CN1071134C - 贵金属/二氧化硅-氧化铝催化剂及重质进料处理方法 - Google Patents
贵金属/二氧化硅-氧化铝催化剂及重质进料处理方法 Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 15
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title abstract description 25
- 238000000034 method Methods 0.000 title abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 61
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 238000009835 boiling Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000011959 amorphous silica alumina Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- 239000003209 petroleum derivative Substances 0.000 claims 1
- 238000009826 distribution Methods 0.000 abstract description 11
- 229930195733 hydrocarbon Natural products 0.000 abstract description 3
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 2
- 238000007600 charging Methods 0.000 description 20
- 239000003921 oil Substances 0.000 description 16
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 125000000524 functional group Chemical group 0.000 description 14
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 238000006317 isomerization reaction Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 239000012188 paraffin wax Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000002199 base oil Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000004517 catalytic hydrocracking Methods 0.000 description 4
- 230000006837 decompression Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010719 annulation reaction Methods 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- -1 boron oxide compound Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004452 microanalysis Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Classifications
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
- C10G45/62—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing platinum group metals or compounds thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/67—Pore distribution monomodal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
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- Oil, Petroleum & Natural Gas (AREA)
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
本发明涉及转化含烃进料所用的催化剂，基本上由0.05-10wt%贵金属和比表面积为100-500m2/g的二氧化硅(5-70%)/氧化铝载体构成，平均孔径为1-12nm，孔径为平均孔径±3mm之间的孔体积为总孔体积的40%以上，贵金属分散值为20-100%，贵金属分布系数大于0.1。该催化剂用于对沸点为350℃以上的进料进行加氢异构化处理，其中温度为200-450℃，压力为2-25MPa，VVH(时空速度)为0.1-10h-1并且氢气/进料体积比例为100-2000。
Description
