CN1938402B - Process to produce synthetic fuels and lubricants - Google Patents
Process to produce synthetic fuels and lubricants Download PDFInfo
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- CN1938402B CN1938402B CN2005800087358A CN200580008735A CN1938402B CN 1938402 B CN1938402 B CN 1938402B CN 2005800087358 A CN2005800087358 A CN 2005800087358A CN 200580008735 A CN200580008735 A CN 200580008735A CN 1938402 B CN1938402 B CN 1938402B
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- 238000000034 method Methods 0.000 title claims abstract description 59
- 239000000314 lubricant Substances 0.000 title claims abstract description 52
- 239000000446 fuel Substances 0.000 title claims abstract description 38
- 230000008569 process Effects 0.000 title claims abstract description 17
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 43
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 43
- 239000002199 base oil Substances 0.000 claims abstract description 33
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 31
- 238000000926 separation method Methods 0.000 claims description 27
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 20
- 238000005984 hydrogenation reaction Methods 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 238000005194 fractionation Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 abstract description 5
- 239000010454 slate Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 42
- 238000009835 boiling Methods 0.000 description 32
- 239000000463 material Substances 0.000 description 23
- 239000003054 catalyst Substances 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 18
- 239000007789 gas Substances 0.000 description 17
- 239000001993 wax Substances 0.000 description 17
- 238000006317 isomerization reaction Methods 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 description 7
- 238000005336 cracking Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 4
- 239000003502 gasoline Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000012188 paraffin wax Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000002303 thermal reforming Methods 0.000 description 3
- 230000001131 transforming effect Effects 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 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 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000010276 construction Methods 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
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
Images
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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
-
- 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
- C10G2400/10—Lubricating oil
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- 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)
- Lubricants (AREA)
Abstract
A process utilizing a low severity hydrocracker prior to a high severity hydrocracker for the processing of petroleum based and synthetic hydrocarbon feedstocks into distillate fuels and high quality lubricant base oils. The process minimizes the size and conditions required by the high severity hydrocracker by closely matching such configuration with the desired product slate.
Description
The cross-reference of relevant application
The application requires the right of priority of the provisional application No.60/536960 of submission on January 16th, 2005.
Federal sponsored research
Inapplicable.
With reference to the fiche annex
Inapplicable.
Technical field
The present invention relates in individual facilities, prepare the method that distillates fuel with lubricant.The invention still further relates to the integrated facility that is used to implement the inventive method.
Background technology
Because world's oil supply reduces, refinery must use more inferior crude oil to prepare high quality lubricant base oils.High quality lubricant base oils be have high viscosity index (HVI) (" VI "), be VI 135, the high quality lubricant base oils of low volatility and low pour point.Owing to have high-caliber relatively aromatic substance, need harsh hydroprocessing condition so that inferior crude oil is converted into high-quality lubricating oil.So not harsh processing (for example distillation) can obtain having the lubricant base oil of high-load cycloparaffin series compound, and known cycloparaffin series compound reduces viscosity index.
In a currently known methods, prepare lubricant base oil and distillating fuel by following method simultaneously by low-quality crude oil: make the heavy hydrocarbon feedstocks hydrocracking, the material of separate lubricant base oil boiling range and be fed to the material that second hydrocracker distillates fuel with production.At first cracking is to prepare required lubricant base oil feed under mild conditions for heavy hydrocarbon, and residuum cracking under severe condition distillates fuel with preparation.
Synthetic charging (for example Fischer-Tropsch (Fischer-Tropsch) synthetic product) is the alternatives that is used for the production high quality lubricant base oils.Usually, for the quality with the Fischer-Tropsch product of the content of wax rises to high quality lubricant base oils, need large-scale high severity hydrocracker.
In addition, the market requirement to lubricant base oil proves that usually the facility of constructing special use or approaching special use is not good means.In fact, to the market requirement that distillates fuel considerably beyond the market requirement to lubricant base oil.Therefore, facility is constructed usually so that the maximum production that distillates fuel, and the high-quality lube base stock of output simultaneously.
