101092575A CN 200610086977 CN200610086977A CN101092575A CN 101092575 A CN101092575 A CN 101092575A CN 200610086977 CN200610086977 CN 200610086977 CN 200610086977 A CN200610086977 A CN 200610086977A CN 101092575 A CN101092575 A CN 101092575A
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- 239000002283 diesel fuel Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 title abstract description 27
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title abstract description 22
- 239000005864 Sulphur Substances 0.000 title description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 68
- 238000000034 method Methods 0.000 claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 41
- 239000001257 hydrogen Substances 0.000 claims abstract description 41
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 20
- 239000011593 sulfur Substances 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 85
- 150000001875 compounds Chemical class 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 13
- 230000000694 effects Effects 0.000 claims description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- 239000011733 molybdenum Substances 0.000 claims description 13
- 239000010941 cobalt Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000005194 fractionation Methods 0.000 claims description 9
- 239000007791 liquid phase Substances 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000010953 base metal Substances 0.000 claims description 2
- 238000004523 catalytic cracking Methods 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 2
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- 239000005416 organic matter Substances 0.000 claims 1
- 239000000377 silicon dioxide Substances 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 239000003502 gasoline Substances 0.000 abstract description 3
- 239000007795 chemical reaction product Substances 0.000 abstract 2
- 239000002199 base oil Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 25
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 20
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 12
- 238000006477 desulfuration reaction Methods 0.000 description 11
- 230000023556 desulfurization Effects 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 239000000295 fuel oil Substances 0.000 description 7
- 229920006395 saturated elastomer Polymers 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000003974 emollient agent Substances 0.000 description 5
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 4
- -1 disulphide Chemical compound 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 2
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
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- 239000012535 impurity Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229930192474 thiophene Natural products 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- BDYBOFJAEBJDMI-ROUUACIJSA-N (1s,4s)-2,5-diphenylbicyclo[2.2.2]octa-2,5-diene Chemical compound C([C@@]1(CC[C@]2(C=C1C=1C=CC=CC=1)[H])[H])=C2C1=CC=CC=C1 BDYBOFJAEBJDMI-ROUUACIJSA-N 0.000 description 1
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 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
- FEWJPZIEWOKRBE-JCYAYHJZSA-L L-tartrate(2-) Chemical compound [O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O FEWJPZIEWOKRBE-JCYAYHJZSA-L 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical class C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 description 1
- 238000007701 flash-distillation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
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- 230000003335 steric effect Effects 0.000 description 1
- 229940095064 tartrate Drugs 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
This invention discloses a method for producing low-sulfur low-arene diesel oil. The method comprises: mixing base oil and hydrogen, introducing into a hydrogenation reactor, reacting in the first hydrogenation region by contacting hydrorefining catalyst I, directly introducing the reaction product into the second hydrogenation region without separation, reacting by contacting hydrorefining catalyst II, cooling and separating the reaction product to obtain hydrogen-rich gas and liquid substance, circulating the hydrogen-rich gas for repeated use, introducing the liquid substance into a fractionating system, fractionating to obtain crude gasoline fraction, light diesel oil fraction and heavy diesel oil fraction, introducing part or all of the heavy diesel oil fraction bake to the hydrogenation reactor. By the method, high-sulfur, high-nitrogen and high-metal content diesel oil fraction can be treated under mild conditions, and clean diesel oil (with low sulfur content and low arene content) can be obtained. The method has such advantages as simple process, low operation pressure, low apparatus investment and low operation cost.
Description
Technical field
The invention belongs to a kind of method at the following refining hydrocarbon ils of the situation that has hydrogen, more particularly, is a kind of method of producing low-sulfur, low aromatics diesel.
