JP5263634B2 - 高品質のナフテン系ベースオイルの製造方法 - Google Patents
高品質のナフテン系ベースオイルの製造方法 Download PDFInfo
- Publication number
- JP5263634B2 JP5263634B2 JP2011514477A JP2011514477A JP5263634B2 JP 5263634 B2 JP5263634 B2 JP 5263634B2 JP 2011514477 A JP2011514477 A JP 2011514477A JP 2011514477 A JP2011514477 A JP 2011514477A JP 5263634 B2 JP5263634 B2 JP 5263634B2
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- Prior art keywords
- oil
- group
- naphthenic base
- fraction
- dewaxing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002199 base oil Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title abstract description 14
- 239000003921 oil Substances 0.000 claims abstract description 97
- 238000000034 method Methods 0.000 claims abstract description 81
- 125000003118 aryl group Chemical group 0.000 claims abstract description 29
- 239000002002 slurry Substances 0.000 claims abstract description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052751 metal Inorganic materials 0.000 claims abstract description 24
- 239000002184 metal Substances 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- 150000002739 metals Chemical class 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 7
- 239000003502 gasoline Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims description 44
- 239000002904 solvent Substances 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 11
- 238000004231 fluid catalytic cracking Methods 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 229910003294 NiMo Inorganic materials 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 7
- 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 7
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 238000000605 extraction Methods 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 5
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 19
- 150000001491 aromatic compounds Chemical class 0.000 abstract description 2
- 238000004523 catalytic cracking Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000002994 raw material Substances 0.000 description 13
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 239000010779 crude oil Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006477 desulfuration reaction Methods 0.000 description 3
- 230000023556 desulfurization Effects 0.000 description 3
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 3