The centre distillates fuel only needs minimum isomerization, promptly isomer align the ratio of structure body be about 0.1: 1 to 1 or 2 about 5: 1 methyl-branched, to satisfy the cloud point requirement.In contrast, more the heavy-gravity lubricant must satisfy stricter pour point requirement, and (for example AIAE American institute of automobile engineers (the SAE J300 that Society of Automotive Engineers publishes) and manufacturers of engines are for the product of the requirement of lubricated and hydraulic fluid to be mixed with the low temperature standards that satisfies harshness.In order to satisfy these standards and requirement, lubricant base oil usually need be than 10: 1 much higher isomer align the ratio of structure body.Therefore, although charging must stand harsh relatively hydrocracking usually to obtain for the required isomerization of lubricant base oil, do not need harsh hydrocracking and distillate fuel in the middle of producing.
If high viscosity index lubricant base oils is a desired product, content of wax materials flow is the desirable materials flow of hydrotreating reactor so.Use simple catalyzer wax to be converted into the high viscosity index (HVI) base oil, produced the isomerization alkanes base oil that almost only constitutes alkyl group side chain that during reaction forms by methyl group as aluminum chloride.Comprise that for the improvement of this batch treatment the hydrotreatment flow process of remarkable quantity, wherein various crude oil or synthetic hydrocarbon flow are processed to the isomerization alkanes of methyl-branched and have more highly saturated and other product branching with comparing with feed steam by hydrogenation conversion catalyst.These currently known methodss almost only use linear flow process, and wherein charging is to use circulation loop hydrotreatment and distillation through some flow processs, with the non-treated content of wax residuum of hydrotreatment from distillation tower.But equipment that uses in these flow processs and catalyzer are bought and the costliness that operates.Capital investment being minimized and increase the output of required high viscosity lubricating base oil simultaneously and keep or increase the output that distillates fuel is unusual ideal plant design feature.The present invention has put down in writing so a kind of plant design, make by allowing the shop equipment that comprises reactor more closely customize to produce required product by minimum requirements, can be from the maximum production that distillates fuel of wax feed, the maximum production of high isomerization alkanes base oil and capital investment cost minimization.
Also exist for using high-quality Fischer-Tropsch synthetic to distillate fuel and the demand of the method for high quality lubricants to produce simultaneously as charging.Also exist for the coincide method of isomerized demand in the product materials flow of the size of hydrocracker and severity.
Summary of the invention
The present invention relates to produce synthetic lubricant base oil and fuel simultaneously from same synthetic charging.Described method comprises: at first use unit separately that the charging fractionation is cut, randomly separate hydrotreatment lighting end and last running to remove the low severity hydroisomerization of pollutent, last running, with the fractionation of whole materials flow secondary is distillating fuel of several types and quality and content of wax lubricant feed, content of wax lubricant feed is hydrodewaxing into low pour point, high quality base oil, randomly hydrofining and finally be distilled into lubricating base oil and distillating fuel, and with separation column bottoms stream (for example raffinate) recirculation for the third time up to disappearance.
In another embodiment of the present invention, after hydrocracking step, part transforms and circulating in first separation column of unconverted wax finished, rather than the 3rd or final separation column in finish.
Of the present inventionly provide the simplified method that is prepared base oil by wax feed with initial low severity hydrocracking and the method that only hydrocracking of unconverted heavy wax reflux materials flow high severity is combined subsequently, this method makes the maximum production of high quality lubricant base oils that cost of equipment is minimized.Produce the wax hydrogenating conversion process of fuel and lubricant with traditional being used to and compare, this method flow makes that total capital investment is less and yield of high value liquid products is higher, has increased the total capital efficient of facility.
The accompanying drawing summary
Fig. 1 is the synoptic diagram of first embodiment of the inventive method.
Fig. 2 is the synoptic diagram of second embodiment of the inventive method.
Embodiment
The inventive method is at first used low severity hydrocracker will overweight the wax feed that distillates fuel and is processed into distillating fuel of low turbidity and/or zero pour, and will be applicable to the heavy isomerization alkanes materials flow catalysis of dewaxing or be processed into the low pour point isomerization alkanes base oil of special high viscosity index (HVI) and low volatility by solvent extraction.