Background technology
Discover, by reducing sulphur content and the aromaticity content in the derv fuel oil, can reduce the generation of sulfurous gas and solid particulate matter in the diesel combustion process, therefore along with the pay attention to day by day of people to environmental protection, the environmental regulation of constantly revising in the world wide constantly proposes strict more restriction to sulphur content in the derv fuel oil and aromaticity content.For example, regulation derv fuel oil sulphur content is less than 350 μ g/g from the Europe III emission standard of enforcement in 2000 in Europe, and polycyclic aromatic hydrocarbons can not be higher than 11 heavy %; Regulation derv fuel oil sulphur content is less than 50 μ g/g in the Europe IV emission standard of implementing in 2005, and polycyclic aromatic hydrocarbons can not be higher than 11 heavy %.In addition, in " world's fuel oil standard " sulphur content in the diesel oil and aromaticity content are proposed harsher requirement, for example its II class diesel oil standard requires sulphur content less than 300 μ g/g, and aromaticity content is less than 25 heavy %, and polycyclic aromatic hydrocarbons is less than 5.0 heavy %; And III class diesel oil standard be sulphur content less than 30 μ g/g, aromaticity content is less than 15 heavy %, polycyclic aromatic hydrocarbons is less than 2.0 heavy %.This shows that producing low-sulfur, hanging down aromatics diesel is the significant problem that each enterprise of great oil refining is faced.
Conventional at present non-noble metal hydrogenation catalyst will reach very high hydrodesulfurization activity, just must improve temperature significantly, this not only can shorten the catalyzer life cycle greatly, and because hydrogenation aromatics-removing (HAD) reaction is subjected to the restriction of thermodynamic(al)equilibrium, under higher temperature of reaction, do not reach deeply hydrodearomatized requirement.Though noble metal catalyst has the hydrogenation activity more much higher than non-precious metal catalyst, can be under than the demulcent operational condition, carry out aromatic hydrocarbons deep hydrogenation saturated reaction, but noble metal catalyst is relatively more responsive to impurity such as sulphur, nitrogen, anti-sulphur, nitrogen poisoning capability are very poor, so cost of investment and running cost are all very high.
EP1120453A2 discloses a kind of method that reduces sulphur content and polycyclic aromatic hydrocarbon content in the distillate, this method adopts two-stage hydrogenation, in first section, mainly carry out hydrogenating desulfurization, resultant of reaction after the desulfurization enters second section after the heat exchange cooling, carry out hydrogenation aromatics-removing, low 50～150 ℃ of the temperature out of second section temperature of reaction than first section, two sections are all adopted non-precious metal catalyst.But polycyclic aromatic hydrocarbon content is higher in the resultant low-sulfur diesel-oil of this method.
CN1415706A discloses a kind of method of producing low-sulfur, low aromatic hydrocarbons clean diesel, this method adopts two conversion zones, after stock oil carries out hydrofining and cracking reaction through first section, the middle stripping stage that enters second section catalysis stripping reactor carries out the weight cut to be separated, light ends fractionation enters the further hydrofining of epimere reaction zone, and heavy fraction components enters the hypomere reaction zone and carries out deep desulfuration, takes off aromatic hydrocarbons.This method can be produced the clean diesel of low-sulfur, low aromatic hydrocarbons, but the pressure-controlling complexity of the catalysis stripping reactor of mentioning in this method, and operation easier is big; The stripping of catalysis simultaneously structure of reactor complexity, the engineering design difficulty is bigger, performance difficulty.
CN1173012C discloses a kind of method of desulfurizing and dearomatizing diesel oil deeply, this method comprises two hydrogenators, in first reactor, load catalyst for hydro-upgrading, hydrocracking catalyst or Hydrobon catalyst, in second reactor, load Hydrobon catalyst, between two, be provided with a hydrogen gas stripping column, to remove gaseous impurities such as hydrogen sulfide that first reactor generates and ammonia.This method adopts under middle pressure, adopts non-precious metal catalyst to remove sulphur, the aromaticity content of diesel raw material, but high pressure hydrogen gas stripping column, cost of investment and running cost height are set in this method.
CN1552820A discloses the method that a kind of fraction oil hydrodesulfurizing takes off aromatic hydrocarbons, this method adopts the two-stage hydrogenation flow process, first section is used the non-noble metal hydrogenation catalyst for refining, second section is adopted the noble metal hydrogenation catalyst for refining, wherein recycle hydrogen and stock oil are mixed into first section reaction, the isolated liquid phase stream of first section product institute with enter second section after newly hydrogen mixes and react.This method can be produced the diesel oil of low-sulfur, low aromatic hydrocarbons, but has adopted noble metal catalyst to make cost up in this method, and running has a big risk, flexibility of operation descends.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of method of producing low-sulfur, low aromatics diesel.