本发明涉及在金属含量低的进料或原料(charges)加氢或氢化转化(hydroconversion)方法中所用的催化剂。
本发明还涉及沸点大大高于350℃并且金属含量低的进料或原料加氢转化和加氢或氢化异构化(hydroisomérisation)方法。
该方法特别有利于对进料(如加氢或氢化裂化或裂解(hydrocraquage)渣油(résidus))进行加氢异构化处理以获得附加值极高的产品如煤油，汽油和基础油(huiles de base)。
已用大量催化剂进行加氢异构化反应。例如，US 4,929,759提出用包括0.6wt％(重量百分比，下同)铂的催化剂从石蜡或链烷烃(paraffines)获得基础油，其中铂沉积在含有7.2wt％氟的含卤的氧化铝上。由于该催化剂要求向催化装置中连续注入含氟的化合物，所以本申请人开发出可以更简便方式应用的无卤催化剂。
US 4,428,819又提出含有沸石的催化剂，可用其进行来自石油的石蜡并混入催化脱蜡所得基础油后的混合物的异构化反应，目的在于改善或改变浊点。最后，US 4,547,283提出来自石油的石蜡加氢异构化催化剂，其中至少含有元素周期表2a,3a,4a和/或4b的活性或反应性金属，其载体优选为二氧化硅。
本申请人已发现用起来更为简便的催化剂，其中在催化剂制备过程中可避免使用沸石或加入补充的或附加的元素。
实际用于加氢转化的所有催化剂均为双官能类催化剂，其中将酸官能团与氢化官能团(fonction hydrogènante)结合起来。酸官能团由表面积大(一般150-800m2/g)并具有表面酸性或酸度的载体如含卤(尤其是含氯或含氟)的氧化铝，含磷的氧化铝，硼氧化物和铝氧化物的混合物，无定形二氧化硅-氧化铝和二氧化硅-氧化铝载带或提供或由其引入。氢化官能团则由一或多种元素周期表中Ⅷ族金属如铁，钴，镍，钌，铑，钯，锇，铱和铂或由至少一种Ⅵ族金属如铬，钼和钨和至少一种Ⅷ族金属共同载带或提供。
酸官能团和氢化官能团两者之间的平衡为决定催化剂活性和选择性的基本参数或因素。弱酸官能团和强氢化官能团会得到对于异构化反应的活性和选择性低的催化剂，而强酸官能团和弱氢化官能团又可得到对于裂化或裂解反应的活性和选择性高的催化剂。第三种可能性是应用强酸官能团和强氢化官能团而得到对异构化反应的活性高且选择性亦高的催化剂。因此可通过合理地选择任何一种官能团而调整催化剂的活性/选择性平衡。
本申请人通过对大量的二氧化硅-氧化铝的深入研究而惊人地发现应用包括特殊的二氧化硅-氧化铝的催化剂可得到对某些反应如对下述进料异构化反应的活性高且选择性亦高的催化剂。
更具体地讲，本发明催化剂基本上由沉积在无定形二氧化硅-氧化铝载体上的0.05-10wt％至少一种Ⅷ族贵金属构成，其中载体含5-70wt％二氧化硅，其BET比表面积为100-500m2/g并且该催化剂具有：
*1-12nm的平均孔径；
*孔径在上述平均孔径减3nm和上述平均孔经加3nm之间的孔的孔体积大于总孔体积的40％，
*贵金属分散值为20-100％，以及
*贵金属分布系数大于0.1。
以下更详细地说明这些特径：
二氧化硅含量：用于制备本说明书所述或本发明催化剂的载体由二氧化硅SiO2和氧化铝Al2O3构成。二氧化硅含量以重量百分比计为5-70％，优选20-60％，更优选22-45％。优选用X射线荧光分析法测定该含量。在整个催化剂中该含量是恒定的，即二氧化硅的浓度在例如催化剂表面上不会更高，也就是说催化剂中二氧化硅是均匀的。
贵金属性质：对于这类特殊的反应，金属官能团由元素周期表中Ⅷ族贵金属，尤其是铂提供。
贵金属含量：贵金属含量以按催化剂计算的wt％表示为0.05-10，优选为0.1-5。
贵金属分散值：分散值表示反应物可接触到的金属相对于催化剂中金属总量的份额或比值，可用例如H2/O2滴定法测定。金属先还原，即在氢气流中高温下于氢可接触到的所有铂原子均可转化成金属态的条件下对该金属进行处理。然后，在可将氧可接触到的所有已被还原的铂原子氧化成PtO2的适当操作条件下通入氧气流。通过计算引入氧气量和排出氧气量之间的差值，即可得出消耗掉的氧气量，从而用该量进一步得出氧可接触到的铂量。而分散值即为氧可接触到的铂量与催化剂中的铂总量之比值。在我们的情况下，分散值为20-100％，优选为30-100％。
贵金属分布：贵金属分布值表示催化剂颗粒内部的金属分布情况，金属分散因而亦有好坏之分。因此，可能使铂分布情况差(例如在厚度大大小于颗粒半径的环中观测到的情形)，但分散性好，即环中所有铂原子均可由反应物接触到。而在我们的情况下，铂分布情况好，即按Castaing微量分析方法测得的铂分布状况显示出大于0.1，优选大于0.2的分布系数。
BET面积：载体BET表面积为100-500m2/g，优选为250-450m2/g，更优选310-450m2/g。
平均孔径：催化剂平均孔径用借助汞泵孔率计得到的孔分布状况测得。平均孔径定义为对应于由汞孔隙率曲线获得的曲线零点(annulation)的直径。这样定义的平均孔径为1-12nm(1nm=1×10-9m)，优选2.5-11nm，更优选4-10.5nm，尤其是3-9nm。
孔分布：本说明书所述或本发明催化剂孔分布情况是使孔径处于上述平均孔径减3nm和上述平均孔径加3nm(即平均孔径±3nm)之间的孔的孔体积大于总孔体积的40％，优选为总孔体积的50-90％，更优选为总孔体积的50-80％，尤其是总孔体积的50-70％。因此，该催化剂的孔分布均匀，更多地是单元的或单型的(monomodal)，而不是二元的或二型的(bimodal)。
载体的总孔体积：一般小于1.0ml/g，优选0.3-0.9ml/g，更优选小于0.85ml/g。一般来说，该载体的总孔体积大于0.55ml/g，优选至少0.6ml/g。
