Hydroconversion of a hydrocarbon-based heavy feedstock in a hybrid ebullated-entrained bed, comprising mixing said feedstock with a catalyst precursor containing an organic additive
A hydroconversion process of a heavy oil feedstock comprises: (a) preparing a conditioned feedstock by mixing said heavy oil feedstock with a catalyst precursor formulation so that a colloidal or molecular catalyst is formed when it reacts with sulfur wherein the catalyst precursor formulation comprises a catalyst precursor composition containing Mo, an organic additive comprising a carboxylic acid function and/or an ester function and/or an acid anhydride function, wherein the molar ratio organic additive/Mo from formulation is between 0.1:1 and 20:1; (b) heating said conditioned feedstock; and (c) introducing the heated conditioned feedstock into at least one hybrid ebullated-entrained bed reactor comprising a hydroconversion porous supported catalyst, wherein the reactor is operated in the presence of hydrogen and at hydroconversion conditions to produce an upgraded material, the colloidal or molecular catalyst being formed during step (b) and/or (c).
1 . A process for 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, 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, said process comprising:
(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 the catalyst precursor formulation ( 104 ) reacts with sulfur, said catalyst precursor formulation ( 104 ) comprising:
a catalyst precursor composition ( 105 ) comprising an oil soluble organo-metallic compound or complex comprising molybdenum, and
an 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, 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 mixtures thereof, and
the molar ratio between said organic chemical compound ( 102 ) and molybdenum in said catalyst precursor formulation ( 104 ) being between 0.1:1 and 20:1;
(b) heating said conditioned heavy oil feedstock ( 103 ) from (a) in at least one preheating device;
(c) introducing said heated conditioned heavy oil feedstock ( 106 ) from (b) into at least one hybrid ebullated-entrained bed reactor comprising a hydroconversion porous supported catalyst and operating said hybrid ebullated-entrained 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 (b) and/or at (c).
2 . The process as claimed in claim 1 , wherein (a) comprises simultaneously mixing said organic chemical compound ( 102 ) with said catalyst precursor composition ( 105 ) and with said heavy oil feedstock ( 101 ).
3 . The process as claimed in claim 1 , wherein (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 . The process as claimed in claim 3 , wherein at (a1) said catalyst precursor composition ( 105 ) is mixed at a temperature between room temperature and 300° C.
5 . The process as claimed in claim 1 , wherein a hydrocarbon oil diluent is used to form the catalyst precursor formulation ( 104 ).
6 . The process as claimed in claim 1 , wherein the organic chemical compound ( 102 ) comprises 2-ethylhexanoic acid.
7 . The process as claimed in claim 1 , wherein the organic chemical compound ( 102 ) comprises ethyl octanoate or 2-ethylhexyl 2-ethylhexanoate.
8 . The 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 between 0.75:1 and 7:1.
9 . The process as claimed in claim 1 , wherein the colloidal or molecular catalyst comprises molybdenum disulfide.
10 . The process as claimed in claim 1 , wherein (b) comprises heating at a temperature between 280° C. and 450° C.
11 . The 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.
12 . The process as claimed in claim 1 , wherein said hydroconversion (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 hybrid reactor of between 0.05 h −1 and 10 h −1 and under an amount of hydrogen mixed with the feedstock entering hybrid bed reactor of between 50 and 5000 normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of feedstock.
13 . The process as claimed in claim 1 , wherein the concentration of molybdenum in the conditioned oil feedstock is in a range of 5 ppm to 500 ppm by weight of the heavy oil feedstock.
14 . The process as claimed in claim 1 , wherein the hydroconversion porous supported catalyst contains at least one metal from the non-noble group VIII chosen from nickel and cobalt, and at least one metal from group VIB chosen from molybdenum and tungsten, and includes an amorphous support.
15 . The process as claimed in claim 1 , further comprising:
a second hydroconversion in a second hybrid ebullated-entrained bed reactor of at least a portion or all of the upgraded material resulting from the hydroconversion (c) or optionally of a liquid heavy fraction that boils predominantly at a temperature greater than or equal to 350° C. resulting from an optional separation separating a portion or all of the upgraded material resulting from the hydroconversion (c), said second hybrid ebullated-entrained bed reactor comprising a second porous supported catalyst and operating in the presence of hydrogen and at hydroconversion conditions to produce a hydroconverted liquid effluent with a reduced heavy residue fraction and a reduced Conradson carbon residue,
fractionating a portion or all of said hydroconverted liquid effluent in a fractionation section (F) to produce at least one heavy cut that boils predominantly at a temperature greater than or equal to 350° C., said heavy cut containing a residual fraction that boils at a temperature greater than or equal to 540° C.;
optionally deasphalting a portion or all of said heavy cut resulting with at least one hydrocarbon solvent to produce a deasphalted oil DAO and a residual asphalt; and
wherein, said hydroconversion (c) and said second hydroconversion are carried out under an absolute pressure of between 2 and 38 MPa, at a temperature of between 300° C. and 550° C., at an hourly space velocity HSV relative to the volume of each hybrid ebullated-entrained bed reactor of between 0.05 h −1 and 10 h −1 and under an amount of hydrogen mixed with the feedstock entering each hybrid ebullated-entrained bed reactor of between 50 and 5000 normal cubic meters (Nm 3 ) per cubic meter (m 3 ) of feedstock.
16 . The 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 1:1 and 5:1.
17 . The process as claimed in claim 1 , wherein (b) comprises heating at a temperature between 300° C. to 400° C.
18 . The process as claimed in claim 1 , wherein (a) comprises simultaneously mixing said organic chemical compound ( 102 ) with said catalyst precursor composition ( 105 ), previously diluted with a hydrocarbon oil diluent, and with said heavy oil feedstock ( 101 ).
19 . The process as claimed in claim 1 , wherein (a) comprises simultaneously mixing said organic chemical compound ( 102 ) with said catalyst precursor composition ( 105 ) and with said heavy oil feedstock ( 101 ) at a temperature between room temperature and 300° C. and for a time period of 1 second to 30 minutes.
20 . The process as claimed in claim 1 , wherein the organic chemical compound ( 102 ) is selected from 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 mixtures thereof.
21 . The process as claimed in claim 1 , wherein the organic chemical compound ( 102 ) is selected from adipic acid, pimelic acid, suberic acid, azelaic acid, and mixtures thereof.