Method provided by the invention comprises: stock oil with enter hydrogenator after hydrogen mixes, contact with Hydrobon catalyst I at first hydroconversion reaction zone and to react, its resultant of reaction directly enters second hydroconversion reaction zone without separating, under the effect of Hydrobon catalyst II, react, its resultant of reaction is through cooling, after the separation, the hydrogen-rich gas of gained recycles, the liquid phase stream of gained enters fractionating system, after fractionation, obtain naphtha fraction, LIGHT DIESEL OIL cut and heavy diesel cut, wherein part or all of heavy diesel cut returns hydrogenator.
Adopt method provided by the invention, can handle high-sulfur, high nitrogen and the high diesel oil distillate of metal content, can be under demulcent operational condition comparatively, obtain the II class that sulphur content, aromaticity content and polycyclic aromatic hydrocarbon content all satisfy " (world's fuel oil standard ", the clean diesel of III class standard.Flow process of the present invention is simple, working pressure is low, facility investment and process cost are all lower.
Description of drawings
Accompanying drawing is a kind of method flow synoptic diagram of producing low-sulfur, low aromatics diesel provided by the invention.
Embodiment
Sulfocompound in diesel oil distillate mainly contains mercaptan, disulphide, thiophene, thionaphthene and dibenzothiophene.All kinds of sulfide are along with the difference of molecular size, molecular structure, substituent quantity and substituting group position, its hydrodesulfurization activity difference is very big, the reactive behavior of mercaptan, disulphide and thiophene just far above dibenzothiophene class sulfide, under the demulcent hydrogenation conditions, just can remove; And substituent dibenzothiophene class sulfide is arranged on the ortho position of sulphur atom, and owing to have space steric effect, its hydrodesulfurization activity is minimum, the speed of its hydrogenating desulfurization is also very low under harsh reaction conditions.But, just the dibenzothiophene class sulfide of these difficult multi-substituents that react must be removed if satisfy the requirement of low-sulfur diesel-oil.All kinds of sulfide are except reactivity worth has difference, and they press the boiling range distribution in distillate situation is also different, and wherein the sulfide of difficult reaction is present in the higher distillate of boiling range.
Aromatic hydrocarbon in diesel oil also has part three rings and the above aromatic hydrocarbons of three rings mainly based on monocycle and dicyclo.Polycyclic aromatic hydrocarbons of the present invention also is condensed-nuclei aromatics, is meant shared respectively two aromatic hydrocarbon that adjacent carbon atom forms of two or more aromatic nucleus, as naphthalene, anthracene and phenanthrene etc.The distribution of aromatic hydrocarbons is also relevant with the boiling range of distillate, and mononuclear aromatics mainly is present in the lighting end, and three rings and the above aromatic hydrocarbons of three rings mainly exist in the last running.From the saturated complexity of hydrogenation, first aromatic ring hydrogenation of condensed-nuclei aromatics is easier to, but the whole hydrogenation of aromatic ring are saturated very difficult.That is to say that thrcylic aromatic hydrocarbon in the raw material and the easy hydrogenation of aromatic hydrocarbons more than three rings are saturated to be two ring or mononuclear aromatics, but the number of total aromatic hydrocarbons does not reduce in the raw material, polycyclic aromatic hydrocarbon content is many more in the raw material, and the arene engaging scraping difficulty is big more.
For these reasons, method provided by the invention is so concrete enforcement:
Stock oil with enter hydrogenator, volume space velocity 0.3～6.0h when first hydroconversion reaction zone contacts at 250～450 ℃ of temperature of reaction, hydrogen dividing potential drop 1.0～12.0MPa, liquid with Hydrobon catalyst I after hydrogen mixes
-1, hydrogen to oil volume ratio 100～1500Nm
3/ m
3Reaction conditions under carry out hydrofining reaction, remove most easy reaction sulfide and part aromatic hydrocarbons in the raw material, its resultant of reaction directly enters second hydroconversion reaction zone without separating, at volume space velocity 0.3～6.0h during at 250～450 ℃ of temperature of reaction, hydrogen dividing potential drop 1.0～12.0MPa, liquid under the effect of Hydrobon catalyst II
-1, hydrogen to oil volume ratio 100～1500Nm
3/ m
3Reaction conditions under react, remove a part difficult reaction sulfide and part aromatic hydrocarbons and polycyclic aromatic hydrocarbons, its resultant of reaction is after cooling, enter high-pressure separator and light pressure separator successively and carry out gas-liquid separation, the hydrogen-rich gas of gained recycles, the product liquid of gained enters fractionating system, after fractionation, obtain naphtha fraction, LIGHT DIESEL OIL cut and heavy diesel cut, wherein part or all of heavy diesel cut returns hydrogenator, the heavy diesel cut of preferred 40～80 heavy % returns hydrogenator, and the heavy diesel cut of remainder and LIGHT DIESEL OIL cut promptly get diesel product after mixing.
