CA2774169A1 - Process for the hydroconversion of hydrocarbon feedstocks via slurry technology allowing the recovery of metals from the catalyst and feedstock using a gasification step - Google Patents

Abstract

A process for hydroconversion of heavy hydrocarbon feedstocks comprising a step of hydroconversion of the feedstock in at least one reactor containing a slurry catalyst and allowing the recovery of metals in the residual unconverted fraction, in particular those used as catalysts. The process comprises a hydroconversion step, a gas / liquid separation step, a gasification step, a metal extraction step and a step of preparing catalytic solutions which are recycled in the hydroconversion step. The process also allows the recovery of synthesis gas from gasification in the form of hydrogen and / or in the form of electricity.

Description

PROCESS FOR HYDROCONVERSION OF HYDROCARBON LOADS
VIA A TECHNOLOGY IN SLURRY FOR THE RECOVERY OF
CATALYST AND LOAD METALS
WORKS A STEP OF GASIFICATION
The invention relates to a process for hydroconversion of heavy loads hydrocarbons into lighter products, recoverable as fuels and / or raw materials for petrochemicals. More particularly, the invention concerned a process for hydroconversion of heavy hydrocarbon feedstocks comprising a step of hydroconversion of the charge in at least one reactor containing a catalyst in slurry and allowing the recovery of metals in the fraction unconverted residual, including those used as catalysts, in order to the to valorize in catalytic solutions and to recycle them upstream of the process of conversion to slurry. The method comprises a hydroconversion step, a separation step gas / liquid without decompression, a step of gasification, a metal extraction step and a solution preparation step (s) catalytic (s) that is / are recycled (s) in the hydroconversion stage.
The conversion of heavy hydrocarbon feedstocks into liquid products can to be done by heat treatments or by treatments hydrogenation, also called hydroconversion. Current research is mainly oriented towards hydroconversion because heat treatments produce generally poor quality products and a significant amount of coke.
The hydroconversion of heavy loads includes the conversion of the load in the presence of hydrogen and a catalyst. The commercialized processes use depending on the load and the desired conversion level, a technology in bed fixed, a bubbling bed technology or driven bed technology (also called technology "slurry" according to the English terminology).

2 The hydroconversion of heavy loads in fixed bed or bubbling bed is made supported catalysts comprising one or more transition metals (Mo, W, Ni, Co, Ru) on supports of silica / alumina or equivalent type.
For the conversion of heavily loaded heavy loads into heteroatoms, metal and asphaltenes, the fixed bed technology is generally limited because contaminants cause rapid deactivation of catalyst thus requiring a frequency of renewal of the bed catalytic too high and therefore too expensive. In order to be able to handle such charges, bubbling bed processes have been developed. However, the level of conversion bubbling bed technologies is usually limited to levels lower 80% because of the catalytic system used and the design of the unit.

Hydroconversion technologies running with slurry technology provide an attractive solution to the disadvantages encountered in the use of fixed bed or bubbling bed. Indeed, the slurry technology allows treat heavy loads heavily contaminated with metals, asphaltenes and heteroatoms, while having conversion rates generally above 85%.

Slurry residue hydroconversion technologies use a dispersed catalyst in the form of very small particles, whose size is lower at 1 mm and preferably a few tens of microns or less (generally from 0.001 to 100 μm). Thanks to this small size of the catalysts, the reactions hydrogenation are facilitated by a uniform distribution throughout the zoned reaction and the formation of coke is greatly reduced. Catalysts, or their precursors, are injected with the charge to be converted at the entrance of reactors. The catalysts go through the reactors with the loads and products in process of conversion and then they are driven with the reaction products out of reactors.
They are found after separation in the heavy residual fraction, as for example, the unconverted vacuum residue. Catalysts used in slurry are generally sulphurized catalysts preferably containing at least one

3 element selected from the group consisting of Mo, Fe, Ni, W, Co, V and Ru.
Usually, molybdenum and tungsten show much higher performance satisfactory than nickel, cobalt or ruthenium and even more than the vanadium and iron (N. Panariti et al., Applied Catalysis A: General 204 (2000), 203-213).

