CN102066530A - 用于制造高品质环烷基油的方法 - Google Patents
用于制造高品质环烷基油的方法 Download PDFInfo
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- CN102066530A CN102066530A CN200880129955XA CN200880129955A CN102066530A CN 102066530 A CN102066530 A CN 102066530A CN 200880129955X A CN200880129955X A CN 200880129955XA CN 200880129955 A CN200880129955 A CN 200880129955A CN 102066530 A CN102066530 A CN 102066530A
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- Prior art keywords
- oil
- dewaxing
- metals
- hydrofinishing
- kilogram
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- 238000000034 method Methods 0.000 title claims abstract description 74
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
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- 238000000926 separation method Methods 0.000 claims description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical group [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 125000005842 heteroatom Chemical group 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
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- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 7
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- 230000000694 effects Effects 0.000 description 6
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- 239000007789 gas Substances 0.000 description 5
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical group [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
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- 238000006317 isomerization reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003209 petroleum derivative Substances 0.000 description 2
- 238000002203 pretreatment Methods 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
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- 241000269350 Anura Species 0.000 description 1
- 241000854350 Enicospilus group Species 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
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- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 239000012530 fluid Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000005555 metalworking Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000010690 paraffinic oil Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 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
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000000341 volatile oil Substances 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
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- 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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- C10G67/0463—The hydrotreatment being a hydrorefining
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- C10G67/0481—The hydrotreatment being an aromatics saturation
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Abstract
本发明揭示了一种从具有高芳族含量和大量沸点高于汽油沸点的杂质的油馏分制造高品质环烷基油的方法。这种方法能够从轻循环油(LCO)和油浆(SLO)制造高品质环烷基油，所述轻循环油和油浆是便宜的，具有高芳族含量和大量杂质，是流化催化裂化(FCC)单元的流出物，该方法还改进了进料的预处理工艺，由此减少进料中的杂质(硫、氮、多核芳族化合物和各种金属组分)量，从而缓和极端操作条件、延长催化剂寿命、并以高产率制得各种高品质环烷基油产品。
Description
发明领域
本发明涉及一种从具有高芳族含量和大量杂质的烃油馏分制造环烷基油的方法，更具体涉及一种将脱沥青油(DAO)作为进料通向加氢处理单元和脱蜡/加氢补充精制单元从而制造高品质环烷基油的方法，所述脱沥青油通过对油浆(SLO)进行溶剂脱沥青(SDA)而得到，所述油浆是流化催化裂化(FCC)单元的流出物。
技术背景
环烷基油是粘度指数等于或小于85的基油(base oil)，其中根据ASTMD-2140，该基油的至少30％的碳键是环烷类型的。
近来，环烷基油广泛用于各种工业领域中，用于各种目的，包括变压器油、绝缘油、制冷机油、用于加工橡胶和塑料的油、印刷油墨或油脂的基础性材料、以及用于金属加工油的基油。
制造环烷基油的常规方法主要按以下方式进行，将具有高环烷含量(环烷含量：30-40％)的环烷原油作为进料通过真空蒸馏单元从而分离链烷组分，然后通过萃取和/或氢化单元从而分离芳族组分和/或将其转化成环烷，之后除去杂质。
但是常规方法的问题在于，具有高环烷含量的环烷原油作为进料的重要用途在其供应方面受到限制，而且，必须进行用于萃取芳族组分的萃取程序，不利地降低了总产率并使产物品质变差。
国际专利第WO 2004/094565号揭示了一种制造环烷基油的方法，该方法将由各种工艺单元的流出物组成的混合物作为进料，对其进行加氢精制从而获得油馏分，然后进行汽提从而只分离沸点在预定范围之内的油馏分，随后将分离的油馏分脱蜡。但是上述方法的缺点在于，在加氢精制单元的流出物中，只使用中间油馏分而不包括轻油馏分和重油馏分来制造环烷基油，不利地降低了总产率。而且，由于在加氢精制过程中并未充分地进行去除杂质的操作，在通过汽提分离的中间油馏分中包含大量硫，显著降低了在下游脱蜡单元中使用的催化剂的活性和选择性。
另外，需要提高工艺总产率的方法。
发明描述
技术问题