Described first hydroconversion reaction zone and the preferred reaction conditions of second hydroconversion reaction zone are: volume space velocity 0.5～4.0h when 300～380 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0～10.0MPa, liquid
-1, hydrogen to oil volume ratio 200～1000Nm
3/ m
3
Described stock oil is selected from one or more mixtures in catalytic cracking diesel oil, straight-run diesel oil, coker gas oil, the visbreaking diesel oil.
The cut point of described LIGHT DIESEL OIL cut and heavy diesel cut is 300～360 ℃, and preferred cut point is 310～350 ℃.Because the boiling range of distribution of sulphide and raw material has very big relation, the most difficult sulfide major part that removes concentrates in the heavy ends of diesel oil distillate, be that to contain the amount of dibenzothiophene of multi-substituent in the heavy more diesel oil distillate of cut many more, the content of polycyclic aromatic hydrocarbons is also many more, therefore with this part difficult reaction sulfide content, the higher heavy diesel cut of polycyclic aromatic hydrocarbon content is separated separately, return first hydroconversion reaction zone or second hydroconversion reaction zone again, further remove residual sulfur, and further saturated aromatic hydrocarbons, thereby the deep desulfuration of realization diesel oil distillate, take off aromatic hydrocarbons.Different according to stock oil character with the specification that product will reach, can adjust the concrete cut point of LIGHT DIESEL OIL cut and heavy diesel cut, the particular location that the heavy diesel cut goes the amount of returning of hydrogenator and returns hydrogenator.
The admission space ratio of Hydrobon catalyst I of the present invention and Hydrobon catalyst is 2: 8～8: 2, Hydrobon catalyst I and Hydrobon catalyst II can be seated in the different catalysts bed of same reactor, can be seated in respectively in the different hydrogenators, the reaction effluent between each reactor does not separate yet.A plurality of beds are arranged in the reactor, use the mode of annotating cold hydrogen between each bed to control bed temperature.
Described Hydrobon catalyst I is a kind of metal load type catalyst, carrier is an aluminum oxide, metal component is group vib metal or group VIII base metal or their combination, and wherein the group vib metal is selected from molybdenum and/or tungsten, and the group VIII metal is selected from cobalt and/or nickel.The metal component of preferred Hydrobon catalyst I is cobalt and molybdenum, is benchmark in oxide compound and with the catalyzer, and the content of cobalt is 1～5 heavy %, and the content of molybdenum is 9～20 heavy %.Preferred Hydrobon catalyst I has good direct desulfurization activity, under demulcent condition comparatively, just can remove those sulfide that easily react in the stock oil.
The preparation method of described preferred Hydrobon catalyst I is:
With hydrated aluminum oxide and auxiliary agent mixing moulding, drying, 500～1000 ℃ of roastings 1～6 hour under air again, make carrier.The aqueous solution that carrier is immersed compound that contains cobalt for preparing and the compound that contains molybdenum is after 2～5 hours, and drying is 1～6 hour under temperature is 100～300 ℃; Promptly obtained catalyst prod in 1～6 hour 350～550 ℃ of following roastings.
The compound of described cobalt and the compound water solution of molybdenum can prepare according to a conventional method.The compound of cobalt and the compound of molybdenum are selected from one or more in their soluble compound respectively.Wherein the compound of cobalt is preferably one or more in Xiao Suangu, cobalt chloride, the cobaltous dihydroxycarbonate respectively, the preferred ammonium molybdate of the compound of molybdenum.The preferred pseudo-boehmite of described hydrated aluminum oxide.
