CN1171430A - A medium-pressure hydrocracking method for heavy distillate oil - Google Patents
A medium-pressure hydrocracking method for heavy distillate oil Download PDFInfo
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- CN1171430A CN1171430A CN 97112239 CN97112239A CN1171430A CN 1171430 A CN1171430 A CN 1171430A CN 97112239 CN97112239 CN 97112239 CN 97112239 A CN97112239 A CN 97112239A CN 1171430 A CN1171430 A CN 1171430A
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- 238000000034 method Methods 0.000 title claims abstract description 66
- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 claims abstract description 53
- 239000003921 oil Substances 0.000 claims abstract description 53
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000000295 fuel oil Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 10
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 61
- 239000011148 porous material Substances 0.000 claims description 40
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000007789 gas Substances 0.000 claims description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 15
- 229910021536 Zeolite Inorganic materials 0.000 claims description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 13
- 239000010457 zeolite Substances 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000004939 coking Methods 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 229910052680 mordenite Inorganic materials 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- -1 alkoxy aluminum Chemical compound 0.000 claims description 2
- 238000005194 fractionation Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims 8
- 229910052593 corundum Inorganic materials 0.000 claims 2
- 238000004821 distillation Methods 0.000 claims 2
- 229910001679 gibbsite Inorganic materials 0.000 claims 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 2
- 239000012263 liquid product Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 5
- 238000002407 reforming Methods 0.000 abstract 1
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- 230000009466 transformation Effects 0.000 description 11
- 239000004215 Carbon black (E152) Substances 0.000 description 10
- 239000003795 chemical substances by application Substances 0.000 description 10
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 5
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- 238000002360 preparation method Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 239000002283 diesel fuel Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- 241000772415 Neovison vison Species 0.000 description 3
- 238000001833 catalytic reforming Methods 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 238000005987 sulfurization reaction Methods 0.000 description 3
- 239000010913 used oil Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 101000809257 Homo sapiens Ubiquitin carboxyl-terminal hydrolase 4 Proteins 0.000 description 2
- 102100038463 Ubiquitin carboxyl-terminal hydrolase 4 Human genes 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 229910001648 diaspore Inorganic materials 0.000 description 2
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004231 fluid catalytic cracking Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229910018104 Ni-P Inorganic materials 0.000 description 1
- 229910018536 Ni—P Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 239000003974 emollient agent Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
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- 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
一种生产中间馏份油的重质油中压加氢裂化方法,采用单段串联一种加氢精制催化剂和一种加氢裂化催化剂的一次通过流程,可获得高达80体%的转化率,中间馏份油的收率可达40重%以上,选择性不低于50重%。该方法适用于氮含量高达1500ppm、硫含量高达3.5重%、馏程干点>500℃的重质油原料制取重整原料、喷气燃料以及符合规格的低硫车用柴油、催化裂化原料和乙烯原料。A medium-pressure hydrocracking method for heavy oil to produce middle distillate oil, which adopts a single-stage series connection of a hydrorefining catalyst and a hydrocracking catalyst in one pass process, and can obtain a conversion rate as high as 80% by volume, The yield of middle distillate oil can reach more than 40% by weight, and the selectivity is not lower than 50% by weight. The method is applicable to the production of reforming feedstock, jet fuel, low-sulfur automotive diesel, catalytic cracking feedstock and Vinyl raw material.
Description
The invention relates to the catalysis conversion method of petroleum hydrocarbon.Specifically, be about heavy fraction of oil is carried out the method that middle distillate oil is produced in catalytic cracking in the presence of hydrogen.
Along with the dieselization of development, transport by road sharp increase and the vehicle of air system, variation has taken place world's oil product market demand structure: heavy oil product reduces, and motor spirit slightly descends, and middle distillate such as rocket engine fuel and derv fuel oil increase.And the trend of crude oil heaviness and poor qualityization makes various countries must take the policy of deep processing could obtain enough middle distillate.Though catalytic cracking and coking all belong to deep process technology, because of it is a decarbonization process, so the middle distillate product quality is relatively poor.
Hydrocracking process not only can be produced fine rocket engine fuel and derv fuel oil from heavy, inferior raw material, can also produce the demand that ethylene raw satisfies petrochemical industry, thereby become one of important process of deep processing, more and more is subject to people's attention.Owing to conventional hydrocracking process working pressure height, plant investment and process cost make its industrial application be subjected to certain restriction greatly, therefore some oil companies and research unit all are devoted to the middle pressure hydrocracking technology of Development and Production middle distillate oil and suitable catalyzer thereof both at home and abroad.