因此，本发明提供了一种以高产率从便宜的具有高芳族含量和大量杂质的烃进料制造昂贵的环烷基油的方法，其中对作为FCC流出物的油浆进行溶剂脱沥青，从而增大可以稳定处理的油浆馏分的产率，因而尽可能减小油馏分的损失和除去。
技术方案
根据本发明，一种从沸点高于汽油沸点并且包含杂原子物质和芳族物质的烃进料制造环烷基油的方法可包括以下步骤：(a)从通过FCC获得的油馏分分离轻循环油和油浆，(b)通过溶剂脱沥青将在(a)中分离的油浆分离成脱沥青油和沥青，(c)使用加氢处理催化剂对在(a)中分离的轻循环油、在(b)中分离的脱沥青油、或它们的混合物进行加氢处理，从而减少杂原子物质的量，(d)使用脱蜡催化剂对在(c)中获得的加氢处理的油馏分进行脱蜡，从而降低倾点，(e)使用加氢精制催化剂对在(d)中获得的脱蜡的油馏分进行加氢精制，从而调节芳族含量至符合产品标准，和(f)根据粘度范围分离在(e)中获得的加氢精制的油馏分。
有利效果
在本发明中，使用通过对作为FCC流出物的油浆进行溶剂脱沥青获得的脱沥青油作为进料。与通过简单蒸馏获得的油浆的杂质含量相比，使用溶剂萃取进行分离使脱沥青油具有较少量的杂质(硫、氮、多核芳族化合物和各种金属组分)，由此可缓和下游加氢处理单元的极端操作条件，并延长使用的催化剂的寿命。而且，可稳定处理的油浆馏分的产率得以提高，最后增大工艺总产率。
附图简要描述
图1显示根据本发明制造环烷基油的方法的示意图。
附图标记的说明
AR：常压重油
FCC：流化的催化裂化
LCO：轻循环油
SLO：油浆
DAO：脱沥青油，其通过对油浆进行溶剂脱沥青而获得
HDT：加氢处理
DW：脱蜡
HDF：加氢精制
N4/9/25/46/110/220/540：环烷基油产品(其中的数字表示40℃的动力粘度)
最佳方式
以下对本发明进行详细说明。
参见图1，根据本发明的制造环烷基油的方法包括：对石油烃类通过FCC获得的油浆(SLO)进行溶剂脱沥青(SDA)从而制造脱沥青油(DAO)；将轻循环油(LCO)、脱沥青油(DAO)或它们的混合物供应到加氢处理单元从而进行加氢处理(HDT)；将加氢处理的油馏分供应到脱蜡单元从而进行脱蜡(DW)；对脱蜡的油馏分进行加氢精制；以及根据粘度范围对加氢精制的油馏分进行分离。
根据本发明的制造环烷基油的方法的特征在于，从具有高芳族含量和大量杂质的轻循环油或油浆制造环烷基油，所述轻循环油或油浆从石油烃类通过FCC获得的产物流出物分离。
本发明中使用的轻循环油或油浆通过FCC制造。所述FCC(流化的催化裂化)过程是一种通过在500-700℃温度和1-3个大气压的压力条件下对常压重油进料进行FCC从而制造轻质石油产品的操作。这种FCC过程能够制造作为主要产物的挥发性油馏分，以及作为副产物的丙烯、重质裂化石脑油(HCN)、轻循环油、油浆等。使用分离塔分离轻循环油或油浆，但不包括轻油馏分。由于这种油包含大量杂质以及高含量的杂原子物质和芳族物质，所以难以将其作为轻油馏分(一种高价值的产品)使用，而是主要用于高硫轻油产品或便宜的重质燃料油。
在根据本发明的方法中，如图1中所示，可以从脱沥青油或轻循环油和脱沥青油的混合物制造高品质环烷基油，其中的脱沥青油是通过以下方式制造的：将常压重油(AR)引到FCC单元，从而获得轻循环油(LCO)和油浆(SLO)，然后将它们相互分离，并且对分离的油浆进行溶剂脱沥青。轻循环油是一种具有高芳族含量并且沸点为300-380℃高于汽油沸点的油馏分，油浆是一种具有高芳族含量并且沸点为350-510℃高于汽油沸点的油馏分。
溶剂脱沥青(SDA)过程是一种使用C3或C4作为溶剂通过萃取分离油馏分的操作，操作条件包括：沥青质分离器的压力为40-50千克/平方厘米，脱沥青油和沥青的分离温度为40-180℃，以及溶剂与油的比例(升/千克)为4∶1至12∶1。
为了进行比较，在下表1中总结了作为进料的轻循环油、脱沥青油及它们的混合物的性质。
表1
注意：
HPNA：重质多核芳族化合物
MAH：单芳烃
DAH：二芳烃
PAH：多芳烃
TAH：总芳烃
从表1明显看出，以上进料的硫含量大于0.5重量％，且氮含量大于1000ppm。在本发明进料的总芳族含量等于或大于60重量％的情况中，杂质和芳族化合物的量远高于在制造环烷基油的典型方法中用作进料的环烷原油的杂质和芳族化合物的量。参考环烷原油的芳族含量通常约为10-20％，硫含量为0.1-0.15％，氮含量约为500-1000ppm。
轻循环油、脱沥青油或它们的混合物包含高芳族含量和大量杂质，因此，通过加氢处理(HDT)除去其中包含的硫、氮、氧和金属组分，并通过氢饱和将其中包含的芳族组分转化成环烷组分。