二氧化硅-氧化铝的制备和成形可按本技术领域众所周知的常规方法进行。优选的是，在金属浸渍之前载体可进行焙烧如在2-30体积％(优选7.5％)水蒸汽中300-750℃(优选600℃)下热处理0.25-10小时(优选2小时)。
金属盐可按用于将金属(优选铂)沉积在载体表面上的常规方法引入。优选方法之一是干浸渍，即其中将金属盐引入体积等于待浸渍催化剂物料的孔体积的溶液之中。在还原操作之前，催化剂可进行焙烧如在空气中300-750℃(优选520℃)下热处理0.25-10小时(优选2小时)。
用于转化反应之前，催化剂中所含金属应还原。进行金属还原的优选方法之一是在氢气中150-650℃温度和0.1-25MPa总压下进行处理。例如，还原可分两步进行，第一步150℃下进行2小时，然后以1℃/min的速度将温度升到450℃，第二步在450℃下进行2小时，其中在整个还原操作期间氢气用量为1000l氢气/l催化剂。还应当注意到任何就地还原方法都是适宜的。
所述催化剂例如对下述进料加氢异构化反应具有活性，因此可得到大量由初始进料中存在的分子经加氢异构化而得到的产品。更具体地讲，可有利地得到可随后用作为润滑产品组分的产品。
可以处理任何合适的进料或原料如真空或称减压(sous vide)蒸馏馏出物，减压蒸馏渣油，常压蒸馏渣油或石油进料脱蜡所得石蜡产品如进料为减压脱沥青的渣油的情况下所得产品。这些进料含有至少约10个碳原子的分子。这些进料也可含有石蜡组分或完全为石蜡分子，并且其中芳族碳原子含量为进料中碳原子总量的至多20wt％。所谓合适的进料，我们指的是硫含量低于1000ppm(重量)，优选低于500ppm(重量)，更优选低于300ppm(量量)并且氮含量低于200ppm(重量)，优选低于100ppm(重量)，更优选低于50ppm(重量)的进料。该进料中金属如镍和钒含量极低如低于50ppm(重量)，优选低于10ppm(重量)。
优选的是，重质进料或原料如加氢裂化的渣油，即沸点大大高于350℃的渣油进行加氢异构化处理。这些进料含有至少约20个碳原子的分子，其中包括石蜡组分或成分或者这些分子完全是石蜡分子。加氢异构化基本上涉及到石蜡或链烷烃，尤其是正链烷烃，结果可得到异链烷烃。
用于进行这种加氢异构化反应的操作条件是温度为200-450℃，优选250-430℃，尤其是高于340℃，氢分压为2-25Mpa，优选3-20MPa，时空速度为0.1-10h-1，优选0.2-2h-1，氢气比例为00-2000l氢气/l进料，优选150-1500l氢气/l进料。
该催化剂的应用不仅限于加氢异构化，而是一般适宜于烃转化，可在达到要求转化率所需条件下应用。
实施例
下述实施例说明本发明特征，但绝不限制本发明范围。
制备催化剂：
载体为二氧化硅-氧化铝，以挤出物形式应用，其中含29.1wt％二氧化硅SiO2和70.9wt％氧化铝Al2O3。在加入贵金属之前，该二氧化硅氧化铝表面积为389m2/g，平均孔径为6.6nm。该载体的总孔体积为0.76ml/g。
用贵金属浸渍载体后可得到相应的催化剂，其中将铂盐Pt(NH3)4Cl2溶解成为体积相当于待浸渍总孔体积的溶液。固体然后在干燥或无水空气流中520℃下焙烧2小时。铂含量为0.60wt％,Pt分散值等于60％，在颗粒中其分布均匀。用该催化剂测得的孔体积为0.75ml/g,BET表面积为332m2/g，平均孔径为6.5nm并且孔径在3.5-9.5nm的孔的孔体积为0.46ml/g，占总孔体积的59％。
该催化剂的孔分布如下：孔径 ＜6nm 孔体积=0.16ml/g，占总孔体积的21％
6-15nm =0.36ml/g，占总孔体积的48％
15-60nm =0.06ml/g，占总孔体积的8％
＞60nm =0.17ml/g，占总孔体积的23％
进料特征如下：
在下表Ⅰ中，我们已列出用于进行加氢异构化反应的进料的物理-化学特性，这是从减压蒸馏馏分获得的加氢裂化渣油。
反应后制备基础油：
以上得到的催化剂用于通过所述进料的加氢异构化而得到基础油。
反应在355℃,12MPa总压，1h-1时空速度和1000l氢气/l进料的氢气量条件下进行。在这些操作条件下，400-净转化率为55wt％，基础油收率为85wt％。回收的油的Ⅵ值等于135。
在下表Ⅱ中，我们将加氢异构化后的油的特征与用普通溶剂萃取方法(MEK/Tol)从加氢裂化渣油中萃取得到的油的特征进行了比较。可以看出，这两种油的密度和粘度很接近。另一方面，在加氢异构化所得产品情况下Ⅵ，倾点及尤其是油/渣收率则更好。
表Ⅰ
dl54 0.859
硫(wt％) 0.0012
氮(ppm(重量) 1.8
倾点 +30℃
PI 104
5％ 327
10％ 385
50％ 452
90％ 519
95％ 536
PF 573
表 Ⅱ
溶剂脱蜡 加氢异构化
dl5/4 0.842 0.840v(100℃)(m2/s) 5.0×10-6 4.9×10-6
Ⅵ 125 135倾点(℃) -15 -18油/渣收率(wt％) 78 88.5
Claims (13)
1．基本上由沉积在无定形二氧化硅-氧化铝载体上的0.05-10wt％铂构成的催化剂，其中在该催化剂制备过程中没有使用沸石或加入补充的或附加的卤素，并且该催化剂显示出均匀的二氧化硅含量，其特征在于所说载体含5-70wt％二氧化硅，其BET比表面积为100-500m2/g以及所说载体总孔体积小于1.0ml/g，并且该催化剂具有：
*1-12nm的平均孔径；
*孔径在上述平均孔径减3nm和上述平均孔经加3nm之间的孔的孔体积大于总孔体积的40％，
*贵金属分散值为20-100％，以及
*贵金属分布系数大于0.1。
2．权利要求1的催化剂，其特征在于载体总孔体积至少0.3ml/g并且小于0.9ml/g。