Spendable in the methods of the invention charging general feature is the charging that is derived from oil of wide boiling range scope, comprising: contain the 50 weight % boiling ranges of having an appointment be higher than 371 ℃ [700 ℉] component heavy gas oil or contain the vacuum gas oil of boiling range between about 316 ℃ [600 ℉] and about 566 ℃ [1050 ℉].Alternatively, charging can be from synthetic, and for example Fischer-Tropsch synthetic is all or part of.
In one embodiment of the invention, the method that is used to improve the charging quality is and Fischer-Tropsch is synthetic integrates mutually.Such embodiment comprises by fischer-tropsch reaction handles synthetic gas with the generation hydrocarbon flow, and reclaims the fischer-tropsch reaction product.Utilize the structure of low severity hydrocracker structure discussed herein to handle Fischer-Tropsch product then.
The technology that is used to produce synthetic gas (charging of fischer-tropsch reactor) is well known in the art, and comprises oxidation, reformation and automatic thermal reforming.For example, use automatic thermal reforming that the Fischer-Tropsch transformation system that appropriate hydrocarbon gas is converted into liquid or hydrocarbon solid product is comprised the synthetic gas unit, it comprises and contains for example synthesis gas reaction device of the automatic thermal reforming reactor of nickel-containing catalyst (" ATR ") form of reforming catalyst.The light hydrocarbon materials flow to be transformed and the oxygen (O that can comprise Sweet natural gas
2) be incorporated in the reactor together.Oxygen can be provided by pressurized air or other compression oxygen-containing gas, perhaps can be pure oxygen stream.The ATR reaction can be an adiabatic, does not promptly remove any heat to the reactor interpolation or from reactor except charging and reaction heat.This is reflected under the substoichiometric condition and carries out, and thus oxygen/materials flow/gaseous mixture is converted into synthetic gas.
Be used for transforming and mainly comprise carbon monoxide (CO) and hydrogen (H
2) the fischer-tropsch reaction of synthetic gas be characterised in that following general reaction:
2nH
2+nCO→(-CH
2-)
n+nH
2O(1)
Non-reactive component, nitrogen for example also can be accommodated in interior or mixes with synthetic gas.This may take place under the situation of using air, condensed air or other non-pure oxygen source during the formation synthetic gas.
Synthetic gas is directed in the synthesis unit that comprises the fischer-tropsch reactor (" FTR ") that contains fischer-tropsch catalysts.When carrying out this reaction, can use multiple fischer-tropsch catalysts.These comprise the combination of cobalt, iron, ruthenium and other VIIIB group 4 transition metal or these metals, thereby prepare saturated or unsaturated hydrocarbons.Described fischer-tropsch catalysts can comprise carrier (for example metal oxide carrier comprises silicon oxide, aluminum oxide, silica-alumina or titanium oxide).For example has about 100-200m
2Cobalt on the transitional alumina of/g surface-area (Co) catalyzer can diameter be the spherical form use of 50-150 μ m.Co concentration on carrier can be 5-30wt%.Can use some catalyst promoting agent and stablizer.Described stablizer comprises IIA family and IIIB family metal, and promotor can comprise the element from VIII family or VIIB family.Can the sorting charge fischer-tropsch catalyst and reaction conditions with optimum for the required reaction product hydrocarbon of certain chain lengths or carbonatoms (for example for).It is synthetic that reactor structure below any all can be used for Fischer-Tropsch, fixed bed, slurry bed bioreactor, ebullated bed, fluidized-bed or continuous stirred tank reactor (" CSTR ").FTR can operation under the about 800psia pressure of about 100-and under about 149 ℃ [300 ℉] to about 316 ℃ [600 ℉].These gas reactor space-time speed (" GHSV ") can be for about 1000 to about 15000hr
-1Prepare synthetic gas useful in the Fischer-Tropsch product in the present invention and can contain hydrocarbon gas, hydrogen, carbon monoxide and nitrogen, its H
2/ CO ratio is about 1.5 to about 3.0.Derive from fischer-tropsch reaction hydrocarbon product can for methane to containing the high molecular weight paraffinic waxes that is higher than 100 carbon.