- 239000012188 paraffin wax Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- -1 first Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 241000269350 Anura Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000010734 process oil Substances 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
- 239000005060 rubber Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
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- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
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- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C10G21/00—Refining of hydrocarbon oils, in the absence of hydrogen, by extraction with selective solvents
- C10G21/003—Solvent de-asphalting
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- C10G67/0454—Solvent desasphalting
- C10G67/0463—The hydrotreatment being a hydrorefining
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- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
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- C10G67/0454—Solvent desasphalting
- C10G67/0481—The hydrotreatment being an aromatics saturation
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- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of catalytic cracking in the absence of hydrogen
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- C10M101/00—Lubricating compositions characterised by the base-material being a mineral or fatty oil
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- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/304—Pour point, cloud point, cold flow properties
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
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- 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
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Description
近年、ナフテン系ベースオイルは、変圧器油、絶縁油、冷凍器油、ゴムおよびプラスチックのプロセスオイル、プリントインクまたはグリース(Grease)の基礎物質、および金属加工油のベースオイルなどの用途に使用されるなど、多様な産業分野で多様な用途で広く用いられている。
ナフテン系ベースオイルを製造する従来の方法は、ナフテン含量が高いナフテン系原油(ナフテン含量30乃至40%)を供給原料として用い、減圧蒸留装置を経てパラフィン成分を分離し、抽出および/または水素化工程によって芳香族成分を分離および/またはナフテン化し、その後に不純物を除去する方式で行われることが大部分であった。
ところが、この従来の方法は、供給原料が本質的にナフテン成分含量の高いナフテン系原油に限定されることにより、原料供給上の限界があり、更に芳香族成分の抽出のための抽出過程を行わなければならないことにより、製品の全体収率および製品の品質が低下するという問題点を抱えている。
上述した問題点の他にも、工程全体の収率を高めるための方法が求められている。
有する炭化水素供給原料からナフテン系ベースオイルを製造する方法であって、(a)流動接触分解工程(FCC)で得られる留分から軽質サイクルオイルおよびスラリーオイルを分離する段階と、(b)前記(a)段階で分離されたスラリーオイルを溶剤脱瀝工程によって脱瀝油とピッチ(pitch)に分離する段階と、(c)前記(a)段階で分離された軽質サイクルオイル、前記(b)段階で分離された脱瀝油、またはこれらの混合物を水素化処理触媒を使用して水素化処理しヘテロ原子種を減少させる段階と、(d)前記(c)段階で得られた水素化処理した留分を脱蝋触媒を使用し脱蝋して流動点を低下させる段階と、(e)前記(d)段階で得られた脱蝋された留分を水素化仕上げ触媒を使用して水素化仕上げ処理し、製品規格に応じて芳香族含量を調節する段階と、(f)前記(e)段階で得られた留分を粘度の範囲によって分離する段階とを含むことを特徴とする、ナフテン系ベースオイルの製造方法を提供する。