在根据本发明的制造环烷基油的方法中，加氢处理(HDT)过程在以下条件下进行：温度为280-430℃，压力为30-220千克/平方厘米，液体时空速度(LHSV)为0.1-3.0小时-1，氢气与进料的体积比为500-2500Nm3/m3。当供应大量氢气并施加极端温度/压力条件时，进料中包含的芳族化合物和杂质的量会显著减小。
加氢处理过程中使用的加氢处理催化剂包括选自元素周期表中第6族、第9族和第10族金属的金属，具体包括选自CoMo、NiMo的一种或多种，以及CoMo和NiMo的组合。但是，本发明中使用的加氢处理催化剂并不限于这些，可以使用任何催化剂，只要它能有效进行氢饱和并除去杂质即可。
加氢处理的油馏分的杂质和芳族化合物的量显著减少。在根据本发明的方法中，加氢处理的油馏分的硫含量小于200ppm，氮含量小于100ppm，芳族含量小于60重量％。具体来说，多芳烃的量减少到不超过5％。
在根据本发明的方法中，由于加氢处理的油馏分包含相当低量的杂质，下游工艺单元中的反应能更稳定地进行，所以能以高产率制造富含环烷和少量杂质的产品。
当在以上所述的最佳操作条件下进行加氢处理时，将全部加氢处理的油馏分(仅排除放出的气体组分)供应到脱蜡单元，而不需要额外的分离或者除去轻油馏分或重油馏分。
根据本发明的脱蜡过程是一种通过裂化或异构化减少正链烷量的操作。
在脱蜡过程中，通过链烷油馏分的选择性反应和异构化认识到倾点标准与产品的低温性能直接相关。
更具体来说，脱蜡(DW)过程在以下条件下进行：温度为250-430℃，压力为10-200千克/平方厘米，LHSV为0.1-3小时-1，氢气与进料的体积比为300-1000Nm3/m3。
用于脱蜡过程的脱蜡催化剂包含其酸中心选自分子筛、氧化铝和氧化硅-氧化铝的载体，以及一种或多种选自元素周期表中第6族、第9族和第10族金属(尤其是具有氢化活性)的金属，例如铂、钯、钼、钴、镍和钨。
具有酸中心的载体的例子包括分子筛，氧化铝和氧化硅-氧化铝。其中，分子筛包括晶体铝硅酸盐(沸石)、SAPO、ALPO等，具有10元氧环的中孔分子筛的例子包括SAPO-11、SAPO-41、ZSM-5、ZSM-11、ZSM-22、ZSM-23、ZSM-35和ZSM-48，具有12元氧环的大孔分子筛的例子包括FAU、Beta和MOR。
具有氢化活性的金属包括一种或多种选自元素周期表中第6族、第8族、第9族和第10族金属的金属。特别合适的是为第9族和第10族(即第VIII族)金属的Co和Ni，以及为第6族(即第VIB族)金属的Mo和W。
在本发明中，使用由Ni(Co)/Mo(W)组成的脱蜡催化剂，其效果如下所述。具体地，i)在性能方面，以上催化剂表现出与常规脱蜡催化剂相等的脱蜡性能，和ii)在经济效益方面，以上催化剂抑制了该过程的加热反应，并降低氢消耗，以及不包含贵金属，从而降低催化剂成本。而且，iii)在性质和稳定性方面，以上催化剂能防止单芳族组分饱和，从而通过控制在下游加氢精制单元中使用的加氢精制催化剂的反应温度来调节环烷基油产品的气体吸收，实现足以满足加氢精制工艺产品所要求标准的性质和稳定性。而且，iv)在进料条件方面，因为包含贵金属的催化剂比较严格地规定了油馏分中可容许的杂质含量，所以缓和了脱蜡过程中可以使用的进料条件。而且，v)在脱蜡催化剂寿命方面，脱蜡催化剂所接触的油馏分已经通过加氢处理过程进行了精制，从而延长了脱蜡催化剂的寿命。
接下来，根据本发明的加氢精制过程是一种在加氢精制催化剂存在下用于调节脱蜡的油馏分的芳族化合物含量、气体吸收和氧化稳定性从而符合要求的产品标准的操作。加氢精制过程是在包括以下条件下进行的：温度为150-400℃，压力为10-200千克/平方厘米，LHSV为0.1-3.0小时-1，氢气与供应的油馏分的体积比为300-1000Nm3/m3。
加氢精制过程中使用的加氢精制催化剂包括一种或多种具有氢化活性的金属，其选自元素周期表中第6、8、9、10和11族的金属。具体来说，加氢精制催化剂包括选自Ni-Mo、Co-Mo和Ni-W的复合金属，或者选自Pt和Pd的贵金属。
具有大的表面积的载体的例子包括氧化硅、氧化铝、氧化硅-氧化铝、氧化钛、氧化锆和沸石。特别合适的是氧化铝或氧化硅-氧化铝。载体起到增大上述金属的分散性从而改善氢化性能的功能。载体的重要功能在于，控制酸中心防止产物裂化和结焦。
对于以上催化剂(用于加氢处理、脱蜡和加氢精制)的活化和预处理，要求进行干燥、还原和预硫化，需要时可以省略或改变这些预处理程序。