Though the mild hydrocracking technology that is used for production middle distillate oil disclosed in the prior art is under the condition of pressure heavy raw oil to be converted into the purpose product, its transformation efficiency generally all is lower than 50 body %.For example: EP93, disclosed single hop two doses (hydrotreatment and hydrocracking catalysts) the one-pass flow process of connecting in 552, its processing condition are: 5.25～7MPa, 360～440 ℃, LHSV 0.1～10 o'clock
-1The transformation efficiency of the product below 345 ℃ is 30～40 body %, raw materials used oil is the heavy gas oil more than 340 ℃, hydrotreating catalyst is VIA or the VIII family metal that loads on unformed aluminum oxide or the silica-alumina supports, and hydrocracking catalyst is VIA or the VIII family metal that loads on X or y-type zeolite or the mordenite.
And for example, USP4, disclosing in 686,030 a kind of is the process of 500～1100F fraction oil mild hydrocracking with boiling range, and its temperature of reaction is 500～900F, and the hydrogen dividing potential drop is 200～1500psig, LHSV 0.05～3.0 o'clock
-1, transformation efficiency is 15～35 body %, gained product liquid mid-boiling point＜700F accounts at least 85 body %.Used catalyzer is the Mo-Ni-P that loads on the unformed porous refractory oxide, and the diameter at least 75% hole is 50～130A in this catalyzer, the pore volume of diameter＞110A＜10%.
Though also there is transformation efficiency to be higher than 50% hydrocracking technology in the prior art, they require harsh to the nitrogen content in the hydrocracking charging.For example, USP4 discloses a kind of method by hydrocracking and isomerization production middle distillate oil in 859,312, this method be with do＞to account at least 90% hydrocarbon be raw material for the fraction of 600F, at 260～482 ℃, LHSV0.1～20 o'clock
-1, 200～3000psig condition under, contact with the catalyzer that contains SAPO-11 or SAPO-41 zeolite, transformation efficiency＞50%, the product yield of gained 300～725F fraction is higher than 40 body %.This method requires the nitrogen content＜50ppmw in the raw materials used oil, and is best＜10ppmw.
And for example, EP19, disclose in 959 that a kind of (fraction accounts for more than the 50 body % more than 350 ℃ with heavy hydrocarbon feedstocks, fraction accounts for more than the 10 body % more than 450 ℃) under the condition of the hydrogen dividing potential drops, 250～450 ℃, LHSV0.2～5.0 of＜100 crust o'clock-1, carry out the process of hydrocracking system lighter hydrocarbons fraction, wherein used catalyzer is the Ni-W that loads on faujusite and the inertia aluminum oxide.This method requires the nitrogen content＜100ppmw in the raw materials used oil equally, and is best＜10ppmw, therefore all needs through pre-hydrodenitrification for the stock oil of nitrogen content above 100ppmw.
Purpose of the present invention is exactly to provide a kind of new for the method for heavy fraction of oil hydrocracking with production middle distillate oil on the basis of existing technology, this method can be in demulcent under the press strip spare operation and can obtain can be up to 80 body % once pass through transformation efficiency, and can directly process the inferior feedstock oil of nitrogen content up to 1500ppm, the organonitrogen content of hydrocracking catalyst charging allows up to 150ppm.
The mink cell focus middle pressure hydrocracking method of production middle distillate oil provided by the invention is:
Is that 6.0～10.0MPa, temperature are that 340～440 ℃, hydrogen/oil volume ratio are 400～1200, liquid hourly space velocity is 0.1～3.0 o'clock with heavy oil feed in the hydrogen dividing potential drop
-1Condition under contact with a kind of hydrocracking catalyst with a kind of Hydrobon catalyst successively and without intermediate section from, reacted effluent through cooling, separate, hydrogen-containing gas recycles, product liquid enters fractionating system.
Used Hydrobon catalyst consists of: 1～5 heavy %NiO, 12～35 heavy %WO
3, 1～9 heavy %F and surplus Al
2O
3, this Al
2O
3Be by one or more apertures Al
2O
3With one or more macropores Al
2O
3Be composited this aperture Al according to 75: 25～50: 50 weight ratios
2O
3The pore volume of median pore diameter＜80A accounts for total pore volume more than 95%, this macropore Al
2O
3The pore volume of median pore diameter 60～600A accounts for total pore volume more than 70%, and described pore volume is measured with B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature.