Hydroconversion technologies for heavy slurry loads marketed are known. For example, the licensed EST technology ENI, the VRSH technology licensed by Chevron-Lummus-Global, the HDH and HDHPLUS technologies licensed by Intevep, SRC-Uniflex licensed by UOP, technology (HC) 3 or HCAT licensed by Headwaters etc ...

Although the small size of the slurry catalysts makes it possible to obtain of very high conversion, this size is problematic with regard to the separation and recovery of the catalyst (s) after the reaction hydroconversion. The catalysts are found after separation in the fraction heavy residual, such as unconverted vacuum residue. In certain processes, a part of the vacuum residue containing the non-converted and the catalysts, is recycled directly into the reactor hydroconversion to increase conversion efficiency and yield final liquid. However, these recycled catalysts generally have a activity reduced compared to fresh catalysts. Moreover the residue under empty containing the unconverted fraction proves to be unresponsive to increase the conversion efficiency and the final liquid yield. In addition, the residue under empty is traditionally used as fuel for the production of heat or electricity. Ashes from combustion contain metals and are generally placed in waste disposal. In this case, the metals are therefore not recovered. In addition, a significant portion of metals are sublimated in the

4 burning and can not be recovered. This is especially true for the molybdenum.
The heavy loads treated contain a high concentration of metals, essentially vanadium and nickel. These metals are largely removed from the charge by settling on the catalysts during the reaction.
They are carried away by the catalyst particles leaving the reactor. So, the activity the intrinsic nature of the catalysts is greatly diminished and accentuated by formation of coke resulting in particular from the high concentration of asphaltenes contained in these charges.
The continuous renewal of the catalytic phase finely dispersed in the reaction zone allows the contact of dissolved hydrogen in the phase liquid to hydrogenate and hydrotreat the injected heavy load. To to ensure high conversion level and maximum hydrotreatment of the feed, the quantity catalytic solution to inject is quite important which represents costs large-scale industrial operations. Thus, the processes hydroconversion slurry are generally consumers of large amount of catalysts, especially in molybdenum which has the most active catalyst, but also the more expensive. The costs of fresh catalysts, catalyst separation and recovery of metals have a major impact on the profitability of such processes. The Selective recovery of molybdenum and its recycling as a catalyst are two indispensable elements for the industrial valorization of processes in slurry.
This recovery is also accompanied by those of other metals such as nickel (the one possibly injected and the one recovered in the charge) and the vanadium recovered in the feed whose contents are comparable to that of molybdenum and which can be resold for metallurgical applications.
Apart from these economic aspects, the recovery of metals is essential also for environmental reasons. Indeed, the ashes from the combustion of the residual fraction have been classified in many countries as hazardous waste, because the metals contained in the ashes put in dump sites pose a danger to the water table.
There is therefore a real need for recovery and recycling of metals from catalysts and the heavy load of hydroconversion process in

5 slurry.

Prior art Metal recovery processes of slurry processes are known in the state of the art and generally include a step of deasphalting, of coking, combustion and / or gasification as a key step in metal recovery.

US Pat. No. 4,548,700 describes a slurry hydroconversion process for heavy charges comprising, after the hydroconversion reaction, a step of separation of the gaseous fraction, a distillation step allowing recover a naphtha fraction, a middle distillate fraction and a residual fraction 650 F +
(343 C +). The residual fraction 650 F + (343 C +), including the distillate under empty (or Vacuum Gas Oil (VGO) according to the English terminology and generally having a range of boiling temperatures of 350 to 550 ° C) and the residue under vacuum (550 C +), is then subjected to a combustion or gasification stage at of the temperatures between 800 and 1200 F (427-1093 C) and under a pressure of 0 to 150 psig (0 to 1 MPa) to obtain ash containing the metals. V metals and Mo are recovered by an oxalic acid extraction step and then recycled in the process.

