CN106479566A - A kind of method for hydrogen cracking for producing premium and diesel oil - Google Patents
A kind of method for hydrogen cracking for producing premium and diesel oil Download PDFInfo
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- CN106479566A CN106479566A CN201510797913.5A CN201510797913A CN106479566A CN 106479566 A CN106479566 A CN 106479566A CN 201510797913 A CN201510797913 A CN 201510797913A CN 106479566 A CN106479566 A CN 106479566A
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- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000002283 diesel fuel Substances 0.000 title claims abstract description 51
- 239000001257 hydrogen Substances 0.000 title claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000005336 cracking Methods 0.000 title abstract description 14
- 239000003921 oil Substances 0.000 claims abstract description 66
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 43
- 241001465754 Metazoa Species 0.000 claims abstract description 40
- 235000013311 vegetables Nutrition 0.000 claims abstract description 34
- 239000000446 fuel Substances 0.000 claims abstract description 28
- 239000003502 gasoline Substances 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 11
- 238000005194 fractionation Methods 0.000 claims abstract description 4
- 235000019198 oils Nutrition 0.000 claims description 64
- 239000000047 product Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000002808 molecular sieve Substances 0.000 claims description 24
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 13
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 8
- 239000008158 vegetable oil Substances 0.000 claims description 8
- 235000019197 fats Nutrition 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 235000019737 Animal fat Nutrition 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 235000019482 Palm oil Nutrition 0.000 claims description 2
- 235000019483 Peanut oil Nutrition 0.000 claims description 2
- 241001494479 Pecora Species 0.000 claims description 2
- 235000019484 Rapeseed oil Nutrition 0.000 claims description 2
- 235000019486 Sunflower oil Nutrition 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000010775 animal oil Substances 0.000 claims description 2
- 235000014121 butter Nutrition 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000003240 coconut oil Substances 0.000 claims description 2
- 235000019864 coconut oil Nutrition 0.000 claims description 2
- 235000005687 corn oil Nutrition 0.000 claims description 2
- 239000002285 corn oil Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 235000012343 cottonseed oil Nutrition 0.000 claims description 2
- 235000021323 fish oil Nutrition 0.000 claims description 2
- 239000000944 linseed oil Substances 0.000 claims description 2
- 235000021388 linseed oil Nutrition 0.000 claims description 2
- 239000004006 olive oil Substances 0.000 claims description 2
- 235000008390 olive oil Nutrition 0.000 claims description 2
- 239000002540 palm oil Substances 0.000 claims description 2
- 239000000312 peanut oil Substances 0.000 claims description 2
- 239000008159 sesame oil Substances 0.000 claims description 2
- 235000011803 sesame oil Nutrition 0.000 claims description 2
- 239000002600 sunflower oil Substances 0.000 claims description 2
- 239000002383 tung oil Substances 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 2
- 235000007164 Oryza sativa Nutrition 0.000 claims 2
- 235000009566 rice Nutrition 0.000 claims 2
- 240000000528 Ricinus communis Species 0.000 claims 1
- 235000004443 Ricinus communis Nutrition 0.000 claims 1
- 238000004939 coking Methods 0.000 claims 1
- 239000002385 cottonseed oil Substances 0.000 claims 1
- 239000010903 husk Substances 0.000 claims 1
- 239000010773 plant oil Substances 0.000 claims 1
- 239000003549 soybean oil Substances 0.000 claims 1
- 235000012424 soybean oil Nutrition 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 abstract description 7
- 238000005984 hydrogenation reaction Methods 0.000 description 23
- 239000002994 raw material Substances 0.000 description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 13
- 241000196324 Embryophyta Species 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 238000004523 catalytic cracking Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000007670 refining Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000006114 decarboxylation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- -1 Linoleic acid, leukotrienes Chemical class 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 235000021314 Palmitic acid Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 235000019774 Rice Bran oil Nutrition 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000004411 aluminium 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
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012075 bio-oil Substances 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004359 castor oil Substances 0.000 description 1
- 235000019438 castor oil Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000005906 dihydroxylation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000008520 organization Effects 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
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008165 rice bran oil Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 150000003384 small molecules Chemical group 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 125000005480 straight-chain fatty acid group Chemical group 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of method for hydrogen cracking for producing premium and diesel oil.Vegetable and animals oils hydrogenated pretreatment after, enter hydrocracking reactor, with hydrocracking catalyst I under relative low temperature, large volume space velocities haptoreaction；After gained product is mixed with poor ignition quality fuel hydrofinishing product again, with II haptoreaction of hydrocracking catalyst；Product is separated and fractionation obtains premium and diesel oil.The present invention has taken into full account the features of vegetable and animals oils hydro-upgrading and poor ignition quality fuel hydroconversion process, reasonably effectively combines two kinds of techniques, can produce high octane gasoline products and diesel product simultaneously, and improve the greasy property of diesel product.