Used hydrocracking catalyst consists of: 2.5～6.0 heavy %NiO, 10～38 heavy %WO
3, 0.5～5.0 heavy %F and balance carriers, this carrier is that the acidity value by 20～90 heavy % is the Al of 0.5～0.8 mmole/gram
2O
3With the acidity value of 10～80 heavy % be that the mesopore or the large pore zeolite of 1.0～2.0 mmole/grams formed, described acidity value is to use NH
3-TPD method records.
Specifically, the present invention thes contents are as follows.
(1) catalyzer of the present invention's use
Used a kind of Hydrobon catalyst and a kind of hydrocracking catalyst among the present invention, be respectively described below:
The Hydrobon catalyst that uses among the present invention be 97112397.7 at application number, denomination of invention is the catalyzer disclosed in the application of " a kind of fraction oil Hydrobon catalyst and preparation thereof ".This catalyzer is by 1～5 heavy %NiO, 12～35 heavy %WO
3, 1～9 heavy %F and surplus Al
2O
3Form this Al
2O
3Be by one or more apertures Al
2O
3With one or more macropores Al
2O
3Be composited according to 75: 25～50: 50 weight ratios.This Al generally
2O
3Be by a kind of aperture Al
2O
3With a kind of macropore Al
2O
3Be composited.This aperture Al
2O
3The volume in median pore diameter＜80A hole should account for total pore volume more than 95%, this macropore Al
2O
3The volume in median pore diameter 60～600A hole should account for total pore volume more than 70%, these two kinds of Al
2O
3The Al of compound back gained
2O
3The carrier median pore diameter is that the pore volume of 40～100A accounts for more than 75% of total pore volume.Described pore volume records with B E T Brunauer Emett Teller method of nitrogen adsorption at low temperature.This aperture Al
2O
3With macropore Al
2O
3Precursor be respectively a diaspore content greater than 60% with greater than 50% hydrated aluminum oxide.
The preparation method of this Hydrobon catalyst is as follows: the precursor of little porous aluminum oxide and macroporous aluminium oxide is pressed the even aftershaping of required mixed, in 550～650 ℃ of roastings 3～5 hours; With fluorine-containing inorganic compound aqueous solution dipping, dry back was in 400～600 ℃ of roastings 3～5 hours then; With the aqueous solution dipping of nickeliferous and tungsten, dry back was in 400～600 ℃ of roastings 3～5 hours at last.
The hydrocracking catalyst that uses among the present invention be 97112396.9 at application number, denomination of invention is the catalyzer disclosed in the application of " a kind of fraction oil hydrocracking catalyst and preparation thereof ".This catalyzer is by 2.5～6.0 heavy %, best 2.0～5.0 heavy %NiO, 10～38 heavy %, best 19～25 heavy %WO
3, 0.5～5.0 heavy %, the carriers of best 1.0～4.0 heavy %F and surplus are formed.This carrier is that the acidity value of best 50～80 heavy % is the Al of 0.5～0.8 mmole/gram by 20～90 heavy %
2O
3With 10～80 heavy %, the acidity value of best 20～50 heavy % is that the mesopore or the large pore zeolite of 1.0～2.0 mmole/grams formed.Described acidity value is to use NH
3-TPD method is measured.This mesopore or large pore zeolite are selected from the y-type zeolite and/or the mordenite of H type or RE type.This Al
2O
3Get through the roasting dehydration by one or more hydrated aluminum oxides that are selected from sodium metaaluminate-carbon dioxide process, sodium metaaluminate-Tai-Ace S 150 method, aluminum alkyls or the preparation of aluminum alkoxide hydrolysis method, diaspore content＞60%.
The preparation method of this hydrocracking catalyst is as follows: hydrated aluminum oxide and zeolite are mixed aftershaping by predetermined proportion, in 550～650 ℃ of roastings 3～5 hours; With fluorine-containing inorganic compound aqueous solution dipping, dry back was in 400～500 ℃ of roastings 3～5 hours then; With the aqueous solution dipping of nickeliferous and tungsten, dry back was in 400～500 ℃ of roastings 3～5 hours at last.