Object of the invention The specificity of slurry processes being to have a catalyst finely dispersed and unsupported on a mineral phase makes the recovery of metals much more complex than those of the supported catalysts of refining used traditionally. The challenge for the industrial development of processes

6 of hydroconversion by slurry technology is the need to recover and to recycle metals from catalysts The present invention aims at improving hydroconversion processes of heavy loads by known slurry technology by allowing the valorization a unconverted residual fraction from conversion to slurry, fraction strongly concentrated in metals and heteroelements and ultimately including recovery said metals in the said unconverted fraction and the production of precursors catalytic systems to recycle them upstream of the conversion process into slurry.
The method comprises a hydroconversion step, a separation step gas / liquid, optionally a fractionation step comprising a vacuum separation, then a gasification step, an extraction step of metals and a catalytic solution (s) preparation step which is / are recycled (s) in the hydroconversion stage.
The research work carried out by the applicant on hydroconversion heavy loads led him to discover that, surprisingly, this process including a separation to maximize the light fraction from the hydroconversion reactor and minimize the residual fraction, coupled with a step of gasification pushed, allowed to prepare the extraction of metals contained in the ashes in such a way that very good rates of Recovery of recyclable metals in the process are possible.
Indeed, one of the critical steps of the method according to the invention is the step of gas / liquid separation which is carried out under operating conditions close to that of the hydroconversion reactor (and in particular without decompression) which allows to obtain a high cutting point (400-500 C). This allows the separation effective in a single step of a light fraction including future bases fuels (gases, naphtha, light diesel or even vacuum distillate) of the unconverted residual fraction containing solids such as metals.
Moreover, the residual fraction of the aforementioned gas / liquid separation is optionally subjected to a separation step comprising a separation

7 under vacuum, for example vacuum distillation. This separation allows recover all of the atmospheric and vacuum distillates that did not not been vaporized in the aforementioned gas / liquid separation step. The combination gas / liquid separation and vacuum separation thus makes it possible to maximize recovery of atmospheric and vacuum distillates, and to produce a residue under vacuum with a boiling point typically greater than 500 C for the gasification. The total yield of the light fraction (and thus the bases fuels) and vacuum distillates are maximized at the same time as the Unconverted residual fraction is minimized.
Similarly, only the residual fraction having a boiling point greater than 500 C is subsequently subjected to gasification. The gasification stage need so compared to the prior art on one side of the operating conditions more outbreaks because of the highly refractory nature of the residual fraction, and the other side a equipment of smaller size thanks to its limited quantity.
Gas / liquid separation operating under close operating conditions of those of the reactor allows in particular to separate most of the diesel under vacuum (VGO) with the light fraction. The vacuum gas fraction is not so no subsequently and contrary to the prior art subjected to gasification, but can be upgraded to fuels (gasoline, diesel) by hydrotreating and / or hydrocracking in particular and / or by catalytic cracking.
The maintenance of the operating conditions during the separation allows also the economic integration of a further hydrotreatment treatment and or hydrocracking of the light fraction without the need for compressors additional.
Another interest is the fact of being able to value the syngas produced then gasification in the form of electricity and / or in the form of hydrogen, preference consumed during hydroconversion reactions and / or steps final hydrotreatment and / or hydrocracking. The production of gas synthesis is important enough to produce at least some, if not all, of

8 the hydrogen necessary for hydroconversion into slurry. Surplus gas synthesis can be used to produce hydrogen from other units (hydrotreatment / hydrocracking) and / or be used to produce electricity by turbine.
The method according to the invention therefore makes it possible to optimize the conversion of heavy fuel-based loads while allowing the recovery of metals with very good recovery rates. The process requires few steps and allows in particular to avoid a deasphalting step and its disadvantages (handling and recycling of solvents), a step that can be used in processes for recovering process metals in slurry.

detailed description The invention relates to a process for hydroconversion of heavy loads hydrocarbon slurry for the recovery and recycling of metals in the unconverted residual fraction, especially those used as catalysts.
More particularly, the invention relates to a hydroconversion process of heavy metal-containing hydrocarbon feeds comprising:
a) a step of hydroconversion of the feedstock in at least one reactor containing a slurry catalyst based on at least one metal, and containing possibly a solid additive, b) a step of separation of the hydroconversion effluent without decompression into a so-called light fraction containing the compounds boiling at at plus 500 C and in a residual fraction, b ') optionally a fractionation step comprising a separation under vacuum of said residual fraction as obtained in step b), and is obtained a vacuum residue concentrated in metals, c) a gasification step in which only said residual fraction as obtained in step b) or only said vacuum residue as obtained at step b ')

9 is subjected to a gasification to obtain ashes concentrated in metals and syngas, d) a step of extracting the metals from the ashes obtained at the step of gasification, e) a step of preparation of (s) metallic solution (s) containing at least minus the catalyst metal, solution (s) that is / are recycled to step hydroconversion.