Described Hydrobon catalyst II is a kind of metal load type catalyst, is benchmark with the catalyzer, and it consists of: nickel oxide 1～10 heavy %, molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 heavy %, fluorine 1～10 heavy %, phosphorus oxide 0.5～8 heavy %, surplus is a silica-alumina.With described carrier is benchmark, and the content of the silicon oxide in the preferred silica-alumina is 2～45 heavy %, and the content of aluminum oxide is 55～98 heavy %; The content of further preferred silicon oxide is 5～40 heavy %, and the content of aluminum oxide is 60～95 heavy %.Described silica-alumina has the specific surface and the pore volume of conventional silica-alumina carrier, and the specific surface of preferred silica-alumina is 150～350m
2/ g, more preferably 180～300m
2/ g, the pore volume of preferred silica-alumina is 0.4～1ml/g, more preferably 0.5～0.8ml/g.Can also contain one or more among the described Hydrobon catalyst II and be selected from and contain oxygen or nitrogenous organism, preferred oxygen-containing organic compound is selected from one or more in organic alcohol, the organic acid; Preferred organic compounds containing nitrogen is selected from one or more in organic amine, the organic ammonium salt.For example, oxygenatedchemicals can be ethylene glycol, glycerol, polyoxyethylene glycol (molecular weight is 200-1500), Diethylene Glycol, butyleneglycol, acetate, toxilic acid, oxalic acid, nitrilotriacetic acid, 1, in 2-CDTA, citric acid, tartrate, the oxysuccinic acid one or more, organic compounds containing nitrogen can be quadrol, EDTA and ammonium salt thereof.Described organism is 0.03-2 with mol ratio in nickel, molybdenum and the tungsten sum of oxide compound, is preferably 0.08-1.5.The Hydrobon catalyst II hydrogenation performance that the present invention adopts is good, and desulphurizing activated height had both helped the carrying out of the hydrogenation reaction of the most difficult reaction sulfide, also helped the carrying out of aromatic hydrocarbons saturated reaction.
Accompanying drawing is the method synoptic diagram of production low-sulfur provided by the invention, low aromatics diesel.Below in conjunction with accompanying drawing method provided by the present invention is further detailed, has omitted many equipment among the figure, as pump, interchanger, compressor etc., but this is known to those of ordinary skills.
The method technical process of production low-sulfur provided by the invention, low aromatics diesel is described in detail as follows: the stock oil from pipeline 1 is extracted out by pipeline 3 after feedstock pump 2 boosts, mix the back enters process furnace 5 by pipeline 4 and heats with hydrogen stream from pipeline 16, material after the heating is contacted with Hydrobon catalyst I by first hydroconversion reaction zone 8 that pipeline 6 enters hydrogenator 7, under appropriate reaction conditions, carry out hydrofining reaction.The resultant of reaction of first hydroconversion reaction zone directly enters second hydroconversion reaction zone 9 without separating, under the effect of Hydrobon catalyst II, further carry out hydrogenating desulfurization and aromatic hydrocarbons saturated reaction, its resultant of reaction enters high-pressure separator 11 after pipeline 10 is extracted out, carry out gas-liquid separation by flash distillation.The hydrogen rich stream at high-pressure separator 11 tops enters circulating hydrogen compressor 13 by pipeline 12, after circulating hydrogen compressor 13 superchargings, extract out by pipeline 14, and mix with new hydrogen from pipeline 15, mixed hydrogen stream mixes with stock oil from pipeline 3 through pipeline 16.The liquid phase stream of high-pressure separator 11 bottoms enters light pressure separator 18 through pipeline 17, carries out further gas-liquid separation at this, and isolated gas is extracted out through pipeline 19; The liquid of light pressure separator 18 bottoms enters separation column 21 through pipeline 20.The liquid phase stream that enters separation column 21 is after fractionation, and the gasoline fraction that cuts into, LIGHT DIESEL OIL cut and heavy diesel cut are extracted out through pipeline 22,24 and 26 successively.The part gasoline fraction is back to the top of separation column 21 through pipeline 23, part or all of heavy diesel cut further reacts through pipeline 27 Returning reacting systems, promptly can return first hydroconversion reaction zone by pipeline 29, also can return second hydroconversion reaction zone by pipeline 28, remaining heavy diesel cut mixes the diesel product that obtains low-sulfur, low aromatic hydrocarbons through pipeline 30 with LIGHT DIESEL OIL cut from pipeline 24, and by pipeline 25 withdrawing devices.