The severity that method of the present invention has utilized the hydrocracker of low severity that the severity of hydrocracking and hydroisomerization is minimized to reach preparation desired product scheme and product requirement to need.Method of the present invention makes reactor size, catalyst content, reactor severity minimize and makes the maximization of reactor utilization ratio by increasing linear space-time speed simultaneously.By by product needed and these parameters of requirement coupling, be used in the required cost of equipment of construction processing facility and minimize and make the operation spending to minimize, make the catalyst life maximization simultaneously.First hydrocracker is through customization and impose a condition with the product that distillates of the hydroisomerization of preparation suitable chain alkane and isomerization alkanes content and hydrocracking, with cloud point and cold filter clogging temperature (CFPP) specification that satisfies the desired product scheme.First hydrocracker size like this and condition also reach above minimizing for the over-conversion that is converted into the required required degree of high quality lubricant base oils product in follow-up processing unit so that pyroparaffine is transformed into the product of lighter products or high isomerization through being provided with.Like this, the size that can significantly reduce the downstream high severity hydrocracker with adaptive boiling range only greater than the cut of the process stream of about 482 ℃ [900 ℉].High severity hydrocracker is used for hydrocracking from the unreacted of the second or the 3rd separation column or the content of wax component that is transforming.Then, the product of high severity hydrocracker is recycled in the after-fractionating tower.In some embodiments of the present invention, this recycle stream disappears through reaction, utilizes the paraffinic feedstock of this method thus to greatest extent.
Have about 121 ℃ [250 ℉] and distillate cut to the centre of about 371 ℃ [700 ℉] boiling ranges and be meant that at least 75 volume % of middle distillate, preferred 85 volume % components have the normal boiling point that is higher than about 121 ℃ [250 ℉], and the component at least about 75 volume %, preferred 85 volume % of this centre effluent has the normal boiling point that is lower than 371 ℃ [700 ℉].Term " middle effluent " means the cut that comprises diesel oil, jet fuel and kerosene boiling range scope.Kerosene or jet fuel boiling range are meant the temperature range of about 138 ℃ [280 ℉] to about 274 ℃ [525 ℉] and the hydrocarbon boiling range that term " diesel boiling range " is meant about 121 ℃ [250 ℉] to about 371 ℃ [700 ℉].Gasoline or petroleum naphtha normally can get the C of hydrocarbon
5-204 ℃ of [400 ℉] ends point of fraction.The boiling spread of the various product cuts that reclaim in any particular refinery will be with following factor (for example the feature of crude petroleum sources, refinery local market, product price etc.) and is changed.
Referring to Fig. 1, hydrocarbon charging 1 at first is distilled into three kinds or more kinds of overhead product materials flow in first separation column 2.Overhead product materials flow 3 contains the nominal boiling range at about C
5Material to about 320 ℉.Overhead product materials flow 3 contains boiling range at the material of gasoline hydrocarbon scope with can further be processed into fuel and petroleum chemistry charging product by the prior art currently known methods, and described petroleum chemistry charging product includes but not limited to ethylene cracking device charging or fuel unit fuel.It is that about 160 ℃ [320 ℉] and final boiling range are about 288 ℃ [550 ℉] material to 371 ℃ [700 ℉] at the initial boiling point of middle distillate scope that overhead product materials flow 4 contains boiling range, and wherein final boiling point is through selected requirement (for example requirement in ASTM975-03) to satisfy the finished product quality.Overhead product materials flow 4 can be randomly in first hydrotreater 6 hydrotreatment so that alkene and other unsaturated component are saturated.Overhead product materials flow 5 is included in and is higher than about 371 ℃ [700 ℉] ebullient hydrocarbon down.The upper limit boiling point of overhead product materials flow 5 depends on feed composition, but is generally about 566 ℃ [1050 ℉] to about 677 ℃ [1250 ℉].Overhead product materials flow 5 can be randomly in second hydrotreater 7 hydrotreatment so that alkene and other unsaturated component are saturated.