hydroconversion The method according to the invention comprises a step of hydroconversion of the charge in at least one reactor containing a slurry catalyst and possibly a solid additive.
In the hydroconversion, hydrogenation reactions occur, hydrotreatment, hydrodesulfurization, hydrodenitrogenation, hydrodemetallisation and hydrocracking.
The heavy hydrocarbon feedstocks concerned are chosen from oil residues, crude oils, crude head oils, oils deasphalted, asphalts or deasphalting pitches, processes oil conversion (for example: HCO (heavy cycle oil), a residual of catalytic cracking fluid bed (FCC), heavy dieselNGO coking, residue of visbreaking or similar thermal process, etc. ...), Sands bituminous or their derivatives, oil shales or their derivatives, coals or their derivatives, organic waste or their derivatives, biomass residues or their derivatives, or mixtures of such fillers. More generally, we will regroup right here under the term "heavy load" hydrocarbon feeds containing at least 50% by weight of product distilling above 250 C and at least 25% wt distilling above 350 C.
The heavy loads concerned according to the invention contain metals, often V and / or Ni, usually at least 50 ppm wt and the most often 100-2000 ppm, at least 0.5% wt sulfur, and at least 1 wt%

asphaltenes (asphaltenes to heptane), often more than 2% wt or 5%
wt, 25% wt% or more of asphaltenes attainable;
they also contain condensed aromatic structures that may contain heteroelements refractory to conversion.
Preferably, the heavy loads concerned come from non-conventional heavy crude type (APIs between 18 and 25 and one viscosity between 10 and 100 cP), extra-heavy crudes (APIs between 7 and 20 and a viscosity between 100 and 10,000 cl?) and the oil sands (API
between 7 and 12 API and a viscosity of less than 10000 cP)

10 present in large quantities in the Athabasca region of Canada and the Orinoco in Venezuela, where the resources are estimated at 1700 Gb and 1300 Gb. These unconventional oils are also characterized by contents of vacuum residues, asphaltenes and heteroelements (sulfur, nitrogen, oxygen, vanadium, nickel, etc.) which require stages of transformation into commercial products such as gasoline, diesel or heavy fuel oil specific.

The heavy load is mixed with a stream of hydrogen and a catalyst too as dispersed as possible to obtain a hydrogenating activity as uniformly distributed as possible in the hydroconversion reaction zone. The catalyst optionally contains a solid additive. This mixture feeds the section catalytic hydroconversion into slurry. This section consists of a oven preheat for charge and hydrogen and a reaction section incorporated one or more reactors arranged in series and / or in parallel, according to the capacity required. In the case of series reactors, one or more separators will be present on the effluent at the head of each of the reactors. In the section reaction, hydrogen can feed one, several or all reactors and this in equal or different proportions. In the section reactionary, the catalyst can feed a single, several or all the reactors and this in

11 equal or different proportions. The catalyst is kept in suspension in the reactor, flows from the bottom to the top of the reactor with the gas and the charge, and is evacuated with the effluent. Preferably at least one (and preferably all) of the reactors is equipped with an internal recirculation pump.
The operating conditions of the catalytic hydroconversion section in slurry are generally a pressure of 2 to 35 MPa, preferably 10 to 25 MPa a hydrogen partial pressure ranging from 2 to 35 MPa and preferentially of at 25 MPa, a temperature of between 300 ° C. and 500 ° C., preferably 420 C at 480 C, a contact time of 0.1 h to 10 h with a preferred duration of 0.5h to 5h.
These operating conditions coupled with the catalytic activity allow to obtain conversion rates per pass of the vacuum residue 500 C + which can from 20 to 95%, preferably from 70 to 95%. The conversion rate mentioned above is defined as the mass fraction of compounds organic compounds with a boiling point above 500 C at the inlet of the section reaction minus the mass fraction of organic compounds having a point boiling point greater than 500 ° C. at the outlet of the reaction section, the all divided by the mass fraction of organic compounds having a boiling point greater than 500 C at the inlet of the reaction section.
The slurry catalyst is in dispersed form in the reaction medium.
he can be formed in situ but it is best to prepare it outside the reactor and to inject it, usually continuously, with the load. The catalyst promotes the hydrogenation of the radicals resulting from thermal cracking and reduces the formation of coke. When coke is formed, it is removed with the catalyst.
The slurry catalyst is a sulfurized catalyst preferably containing at least minus one element selected from the group consisting of Mo, Fe, Ni, W, Co, V, Ru. These catalysts are usually monometallic or bimetallic (combining by example, a non-noble element VIIIB (Co, Ni, Fe) and an element of group VIB (Mo, W)). Preferably, NiMo, Mo or Fe catalysts are used.