Above-mentioned Hydrobon catalyst and hydrocracking catalyst should carry out prevulcanized before use.Prevulcanized can be carried out according to the method for common Hydrobon catalyst and hydrocracking catalyst prevulcanized.The general gas phase sulfuration method that adopts among the present invention, vulcanizing agent can be selected dithiocarbonic anhydride or dimethyl disulfide for use, and sulfide stress is generally 3.0～8.0MPa, and the volume ratio of vulcanizing agent gas and catalyzer is generally 300～600 during sulfuration: 1.Sulfuration is that the segmentation alternating temperature carries out, and generally vulcanizes 2～6 hours down at 200～240 ℃, vulcanizes 8～12 hours down at 320～360 ℃ again.The injection rate of vulcanizing agent should be with H in sulfurized different steps and the circulation gas
2The concentration of S is regulated: the injection rate of cryogenic vulcanization vulcanizing agent during the stage should be controlled at and make H in the circulation gas
2The concentration of S remains in 0.1～0.5% scope; Along with the rising of curing temperature, the injection rate of vulcanizing agent can be controlled in the H that makes in the circulation gas
2S concentration is increased to 1.0% gradually; During high temperature vulcanized stage, the injection rate of vulcanizing agent then should make H
2The concentration of S is controlled in 1.0～2.0% scopes.
(2) hydrocarbon feed that is suitable for of the present invention
Used hydrocarbon feed can be the various raw materials that common hydrocracking is suitable among the present invention.Because the Hydrobon catalyst that the present invention uses has the saturated performance of good desulfurization, nitrogen and aromatic hydrocarbons, simultaneously again because the hydrocracking catalyst that the present invention uses has good anti-nitrogen ability (nitrogen content in the hydrocracking charging allows up to 150ppmw), thereby the present invention more is applicable to sulphur, the heavy raw oil that nitrogen content is high, for example boiling range do＞500 ℃, be generally 500～580 ℃, density is 0.8～0.93 gram per centimeter
3, nitrogen content can be up to the poor quality oil raw material of the heavy % in 1500ppmw, sulphur content ≯ 3.5, as normal pressure or vacuum gas oil, coker gas oil, mix slag catalytic cracking circulation wet goods.
In order to prolong the running period of catalyzer, the nitrogen content in the stock oil preferably is controlled at ≯ 1300ppmw, and sulphur content preferably is controlled at ≯ 3.0 heavy %, can guarantee that like this catalyzer is no less than 1 year the running period before regeneration.
(3) processing method provided by the invention and operational condition
The one-pass flow process of process using single hop provided by the invention is being loaded Hydrobon catalyst and hydrocracking catalyst with series system in the bed.
Specifically, this processing method is such: is 340～440 ℃ with hydrogen in hydrogen dividing potential drop 6.0～10.0MPa, best 6.5～9.5MPa, average reaction temperature with the heavy feed stock of sulfur-bearing, nitrogen and polycyclic aromatic hydrocarbons, best 350～420 ℃, stock liquid hourly space velocity LHSV0.1～3.0 o'clock
-1, best 0.2～1.0 o'clock
-1, hydrogen/oil volume is than 400～1200, contact with Hydrobon catalyst under best 600～1000 the condition.Hydrogen dividing potential drop wherein should account for 85% of stagnation pressure at least, and the raw material after refining need not isolated H
2S and NH
3, directly contact with hydrocracking catalyst according to above-mentioned reaction conditions with hydrogen.Reaction effluent enters high-pressure separator through cooling, and isolated product liquid enters fractionating system, and rich hydrogenous gas circulation is returned conversion zone.
The temperature of hydrofining and hydrocracking reaction can adopt cold hydrogen to control.
Hydrobon catalyst and hydrocracking catalyst can be seated in the same reactor, also can be seated in two placed in-line reactors, and its loadings separately can be adjusted its relative proportion according to the employing raw material properties.Raw materials quality is poor more, and the ratio that Hydrobon catalyst accounts for is also just big more.The admission space ratio of this two catalyzer can be adjusted in 25: 75～75: 25 scope.
If carbon residue, bituminous matter or metal content are higher in the raw material; for falling, the pressure that prevents beds reaches limit value too quickly; can before the hydrofining agent, add a certain amount of protective material with the running of assurance device long period ground; protectant add-on is generally 1～20% of Hydrobon catalyst volume, decides according to feedstock property.