Used catalyzer is well known in the art and forms by the hydrogenation shift reaction being active sulfuration or unvulcanised metal (for example cobalt, nickel, platinum, palladium) in hydrotreater 6 and 7.0.1-10LHSV reactor flow velocity be typical, and the temperature of reactor of 93 ℃ of [200 ℉]-399 ℃ [750 ℉] is the feature of hydrotreatment process.The hydrogen flow velocity of 500-10000SCF/bb1 and the hydrogen pressure of 200-2500psig also are typical for this hydrotreatment process.Also can use other acceptable hydroprocessing condition known in the art.
Effluent 8 from hydrotreater 7 is fed to low severity hydrocracker 9.Condition in the low severity hydrocracker 9 comprises as follows: about 204 ℃ [400 ℉] to about 399 ℃ [750 ℉]; About 200 to about 3000psig; About 1000 to about 20000SCF/BBL; With about 0.25 to about 10LHSV.Hydrocracker makes linear paraffins be converted into branched paraffin and the paraffin conversion of slight branching is more highly branched paraffinic hydrocarbons.To a certain degree also can be hydrogenated cracking be boiling range to the paraffinic hydrocarbons of branching and higher degree branching at the product of gasoline and the middle scope that distillates fuel.
The preferred catalyst that uses in hydrocracker 9 comprises wherein having is enough to cause positive structure linear hydrocarbon isomery to turn to the hydrocarbon and the hydrogenation/dehydrogenation catalyzer of the hydrocarbon isomerization that makes slight branching for the acidic components of more highly branched hydrocarbon of branching, and wherein said side chain mainly is made of methyl.The example of these catalyzer is at S.Tiong Sie, and Ind.Eng.Chem.Res. discusses in 31 (8) 1881 (1992).Isocrackate 10 from hydrocracker 9 is directed into after-fractionating tower 11.Effluent 12 from hydrotreater 6 also is fed to separation column 11.
Separation column 11 is separated into two kinds or more middle cuts with isocrackate 10.One or more lighting ends 13 that contain the hydrocarbon of the boiling range that distillates fuel from separation column 11, reclaim and comprise contain positive structure, the distillating fuel of slight paraffinic hydrocarbons methyl-branched and more highly branched.Light lubricant feed stream 14 can also reclaim from separation column 11.It is about 260 ℃ [500 ℉] paraffinic hydrocarbons to about 510 ℃ [950 ℉] scopes that light lubricant feed stream 14 generally includes boiling range.Lubricant feed stream 15 reclaims as tower bottom distillate from separation column 11, and to contain boiling range be about 371 ℃ [700 ℉] paraffinic hydrocarbons to about 593 ℃ [1100 ℉] scopes.In Hydrodewaxing device 16, lubricant feed stream 15 is carried out Hydrodewaxing to remove the paraffinic hydrocarbons of normal paraffin and slight branching then.The severity of the operation of Hydrodewaxing device 16 also satisfies product quality requirement through control simultaneously so that lubricant base oil production maximizes.The typical operation conditions of Hydrodewaxing device 16 is as follows: about 204 ℃ [400 ℉] to about 371 ℃ [700 ℉]; About 0.1 to about 5LHSV; About 1000 to about 10000SCF/BBL; With about 200 to about 2000psig.From the effluent 17 of Hydrodewaxing device 16 randomly in hydrofinisher 18 hydrofining with the olefin product of saturated remnants.In the 3rd separation column 19, reclaim lubricant base oil products 20 by distillation.Top stream 21 from the paraffinic hydrocarbons of the scope that distillates fuel in the middle of the containing of separation column 19 also can be recovered.Contain boiling point greater than the lubricant base oil distillation range〉566 ℃ of [〉 1050 ℉] the raffinate 22 of wax of unconverted also can be recovered.Raffinate 22 mainly comprises unconverted and waxy hydrocarbon that transforming.Raffinate 22 is treated to low boiling range product in high severity hydrocracker 23, for example than the hydrocarbon of low carbon number, it is fed in the after-fractionating device 11.The typical hydrocracking condition that is known in the art can be used for hydrocracker 23.These conditions comprise for example those disclosed in U.S. Patent No. 6379535.Raffinate 22 can be recirculated to and disappear or alternatively, if the infusibility component that exists can be removed by effluent discharging diffluence.