本発明に係るナフテン系ベースオイルの製造工程は、図1に示すように、石油系炭化水素の流動接触分解(FCC)工程で生産されるスラリーオイル(SLO)を溶剤脱瀝工程(SDA)によって処理し、脱瀝油(DAO)を生成する段階と、軽質サイクルオイル(LCO)、脱瀝油(DAO)、またはこれらの混合物を水素化処理工程に供給して水素化処理(HDT、Hydrotreating)する段階と、前記水素化処理された留分を脱蝋工程に供給して脱蝋(DW、Dewaxing)する段階と、前記脱蝋された留分の水素化仕上げ段階と、水素化仕上げ留分を粘度の範囲によって分離する段階とを含んでなる。
て使用され難く、主に高硫黄軽油製品または安価の重質燃料油として使用されることが一般的である。
前述したように最適化された操作条件で水素化処理が行われる場合には、水素化処理された留分から軽質留分または塔底留分を別途分離または除去する必要がなく、放出されるガス成分を唯一の例外として、全量を脱蝋工程(DW)へ供給する。
脱蝋工程で、パラフィン留分の選択的反応と異性化反応により、製品の低温性能に直結する流動点の規格は実現される。
より具体的に、本発明に係る脱蝋工程(DW)は、250乃至430℃の温度、10乃至200kg/cm2の圧力、0.1乃至3h−1の液空間速度(LHSV)および300乃至1000Nm3/m3の供給原料に対する水素の体積比の条件下で行われる。
−23、ZSM−35、ZSM−48などが含まれ、12員酸素環を有する大孔径(Large pore)分子篩としてはFAU、BetaおよびMORが含まれる。
水素化仕上げ工程に使用される触媒は、水素化活性を有する周期律表の第6族、第8族、第9族、第10族、および第11族の金属から選択された少なくとも一つの金属を含み、好ましくはNi−Mo、Co−Mo、およびNi−Wから選択される複合金属、またはPtおよびPdから選択される貴金属を含む。
流動接触分解工程(FCC)流出物から沸点300乃至380℃の軽質サイクルオイル留分を分離して水素化処理反応器に供給した。
水素化処理工程は、水素化処理用触媒としてニッケル−モリブデン組み合わせ触媒を使用し、LHSVは0.1乃至3.0h-1とし、供給原料に対する水素の体積比は500乃至2500Nm3/m3とし、反応圧力および温度はそれぞれ30乃至220kg/cm2
、280乃至430℃とする条件で行った。
水素化処理を済ませた中間留分は、200ppm未満の硫黄含量、100ppm未満の窒素含量および70wt%未満の芳香族含量を有し、好ましい実施態様では100ppm未満の硫黄含量、100ppm未満の窒素含量および50wt%未満の芳香族含量を有した。
とする条件で行った。脱蝋工程は250乃至430℃、水素化仕上げ工程は150乃至400℃の反応温度で行った。本参考例の場合、別途の分離工程を経ることなく、水素化仕上げを経た留分全体を製品として使用することができた。
実施例2は、スラリーオイルを溶剤脱瀝工程で処理して得た脱瀝油を供給原料としてナフテン系ベースオイルを製造する方法に関するもので、溶媒としてプロパンを活用してスラリーオイルを溶剤抽出した脱瀝油を実際反応原料としてナフテン系ベースオイルを製造し
た。
スラリーオイル前処理のための溶剤脱瀝の操作条件は、アスファルテン分離機の圧力を40乃至50kg/cm2、脱瀝油/ピッチの分離抽出温度を40乃至180℃、溶媒:オイルの比(L/kg)を4:1乃至12:1とする範囲である。
イルの基準で500乃至2500Nm3/m3、反応圧力および温度はそれぞれ30乃至220kg/cm2、280乃至430℃とする条件で行った。
脱蝋工程はNiMo/ゼオライト触媒、水素化仕上げ工程はPtPd/Al2O3触媒を用いて行った。これらの工程は、LHSVは0.1乃至3.0h-1、水素消費量はH2/
オイルの基準で300乃至1000Nm3/m3、反応圧力は10乃至200kg/cm2
とする条件で行った。脱蝋は250乃至430℃、水素化仕上げは150乃至400℃の反応温度で行った。
実施例3は、スラリーオイルを溶剤脱瀝工程で処理して得た脱瀝油(DAO)と軽質サイクルオイル(LCO)との混合留分を供給原料としてナフテン系ベースオイルを製造する方法に関するものである。
前記脱瀝油(DAO)留分を軽質サイクルオイルと約1:1の質量比で混合した。
/cm2とする条件で行った。また、脱蝋は250乃至430℃、水素化仕上げは150乃至400℃の反応温度で行った。
AR:常圧残渣油
FCC:流動接触分解工程
LCO:軽質サイクルオイル
SLO:スラリーオイル
DAO:スラリーオイルを溶剤脱瀝工程によって処理して得た脱瀝油
HDT:水素化処理
DW:脱蝋
HDF:水素化仕上げ
N4/9/25/46/110/220/540:ナフテン系ベースオイル製品名(数字は40℃での動粘度を意味する)
Claims (13)
- ガソリンの沸点よりもより高い沸点を有する、ヘテロ原子種および芳香族物質を含有する炭化水素供給原料からナフテン系ベースオイルを製造する方法であって、
(a)流動接触分解で得られる留分から軽質サイクルオイルおよびスラリーオイルを分離する段階と、
(b)前記(a)段階で分離されたスラリーオイルを溶剤脱瀝によって脱瀝油とピッチに分離する段階と、
(c)前記(b)段階で分離された脱瀝油、または(a)段階で分離された軽質サイクルオイルと(b)段階で分離された脱瀝油との混合物を水素化処理触媒を用いて水素化処理して、ヘテロ原子種の量を減少させる段階と、
(d)前記(c)段階で得られた水素化処理された留分を脱蝋触媒を用いて脱蝋して流動点を降下させる段階と、