Description
Technical field
The invention discloses a kind of method for hydrogen cracking, more specifically a kind of with high arene content diesel oil distillate and dynamic
Vegetable oil is raw material, and produce high-knock rating gasoline and fine-quality diesel oil is hydrocracked combined method.
Background technology
Enter 21st century since, with people's environmental consciousness increasingly strengthen, national environmental protection regulation increasingly strict
And the fast development of national economy, countries in the world are all being continuously increased to the demand for cleaning automotive fuel.
Catalytic cracking（FCC）Technology is one of main technique means of heavy oil lighting, in the oil refining enterprise of countries in the world
In all occupy important status.In Chinese heavy oil lighting processing unit (plant), catalytic cracking unit working ability institute accounting
Example is more projected, and in petrol and diesel oil product are constituted, catalytically cracked gasoline accounts for 80% or so, and catalytic diesel oil accounts for 30% or so.In recent years,
With the increasingly heaviness of crude oil, the raw material processed by catalytic cracking also heaviness and in poor quality increasingly, in addition many enterprises be
The purpose for improving quality of gasoline or propylene enhancing is reached, catalytic cracking unit has been carried out transforming or improve catalytic cracking dress
The operating severity that puts, causes the quality of the product of catalytic cracking, particularly catalytic diesel oil more to deteriorate, and its performance is predominantly close
Degree is high, and arene content is high, and sulphur nitrogen content is high, and Cetane number is low.Also include coal tar with above-mentioned property diesel oil distillate raw material,
Coal direct liquefaction oil etc..
Existing diesel oil distillate Raw material processing mode mainly includes hydrofinishing, hydro-upgrading and is hydrocracked.Hydrogenation essence
System can only remove the impurity such as sulphur in raw material, nitrogen, and Cetane number can only typically improve several units, and refined products are evaporated for diesel oil
Point, but product cannot meet other index requests of vehicle fuel.Hydro-upgrading purpose product be diesel product, removing sulphur,
While nitrogen change molecular structure, to effectively improve Cetane number index, in general can by raw material Cetane number improve 10 ~
15 units, but for the too low raw material of Cetane number, the diesel oil that the method is obtained cannot still meet use requirement.It is hydrocracked
It is small molecule by macromolecular cleavage to be, during with catalytic diesel oil as raw material, main purpose product is gasoline fraction, but art technology
Personnel know that the octane number for being hydrocracked gasoline is too low, it is impossible to for blended gasoline product, the gasoline fraction in general obtaining
It is divided into light naphthar and heavy naphtha two parts, light naphthar octane number is slightly higher, can be used for blended gasoline product, it is also possible to use
Preparing ethylene by steam cracking raw material is done, heavy naphtha octane number is lower, and reformer feed is generally used for, and is in addition hydrocracked gasoline fraction
Can be also used for producing solvent oil product.
As world oil reserves are fewer and feweri, the utilization of the renewable resource such as vegetable and animals oils is also increasingly taken seriously.
The main component of animal and plant fat is straight chain fatty acid triglyceride, and wherein aliphatic acid face length is generally C12～C24, and
In the majority with C16 and C18.The Typical fatty acid that animal and plant fat contains includes saturated acid（Palmitic acid, stearic acid）, unitary unsaturated
Acid（Oleic acid）And polyunsaturated polycarboxylic acid（Linoleic acid, leukotrienes）, vegetable oil based on a unsaturated diluted acid and dienoic acid, tallow
Then based on saturated fatty acid.Generation oil of these vegetable and animals oils after hydrogenation is exactly diesel component, and which is mainly straight chain
Alkane, therefore, condensation point is higher, it is impossible to meet the requirement of condensation point of diesel oil, but Cetane number is very high.Meanwhile, vegetable and animals oils are hydrogenated with
The greasy property of the diesel oil for arriving is relatively low, causes its wearability also poor.