Above-mentioned all processing condition are used in the ordinary course of things, it is not definitely immutable, according to raw materials used kind, different in kind, hope for the distribution difference of purpose product, different with the combination of technologies such as coking, catalytic cracking, catalytic reforming, steam cracking, it can be adjusted the demand that product is distributed to satisfy.
Processing method provided by the invention can be in a particular design, implement on the form device similar to existing middle pressure hydrocracking device, also can on existing medium-pressure hydrocracking refining plant, do the change of a little necessity, can implement as enlarging or increase reactor, increase fractionation plant etc.
Method provided by the invention has following characteristics and advantage:
1. having selected two kinds of special catalyst series connection uses, realized under middle pressure the high heavy of sulphur, nitrogen and aromaticity content and the processing of inferior raw material, can directly process nitrogen content and do stock oil more than 500 ℃ up to 1500ppmw, boiling range, the nitrogen content of hydrocracking charging allows up to 150ppmw, and this is that prior art institute is incomparable.
2. under the transformation efficiency of heavy or inferior raw material can the situation up to 80 body %, middle distillate oil product selectivity ≮ 50 body %, and good product quality, light naphthar fraction saturated hydrocarbon content height can be done ethylene raw; Heavy naphtha fraction nitrogen content＜0.5ppmw, virtue is dived high, is suitable for doing catalytic reforming raw material; Kerosene fraction aromaticity content is low, has good burning performance, and meets the rocket engine fuel specification; Fraction of diesel oil sulphur content＜0.05% reaches low-sulfur derv fuel oil specification; Tail oil fraction characterization factor＞12, aromatic hydrocarbons correlation index＜11, sulphur, nitrogen content are low, not only can do catalytically cracked material but also can make ethylene raw.
3. the selected and collocation of specific Hydrobon catalyst and hydrocracking catalyst has not only reduced the generation of coke, and has guaranteed that the stability of hydrocracking catalyst was not less than 1 year.
4. present method has the big advantage of other hydrocracking process production handiness equally, can with technology flexible combination such as coking, catalytic cracking, catalytic reforming and steam cracking, adjust products scheme as required.
5. the transformation that only needs existing medium-pressure hydrocracking refining plant slightly to be done a little necessity can be implemented the present invention.
Following example will give further instruction to the present invention, but not thereby limiting the invention.
Employed Hydrobon catalyst is to be that method described in 97112397.7 makes according to application number in the example.Specifically, that is: predecessor's hydrated aluminum oxide (Shandong Aluminum Plant's production) of the little porous aluminum oxide that will make with sodium metaaluminate-carbon dioxide process mixes according to 70: 30 weight ratios with predecessor's hydrated aluminum oxide (production of Chang Ling refinery catalyst plant) with the macroporous aluminium oxide that sodium metaaluminate-the Tai-Ace S 150 method makes, making circumscribed circle diameter is the trilobal cross bar of 1.4mm, dries back 550 ℃ of roastings 4 hours; Use NH then
4The F aqueous solution soaked 1 hour, dried back 500 ℃ of roastings 4 hours; Mixed aqueous solution with ammonium metawolframate and nickelous nitrate flooded 4 hours at last, dried back 480 ℃ of roastings 4 hours.This catalyst chemical consists of: NiO2.3 heavy %, WO
322.1 the Al of heavy % of heavy %, F4.1 and surplus
2O
3Carrier, this carrier A l
2O
3In the hole of 40～100A account for 84.5% of total pore volume.The specific surface of this catalyzer is 232 meters
2/ gram, pore volume are 0.31 milliliter/gram, and crushing strength is 23.1 Newton/millimeter.
