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    • 7. 发明申请
    • CATALYTIC SYSTEM AND PROCESS FOR THE TOTAL HYDROCONVERSION OF HEAVY OILS
    • 催化体系及重油总氢过程
    • WO2013034642A1
    • 2013-03-14
    • PCT/EP2012/067412
    • 2012-09-06
    • ENI S.P.A.MOLINARI, DanieleBELLUSSI, GiuseppeLANDONI, AlbertoPOLLESEL, Paolo
    • MOLINARI, DanieleBELLUSSI, GiuseppeLANDONI, AlbertoPOLLESEL, Paolo
    • B01J27/051B01J29/78C10G45/12
    • B01J29/89B01J27/051B01J29/7876C10G45/12C10G47/16C10G65/12
    • A catalytic system characterized in that it comprises: a first catalyst, having a hydrogenating function, consisting of solid particles of which at least 95% by volume having an equivalent diameter smaller than 20 μm, containing one or more sulfides of metals of group VI and/or VIII B, possibly prepared starting from an oil- soluble precursor of the same; and a second catalyst, having a cracking function, consisting of solid particles of which at least 90% by volume having an equivalent diameter larger than 5 μm and smaller than 5 mm, containing an amorphous silico- aluminate and/or a crystalline silico-aluminate and/or an alumina, the equivalent average diameter of the solid particles of the second catalyst being greater than the equivalent average diameter of the solid particles of the first catalyst. Said catalytic system can be used in a process for the hydroconversion of heavy oils which comprises sending the heavy oil to a hydroprocessing step carried out in one or more slurry reactors, in the presence of hydrogen or a mixture of hydrogen and H 2 S, obtaining a stream of products in vapour or liquid-vapour phase, and extracting at the bottom, in continuous or discontinuous, a liquid stream containing non-converted products together with the two catalysts of said catalytic system, said liquid stream extracted then being separated into a clarified primary stream containing the first catalyst, which is at least partially recycled to the hydroprocessing step, and a stream rich in the second catalyst, which is regenerated in a regeneration step and at least partially recycled to the hydroprocessing step.
    • 一种催化体系,其特征在于它包括:具有氢化功能的第一催化剂,其由至少95体积%的当量直径小于20μm的固体颗粒组成,其含有一种或多种第VI族金属的硫化物,和 /或VIII B,可能从其油溶性前体开始制备; 和具有裂化功能的第二催化剂,其由固体颗粒组成,其中至少90体积%的当量直径大于5μm且小于5mm,其含有非晶硅铝酸盐和/或结晶硅铝酸盐 和/或氧化铝,所述第二催化剂的固体颗粒的当量平均直径大于所述第一催化剂的固体颗粒的当量平均直径。 所述催化体系可用于重油加氢转化的方法,其包括将重油送入在一种或多种淤浆反应器中,在氢气或氢气和H 2 S的混合物存在下进行的加氢处理步骤,获得流 的蒸气或液相 - 蒸气相中的产物,并且连续或不连续地将含有未转化产物的液体物流与所述催化体系的两种催化剂一起萃取,然后将所述液体流分离成澄清的初级 含有至少部分再循环到加氢处理步骤的第一催化剂的物流和富含第二催化剂的物流,其在再生步骤中再生并且至少部分地循环到加氢处理步骤。
    • 9. 发明申请
    • MIXED OXIDES OF TRANSITION METAL, HYDROTREATMENT CATALYSTS OBTAINED THEREFROM, AND PREPARATION PROCESS COMPRISING SOL -GEL PROCESSES
    • 过渡金属的混合氧化物,其获得的加氢催化剂以及包含溶解过程的制备方法
    • WO2011039595A2
    • 2011-04-07
    • PCT/IB2010/002392
    • 2010-09-23
    • ENI S.P.A.BELLUSSI, GiuseppeCARATI, AngelaGAGLIARDI, Maria, FedericaZANARDI, StefanoMARELLA, MarcelloSCATTOLIN, RobertoTOMASELLI, Michele