12 The catalysts used may be heterogeneous solid powders (such as than natural ores, iron sulphate, etc.), dispersed catalysts from water soluble dispersed catalyst ("water soluble dispersed catalyst") such as acid phosphomolybdic, ammonium molybdate, or a mixture of Mo or Ni oxide with aqueous ammonia. Preferably, the catalysts used are from soluble precursors in an organic phase ("oil soluble dispersed Catalyst ").
Precursors are organometallic compounds such as naphthenates of Mo, Co, Fe, or Ni, or Mo octoates, or multi-component compounds.
carbonyl of these metals, for example 2-ethyl hexanoates of Mo or Ni, acetylacetonates of Mo or Ni, salts of fatty acids C7-C12 of Mo or W, etc ... They can be used in the presence of a surfactant to improve the metal dispersion, when the catalyst is bimetallic. Catalysts himself in the form of dispersed particles, whether colloidal or not, depending on the nature of catalyst. Such precursors and catalysts that can be used in the process according to the invention are widely described in the literature.
In general, the catalysts are prepared before being injected into the charge. The preparation process is adapted according to the state in which himself finds the precursor and its nature. In all cases, the precursor is sulfide (ex-situ or in-situ) to form the catalyst dispersed in the feedstock. For the case preferred so-called oil-soluble catalysts, in a typical process, the precursor is mixed with a petroleum charge (which may be a part of the charge to be treated, an external charge, a recycled charge ...), the mixture is optionally dried at least in part, then or simultaneously sulphurated by addition of a sulfur compound (preferred H2S) and heated. The preparations of these Catalysts are described in the prior art.
The preferred solid additives are inorganic oxides such as alumina, silica, mixed oxides AI / Si, used catalysts supported (by example, on alumina and / or silica) containing at least one group VIII element (such as Ni, Co) and / or at least one group VIB element (such as Mo, W). For example,

13 the catalysts described in US2008 / 177124. Carbonaceous solids low hydrogen content (eg 4% hydrogen), possibly pretreated can also be used. It is also possible to use mixtures of such additives. The particle size is preferably less than 1 mm. The content any solid additive present at the inlet of the reaction zone of the process hydroconversion in slurry is between 0 and 10% wt, preferably between 1 and 3 wt.%, and the content of the catalytic solutions is between 0 and 10% by weight, preferably between 0 and 1% by weight.

The processes of hydroconversion of heavy loads by slurry technology known are EST ENI operating at temperatures of the order of 400-420 C, under pressures of 10-16 MPa with a particular catalyst (molybdenite);
(HC) 3 or HCAT of Headwaters operating at temperatures in the range of 400-450 C, under pressures of 10-15 MPa with Fe pentacarbonyl or 2-ethyl hexanoate Mo, the catalyst being dispersed in the form of colloidal particles; HDH
and HDHPLUS licensed by Intevep / PDVSA operating at temperatures in the range of 420-480 C, at pressures of 7-20 MPa, using a metal catalyst scattered ; Chevron CASH or VRSH using a sulphide catalyst of Mo or W
prepared by the aqueous route; SRC-Uniflex of UOP operating at temperatures of the order of 430-480 C, under pressures of 10-15 MPa; VCC developed by Veba and belonging to BP operating at temperatures of the order of 400-480 C, under of pressures of 15-30 MPa, using an iron-based catalyst; Microcat Exxonmobil; etc ...
All these slurry processes can be used in the process according to the invention.
Separation The totality of the effluent resulting from the hydroconversion is directed towards a section separation, usually in a high pressure separator and high temperature (HPHT), which separates a fraction converted to the state gas, so-called light fraction, and an unconverted liquid fraction containing solid, so-called