(e)前記(d)段階で得られた脱蝋された留分を水素化仕上げ触媒を用いて水素化仕上げ処理すると共に、製品規格に応じて芳香族の含量を調節する段階と、
(f)前記(e)段階で得られた水素化仕上げ処理された留分を粘度の範囲によって分離する段階とを含み、
前記段階(c)、段階(d)、及び段階(e)は連続に行われ、
前記(b)段階で分離した脱瀝油、または(a)段階で分離した軽質サイクルオイルと(b)段階で分離した脱瀝油との混合物中の全芳香族含量は60wt%以上であり、
前記(c)段階で水素化処理された留分は200ppm未満の硫黄含量および100ppm未満の窒素含量、60wt%未満の芳香族含量および5wt%以下の多環芳香族含量を有し、
前記(d)段階で使用される脱蝋触媒は、分子篩、アルミナ、およびシリカ−アルミナからなる群から選択される酸点を有する担体、ならびに水素化活性を有する金属成分として(i)NiまたはCo、および(ii)MoまたはWの組み合わせを含み、
前記ナフテン系ベースオイルは85以下の粘度指数、ASTM D−2140による分析で炭素結合の中で少なくとも30%のナフテン系組成、200ppm未満の硫黄含量、および40wt%以上のナフテン含量を有することを特徴とするナフテン系ベースオイルの製造方法。 - 前記(c)段階で使用される、脱瀝油、または軽質サイクルオイルと脱瀝油との混合物は、硫黄含量が0.5wt%以上であり、窒素含量が1000ppm以上であることを特徴とする、請求項1に記載の方法。
- 前記(b)段階での分離は、アスファルテン分離機の圧力を40乃至50kg/cm2
、脱瀝油とピッチの分離抽出温度を40乃至180℃、溶媒:オイルの比(L/kg)を4:1乃至12:1とする操作条件で行われることを特徴とする、請求項1に記載の方法。 - 前記(c)段階での水素化処理は、280乃至430℃の温度、30乃至220kg/cm2の圧力、0.1乃至3.0h-1の液空間速度(LHSV)および500乃至250
0Nm3/m3の供給原料に対する水素の体積比である操作条件で行われることを特徴とする、請求項1に記載の方法。 - 前記(c)段階で使用される水素化処理触媒は、周期律表の第6族、第9族および第10族の金属から選択される金属を含むことを特徴とする、請求項1に記載の方法。
- 前記(c)段階で使用される水素化処理触媒は、CoMo、NiMo、およびCoMoとNiMoとの組み合わせから選択された一種以上を含むことを特徴とする、請求項5に記載の方法。
- 前記(d)段階での脱蝋は、250乃至430℃の温度、10乃至200kg/cm2
の圧力、0.1乃至3h-1の液空間速度(LHSV)、および300乃至1000Nm3
/m3の供給原料に対する水素の体積比である操作条件で行われることを特徴とする、請
求項1に記載の方法。 - 前記酸点を有する担体は、SAPO−11、SAPO−41、ZSM−5、ZSM−11、ZSM−22、ZSM−23、ZSM−35、ZSM−48、FAU、BetaおよびMORから選択される少なくとも一種の分子篩であることを特徴とする、請求項1に記載の方法。
- 前記(e)段階の水素化仕上げ処理は、150乃至400℃の温度、10乃至200kg/cm2の圧力、0.1乃至3.0h-1の液空間速度(LHSV)、および300乃至
1000Nm3/m3の流入された留分に対する水素の体積比である操作条件で行われることを特徴とする、請求項1に記載の方法。 - 前記(e)段階に使用される水素化仕上げ処理触媒は、周期律表の第6族、第8族、第9族、第10族および第11族の金属から選択される一種以上の金属を含むことを特徴とする、請求項1に記載の方法。
- 前記(e)段階に使用される水素化仕上げ処理触媒の一種以上の金属はPt、Pd、Ni、Co、MoおよびWからなる群から選択される一種以上の金属を含むことを特徴とする、請求項10に記載の方法。
- 前記(f)段階での分離は40℃での動粘度を基準として行うものであって、前記分離によって、前記水素化仕上げされた留分を、40℃での動粘度が3乃至5cSt、8乃至10cSt、18乃至28cSt、43乃至57cSt、90乃至120cSt、200乃至240cSt、および400cSt以上のナフテン系ベースオイル製品に分離されることを特徴とする、請求項1に記載の方法。
- 前記(f)段階で分離された留分内の全芳香族含量は21.09乃至51.54%の範囲であることを特徴とする、請求項1に記載の方法。
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GB201100665D0 (en) | 2011-03-02 |
US8585889B2 (en) | 2013-11-19 |
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JP2011530610A (ja) | 2011-12-22 |
WO2009154324A1 (en) | 2009-12-23 |
GB2473992A (en) | 2011-03-30 |
GB2473992B (en) | 2012-03-07 |
CN102066530B (zh) | 2013-11-06 |
TWI458819B (zh) | 2014-11-01 |
CN102066530A (zh) | 2011-05-18 |
TW201000621A (en) | 2010-01-01 |
US20110089080A1 (en) | 2011-04-21 |
KR100934331B1 (ko) | 2009-12-29 |
JP5692545B2 (ja) | 2015-04-01 |
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