Than larger, operating cost is also higher for hydrocracking unit one-time investment.Therefore, each big research in countries in the world is public
Department all carries out substantial amounts of research positive for reducing the cost being hydrocracked, and makes great progress.In terms of catalyst：
The emphasis that each big patent business in the world is all developed the update of catalyst as oneself technology, in recent years, constantly in catalysis
The material of agent, the aspect such as the activity of catalyst, life-span, stability and reduction catalyst cost have done substantial amounts of work.In work
In terms of skill：Distillate hydrocracking technology is quite ripe, and each major oil companies are optimizing the same of hydrocracking operation further
When, innovative point is placed on and is hydrocracked on related group technology, by optimum organization technique come reduces cost；In addition, logical
The further investigation to being hydrocracked is crossed, seeks the inherent connection between catalyst performance and feedstock property and purpose product quality
System, sets up the emphasis that suitable catalyst grade part system is also the current area research.
Existing animal and plant fat hydrogenation method produces the process technology of automotive fuel, US20060186020, EP1693432,
CN201110217561.3、CN101321847A、CN200710012090.6、CN200680045053.9、
CN200710065393.4, CN200780035038.0, CN200710012208.5, CN200780028314.0 and
The patents such as CN101029245A disclose vegetable oil hydroconversion process, using coker naphtha, diesel oil distillate（Straight run bavin
Oil, LCO and coker gas oil）, the petroleum hydrocarbon such as wax oil cut cut and bio-oil be mixed into hydrogenation catalyst bed,
Production diesel product or preparing ethylene by steam cracking raw material etc..US5705722 is disclosed containing plants such as unrighted acid, fat
Oil and animal oil mixing back end hydrogenation produce the diesel oil blending component of diesel oil distillate scope.EP1741767 and EP1741768 are disclosed
A kind of method for producing diesel oil distillate with animal and plant fat, predominantly animal and plant fat first pass around hydrotreating, Ran Houtong
Isomerization catalyst bed layer is crossed, obtains low freezing point diesel fuel component.
US 4676887 discloses a kind of technique for producing high-knock rating gasoline.By catalytic cracking diesel oil (LCO) etc., first
First passing through refining reaction area carries out imurity-removal, and carries out aromatic moiety saturation, and the cracking reaction area of entrance afterwards carries out open loop and splits
Change reaction, be hydrocracked the diesel oil distillate for obtaining afterwards and enter into catalyst cracker and processed, the essence that the technique is adopted
Catalyst processed is also existing commercial catalyst for refining.The technology refining stage severe reaction conditions, polycyclic aromatic hydrocarbon can be supersaturated, difficult
To reach the purpose of production high-knock rating gasoline.
Content of the invention
For the deficiencies in the prior art, the invention provides one kind is with high arene content poor-quality diesel-oil by cut fraction and vegetable and animals oils
For raw material, produce high-knock rating gasoline and fine-quality diesel oil is hydrocracked combined method.The inventive method has given full play to beta molecule
Sieve and Y molecular sieve type hydrocracking catalyst couple advantage, while scientific utilization reaction heat, can produce high-octane rating vapour
The good diesel oil of oil and super-low sulfur, high cetane number, greasy property.
The present invention a kind of produce high-knock rating gasoline and fine-quality diesel oil be hydrocracked combined method, including following interior
Hold：
（1）Vegetable and animals oils and hydrogen are mixed into vegetable and animals oils hydrofining reactor, and poor ignition quality fuel is mixed into bad with hydrogen
Matter diesel oil hydrofining reactor, is contacted with Hydrobon catalyst, carries out hydrofining reaction respectively；
（2）Vegetable and animals oils hydrofinishing effluent together with hydrogen, is entered from reactor head and is hydrocracked instead after dehydration
Device is answered, is contacted with the hydrocracking catalyst I containing beta-molecular sieve first, under the conditions of hydroisomerizing, carry out isomerization-visbreaking anti-
Should；
（3）Step（2）Gained reaction product, then mix with the poor ignition quality fuel hydrofinishing product of reactor middle and upper part introducing
Afterwards, contact with the hydrocracking catalyst II containing Y molecular sieve, under hydrocracking condition, carry out hydroconversion reactions；
（4）Step（3）The reaction effluent for obtaining carries out gas-liquid separation, obtains hydrogen-rich gas and fluid product；Hydrogen-rich gas can
To be recycled by circulating hydrogen compressor after purification, fluid product carries out fractionation and obtains gas, gasoline, diesel oil and a small amount of
Tail oil fraction.