Employed hydrocracking catalyst I and II are to be that method described in 97112396.9 makes according to application number in the example.Specifically, that is: be that acidity value is the Al of 0.7028 mmole/gram after the HY zeolite of 1.5672 mmole/grams and the roasting with acidity value
2O
3Predecessor's hydrated aluminum oxide mix according to certain weight ratio, making circumscribed circle diameter is the trilobal cross bar of 1.8mm, dries back 600 ℃ of roastings 4 hours; Burning the back acidity value then is the Al of 0.7028 mmole/gram
2O
3Predecessor's hydrated aluminum oxide mix according to certain weight ratio, making circumscribed circle diameter is the trilobal cross bar of 1.8mm, dries back 600 ℃ of roastings 4 hours; Use NH then
4The F aqueous solution soaked 1 hour, dried back 500 ℃ of roastings 4 hours; Mixed aqueous solution with ammonium metawolframate and nickelous nitrate flooded 4 hours at last, dried back 480 ℃ of roastings 4 hours.Catalyst I that makes and the composition of II and physico-chemical property are as follows:
Zeolite and hydration oxygen NiO, WO
3, F, specific surface, pore volume, crushing strength,
Change the heavy % rice of the heavy % of aluminium weight proportion %
210: 37 4.0 20.8 2.0 230 0.27 27.5 II of/gram milliliter/gram Newton/millimeter I 30: 37 4.6 19.0 2.1 242 0.22 31.0
Wherein used hydrated aluminum oxide prepares according to the CN85100218B disclosed method, that is: the aluminium isopropoxide that drips fusing in being heated to the ebullient isopropanol water solution carried out back flow reaction 6 hours, steam Virahol, add deionized water and wore out 16 hours for 80 ℃, 120 ℃ of oven dry of gained solid product are got final product.
Employed three kinds of stock oils in the example: the vacuum gas oil of matter crude oil in A-Saudi Arabia; B-China's intermediate base vacuum gas oil; The diesel oil of C-mix slag heavy oil fluid catalytic cracking gained and straight-run light gas oil are by the mixing oil of 69: 31 weight ratio gained, their character is all listed in down: stock oil numbering A B C boiling range, ℃ 299～553 267～532 204～402 density (20 ℃), g/cm
30.9235 0.8877 0.8425 carbon, heavy % 85.20 86.03 86.74 hydrogen, heavy % 11.61 12.98 13.13 sulphur, heavy % 3.10 0.66 0.07 nitrogen, ppm 898 1,300 548 alkali nitrogen, ppm 212 447 252 condensation points, ℃ 31 40 14 aniline points, ℃ 77.5 91.0 73.8 C
5Insolubles, heavy % 0.04 0.15-carbon residue
*, heavy % 0.23 0.10 0.05 viscosity (80 ℃), mm
2/ s 12.7 26.4 6.30 forms, heavy %
Alkane 18.2 69.2 41.4
Naphthenic hydrocarbon 26.5 29.4
Aromatic hydrocarbons 53.6 27.2 28.4
Colloid 1.7 3.6 0.8
*Electric furnace process records
Example 1
The explanation of this example the invention provides the enforcement of method when being raw material with Saudi Arabia's vacuum gas oil.
Process is to carry out on the middle-scale device of 0.4 liter, and operational condition is as follows: hydrogen dividing potential drop 9.6MPa, and stagnation pressure 11.3MPa, 383/380 ℃ of temperature of reaction (hydrofining/hydrocracking) is during liquid hourly space velocity 0.5
-1, hydrogen/oil volume is than 1000, and through the nitrogen content 25.3ppm of refining back end hydrogenation cracked charge, finishing agent is 50: 50 with the admission space ratio of cracking agent I, and two doses of filling cumulative volumes are 0.3 liter.What be converted into product below 350 ℃ is 63.7 body % by transformation efficiency once.The distribution and the character of products obtained therefrom are listed in table 1.
By table 1 data as can be known: the method for the invention provides can be under middle press strip spare changes into the light naphtha fraction of saturated hydrocarbon content up to 97 heavy % with the mink cell focus of high-sulfur, high aromaticity content; Nitrogen content＜0.5ppmw, virtue are dived up to the heavy naphtha fraction of 58 heavy %; Smoke point and aromatic hydrocarbons meet the kerosene(oil)fraction of rocket engine fuel specification; Sulphur content only is 21ppmw, condensation point-28 ℃, the diesel oil distillate of cetane value nearly 62; And the tail oil cut of characterization factor＞12, aromatic hydrocarbons correlation index＜11, sulphur content 23ppmw, nitrogen content 1.3ppmw.Boiling range is that the yield of 145～350 ℃ middle distillate oil reaches 46 heavy %, selectivity reaches 65.6 heavy %.