Advantage of the present invention is:
1, adopts method provided by the invention, can under demulcent operational condition comparatively, obtain sulphur content, aromaticity content and polycyclic aromatic hydrocarbon content and all satisfy the II class of " world's fuel oil standard ", the clean diesel of III class standard.This is because the present invention utilizes difficult reaction sulfide and polycyclic aromatic hydrocarbons to be distributed in the characteristics of diesel oil last running, the heavy diesel cut is separated carried out further hydrotreatment.In addition, this catalyzer with different systems carries out rational gradation composition, gives full play to separately catalyzer at the different desulfurization stage and the advantage function in Tuo Fang stage, by the synergy between each catalyzer, improved the integer catalyzer activity, obtained good desulfurization, taken off fragrant effect.
2, adopt method provided by the invention, adaptability to raw material is good, can handle high-sulfur, high nitrogen and the high diesel oil distillate of metal content, and the catalyst activity height, and activity stability is good, and the device cycle of operation is long.
3, method flow provided by the invention is simple, working pressure is low, facility investment and process cost are all lower.Both can be used in new device, also can be used on the old plant modification, particularly be used in the old plant modification, employing present method can improve desulfurization degree and take off the aromatic hydrocarbons rate under the identical operations condition, perhaps in identical desulfurization degree decline low reaction temperatures, raising unit capacity, thereby reduce the device process cost, improve the economy of device.
The following examples will give further instruction to method provided by the invention, but not thereby limiting the invention.
The preparation process of used Hydrobon catalyst I is as follows among the embodiment:
1. with pseudo-boehmite (Shandong Aluminum Plant's production) and extrusion aid, tackiness agent mixes, add water after mix pinch, extrusion, make three leaf stripe shapes.Extrudate 130 ℃ of oven dry down, again in 900 ℃ of following roastings 4 hours, is promptly obtained alumina supporter.
2. alumina supporter is immersed in the aqueous solution of the Xiao Suangu (Beijing Chemical Plant) prepare and ammonium molybdate (Beijing Chemical Plant), flooded 4 hours, 120 ℃ of dryings 4 hours, obtained Hydrobon catalyst I in 4 hours then 530 ℃ of following roastings.
The composition of obtained Hydrobon catalyst I: in oxide compound and with the total catalyst weight is benchmark, and cobalt is 3.0 heavy %, and molybdenum is 13.5 heavy %.The specific surface area of Hydrobon catalyst I is 198m
2/ g, pore volume are 0.35ml/g.
The trade names of used Hydrobon catalyst II are RS-1000 among the embodiment, for catalyzer Chang Ling branch office of China Petrochemical Corp. produces.
Used stock oil A is a kind of straight-run diesel oil among the embodiment, and stock oil B is the mixing oil of a kind of straight-run diesel oil and catalytic diesel oil, and its main character is as shown in table 1.
Embodiment 1
Stock oil A with enter hydrogenator after hydrogen mixes, successively by first hydroconversion reaction zone and second hydroconversion reaction zone, contact with Hydrobon catalyst II with Hydrobon catalyst I respectively and react, its resultant of reaction is through cooling, after the separation, the hydrogen-rich gas of gained recycles, the liquid phase stream of gained enters fractionating system, after fractionation, obtain naphtha fraction, LIGHT DIESEL OIL cut and heavy diesel cut, wherein the heavy diesel cut of 40 heavy % returns second hydroconversion reaction zone in the hydrogenator, 330 ℃ of the cut points of LIGHT DIESEL OIL cut and heavy diesel cut, the admission space ratio of Hydrobon catalyst I and Hydrobon catalyst II is 5: 5.The reaction conditions of present embodiment is as shown in table 2, and the product main character is as shown in table 3, as can be seen from Table 3, the sulphur content of product is 202 μ g/g, aromaticity content is 18.3 heavy %, and polycyclic aromatic hydrocarbon content is 3.7 heavy %, all satisfies " world fuel standards II class diesel oil standard.
Embodiment 2
Stock oil A with enter hydrogenator after hydrogen mixes, successively by first hydroconversion reaction zone and second hydroconversion reaction zone, contact with Hydrobon catalyst II with Hydrobon catalyst I respectively and react, its resultant of reaction is through cooling, after the separation, the hydrogen-rich gas of gained recycles, the liquid phase stream of gained enters fractionating system, after fractionation, obtain naphtha fraction, LIGHT DIESEL OIL cut and heavy diesel cut, wherein the heavy diesel cut of 80 heavy % returns second hydroconversion reaction zone in the hydrogenator, 320 ℃ of the cut points of LIGHT DIESEL OIL cut and heavy diesel cut, the admission space ratio of Hydrobon catalyst I and Hydrobon catalyst II is 3: 7.The reaction conditions of present embodiment is as shown in table 2, and the product main character is as shown in table 3, as can be seen from Table 3, the sulphur content of product is 12 μ g/g, aromaticity content is 13.9 heavy %, and polycyclic aromatic hydrocarbon content is 1.4 heavy %, all satisfies " world fuel standards III class diesel oil standard.