    • BELLUSSI, GiuseppeCARATI, AngelaGAGLIARDI, Maria, FedericaZANARDI, StefanoMARELLA, MarcelloSCATTOLIN, RobertoTOMASELLI, Michele
    • B01J27/049B01J27/051B01J37/03B01J37/20B01J35/10
    • B01J27/0515B01J23/002B01J23/883B01J23/8885B01J27/049B01J35/1014B01J35/1019B01J35/1038B01J37/033B01J37/20B01J2523/00C10G45/08C10G2300/1044C10G2300/1062C10G2300/107C10G2300/1077C10G2300/202C10G2400/04C10G2400/06B01J2523/31B01J2523/68B01J2523/69B01J2523/845B01J2523/847B01J2523/41
    • New sulfided metal catalysts are described, containing a metal X selected from Ni, Co and mixtures thereof, a metal Y selected from Mo, W and mixtures thereof, an element Z selected from Si, Al and mixtures thereof, and possibly an organic residue, obtained by the sulfidation of mixed oxide precursors, also new, having general formula (A) X a Y b Z c O d . pC (A) possibly shaped without a binder, or by sulfidation of mixed oxides having formula (A), in shaped form with a binder, wherein X is selected from Ni, Co and mixtures thereof, Y is selected from Mo, W and mixtures thereof, Z is selected from Si, Al and mixtures thereof, 0 is oxygen, C is selected from: a nitrogenated compound N, an organic residue deriving from the partial calcination of the nitrogenated compound N, said nitrogenated compound N, when present, being selected from: a) an alkyl ammonium hydroxide having formula (I) R I R II R III R IV NOH ( I ) wherein the groups R I -R IV , the same or different, are aliphatic groups containing from 1 to 7 carbon atoms, b) an amine having formula (II) R 1 R 2 R 3 N (II) wherein R 1 is a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, and R 2 and R 3 , the same or different, are selected from H and a linear, branched or cyclic alkyl, containing from 4 to 12 carbon atoms, said alkyl being equal to or different from R 1 , a, b, c, d are the number of moles of the elements X, Y, Z, O, respectively, p is the weight percentage of C with respect to the total weight of the precursor having formula (A), a, b, c, d are higher than 0 a/b is higher than or equal to 0.3 and lower than or equal to 2, (a+b) /c is higher than or equal to 0.3 and lower than or equal to 10, preferably varying from 0.8 to 10 d = (2a+6b+Hc)/2 wherein H = 4 when Z = Si H = 3 when Z = Al and p is higher than or equal to 0 and lower than or equal to 40%. Said catalysts can be used as hydrotreating catalysts.
    • 描述了新的硫化金属催化剂,其含有选自Ni,Co及其混合物的金属X,选自Mo,W及其混合物的金属Y,选自Si,Al及其混合物的元素Z以及可能的有机残基, 通过硫化混合氧化物前体获得,也是新的,具有通式(A)Xa Yb Zc Od。 pC(A)可以成形为没有粘合剂,或通过硫化具有式(A)的混合氧化物,成型为粘合剂,其中X选自Ni,Co及其混合物,Y选自Mo,W和混合物 Z选自Si,Al及其混合物,0为氧,C选自:氮化合物N,衍生自含氮化合物N的部分煅烧的有机残基,所述含氮化合物N当存在时为 选自:a)具有式(I)RIRIIRIIIRIVNOH(I)的烷基氢氧化铵,其中基团RI-RIV相同或不同,是含有1至7个碳原子的脂族基团,b)具有式(II)的胺, R 1 R 2 R 3 N(II)其中R 1是含有4至12个碳原子的直链,支链或环状烷基,R 2和R 3相同或不同,选自H和直链,支链或环状的烷基,其含有4〜 12个碳原子,所述烷基等于或不同于R 1,a,b,c,d ar e分别是元素X,Y,Z,O的摩尔数,p是C相对于具有式(A)的前体的总重量的重量百分比,a,b,c,d高于 (a + b)/ c高于或等于0.3且低于或等于10,优选从0.8至10d =( 2a + 6b + Hc)/ 2,其中当Z = Al时,当Z = Si H = 3时,H = 4,p大于或等于0且小于或等于40%。 所述催化剂可用作加氢处理催化剂。