In the inventive method, described vegetable and animals oils include vegetable oil and/or animal fat.Described vegetable oil is selected from big
Soya-bean oil, peanut oil, castor oil, rapeseed oil, corn oil, olive oil, palm oil, coconut oil, tung oil, linseed oil, sesame oil, cottonseed
One or more in one group of materials of composition such as oil, sunflower oil and rice bran oil, animal fat are selected from butter, lard, sheep oil
With one or more in one group of material of the compositions such as fish oil.Described poor ignition quality fuel is catalytic diesel oil and/or coker gas oil etc..
Arene content in poor ignition quality fuel is generally 70 more than w%, and preferably more than 80w%, its Cetane number are generally less than 30, are
It is qualified that the unmanageable inferior raw material of commonsense method, common hydrofining technology or hydrogenation modifying process are difficult to be processed as
Diesel product or diesel oil blending component.
In the inventive method, the hydrogenation metal component of described Hydrobon catalyst and hydrocracking catalyst is being used
Sulphided state is under state.Hydrogenation metal component is generally one or more in W, Mo, Ni and Co.In terms of oxide weight
In Hydrobon catalyst and hydrocracking catalyst, the content of hydrogenation metal component is generally 15wt%～45wt%.Catalyst exists
Hydrogenation metal component is converted into sulphided state using front being vulcanized, vulcanization process is well known to those skilled in the art.
In the inventive method, described Hydrobon catalyst typically with aluminum oxide as carrier, or with containing auxiliary agent oxygen
Change aluminium is carrier, and auxiliary agent is generally one or more in silicon, phosphorus, boron, fluorine, titanium, zirconium etc., and auxiliary agent can be in carrier preparation process
Middle introducing, it is also possible to introduce in hydrogenation metal component loading process.The hydrogenation loaded in vegetable and animals oils hydrofining reactor
Catalyst for refining, Main Function be the hydrogenation saturation of unrighted acid in vegetable and animals oils, hydrogenation deoxidation, hydrogenation decarboxylation, plus
Hydrogen decarboxylation reaction etc..Hydrobon catalyst can select suitable commercial catalyst, it is also possible to commonly be known according to this area
Know and prepare suitable catalyst.
In poor ignition quality fuel hydrofining reactor load Hydrobon catalyst, Main Function poor ignition quality fuel is carried out plus
Hydrogen desulfurization, hydrodenitrogeneration etc. are reacted.Hydrobon catalyst can be conventional for processing diesel oil distillate or heavy oil fraction
Hydrobon catalyst, can such as select suitable commercial catalyst, it is also possible to be prepared according to this area general knowledge.
In the inventive method, containing molecular sieve and/or amorphous silica-alumina in the carrier of described hydrocracking catalyst, point
Son sieve is generally one or two in Y molecular sieve, beta-molecular sieve, general simultaneously containing aluminum oxide etc. in hydrocracking catalyst
Inorganic refractory oxide.
In described hydrocracking catalyst I, the weight content of beta-molecular sieve is 3～50 wt%, preferably 10～25 wt%,
The acid amount of beta-molecular sieve is generally 0.1～0.4mmol/g.In described hydrocracking catalyst II containing Y molecular sieve 3～
50wt%, preferably 15～25wt%, the lattice constant of Y molecular sieve are generally 2.425～2.435nm, the SiO of Y molecular sieve2/
Al2O3Mol ratio is general 5.0～50.0, its relative crystallinity generally 80%～130%.Hydrocracking catalyst I and hydrogenation split
Change catalyst II and can select suitable commercial catalyst as needed, it is also possible to be prepared according to this area general knowledge.
In the inventive method, the volume ratio of hydrocracking catalyst I and hydrocracking catalyst II is generally 1:5～5:
1, preferably 1:3～3:1.