As using in this article, term " hydrotreatment " is meant the processing of using hydrogen-containing treat gas under the condition that suitable catalyst exists, and wherein said catalyzer mainly is to be active catalyzer for the removal of heteroatoms (for example sulphur and nitrogen) and the saturation of alkene and aromatic substance.Being used for suitable hydrotreating catalyst of the present invention is any known conventional hydrotreating catalyst.The example of this hydrotreating catalyst comprises that for example being included in high surface area support material (for example aluminum oxide) goes up VIII family metal, preferred iron, cobalt and nickel, and more preferably cobalt and/or nickel is at least a.Other suitable hydrotreating catalyst comprises zeolite catalyst, and noble metal catalyst, and wherein this precious metal is selected from palladium and platinum.Can use more than a kind of hydrotreating catalyst in the present invention.Typical hydrotreatment temperature is about 204 ℃ [400 ℉] to about 482 ℃ [900 ℉], and pressure is that about 500psig is to about 2500psig.
As using in this article, term " hydrocracking " is meant to have all or part of reaction relevant with hydrotreatment and the technology of cracking reaction, and this technology causes reduction and the molecular transposition or the isomerization of molecular weight and boiling point.
Hydrocracker 9 and 23 can contain the bed of one or more identical or different catalyzer.In some embodiments, when preferred product is when distillating fuel, amorphous substrate or low zeolite substrate that preferred hydrocracking catalyst utilization combines with one or more VIII families or group vib metallic hydrogenation component.In another embodiment, when preferred product was the gasoline boiling range, described hydrocracking zone contained catalyzer, and this catalyzer contains any crystalline zeolite cracking substrate usually, was provided with a spot of VIII family metallic hydrogenation component thereon.Can combine with zeolite base from the hydrogenation component of selecting other from group vib.In the art, the zeolite as cracking substrate is meant molecular sieve sometimes, and this substrate generally includes silicon oxide, aluminum oxide and one or more replaceable positively charged ions (for example sodium, magnesium, calcium, rare earth metal etc.).
Referring to Fig. 2, shown second embodiment according to facility of the present invention and method.In this second embodiment, technology is by carrying out up to being fed to after-fractionating tower 11 referring to the description of Fig. 1.
Separation column 11 is divided into two kinds or more kinds of cut with isocrackate 10.Contain one or more lighting ends 13 at the hydrocarbon of the boiling range scope that distillates fuel and reclaim in by separation column 11, and comprise and contain distillating fuel of positive structure, slight methyl-branched and more highly branched paraffinic hydrocarbons.Light lubricant feed stream 14 also can reclaim from separation column 11.Light lubricant feed stream 14 contains the paraffinic hydrocarbons that boiling range is about 260 ℃ [500 ℉] to about 510 ℃ [950 ℉] usually.Heavy lubricant feed steam 24 is about 371 ℃ [700 ℉] extremely paraffinic hydrocarbons of about 593 ℃ [1100 ℉] by reclaiming in the separation column 11 and comprising boiling range.The raffinate stream 26 that contains the wax of unconverted also reclaims from separation column 11.That is to say, in second embodiment, before Hydrodewaxing and hydrofining, remove the wax of unconverted as raffinate 26.Raffinate 26 is processed into low boiling range product in high severity hydrocracker 23, for example than the hydrocarbon of low carbon number, then they are fed to after-fractionating tower 11.Raffinate 26 can be recycled to disappearance or alternatively, the infusibility component that may exist can go out materials flow by effluent and be removed.In Hydrodewaxing device 16, heavy lubricant feed stream 24 is carried out Hydrodewaxing to remove the paraffinic hydrocarbons of normal paraffin and slight branching then.The severity of the operation of Hydrodewaxing device 16 is controlled so that lubricant base oil production maximization and satisfy product quality requirement simultaneously.The typical operation conditions of Hydrodewaxing device 16 as mentioned above.From the effluent 25 of Hydrodewaxing device randomly through hydrofining 18 so that remaining olefin product is saturated.By in 19 vapor enrichments of the 3rd separation column to reclaim lubricant base oil products 20.Top stream 21 from the paraffinic hydrocarbons of the scope that distillates fuel in the middle of the containing of separation column 19 also can be recovered.
