US-12624299-B2 - Hydroconversion of a hydrocarbon-based heavy feedstock in a hybrid ebullated-entrained bed, comprising premixing said feedstock with an organic additive

US12624299B2US 12624299 B2US12624299 B2US 12624299B2US-12624299-B2

Abstract

A hydroconversion process of a heavy oil feedstock including (a) preparing a first conditioned feedstock ( 103 ) by blending heavy oil feedstock ( 101 ) with an organic chemical compound ( 102 ) containing at least one carboxylic acid function and/or at least one ester function and/or an acid anhydride function; (b) preparing a second conditioned feedstock ( 105 ) by mixing a catalyst precursor composition ( 104 ) with the first conditioned feedstock in a manner such that a colloidal or molecular catalyst is formed when it reacts with sulfur; (c) heating the second conditioned feedstock in at least a preheating device; (d) introducing the heated second conditioned feedstock ( 106 ) into at least one hybrid ebullated-entrained bed reactor containing a hydroconversion porous supported catalyst and operating the 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 (c) and/or (d).

Inventors

Joao Marques
Thibaut CORRE
Jeremie BARBIER
Brett Matthew SILVERMAN
David M. Mountainland
Sukesh Parasher

Assignees

IFP Energies Nouvelles

Dates

Publication Date: 20260512
Application Date: 20220627
Priority Date: 20210708

Claims (18)

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 first conditioned heavy oil feedstock ( 103 ) by blending said heavy oil feedstock ( 101 ) with 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; (b) preparing a second conditioned heavy oil feedstock ( 105 ) by mixing a catalyst precursor composition ( 104 ) comprising an oil soluble organo-metallic compound or complex selected from the group consisting of molybdenum 2-ethylhexanoate, molybdenum naphthanate, vanadium naphthanate, vanadium octoate, molybdenum hexacarbonyl, vanadium hexacarbonyl, and iron pentacarbonyl with the first conditioned heavy oil feedstock ( 103 ) from step (a) in a manner such that a colloidal or molecular catalyst is formed when it reacts with sulfur; (c) heating the second conditioned heavy oil feedstock from step (b) in at least one preheating device; d) introducing said heated second conditioned heavy oil feedstock ( 106 ) from step (c) 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 second conditioned heavy oil feedstock at step (c) and/or at step (d).
2 . The process as claimed in claim 1 , wherein step (a) comprises mixing said organic chemical compound ( 102 ) and said heavy oil feedstock ( 101 ) in a dedicated vessel of an active mixing device.
3 . The process as claimed in claim 1 , wherein step (a) comprises injecting said organic chemical compound ( 102 ) into a pipe conveying said heavy oil feedstock ( 101 ) toward the hybrid ebullated-entrained bed reactor.
4 . The process as claimed in claim 1 , wherein step (a) is carried out at a temperature between room temperature and 300° C., and the residence time of the organic chemical compound with said heavy oil feedstock before step (b) is between 1 second and 10 hours.
5 . The process as claimed in claim 1 , wherein the organic chemical compound ( 102 ) is selected from the group consisting of 2-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 a mixture thereof.
6 . The process as claimed in claim 5 , wherein the organic chemical compound ( 102 ) comprises 2-ethylhexanoic acid.
7 . The process as claimed in claim 5 , 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 ) added at step a) and the active metal(s) of the catalyst precursor composition ( 104 ) added at step (b), in said second conditioned heavy oil feedstock is between 0.1:1 and 20:1.
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 step (b) comprises: (b1) pre-mixing the catalyst precursor composition with a hydrocarbon oil diluent below a temperature at which a substantial portion of the catalyst precursor composition begins to decompose thermally in order to form a diluted precursor mixture; and (b2) mixing said diluted precursor mixture with the first conditioned heavy oil feedstock.
11 . The process as claimed in claim 10 , wherein step (b1) is carried out at a temperature between room temperature and 300° C. and for a period of time from 1 second to 30 minutes, and step (b2) is carried out at a temperature between room temperature and 300° C. and for a period of time from 1 second to 30 minutes.
12 . The process as claimed in claim 1 , wherein step (c) comprises heating at a temperature between 280° C. and 450° C.
13 . The 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/or heavy oils comprising plastic waste and/or a plastic pyrolysis oil.
14 . The process as claimed in claim 1 , wherein the heavy oil feedstock ( 101 ) has a sulfur 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 . The process as claimed in claim 1 , wherein said hydroconversion step (d) 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 the hybrid 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 concentration of the catalyst metal in the second conditioned oil feedstock ( 105 ) is in a range of 5 ppm to 500 ppm by weight of the heavy oil feedstock.
17 . The process as claimed in claim 1 , further comprising a step (e) of further processing the upgraded material, said step (e) comprising: a second hydroconversion step in a second hybrid ebullated-entrained bed reactor ( 260 ) of at least a portion or all of the upgraded material resulting from the hydroconversion step (d) 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 step separating a portion or all of the upgraded material resulting from the hydroconversion step (d), said second hybrid ebullated-entrained bed reactor ( 260 ) comprising a second porous supported catalyst and operating in the presence of hydrogen ( 204 ) and at hydroconversion conditions to produce a hydroconverted liquid effluent ( 205 ) with a reduced Conradson carbon residue, and possibly a reduced quantity of sulfur, and/or nitrogen, and/or metals, a step of fractionating a portion or all of said hydroconverted liquid effluent ( 205 ) in a fractionation section ( 270 ) to produce at least one heavy cut ( 207 ) 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.; an optional step of deasphalting, in a deasphalter ( 280 ), a portion or all of said heavy cut ( 207 ) with at least one hydrocarbon solvent to produce a deasphalted oil DAO and a residual asphalt; and wherein, said hydroconversion step (d) and said second hydroconversion step are carried out under an absolute pressure of between 2 and 38 MPa, at a temperature of between 300° C. and 550° C., at a liquid hourly space velocity LHSV 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.
18 . The process as claimed in claim 1 , wherein step (a) is carried out at a temperature between 70° C. and 200° C. and the residence time of the organic chemical compound with said heavy oil feedstock before step (b) is between 1 second and 10 hours.