In the inventive method, the operating condition of hydrogenation reaction is generally：Reaction pressure 3.0MPa～20.0MPa, hydrogen oil body
Product is than being 200:1～3000:1, during the liquid of feedstock oil, volume space velocity is 0.1h-1～6.0h-1, 180 DEG C of average reaction temperature～
465℃；Preferred operating condition is reaction pressure 4.0MPa～18.0MPa, hydrogen to oil volume ratio 300:1～2500:1.
Hydrocracking catalyst I containing beta-molecular sieve should be reacted under conditions of relative low temperature, large volume air speed, subtracted
Few raw material hydro carbons is in the time of contact of catalyst active center, it is to avoid the excessive second pyrolysis of vegetable and animals oils, to ensure animals and plants
Only there is either shallow cracking in oil, while there is depth isomerization reaction.The condition of hydroisomerizing is preferably, and during liquid, volume space velocity is
2.0h-1～4.0h-1, average reaction temperature is 340 DEG C～385 DEG C.
The effect of the hydrocracking catalyst II containing Y molecular sieve is so that most of aromatic hydrocarbons is converted into mononuclear aromatics and be distributed to
In gasoline fraction, and while retaining a certain amount of（Typically ≮ 1.0wt%）Polycyclic aromatic hydrocarbon in diesel oil distillate.Inventor is grinding
Study carefully middle discovery, when polycyclic aromatic hydrocarbon content is more than 1.0% in diesel oil distillate, the abrasion resistance of diesel oil strengthens.The big bavin inferior of molecular weight
Oily raw material on hydrocracking catalyst containing Y molecular sieve II, at a relatively high temperature（The balance controlled area of aromatic hydrogenation reaction）
Preferential there is cracking reaction, orients most of aromatic hydrocarbons and is transformed in gasoline fraction.Laboratory and Commercial application show, when
When the poor ignition quality fuel of arene content ＞ 70wt% is more than 210 DEG C of yield ＞ 50wt%, in diesel oil distillate product, polycyclic aromatic hydrocarbon content can
To be more than 1.0wt%.For making up the deficiency of vegetable and animals oils hydrogenated diesel oil product greasy property difference, it is contemplated that vegetable and animals oils are hydrogenated
Cracking catalyst I and hydrocracking catalyst II can occur a small amount of either shallow cracking, generate the cut of 210 DEG C a small amount of of ＜, this
The reactive moieties of the invention control II of hydrocracking catalyst containing Y molecular sieve, vegetable and animals oils are more than with catalytic diesel oil miscella inferior
210 DEG C of yield ≮ 60wt%, preferably 65～75 wt%.During preferred raw material fluid, volume space velocity is 0.8h-1～1.5h-1,
Preferred 390 DEG C～435 DEG C of average reaction temperature.
The processing capacity of vegetable and animals oils and poor ignition quality fuel can be arbitrarily determined in principle according to actual needs, and preferably 1:3
～3:1.
Compared with prior art, the method for hydrogen cracking of the present invention has advantages below：
1st, the present invention has taken into full account the features of vegetable and animals oils hydro-upgrading and poor ignition quality fuel hydroconversion process, reasonably
Two kinds of techniques are effectively combined：After the hydrogenated pretreatment of vegetable and animals oils, hydrocracking reactor is entered, is urged with being hydrocracked
The haptoreaction under relative low temperature, large volume space velocities of agent I, while reduction condensation point improves product quality, produces reaction
Heat, generates oil and generates oil with poor ignition quality fuel hydrofinishing again and mixes, and II haptoreaction of hydrocracking catalyst is scientific and effective
Make use of vegetable and animals oils hydro-upgrading and the hydrorefined reaction heat of poor ignition quality fuel.
2nd, the beta molecule sieve-type hydrocracking catalyst of hydrocracking reactor top filling, due to ten binary of beta-molecular sieve
The straight pore passage structure of ring is conducive to the shape-selective isomery of alkane and cracking, be also beneficial to react generate small molecule hydro carbons quickly from
Open, while vegetable and animals oils condensation point is reduced, avoid unnecessary second pyrolysis to greatest extent, reduce dry gas yield；
The Y molecular sieve type hydrocracking catalyst of reactor lower part filling, as Y molecular sieve is supercage structure, which contributes to polycyclic ring
The selective opening cracking of shape hydrocarbon and aromatic hydrocarbons, by controlling suitable acidity, retains mononuclear aromatics to gasoline component as far as possible,
The inventive method can produce high octane gasoline products and high cetane number, ultra-low-sulphur diesel product simultaneously.