In the 3rd embodiment, hydrotreater 6 and 7 can be merged into the single hydrotreater that places first separation column, 2 upstreams.Then, ensuing processing can be carried out according to first or second embodiment as discussed above.In the 3rd embodiment, the operational condition of single hydrotreater can be carried out as described at hydrotreater 6 and 7.
Claims (21)
1. be used to produce the method for synthetic lubricant and fuel, may further comprise the steps:
(a) with the charging fractionation for comprising C
5First overhead product of-160 ℃ of [320] hydrocarbon and comprise that 160 ℃ [320] are to second overhead product of 371 ℃ of [700] hydrocarbon with comprise the 3rd overhead product of 371 ℃+[700+] hydrocarbon;
(b) with the 3rd overhead product in low severity hydrocracker hydrocracking to produce isocrackate;
(c) second overhead product is fed to the after-fractionating tower;
(d) isocrackate is fed to the after-fractionating tower;
(e) reclaim first distillate fuel cut, the light lubricant cut and contain the wax lubricant cut from the after-fractionating tower;
(f) make the lubricant cut fraction hydrogenation dewaxing of the content of wax to form the product of dewaxing;
(g) product of fractionation in the 3rd separation column through dewaxing;
(j) reclaim raffinate from the 3rd separation column;
(k) hydrocracking raffinate in high severity hydrocracker; With
(m) effluent with high severity hydrocracker is recycled in the after-fractionating tower.。
2. the method for claim 1 also comprises following step:
(a1) hydrotreatment second overhead product before being fed to the after-fractionating tower.
3. the method for claim 1 also comprises following step:
(a2) hydrotreatment the 3rd overhead product before the hydrocracking in step (b).
4. the process of claim 1 wherein and before being fed to the after-fractionating tower, merge described second overhead product and isocrackate.
5. the method for claim 1 also comprises following step:
(f1) at the product of fractionating step (g) hydrofining before through dewaxing.
6. the method for claim 1 also comprises following step:
(h) reclaim second cut that distillates fuel from the 3rd separation column.
7. the method for claim 1 also comprises following step:
(i) from the 3rd separation column, reclaim one or more lubricant base oil cuts.
8. the process of claim 1 wherein that containing the wax lubricant cut handles by step (f) with (g).
9. the method for claim 1 also comprises the following steps:
(n) the lubricant cut of the hydrocracking part content of wax in high severity hydrocracker; With
(p) will be recycled to from the effluent in the high severity hydrocracker in the after-fractionating tower.
14. be used to produce the method for synthetic lubricant and fuel, comprise the following steps:
(a) with the charging fractionation for comprising C
5First overhead product of-160 ℃ of [320] hydrocarbon and comprise that 160 ℃ [320] are to second overhead product of 371 ℃ of [700] hydrocarbon with comprise the 3rd overhead product of 371 ℃+[700+] hydrocarbon;
(b) with the 3rd overhead product in low severity hydrocracker hydrocracking to produce isocrackate;
(c) second overhead product is fed to the after-fractionating tower;
(d) isocrackate is fed to the after-fractionating tower;
(e) reclaim first distillate fuel cut, light lubricant cut, lubricant cut and the content of wax raffinate from the after-fractionating tower;
(f) make the dewaxing of lubricant cut fraction hydrogenation to form the product of dewaxing;
(g) product of fractionation in the 3rd separation column through dewaxing;
(j) hydrocracking content of wax raffinate in high severity hydrocracker; With
(k) effluent with high severity hydrocracker is recycled in the after-fractionating tower.
15. the method for claim 14 also comprises following step:
(a1) hydrotreatment second overhead product before being fed to the after-fractionating tower.
16. the method for claim 14 also comprises following step:
(a2) hydrotreatment the 3rd overhead product before the hydrocracking in step (b).
17. the method for claim 14 wherein merged described second overhead product and isocrackate before being fed to the after-fractionating tower.
18. the method for claim 14 also comprises following step:
(f1) at the product of fractionating step (g) hydrofining before through dewaxing.
