Entrained-bed hydroconversion of a heavy hydrocarbon feedstock, comprising mixing said feedstock with a catalyst precursor containing an organic additive

Abstract

The present invention relates to a slurry hydroconversion process of a heavy oil feedstock (101) comprising: (a) preparing a conditioned feedstock (103) by mixing said feedstock with a catalyst precursor formulation (104) so that a colloidal or molecular catalyst is formed when it reacts with sulfur, said catalyst precursor formulation (104) comprising a catalyst precursor composition (105) comprising Mo, an organic additive (102) comprising a carboxylic acid function and/or an ester function and/or an acid anhydride function, and a molar ratio organic additive (102)/Mo from formulation (4) ranging between 0.1:1 and 20:1; (b) heating said conditioned feedstock; (c) introducing the heated conditioned feedstock (106) into at least one slurry bed reactor and operating said reactor in the presence of hydrogen and at hydroconversion conditions to produce an upgraded material (107), the colloidal or molecular catalyst being formed during step (b) and/or (c).

The invention claimed is: 
     
         1 . A process for the hydroconversion of a heavy oil feedstock ( 101 ) containing a fraction of at least 50% by weight having a boiling point of at least 300° C., and containing metals and asphaltenes, comprising the following steps:
 (a) preparing a conditioned heavy oil feedstock ( 103 ) by mixing said heavy oil feedstock ( 101 ) with a catalyst precursor formulation ( 104 ) in a manner so that a colloidal or molecular catalyst is formed when it reacts with sulfur, said catalyst precursor formulation ( 104 ) comprising:
 a catalyst precursor composition ( 105 ) comprising molybdenum, and 
 an organic chemical compound ( 102 ) comprising at least one carboxylic acid function and/or at least one ester function and/or an acid anhydride function, and 
 a molar ratio between said organic chemical compound ( 102 ) and molybdenum in said catalyst precursor formulation ( 104 ) being comprised between 0.1:1 and 20:1; 
 
 (b) heating said conditioned heavy oil feedstock ( 103 ) from step (a) in at least one preheating device; 
 (c) introducing said heated conditioned heavy oil feedstock ( 106 ) from step (b) into at least one slurry bed reactor and operating said slurry bed reactor in the presence of hydrogen and at hydroconversion conditions to produce an upgraded material ( 107 ); and wherein the colloidal or molecular catalyst is formed in situ within the conditioned heavy oil feedstock at step (b) and/or at step (c). 
 
     
     
         2 . A process as claimed in  claim 1 , wherein step (a) comprises simultaneously mixing said organic chemical compound ( 102 ) with said catalyst precursor composition ( 105 ), preferably previously diluted with a hydrocarbon oil diluent, and with said heavy oil feedstock ( 101 ), preferably below a temperature at which a substantial portion of the catalyst precursor composition begins to thermally decompose, such as at a temperature between room temperature and 300° C., and for a period of time from 1 second to 30 minutes. 
     
     
         3 . A process as claimed in  claim 1 , wherein step (a) comprises (a1) pre-mixing said organic chemical compound ( 102 ) with said catalyst precursor composition ( 105 ) to produce said catalyst precursor formulation ( 104 ) and (a2) mixing said catalyst precursor formulation ( 104 ) with said heavy oil feedstock ( 101 ). 
     
     
         4 . A process as claimed in  claim 3 , wherein at step (a1) said catalyst precursor composition ( 105 ) is mixed below a temperature at which a substantial portion of the catalyst precursor composition begins to thermally decompose, preferably at a temperature comprised between room temperature and 300° C. 
     
     
         5 . A process as claimed in  claim 1 , wherein a hydrocarbon oil diluent is used to form the catalyst precursor formulation ( 104 ), said hydrocarbon oil diluent being preferably selected from the group consisting of vacuum gas oil, decant oil or cycled oil, light gas oil, vacuum residues, deasphalted oils, and resins. 
     
     
         6 . A process as claimed in  claim 1   any one of the preceding claims , wherein the organic chemical compound ( 102 ) is selected from the group consisting of ethylhexanoic acid, naphthenic acid, caprylic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, ethyl octanoate, ethyl 2-ethylhexanoate, 2-ethylhexyl 2-ethylhexanoate, benzyl 2-ethylhexanoate, diethyl adipate, dimethyl adipate, bis(2-ethylhexyl) adipate, dimethyl pimelate, dimethyl suberate, monomethyl suberate, hexanoic anhydride, caprylic anhydride, and a mixture thereof. 
     
     
         7 . A process as claimed in  claim 6 , wherein the organic chemical compound ( 102 ) comprises 2-ethylhexanoic acid, and preferably is 2-ethylhexanoic acid. 
     
     
         8 . A process as claimed in  claim 6 , wherein the organic chemical compound ( 102 ) comprises ethyl octanoate or 2-ethylhexyl 2-ethylhexanoate, and preferably is ethyl octanoate or 2-ethylhexyl 2-ethylhexanoate. 
     
     
         9 . A process as claimed in  claim 1 , wherein the catalyst precursor composition comprises an oil soluble organo-metallic compound or complex selected from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthanate, molybdenum hexacarbonyl, and is preferably molybdenum 2-ethylhexanoate. 
     
     
         10 . A process as claimed in  claim 1 , wherein the molar ratio between said organic chemical compound ( 102 ) and molybdenum of said catalyst precursor formulation ( 104 ) is comprised between 0.75:1 and 7:1, and preferably between 1:1 and 5:1. 
     
     
         11 . A process as claimed in  claim 1 , wherein the colloidal or molecular catalyst comprises molybdenum disulfide. 
     
     
         12 . A process as claimed in  claim 1 , wherein step (b) comprising heating at a temperature between 280° C. and 450° C., more preferably between 300° C. to 400° C., and most preferably in a range of 320° C. to 365° C. 
     
     
         13 . A process as claimed in  claim 1 , wherein the heavy oil feedstock ( 101 ) comprises at least one of the following feedstocks: heavy crude oil, oil sand bitumen, atmospheric tower bottoms, vacuum tower bottoms, resid, visbreaker bottoms, coal tar, heavy oil from oil shale, liquefied coal, heavy bio oils, and heavy oils comprising plastic waste and/or a plastic pyrolysis oil. 
     
     
         14 . A process as claimed in  claim 1 , wherein the heavy oil feedstock ( 101 ) has a sulfur at a content of greater than 0.5% by weight, a Conradson carbon residue of at least 0.5% by weight, C 7  asphaltenes at a content of greater than 1% by weight, transition and/or post-transition and/or metalloid metals at a content of greater than 2 ppm by weight, and alkali and/or alkaline earth metals at a content of greater than 2 ppm by weight. 
     
     
         15 . A process as claimed in  claim 1 , wherein said hydroconversion step (c) is carried out under an absolute pressure of between 2 MPa and 38 MPa, at a temperature of between 300° C. and 550° C., at an liquid hourly space velocity LHSV relative to the volume of each slurry bed reactor of between 0.05 h −1  and 10 h −1  and under an amount of hydrogen mixed with the feedstock entering slurry bed reactor of between 50 and 5000 normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of feedstock. 
     
     
         16 . A process as claimed in  claim 1 , wherein the concentration of molybdenum in the conditioned oil feedstock is in a range of 10 ppm to 10000 ppm by weight of the heavy oil feedstock.