3rd, in hydrocracking reactor, be hydrocracked through the either shallow of top vegetable and animals oils/isomery after, atmosphere is reacted in bottom
The hydrogen dividing potential drop that encloses reduces, and is conducive to suppressing aromatic hydrogenation saturation in poor ignition quality fuel, so that more aromatic hydrocarbons remain into gasoline product
In product.
4th, the present invention solve vegetable and animals oils hydro-upgrading generation diesel oil wear no resistance and poor ignition quality fuel hydro-conversion
The exceeded and low problem of Cetane number of production high-knock rating gasoline by-product diesel oil sulfur content, in production high cetane number, super-low sulfur
While diesel oil, arene content in diesel product is suitably increased, so as to improve the greasy property of diesel product.
5th, two kinds of technology depth couplings, share hydrocracking reactor, a set of separation, fractionation and a recycle hydrogen
System, technical process are simple, and equipment investment and operating cost are low, flexible operation, good economy performance.
Description of the drawings
Fig. 1 is a kind of principle process flow diagram of the inventive method.
Specific embodiment
Below in conjunction with the accompanying drawings the method for the present invention is described in detail.
As shown in figure 1, a kind of technological process of the method for hydrogen cracking for producing premium and diesel oil of the present invention is as follows：Dynamic
Vegetable oil 1 is mixed into vegetable and animals oils hydrofining reactor 2 with hydrogen 12, carries out the hydrogenation saturation of unrighted acid, adds
Hydrogen deoxidation, hydrogenation decarboxylation, the hydrogenation reaction such as dehydroxylation, generate oil 5 after dehydration, enter together with hydrogen 12 be hydrocracked anti-
Device 6 is answered, and modification reaction is carried out with hydrocracking catalyst I 7 under conditions of relative low temperature, large volume air speed；Poor ignition quality fuel 3 with
After hydrogen mixing, poor ignition quality fuel hydrofining reactor 4 is entered, the reaction such as hydrodesulfurization, hydrodenitrogeneration, reaction effluent occur
8 directly enter reactor from the middle and upper part of hydrocracking reactor 6 without isolation, mixed with vegetable and animals oils hydroisomerizing product
Close, obtain through piece-rate system 11 with II 9 haptoreaction of hydrocracking catalyst, reaction effluent 10 after obtaining certain heat
Gas purified after recycle with new hydrogen, the fluid product 13 of acquisition enters fractionating system 14, obtains gas 15, gasoline
16th, diesel oil 17 and a small amount of hydrogenation tail oil 18.
A kind of method for hydrogen cracking for producing premium and diesel oil of the present invention is made followed by specific embodiment
Further instruction.
Embodiment 1-2 is the embodiment of the inventive method, the weight ratio of vegetable and animals oils and catalytic diesel oil inferior in embodiment
Example is 1:1.Reference Example 1 is the implementation result of catalytic diesel oil hydro-conversion technology, and Reference Example 2 is vegetable and animals oils hydro-upgrading technology
Implementation result.Table 1 is feedstock property, lists the property of hydrocracking catalyst used, be classified as operation in table 3 in table 2
Condition and result.
1 raw material oil nature of table.
2 hydrocracking catalyst property of table.
3 operating condition of table and result.
* the lubricity in derv fuel quality standard is typically characterized with 60 DEG C of grinding defect diameter of correction, it is desirable to which which is not more than
460μm.
The present invention has taken into full account the features of vegetable and animals oils hydro-upgrading and poor ignition quality fuel hydroconversion process, rationally
Two kinds of techniques are effectively combined.Embodiment 1 is 385 DEG C in the reaction temperature of catalyst I, and the reaction temperature of catalyst II is
Under conditions of 400 DEG C, at the same obtain gasoline products that octane number is 93.8 and Cetane number be 59, sulfur content be 8 μ g g-1's
Diesel product；Embodiment 2 is 365 DEG C in the reaction temperature of catalyst I, under conditions of the reaction temperature of catalyst II is 425 DEG C,
While obtain gasoline products that octane number is 94.4 and Cetane number be 63, sulfur content be 7 μ g g-1Diesel product, effect show
Write, all achieve the purpose of this technology invention.