3．上述权利要求中任一项的催化剂，其特征在于载体总孔体积小于0.85ml/g。
4．上述权利要求中任一项的催化剂，其特征在于其平均孔径为2.5-11nm。
5．上述权利要求中任一项的催化剂，其特征在于其中平均孔径为4-10.5nm。
6．上述权利要求中任一项的催化剂，其特征在于孔径在平均孔径减3nm和平均孔径加3nm之间的孔的孔体积为总孔体积的50-90％。
7．上述权利要求中任一项的催化剂，其特征在于孔径在平均孔径减3nm和平均孔径加3nm之间的孔的孔体积为总孔体积的50-80％。
8．上述权利要求中任一项的催化剂，其特征在于孔径在平均孔径减3nm和平均孔径加3nm之间的孔的孔体积为总孔体积的50-70％。
9．上述权利要求中任一项的催化剂，其特征在于载体含20-60wt％的二氧化硅。
10．上述权利要求中任一项的催化剂，其特征在于载体含22-45％的二氧化硅。
11．上述权利要求中任一项的催化剂，其特征在于载体的BET表面积为250-450m2/g。
12．上述权利要求中任一项的催化剂，其特征在于载体的BET表面积为310-450m2/g。
13．沸点大大高于350℃，氮含量低于220ppm(重量)和金属含量低于50ppm(重量)的重质含烃石油馏分加氢异构化处理方法，其特征在于用权利要求书1-12中任一项的催化剂进行操作，其中温度为200-450℃，氢分压为2-25MPa，时空速度为0.1-10h-1，而氢气/进料体积比例为100-2000。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR94/03867 | 1994-04-01 | ||
| FR94/03866 | 1994-04-01 | ||
| FR9403866A FR2718060B1 (fr) | 1994-04-01 | 1994-04-01 | Catalyseur pour la conversion de charges hydrocarbonées, à base de métal noble et silice-alumine. |
| FR9403867A FR2718144B1 (fr) | 1994-04-01 | 1994-04-01 | Procédé de traitement avec hydroisomérisation de charges lourdes. |
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| CN1125912A CN1125912A (zh) | 1996-07-03 |
| CN1071134C true CN1071134C (zh) | 2001-09-19 |
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| CN95190229A Expired - Lifetime CN1071134C (zh) | 1994-04-01 | 1995-03-22 | 贵金属/二氧化硅-氧化铝催化剂及重质进料处理方法 |
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| US (1) | US5879539A (zh) |
| EP (1) | EP0701480B1 (zh) |
| JP (1) | JP3843345B2 (zh) |
| KR (1) | KR100336723B1 (zh) |
| CN (1) | CN1071134C (zh) |
| DE (1) | DE69511974T2 (zh) |
| ES (1) | ES2138730T3 (zh) |
| NO (1) | NO311501B1 (zh) |
| RU (1) | RU2141380C1 (zh) |
| WO (1) | WO1995026819A1 (zh) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1123383C (zh) * | 1997-09-10 | 2003-10-08 | 中国石油化工集团公司 | 一种无定形硅铝及其制备方法 |
| NL1015035C2 (nl) * | 1999-04-29 | 2001-02-12 | Inst Francais Du Petrole | Flexibel proces voor de productie van basisoliÙn en destillatieproducten door een omzetting-hydroisomerisatie op een weinig gedispergeerde katalysator, gevolgd door een katalytische ontparaffinering. |
| FR2792851B1 (fr) * | 1999-04-29 | 2002-04-05 | Inst Francais Du Petrole | Catalyseur a base de metal noble faiblement disperse et son utilisation pour la conversion de charges hydrocarbonees |
| CN1102077C (zh) * | 1999-06-25 | 2003-02-26 | 李海 | 一种支撑、复盖催化剂的保护剂及其制造方法 |