Embodiment 3
Stock oil B with enter hydrogenator after hydrogen mixes, successively by first hydroconversion reaction zone and second hydroconversion reaction zone, contact with Hydrobon catalyst II with Hydrobon catalyst I respectively and react, its resultant of reaction is through cooling, after the separation, the hydrogen-rich gas of gained recycles, the liquid phase stream of gained enters fractionating system, after fractionation, obtain naphtha fraction, LIGHT DIESEL OIL cut and heavy diesel cut, wherein the heavy diesel cut of 70 heavy % returns second hydroconversion reaction zone in the hydrogenator, 320 ℃ of the cut points of LIGHT DIESEL OIL cut and heavy diesel cut, the admission space ratio of Hydrobon catalyst I and Hydrobon catalyst II is 4: 6.The reaction conditions of present embodiment is as shown in table 2, and the product main character is as shown in table 3, as can be seen from Table 3, the sulphur content of product is 286 μ g/g, aromaticity content is 23.5 heavy %, and polycyclic aromatic hydrocarbon content is 4.8 heavy %, all satisfies " world fuel standards II class diesel oil standard.
Embodiment 4
Stock oil B with enter hydrogenator after hydrogen mixes, successively by first hydroconversion reaction zone and second hydroconversion reaction zone, contact with Hydrobon catalyst II with Hydrobon catalyst I respectively and react, its resultant of reaction is through cooling, after the separation, the hydrogen-rich gas of gained recycles, the liquid phase stream of gained enters fractionating system, after fractionation, obtain naphtha fraction, LIGHT DIESEL OIL cut and heavy diesel cut, wherein the heavy diesel cut of 80 heavy % returns first hydroconversion reaction zone in the hydrogenator, 310 ℃ of the cut points of LIGHT DIESEL OIL cut and heavy diesel cut, the admission space ratio of Hydrobon catalyst I and Hydrobon catalyst II is 2: 8.The reaction conditions of present embodiment is as shown in table 2, and the product main character is as shown in table 3, as can be seen from Table 3, the sulphur content of product is 19 μ g/g, aromaticity content is 14.2 heavy %, and polycyclic aromatic hydrocarbon content is 1.6 heavy %, all satisfies " world fuel standards III class diesel oil standard.
Table 1
| Raw material diesel oil numbering | A | B |
| Density (20 ℃), g/cm 3 | 0.8506 | 0.8735 |
| Refractive power, n d 20 | 1.4754 | 1.4976 |
| Sulphur content, μ g/g | 14000 | 11000 |
| Nitrogen content, μ g/g | 121 | 202 |
| The bromine valency, gBr/100g | 1.6 | 3.2 |
| Aromatic hydrocarbons, heavy % | 31.4 | 40.6 |
| Polycyclic aromatic hydrocarbons, heavy % | 12.7 | 17.2 |
| Boiling range ASTM D-1160, ℃ | ||
| IBP | 189 | 196 |
| 5％ | 213 | 220 |
| 10％ | 225 | 232 |
| 50％ | 276 | 287 |
| 90％ | 342 | 353 |
| FBP | 366 | 375 |
Table 2
| Numbering | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Stock oil | A | A | B | B |
| First hydroconversion reaction zone | ||||
| The hydrogen dividing potential drop, MPa | 4.8 | 6.4 | 4.8 | 6.4 |
| Temperature of reaction, ℃ | 350 | 360 | 350 | 360 |
| Volume space velocity during liquid, h -1 | 4.0 | 6.7 | 5.0 | 12.8 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 400 | 400 | 400 | 400 |
| Second hydroconversion reaction zone | ||||
| The hydrogen dividing potential drop, MPa | 4.8 | 6.4 | 4.8 | 6.4 |
| Temperature of reaction, ℃ | 350 | 360 | 350 | 360 |
| Volume space velocity during liquid, h -1 | 4.2 | 3.3 | 4.0 | 3.2 |
| Hydrogen to oil volume ratio, Nm 3/m 3 | 380 | 350 | 330 | 400 |
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Density (20 ℃), g/cm 3 | 0.8302 | 0.8283 | 0.8550 | 0.8496 |
| Sulphur content, μ g/g | 202 | 12 | 286 | 19 |
| Aromatic hydrocarbons, heavy % | 18.3 | 13.9 | 23.5 | 14.2 |
| Polycyclic aromatic hydrocarbons, heavy % | 3.7 | 1.4 | 4.8 | 1.6 |
Claims (13)