虽然对进行全部的加氢处理、脱蜡和加氢精制之后的流出物可以按其状态用作环烷基油，但是在本发明中，考虑到环烷基油的各种应用，采用分馏器将最终油馏分分离成多种其粘度足以用于对应应用的环烷基油产品。例如，分离过程能将油馏分分离成多个在40℃的动力粘度分别为3-5厘斯(cSt)、8-10厘斯、18-28厘斯、43-57厘斯、90-120厘斯、200-240厘斯和等于或大于400厘斯的环烷基油产品。
发明模式
通过以下实施例能更好地理解本发明，提出这些实施例作为说明，而不应理解为限制本发明
实施例1：从轻循环油制造环烷基油
从FCC流出物分离沸点为300-380℃的轻循环油馏分，然后供应到加氢处理单元。
使用镍-钼催化剂作为加氢处理催化剂，在以下操作条件下进行加氢处理过程：LHSV为0.1-3.0小时-1，氢气与原料的体积比为500-2500Nm3/m3，反应压力为30-220千克/平方厘米，反应温度为280-430℃。
加氢处理过程之后，得到的中间油馏分的硫含量小于200ppm，氮含量小于100ppm，芳族含量小于70重量％。根据一种优选的实施方式，这种油馏分的硫含量小于100ppm，氮含量小于100ppm，芳族含量小于50重量％。
使用NiMo/沸石催化剂进行脱蜡过程，使用PtPd/Al2O3催化剂进行加氢精制过程。这些过程都在以下操作条件下进行：LHSV为0.1-3.0小时-1，氢气与进料的体积比为300-1000Nm3/m3，反应压力为10-200千克/平方厘米。因此，对于脱蜡，将反应温度设定为250-430℃，对于加氢精制，将反应温度设定为150-400℃。在本实施例的情况中，经过加氢精制的全部油馏分都能用作产品而无须进行额外的分离。
下表2显示本实施例的进料(LCO)以及通过对进料进行加氢处理和脱蜡获得的环烷基油(产品：N9)的性质。从表2中明显看出，通过根据本发明的方法，制得高品质环烷基油，该产品的环烷含量约为57.7％，因此是富含环烷的，在40℃的动力粘度约为9.314厘斯，其中硫、氮和芳族化合物组分的量明显低于进料中的情况。
表2
实施例2：从脱沥青油制造环烷基油
在涉及从通过油浆的溶剂脱沥青获得的脱沥青油制造环烷基油的方法的本实施例中，使用丙烷作为溶剂对油浆进行溶剂萃取，从而获得脱沥青油，然后将其用作实际进料，从而制造环烷基油。
溶剂脱沥青(用于预处理油浆)在以下操作条件下进行：沥青质分离器的压力为40-50千克/平方厘米，脱沥青油与沥青的分离温度为40-180℃，溶剂与油的比例为4∶1至12∶1。
使用与实施例1中相同的镍-钼催化剂，在以下操作条件下进行加氢处理过程：LHSV为0.1-3.0小时-1，以H2/油为基准的氢气消耗为500-2500NM3/M3，反应压力为30-220千克/平方厘米，反应温度为280-430℃。
使用NiMo/沸石催化剂进行脱蜡过程，使用PtPd/Al2O3催化剂进行加氢补充精制过程。这些过程在以下操作条件下进行：LHSV为0.1-3.0小时-1，以H2/油为基准的氢消耗为300-1000NM3/M3，反应压力为10-200千克/平方厘米。因此，对于脱蜡，将反应温度设定为250-430℃，对于加氢补充精制，将反应温度设定为150-400℃。
下表3显示了第一进料(SLO)、实际进料(DAO)和DW之后的油馏分(使用分馏器分离之前)的性质。
表3
在通过溶剂脱沥青获得的脱沥青油中，相较于用作第一进料的油浆，硫减少约16.67％，氮减少约50.77％。而且，总芳族含量减少约15.85％。虽然脱蜡的油馏分可以按其状态用作产品，但是为了确保获得各种产品，在加氢精制过程中使用分馏器对其进行分离。最终产品的性质总结在下表4中。
在N9产品的情况中，测得气体吸收为+14.96。由此可知，可以证实通过利用加氢补充精制来控制芳族含量，能够对作为产品标准的气体吸收进行调节。
表4
在本实施例中，脱沥青油中的杂质和芳族化合物的量明显低于轻油浆中的情况。因此，可以认为相当大地缓和了加氢处理过程的极端条件。在加氢精制过程中使用分馏器将最终油馏分分离成包括N9/46/110/540的各种产品。
而且，在脱蜡过程中，使用NiMo/沸石催化剂，从而防止单芳族组分过度饱和，因此在随后的加氢精制过程中，芳族组分保持合适的量。当将芳族饱和控制在所需水平时，可以根据产品标准适当调节气体吸收和氧化稳定性。
实施例3：从脱沥青油和轻循环油的混合物制造环烷基油
在本实施例中，从通过油浆的溶剂脱沥青获得的轻循环油和脱沥青油的混合物制造环烷基油。
因此，使用丙烷作为溶剂在以下操作条件下进行溶剂脱沥青过程：沥青质分离器的压力为40-50千克/平方厘米，脱沥青油与沥青的分离温度为40-180℃，溶剂与油的比例(升/千克)为4∶1至12∶1。