Description

TECHNICAL FIELD The present invention relates to a process for converting heavy oil feedstocks in the presence of hydrogen, a catalyst system comprising a porous supported catalyst and a colloidal or molecular catalyst, and an organic additive. In particular, the present invention relates to a process for hydroconversion of heavy oil feedstocks containing a fraction of at least 50% by weight having a boiling point of at least 300° C., and especially heavy oil feedstocks including a significant quantity of asphaltenes and/or fractions boiling above 500° C., such as crude oils or heavy hydrocarbon fractions resulting from the atmospheric and/or vacuum distillation of a crude oil, to yield lower boiling, higher quality materials. The process specifically comprises premixing said feedstock with an organic additive, before being brought into contact with the catalysts, these catalysts operating in one or several hybrid ebullated bed reactors, in order to allow upgrading of said low-quality feedstock while minimizing fouling in equipment prior to hydroconversion in the hybrid ebullated bed reactor(s). PRIOR ART Converting heavy oil feedstocks into useful end products requires extensive processing, including reducing the boiling point of the heavy oil, increasing the hydrogen-to-carbon ratio, and removing impurities such as metals, sulfur, nitrogen and high carbon content compounds. Catalytic hydroconversion is commonly used for the heavy oil feedstocks and is generally carried out using three-phase reactors in which the feedstock is brought into contact with hydrogen and a catalyst. In the reactor, the catalyst can be used in the form of a fixed bed, a moving bed, an ebullated bed or an entrained bed, as for example described in chapter 18 “Catalytic Hydrotreatment and Hydroconversion: Fixed Bed, Moving Bed, Ebullated Bed and Entrained Bed” of the book “Heavy Crude Oils: From Geology to Upgrading, An Overview”, published by Éditions Technip in 2011. In the case of an ebullated bed or an entrained bed, the reactor comprises an upflow of liquid and of gas. The choice of the technology generally depends on the nature of the feedstock to process, and in particular its metal content, its tolerance for impurities and the conversion targeted. Some heavy feedstock hydroconversion processes are based on hybrid technologies mixing the use of different catalyst bed types, for example hybrid processes using ebullated bed and entrained bed technologies, or fixed bed and entrained bed technologies, thus generally taking advantage of each technology. For example, it is known from the art to use contemporarily in a same hydroconversion reactor a supported catalyst maintained in the ebullated bed in the reactor and an entrained catalyst of smaller size, also commonly known as a “slurry” catalyst, which is entrained out of the reactor with the effluents. This entrainment of the second catalyst is in particular enabled by a suitable density and a suitable particle size of the slurry catalyst. Hence a “hybrid ebullated-entrained bed” process, also herein called “hybrid ebullated bed” or simply “hybrid bed” process, is defined in the present description as referring to the implementation of an ebullated bed comprising an entrained catalyst in addition to a supported catalyst maintained in the ebullated bed, which can be seen as a hybrid operation of an ebullated bed and an entrained bed. The hybrid bed is in a certain sense a mixed bed of two types of catalysts of necessarily different particle size and/or density, one type of catalyst being maintained in the reactor and the other type of catalyst, the slurry catalyst, being entrained out of the reactor with the effluents. Such a hybrid bed hydroconversion process is known to improve the traditional ebullated bed process, in particular as the addition of a slurry catalyst reduces the formation of sediments and coke precursors in the hydroconversion reactor system. Indeed, it is known that during operation of an ebullated bed reactor for upgrading a heavy oil, the heavy oil is heated to a temperature at which the high boiling fractions of the heavy oil feedstock typically having a high molecular weight and/or low hydrogen/carbon ratio, an example of which is a class of complex compounds collectively referred to as “asphaltenes”, tend to undergo thermal cracking to form free radicals of reduced chain length. These free radicals have the potential of reacting with other free radicals, or with other molecules, to produce coke precursors and sediments. A slurry catalyst passing through the reactor, while the reactor already comprises a supported catalyst maintained in the reactor, provides an additional catalytic hydrogenation activity, especially in zones of the reactor generally free of supported catalyst. The slurry catalyst hence reacts with the free radicals in these zones, forming stable molecules, and thus contributes to control and reduce the formation of sediments and coke precur