19. the method for claim 14 also comprises following step:
(h) reclaim second cut that distillates fuel from the 3rd separation column.
20. the method for claim 14 also comprises following step:
(i) from the 3rd separation column, reclaim one or more lubricant base oil cuts.
21. the method for claim 14, wherein the lubricant cut is handled by step (f) with (g).
10. the process of claim 1 wherein that charging is all or part of product of Fischer-Tropsch synthetic.
11. the process of claim 1 wherein that charging is selected from heavy gas oil and vacuum gas oil.
22. the method for claim 14, wherein charging is all or part of product of Fischer-Tropsch synthetic.
23. the method for claim 14, wherein charging is selected from heavy gas oil and vacuum gas oil.
12. the process of claim 1 wherein that the processing condition of low severity hydrocracker are about 204 ℃ [400 °F] to about 399 ℃ [750 °F]; About 200 to about 3000psig; About 1000 to about 20000SCF/BBL; With about 0.25 to about 10LHSV.
13. the process of claim 1 wherein that the processing condition of high severity hydrocracker are about 204 ℃ [400 °F] to about 427 ℃ [800 °F]; About 200 to about 3000psig; About 1000 to about 20000SCF/BBL; With about 0.1 to about 5LHSV.
24. the method for claim 14, wherein the processing condition of low severity hydrocracker are about 204 ℃ [400 °F] to about 399 ℃ [750 °F]; About 200 to about 3000psig; About 1000 to about 20000SCF/BBL; With about 0.25 to about 10LHSV.
25. the method for claim 14, wherein the processing condition of high severity hydrocracker are about 204 ℃ [400 °F] to about 427 ℃ [800 °F]; About 200 to about 3000psig; About 1000 to about 20000SCF/BBL; With about 0.1 to about 5LHSV.
Applications Claiming Priority (3)
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| US53696004P | 2004-01-16 | 2004-01-16 | |
| US60/536,960 | 2004-01-16 | ||
| PCT/US2005/001311 WO2005073349A1 (en) | 2004-01-16 | 2005-01-18 | Process to produce synthetic fuels and lubricants |
Publications (2)
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| CN1938402A CN1938402A (en) | 2007-03-28 |
| CN1938402B true CN1938402B (en) | 2010-12-01 |
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| CN2005800087358A Active CN1938402B (en) | 2004-01-16 | 2005-01-18 | Process to produce synthetic fuels and lubricants |
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| EP (1) | EP1720960A1 (en) |
| JP (1) | JP2007517969A (en) |
| CN (1) | CN1938402B (en) |
| AU (1) | AU2005207842A1 (en) |
| WO (1) | WO2005073349A1 (en) |
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| US8513478B2 (en) * | 2007-08-01 | 2013-08-20 | Exxonmobil Chemical Patents Inc. | Process to produce polyalphaolefins |
| ATE524500T1 (en) * | 2008-01-31 | 2011-09-15 | Exxonmobil Chem Patents Inc | IMPROVED USE OF LINEAR ALPHA-OLEFINS IN THE PRODUCTION OF METALLOCENE-CATALYzed POLY-ALPHA-OLEFINS |
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| ATE557045T1 (en) | 2008-03-31 | 2012-05-15 | Exxonmobil Chem Patents Inc | PRODUCTION OF SHEAR STABLE HIGH VISCOSITY PAO |
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| US9359565B2 (en) * | 2013-01-16 | 2016-06-07 | Exxonmobil Research And Engineering Company | Field enhanced separation of hydrocarbon fractions |
| RU2527564C1 (en) * | 2013-03-12 | 2014-09-10 | Открытое акционерное общество "Всероссийский научно-исследовательский институт по переработке нефти" (ОАО "ВНИИ НП") | Method of manufacturing waxy diesel fuel |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2007517969A (en) | 2007-07-05 |
| CN1938402A (en) | 2007-03-28 |
| WO2005073349A1 (en) | 2005-08-11 |
| US20050183988A1 (en) | 2005-08-25 |
| AU2005207842A1 (en) | 2005-08-11 |
| EP1720960A1 (en) | 2006-11-15 |
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