Table 1
| The cut scope, ℃ | ??＜65 | ??65～145 | ??145～260 | ???260～350 | ????＞350 |
| Product distributes, heavy % density (20 ℃), g/cm 3Sulphur, ppm nitrogen, the ppm stable hydrocarbon, heavy % virtue is dived, heavy % viscosity (20 ℃), mm 2/ S freezing point, ℃ condensation point, ℃ aromatic hydrocarbons, body % smoke point, the mm naphthalene is a hydrocarbon, body % cetane value characterization factor aromatic hydrocarbons correlation index | ??3.61 ??0.6546 ???- ??＜0.5 ??97.46 | ??20.57 ??0.7441 ???- ??＜0.5 ? ??58.59 | ????31.12 ????0.8042 ????9.2 ????0.8? ? ? ????1.7 ????＜-50 ? ????10.7 ????22.7 ????0.14 | ????14.98 ????0.8236 ????21 ????0.8 ? ? ????7.1 ? ????-28 ? ? ? ????61.8 | ????29.72 ????0.8359 ????23 ????1.3? ? ? ? ? ????39 ? ? ? ? ????12.85 ????10.4 |
Example 2
This example explanation the invention provides the enforcement of method when being raw material with China's intermediate base vacuum gas oil of high nitrogen-containing.
Reactor assembly, catalyst system therefor and filling ratio are with example 1.Operational condition is as follows: hydrogen dividing potential drop 6.4MPa, and stagnation pressure 7.5MPa, 391/384 ℃ of temperature of reaction (hydrofining/hydrocracking) is during liquid hourly space velocity 0.5
-1, hydrogen/oil volume is than 1000, and the nitrogen content through making with extra care the back end hydrogenation cracked charge is 46ppmw.What be converted into product below 350 ℃ is 55.9 body % by transformation efficiency once.The distribution and the character of products obtained therefrom are listed in table 2.
By table 2 data as can be known: the method for the invention provides can be under middle press strip spare changes into the mink cell focus of high nitrogen-containing and example 1 same high-quality various products.Boiling range is that the yield of 145～370 ℃ middle distillate oil reaches 46.7 heavy %, selectivity reaches 70.2 heavy %.
Table 2
| The cut scope, ℃ | ???＜65 | ??65～145 | ???145～215 | ??215～370 | ????＞370 |
| Product distributes, heavy % density (20 ℃), g/cm 3Sulphur, ppm nitrogen, the ppm stable hydrocarbon, heavy % virtue is dived, heavy % viscosity (20 ℃), mm 2/ S freezing point, ℃ condensation point, ℃ aromatic hydrocarbons, body % smoke point, the mm naphthalene is a hydrocarbon, body % cetane value characterization factor aromatic hydrocarbons correlation index | ???2.96? ? ? ???＜0.5 ???66.81 | ??16.85 ??0.7440 ? ??＜0.5 ? ??57.50 | ????18.26 ????0.8022 ????9.7 ????0.5? ? ? ????1.4 ????＜-50? ? ????16.0 ????20.7 ????＜1 | ????28.45 ????0.8266 ????29.6 ????1.0? ? ? ????5.1 ? ????-8 ? ? ? ????62.8 | ????33.48 ????0.8269 ????34 ????1.5? ? ? ? ? ????42? ? ? ? ? ????12.98 ????5.90 |
Example 3
This example explanation the invention provides the enforcement of method when being raw material with the diesel oil of mixing slag heavy oil fluid catalytic cracking gained and straight-run light gas oil by the mixing oil of 69: 31 weight ratios.
Reactor assembly is with example 1.Operational condition is as follows: hydrogen dividing potential drop 7.8MPa, and stagnation pressure 9.2MPa, 360/367 ℃ of temperature of reaction (hydrofining/hydrocracking) is during liquid hourly space velocity 0.85
-1, hydrogen/oil volume is than (hydrofining/hydrocracking) 807/1003, and finishing agent is 60: 40 with the admission space ratio of cracking agent II.What be converted into product below 350 ℃ is 77.0 body % by transformation efficiency once.The distribution and the character of products obtained therefrom are listed in table 3.
The invention provides method once more as can be known by table 3 data and can obtain various high-quality product under middle press strip spare, the yield of 145～350 ℃ of middle distillate oil reaches 67.8 heavy %, and selectivity reaches 75.4 heavy %.