脱沥青油(DAO)与轻循环油的混合比例接近1∶1质量比。
使用与实施例2中相同的镍-钼催化剂在以下操作条件下进行加氢处理过程：LHSV为0.1-3.0小时-1，以H2/油为基准的氢消耗为500-2500NM3/M3，反应压力为30-220千克/平方厘米，反应温度为280-430℃。
使用NiMo/沸石催化剂进行脱蜡过程，使用PtPd/Al2O3催化剂进行加氢补充精制过程。这些过程在以下操作条件下进行：LHSV为0.1-3.0小时-1，以H2/油为基准的氢消耗为300-1000NM3/M3，反应压力为10-200千克/平方厘米。因此，对于脱蜡，将反应温度设定为250-430℃，对于加氢精制，将反应温度设定为150-400℃。
下表5显示了第一进料(LCO/SLO)与实际进料(LCO+DAO)的性质。
表5
根据粘度将脱蜡单元的流出物分离成最终产品。产品的性质总结在下表6中。
表6
在本实施例中，虽然最终油馏分能按其状态用作产品，但是考虑到环烷基油的各种不同的应用，根据在40℃的动力粘度使用分馏器将其分离成四种产品。因此，在具有各种粘度标准的产品中，相较于进料的情况，硫、氮等的量明显降低，制得富含环烷并且具有优良低温性能的产品。
Claims (15)
1.一种从沸点高于汽油沸点并且包含杂原子物质和芳族物质的烃进料制造环烷基油的方法，其包括：
(a)从通过流化催化裂化获得的油馏分分离轻循环油和油浆；
(b)通过溶剂脱沥青将在(a)中分离的油浆分离成脱沥青油和沥青；
(c)使用加氢处理催化剂对在(a)中分离的轻循环油、在(b)中分离的脱沥青油或其混合物进行加氢处理，从而降低杂原子物质的量；
(d)使用脱蜡催化剂对在(c)中获得的加氢处理的油馏分进行脱蜡，从而降低倾点；
(e)使用加氢补充精制催化剂对在(d)中获得的经过脱蜡的油馏分进行加氢补充精制，从而调节芳族含量以符合产品要求；和
(f)根据粘度范围将在(e)中获得的经过加氢补充精制的油馏分进行分离。
2.如权利要求1所述的方法，其特征在于，在(c)中使用的所述轻循环油、脱沥青油或它们的混合物的硫含量等于或大于0.5重量％，氮含量等于或大于1000ppm。而且芳族含量等于或大于60重量％。
3.如权利要求1所述的方法，其特征在于，在(b)中进行的所述分离步骤在以下操作条件下进行：沥青质分离器压力为40-50千克/平方厘米，脱沥青油与沥青的分离温度为40-180℃，溶剂与油的比例(升/千克)为4∶1至12∶1。
4.如权利要求1所述的方法，其特征在于，在(c)中进行的所述加氢处理步骤在以下操作条件下进行：温度为280-430℃，压力为30-220千克/平方厘米，液体时空速度为0.1-3.0小时-1，氢气与进料的体积比为500-2500Nm3/m3。
5.如权利要求1所述的方法，其特征在于，在(c)中使用的加氢处理催化剂包含选自元素周期表第6、9和10族金属的金属。
6.如权利要求5所述的方法，其特征在于，在(c)中使用的加氢处理催化剂包含选自CoMo、NiMo的一种或多种，以及CoMo和NiMo的组合。
7.如权利要求1所述的方法，其特征在于，在(d)中进行的所述脱蜡步骤在以下操作条件下进行：温度为250-430℃，压力为10-200千克/平方厘米，液体时空速度为0.1-3小时-1，氢气与进料的体积比为300-1000Nm3/m3。
8.如权利要求1所述的方法，其特征在于，在(d)中使用的脱蜡催化剂包含选自分子筛、氧化铝和氧化硅-氧化铝的具有酸中心的载体，以及一种或多种选自元素周期表第6、9和10族金属的金属。
9.如权利要求8所述的方法，其特征在于，所述具有酸中心的载体是选自下组的至少一种分子筛：SAPO-11、SAPO-41、ZSM-5、ZSM-11、ZSM-22、ZSM-23、ZSM-35、ZSM-48、FAU、Beta和MOR。
10.如权利要求8所述的方法，其特征在于，所述一种或多种选自元素周期表第6、9和10族金属的金属包括选自下组的一种或多种金属：铂、钯、钼、钴、镍和钨。
11.如权利要求1所述的方法，其特征在于，在(e)中进行的所述加氢补充精制步骤在以下操作条件下进行：温度为150-400℃，压力为10-200千克/平方厘米，液体时空速度为0.1-3.0小时-1，氢气与供应的油馏分的体积比为300-1000Nm3/m3。
12.如权利要求1所述的方法，其特征在于，在(e)中使用的所述加氢补充精制催化剂包含一种或多种选自元素周期表第6、8、9、10和11族金属的金属。