Additionally, the correction grinding defect diameter as shown by data of the diesel product of embodiment and comparative example, the present invention solves dynamic plant
The problem that the diesel oil that thing oil hydro-upgrading is generated wears no resistance.
Claims (14)
1. a kind of produce high-knock rating gasoline and fine-quality diesel oil be hydrocracked combined method, including herein below：
（1）Vegetable and animals oils and hydrogen are mixed into vegetable and animals oils hydrofining reactor, and poor ignition quality fuel is mixed into bad with hydrogen
Matter diesel oil hydrofining reactor, is contacted with Hydrobon catalyst, carries out hydrofining reaction respectively；
（2）Vegetable and animals oils hydrofinishing effluent together with hydrogen, is entered from reactor head and is hydrocracked instead after dehydration
Device is answered, is contacted with the hydrocracking catalyst I containing beta-molecular sieve first, under the conditions of hydroisomerizing, carry out isomerization-visbreaking anti-
Should；
（3）Step（2）Gained reaction product, then mix with the poor ignition quality fuel hydrofinishing product of reactor middle and upper part introducing
Afterwards, contact with the hydrocracking catalyst II containing Y molecular sieve, under hydrocracking condition, carry out hydroconversion reactions；
（4）Step（3）The reaction effluent for obtaining carries out gas-liquid separation, obtains hydrogen-rich gas and fluid product；Fluid product enters
Row fractionation obtains gas, gasoline, diesel oil and tail oil fraction.
2. in accordance with the method for claim 1, it is characterised in that described vegetable and animals oils include vegetable oil and/or animal oil
Fat.
3. in accordance with the method for claim 2, it is characterised in that described vegetable oil is selected from soybean oil, peanut oil, castor-oil plant
Oil, rapeseed oil, corn oil, olive oil, palm oil, coconut oil, tung oil, linseed oil, sesame oil, cottonseed oil, sunflower oil and rice
One group of material that oil extracted from rice husks is constituted, described animal fat include one or more in butter, lard, sheep oil and fish oil.
4. in accordance with the method for claim 1, it is characterised in that the arene content in described poor ignition quality fuel be 70 w% with
On.
5. according to the method described in claim 1 or 4, it is characterised in that the arene content in described poor ignition quality fuel is 80w%
More than.
6. in accordance with the method for claim 4, it is characterised in that described poor ignition quality fuel is catalytic diesel oil and/or coking bavin
Oil.
7. in accordance with the method for claim 1, it is characterised in that the weight of beta-molecular sieve in described hydrocracking catalyst I
Content is 3～50 wt%, and the acid amount of beta-molecular sieve is 0.1～0.4 mmol/g.
8. according to the method described in claim 1 or 7, it is characterised in that contain Y molecule in described hydrocracking catalyst II
3～50 wt% of sieve, the lattice constant of Y molecular sieve is 2.425～2.435nm, the SiO of Y molecular sieve2/Al2O3Mol ratio be 5.0～
50.0, its relative crystallinity is 80%～130%.
9. in accordance with the method for claim 1, it is characterised in that described hydrocracking catalyst I and hydrocracking catalyst
The volume ratio of agent II is 1:5～5:1.
10. in accordance with the method for claim 1, it is characterised in that described hydroisomerizing and the operating condition being hydrocracked
For：Reaction pressure 3.0MPa～20.0MPa, hydrogen to oil volume ratio are 200:1～3000:1, during the liquid of feedstock oil, volume space velocity is
0.1h-1～6.0h-1, 180 DEG C～465 DEG C of average reaction temperature.
11. in accordance with the method for claim 10, it is characterised in that the condition of described hydroisomerizing is that volume is empty during liquid
Speed is 2.0h-1～4.0h-1, average reaction temperature is 340 DEG C～385 DEG C.
12. according to the method described in claim 10 or 11, it is characterised in that the described process conditions being hydrocracked are, liquid
When volume space velocity be 0.8h-1～1.5h-1, 390 DEG C～435 DEG C of average reaction temperature.
13. in accordance with the method for claim 12, it is characterised in that step（3）Middle control vegetable and animals oils and catalysis bavin inferior
Yield ≮ 60wt% of the oily miscella more than 210 DEG C.
14. in accordance with the method for claim 1, it is characterised in that described vegetable and animals oils with the weight ratio of poor ignition quality fuel are
1:3～3:1.
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