Table 3
| The cut scope, ℃ | ????＜65 | ??65～145 | ??145～260 | ??260～350 | ????＞350 |
| Product distributes, heavy % density (20 ℃), g/ 3Sulphur, ppm nitrogen, the ppm stable hydrocarbon, heavy % virtue is dived, heavy % viscosity (20 ℃), mm 2/ S freezing point, ℃ condensation point, ℃ aromatic hydrocarbons, body % smoke point, mm cetane value characterization factor aromatic hydrocarbons correlation index | ????3.50 ????0.6494 ? ????＜0.5 ????99.52 | ????18.58 ????0.7265? ? ????＜0.5 ? ????48.87 | ????41.93 ????0.7920 ????4.5 ????＜0.5? ? ? ????2.0 ????-49? ? ????5.4 ????30? | ????25.91 ????0.7974 ????4.9 ????0.6? ? ? ????7.1? ? ????-8? ? ? ????＞75 | ????7.60 ????0.8117 ????4.5 ????4.1? ? ? ? ? ? ? ? ? ????12.95 ????3.6 |
Claims (10)
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|---|---|---|---|
| CN97112239A CN1045462C (en) | 1996-07-22 | 1997-07-17 | Middle-pressure hydrocracking process for heavy fractional oil |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96109007 | 1996-07-22 | ||
| CN96109007.3 | 1996-07-22 | ||
| CN97112239A CN1045462C (en) | 1996-07-22 | 1997-07-17 | Middle-pressure hydrocracking process for heavy fractional oil |
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| CN1171430A true CN1171430A (en) | 1998-01-28 |
| CN1045462C CN1045462C (en) | 1999-10-06 |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1072707C (en) * | 1998-12-16 | 2001-10-10 | 中国石油化工集团公司 | Medium pressure hydrocracking method |
| CN1088089C (en) * | 1999-10-13 | 2002-07-24 | 中国石油化工集团公司 | Process for hydrogenating raw material of hydrocarbon |
| CN100345945C (en) * | 2004-10-29 | 2007-10-31 | 中国石油化工股份有限公司 | Two-stage hydrocracking method for increasing yield of middle distillate oil |
| CN100364668C (en) * | 2004-10-29 | 2008-01-30 | 中国石油化工股份有限公司 | A kind of preparation method of surface-modified hydrogenation catalyst of II B group metal oxide |
| CN100381543C (en) * | 2004-10-29 | 2008-04-16 | 中国石油化工股份有限公司 | A kind of hydrocracking method of composite catalyst bed |
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| US4572778A (en) * | 1984-01-19 | 1986-02-25 | Union Oil Company Of California | Hydroprocessing with a large pore catalyst |
| JPS62199687A (en) * | 1986-04-28 | 1987-09-03 | ユニオン・オイル・コンパニ−・オブ・カリフオルニア | Hydrogenation using catalyst having large pores |
| US4859312A (en) * | 1987-01-12 | 1989-08-22 | Chevron Research Company | Process for making middle distillates using a silicoaluminophosphate molecular sieve |
| GB8727777D0 (en) * | 1987-11-27 | 1987-12-31 | Shell Int Research | Heavy oil cracking process |
| US5089239A (en) * | 1989-04-18 | 1992-02-18 | Shin-Etsu Handotai Company Limited | Wire vibration prevention mechanism for a single crystal pulling apparatus |
| US5294330A (en) * | 1992-08-12 | 1994-03-15 | Mobil Oil Corp. | Hydrocracking process with a catalyst comprising MCM-36 |
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| CN1072707C (en) * | 1998-12-16 | 2001-10-10 | 中国石油化工集团公司 | Medium pressure hydrocracking method |
| CN1088089C (en) * | 1999-10-13 | 2002-07-24 | 中国石油化工集团公司 | Process for hydrogenating raw material of hydrocarbon |
| CN100345945C (en) * | 2004-10-29 | 2007-10-31 | 中国石油化工股份有限公司 | Two-stage hydrocracking method for increasing yield of middle distillate oil |
| CN100364668C (en) * | 2004-10-29 | 2008-01-30 | 中国石油化工股份有限公司 | A kind of preparation method of surface-modified hydrogenation catalyst of II B group metal oxide |
| CN100381543C (en) * | 2004-10-29 | 2008-04-16 | 中国石油化工股份有限公司 | A kind of hydrocracking method of composite catalyst bed |
| CN100439479C (en) * | 2005-10-24 | 2008-12-03 | 中国石油化工股份有限公司 | A combined processing method for low-quality catalytic cracking diesel oil |
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| CN101280216B (en) * | 2007-04-04 | 2011-11-30 | 中国石油化工股份有限公司 | Method for producing ultra-low sulfur diesel |
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