1, a kind of production low-sulfur, the method of low aromatics diesel, enter hydrogenator after it is characterized in that stock oil and hydrogen mixing, contact with Hydrobon catalyst I at first hydroconversion reaction zone and to react, its resultant of reaction directly enters second hydroconversion reaction zone without separating, under the effect of Hydrobon catalyst II, react, its resultant of reaction is through cooling, after the separation, the hydrogen-rich gas of gained recycles, the liquid phase stream of gained enters fractionating system, after fractionation, obtain naphtha fraction, LIGHT DIESEL OIL cut and heavy diesel cut, wherein part or all of heavy diesel cut returns hydrogenator.
2, method according to claim 1 is characterized in that the reaction conditions of described first hydroconversion reaction zone and second hydroconversion reaction zone is: volume space velocity 0.3～6.0h when 250～450 ℃ of temperature of reaction, hydrogen dividing potential drop 1.0～12.0MPa, liquid
-1, hydrogen to oil volume ratio 100～1500Nm
3/ m
3
3, method according to claim 2 is characterized in that the reaction conditions of described first hydroconversion reaction zone and second hydroconversion reaction zone is: volume space velocity 0.5～4.0h when 300～380 ℃ of temperature of reaction, hydrogen dividing potential drop 2.0～10.0MPa, liquid
-1, hydrogen to oil volume ratio 200～1000Nm
3/ m
3
4, method according to claim 1 is characterized in that described stock oil is selected from one or more mixtures in catalytic cracking diesel oil, straight-run diesel oil, coker gas oil, the visbreaking diesel oil.
5, method according to claim 1, the cut point that it is characterized in that described LIGHT DIESEL OIL cut and heavy diesel cut is 300～360 ℃.
6, method according to claim 5, the cut point that it is characterized in that described LIGHT DIESEL OIL cut and heavy diesel cut is 310～350 ℃.
7, method according to claim 1 is characterized in that the heavy diesel cut of 40～80 heavy % returns hydrogenator.
8, method according to claim 1, it is characterized in that described Hydrobon catalyst I is a kind of metal load type catalyst, carrier is an aluminum oxide, metal component is group vib metal or group VIII base metal or their combination, wherein the group vib metal is selected from molybdenum and/or tungsten, and the group VIII metal is selected from cobalt and/or nickel.
9, method according to claim 8, the metal component that it is characterized in that described Hydrobon catalyst I is cobalt and molybdenum, is benchmark in oxide compound and with the catalyzer, and the content of cobalt is 1～5 heavy %, and the content of molybdenum is 9～20 heavy %.
10, method according to claim 1, it is characterized in that described Hydrobon catalyst II, with the catalyzer is benchmark, and it consists of: nickel oxide 1～10 heavy %, and molybdenum oxide and Tungsten oxide 99.999 sum are 10～50 heavy %, fluorine 1～10 heavy %, phosphorus oxide 0.5～8 heavy %, surplus is a silica-alumina, is benchmark with the carrier, silica content is 2～45 heavy %, and alumina content is 55～98 heavy %.
11, method according to claim 10 is characterized in that described Hydrobon catalyst II contains to be selected from and contains in oxygen or the nitrogenous organism one or more, and described organism is 0.03～2 with mol ratio in nickel, molybdenum and the tungsten sum of oxide compound.
12, method according to claim 11 is characterized in that described oxygen-bearing organic matter is selected from one or more in organic alcohol, the organic acid, and described itrogenous organic substance is selected from one or more in organic amine, the organic ammonium salt.
13, method according to claim 1 is characterized in that the admission space ratio of described Hydrobon catalyst I and Hydrobon catalyst is 2: 8～8: 2.
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