13.如权利要求12所述的方法，其特征在于，在(e)中使用的所述加氢补充精制催化剂的一种或多种金属包括选自Pt、Pd、Ni、Co、Mo和W的一种或多种金属。
14.如权利要求1所述的方法，其特征在于，根据在40℃的动力粘度进行(f)中的所述分离，该分离步骤能将经过加氢补充精制的油馏分分离成在40℃的动力粘度为3-5厘斯、8-10厘斯、18-28厘斯、43-57厘斯、90-120厘斯、200-240厘斯、和等于或大于400厘斯的环烷基油产品。
15.如权利要求1-14中任一项所述的方法，其特征在于，所述环烷基油的硫含量等于或小于200ppm，且环烷含量等于或大于40重量％。
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| CN1703496A (zh) * | 2002-10-08 | 2005-11-30 | 埃克森美孚研究工程公司 | 制备具有高ⅵ基础料的方法 |
| CN1703498A (zh) * | 2002-10-08 | 2005-11-30 | 埃克森美孚研究工程公司 | 高粘度指数基础料、基础油和润滑油组合物以及它们的制备方法和用途 |
| CN1703497A (zh) * | 2002-10-08 | 2005-11-30 | 埃克森美孚研究工程公司 | 制备润滑油基础料的方法 |
| US20060118463A1 (en) * | 2004-12-06 | 2006-06-08 | Colyar James J | Integrated SDA and ebullated-bed process |
Cited By (7)
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| CN106715658A (zh) * | 2014-09-17 | 2017-05-24 | 埃尔根公司 | 生产环烷光亮油的方法 |
| CN106715659A (zh) * | 2014-09-17 | 2017-05-24 | 埃尔根公司 | 生产环烷基础油的方法 |
| CN106715658B (zh) * | 2014-09-17 | 2019-07-19 | 埃尔根公司 | 生产环烷光亮油的方法 |
| CN106715659B (zh) * | 2014-09-17 | 2019-08-13 | 埃尔根公司 | 生产环烷基础油的方法 |
| US10479949B2 (en) | 2014-09-17 | 2019-11-19 | Ergon, Inc. | Process for producing naphthenic bright stocks |
| US10800985B2 (en) | 2014-09-17 | 2020-10-13 | Ergon, Inc. | Process for producing naphthenic bright stocks |
| CN104342251A (zh) * | 2014-09-24 | 2015-02-11 | 中国石油化工股份有限公司 | 高燃点电气绝缘油组合物及其用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102066530B (zh) | 2013-11-06 |
| TWI458819B (zh) | 2014-11-01 |
| WO2009154324A1 (en) | 2009-12-23 |
| KR20090131072A (ko) | 2009-12-28 |
| GB201100665D0 (en) | 2011-03-02 |
| JP2013151685A (ja) | 2013-08-08 |
| JP5692545B2 (ja) | 2015-04-01 |
| JP2011530610A (ja) | 2011-12-22 |
| KR100934331B1 (ko) | 2009-12-29 |
| GB2473992B (en) | 2012-03-07 |
| JP5263634B2 (ja) | 2013-08-14 |
| TW201000621A (en) | 2010-01-01 |
| US20110089080A1 (en) | 2011-04-21 |
| GB2473992A (en) | 2011-03-30 |
| US8585889B2 (en) | 2013-11-19 |
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