| FR2846574B1 (fr) * | 2002-10-30 | 2006-05-26 | Inst Francais Du Petrole | Catalyseur et procede d'hydrocraquage de charges hydrocarbonees |
| US7030053B2 (en) * | 2002-11-06 | 2006-04-18 | Conocophillips Company | Catalyst composition comprising ruthenium and a treated silica support component and processes therefor and therewith for preparing high molecular weight hydrocarbons such as polymethylene |
| US6995112B2 (en) * | 2002-11-08 | 2006-02-07 | Chevron U.S.A. Inc. | Highly homogeneous amorphous silica-alumina catalyst composition |
| US6902664B2 (en) * | 2002-11-08 | 2005-06-07 | Chevron U.S.A. Inc. | Extremely low acidity USY and homogeneous, amorphous silica-alumina hydrocracking catalyst and process |
| FR2851569B1 (fr) * | 2003-02-21 | 2007-04-20 | Inst Francais Du Petrole | Procede d'hydrocraquage en deux etapes utilisant un catalyseur amorphe a base de platine et de palladium |
| US7943547B2 (en) * | 2005-09-14 | 2011-05-17 | Hamilton Sundstrand Space Systems International, Inc. | Selective catalytic oxidation of ammonia to water and nitrogen |
| US8114806B2 (en) | 2008-04-10 | 2012-02-14 | Shell Oil Company | Catalysts having selected pore size distributions, method of making such catalysts, methods of producing a crude product, products obtained from such methods, and uses of products obtained |
| US9187702B2 (en) * | 2009-07-01 | 2015-11-17 | Chevron U.S.A. Inc. | Hydroprocessing catalyst and method of making the same |
| KR101833077B1 (ko) * | 2009-12-15 | 2018-02-27 | 바스프 에스이 | 방향족 화합물의 수소화를 위한 촉매 및 방법 |
| US11559789B2 (en) * | 2021-03-11 | 2023-01-24 | Chevron U.S.A. Inc. | Base oil hydrotreating catalyst and process of use |
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| EP0131925A2 (en) * | 1983-07-15 | 1985-01-23 | Daido Sanso K.K. | Metal oxide having uniform pore sizes, the process for producing said metal oxide, and catalyst carrier comprising the said metal oxide |
| DD223077A1 (de) * | 1984-04-23 | 1985-06-05 | Leuna Werke Veb | Verfahren zur herstellung eines katalysators fuer die kohlenwasserstoffreformierung |
| FR2565504A1 (fr) * | 1984-06-07 | 1985-12-13 | Inst Francais Du Petrole | Procede de fabrication d'un catalyseur d'hydrocraquage de fractions petrolieres lourdes |
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| FR2563120A1 (fr) * | 1984-04-23 | 1985-10-25 | Leuna Werke Veb | Catalyseur pour le reformage d'hydrocarbures, et procede pour sa fabrication |
| JPS6115739A (ja) * | 1984-04-25 | 1986-01-23 | Toa Nenryo Kogyo Kk | 水素化処理用触媒 |
| US5157187A (en) * | 1991-01-02 | 1992-10-20 | Mobil Oil Corp. | Hydroisomerization process for pour point reduction of long chain alkyl aromatic compounds |
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- 1995-03-22 EP EP95914399A patent/EP0701480B1/fr not_active Expired - Lifetime
- 1995-03-22 JP JP52544095A patent/JP3843345B2/ja not_active Expired - Lifetime
- 1995-03-22 ES ES95914399T patent/ES2138730T3/es not_active Expired - Lifetime
- 1995-03-22 WO PCT/FR1995/000352 patent/WO1995026819A1/fr active IP Right Grant
- 1995-03-22 CN CN95190229A patent/CN1071134C/zh not_active Expired - Lifetime
- 1995-03-22 US US08/556,943 patent/US5879539A/en not_active Expired - Lifetime
- 1995-03-22 DE DE69511974T patent/DE69511974T2/de not_active Expired - Lifetime
- 1995-03-22 KR KR1019950705395A patent/KR100336723B1/ko not_active IP Right Cessation
- 1995-03-31 RU RU95104891A patent/RU2141380C1/ru active
- 1995-11-30 NO NO19954876A patent/NO311501B1/no not_active IP Right Cessation
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| EP0131925A2 (en) * | 1983-07-15 | 1985-01-23 | Daido Sanso K.K. | Metal oxide having uniform pore sizes, the process for producing said metal oxide, and catalyst carrier comprising the said metal oxide |
| DD223077A1 (de) * | 1984-04-23 | 1985-06-05 | Leuna Werke Veb | Verfahren zur herstellung eines katalysators fuer die kohlenwasserstoffreformierung |
| FR2565504A1 (fr) * | 1984-06-07 | 1985-12-13 | Inst Francais Du Petrole | Procede de fabrication d'un catalyseur d'hydrocraquage de fractions petrolieres lourdes |
| US5187138A (en) * | 1991-09-16 | 1993-02-16 | Exxon Research And Engineering Company | Silica modified hydroisomerization catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0701480B1 (fr) | 1999-09-08 |
| WO1995026819A1 (fr) | 1995-10-12 |
| NO954876D0 (no) | 1995-11-30 |
| JPH08511199A (ja) | 1996-11-26 |
| NO954876L (no) | 1995-11-30 |
| KR100336723B1 (ko) | 2002-11-18 |
| DE69511974T2 (de) | 2000-05-31 |
| ES2138730T3 (es) | 2000-01-16 |
| CN1125912A (zh) | 1996-07-03 |
| EP0701480A1 (fr) | 1996-03-20 |
| RU2141380C1 (ru) | 1999-11-20 |
| DE69511974D1 (de) | 1999-10-14 |
| JP3843345B2 (ja) | 2006-11-08 |
| NO311501B1 (no) | 2001-12-03 |
| US5879539A (en) | 1999-03-09 |
| RU95104891A (ru) | 1996-12-27 |
| KR960702770A (ko) | 1996-05-23 |
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