14 residual fraction. This separation section is operated without decompression and preferably under identical or similar operating conditions of the hydroconversion stage which are usually a pressure of 2 to 35 MPa with a preferred pressure of 10 to 25 MPa, varying hydrogen partial pressure from 2 to 35 MPa and preferably from 10 to 25 MPa and a temperature of between 300 C and 500 C, preferably 380 C to 460 C. The residence time of effluent in this separation section is 0.5 to 60 minutes and preferably 1 at 5 minutes. The light fraction contains, for the most part, the compounds boiling at at plus 450 ° C, or at most 500 ° C or 550 ° C; they correspond to the compounds present in gases, naphtha, diesel and most of the distillate under empty. It is indicated that the cup contains, for the most part, these compounds because the separation is not made according to a precise cutting point, it is similar rather to a flash. If we had to speak in terms of cutting point, we could say that it is between 400 and 500 C.

The valuation of the light fraction is not the object of this invention and these methods are well known to those skilled in the art. The so-called fraction light from the step of separation without decompression is preferably subject to at least one step of hydrotreatment and / or hydrocracking, the objective being to bring the different cuts to specifications (sulfur content, smoke point, cetane, aromatic content, etc ...). The light fraction can also be mixed with a other load before being directed to a hydrotreatment section and / or hydrocracking. An external cut generally from another process existing in the refinery or possibly out of the refinery may be feed before hydrotreatment and / or hydrocracking, advantageously cutting external for example, is the VGO resulting from the fractionation of crude oil (VGO straight-run), VGO from a conversion, a light cycle oil (LCO) or a heavy cycle (HCO) oil) fluidized catalytic cracking (FCC).

In general, hydrotreatment and / or hydrocracking after hydroconversion can be done conventionally via a section of Intermediate classical separation (with decompression) using after high pressure high temperature separator for example, a high separator Low temperature pressure and / or atmospheric distillation and / or vacuum distillation. Preferably, the hydrotreatment section and / or hydrocracking is directly integrated into the hydroconversion section without intermediate decompression. In this case, the light fraction is subject directly, without additional steps of separation and without decompression at At least one hydrotreatment and / or hydrocracking step. This last mode of realization makes it possible to optimize the conditions of pressure and temperatures, avoid additional compressors and thus minimizes equipment costs additional.

The residual fraction resulting from the separation (for example via the separator

15 HPHT) and containing the metals and a fraction of solid particles used as possible additive and / or formed during the reaction can be directed to a fractionation step comprising vacuum separation. This splitting is optional and includes one or more flash balloons and / or preferably, a vacuum distillation, which makes it possible to concentrate balloons or column one metal-rich vacuum residue and recover at the top of column one or many effluents. Additional fractionation steps at reduced pressure before the Vacuum separation can complete the vacuum fractionation step.

Preferably, the residual fraction resulting from the separation step without decompression is fractionated by vacuum distillation in at least one fraction vacuum distillate and a vacuum residue fraction, at least a portion and of preferably all of said vacuum residue fraction being sent to the stage of gasification, at least a part and preferably all of said fraction

16 vacuum distillate being preferably subjected to at least one step hydrotreatment and / or hydrocracking.
The liquid effluent (s) of the vacuum distillate fraction and the Product (s) is (are) usually directed to a small extent to the unit hydroconversion in slurry where they can be directly recycled into the reaction zone or then it (s) can (wind) be used for the preparation of catalytic precursors or to the preparation of solid additives before injection into the load. Another part of or effluent (s) is directed to the hydrotreatment section and / or hydrocracking optionally mixed with other loads, such as fraction light from the HPHT separator or a vacuum distillate from another unit, in equal or different proportions depending on the quality of the products obtained.
The purpose of vacuum distillation is to increase the yield of liquid effluents for further hydrotreatment treatment and / or hydrocracking and thus increase the yield of fuel bases. Same time, the amount of the residual fraction containing the metals is reduced, thus facilitating the concentration of metals.

Gasification The residual fraction resulting from the separation without decompression (via the HPHT separator for example) and / or the vacuum residue fraction of the separation under vacuum (for example, withdrawn at the bottom of vacuum distillation) are then directed to a gasification step. This stage aims to de concentrate the metals in the mineral phase and produce synthesis gas recoverable as electricity or as a necessary hydrogen in the process.
The operating conditions of the gasification step determined so as to optimize the recovery of metals in the mineral matrix are usually a pressure of 2.5 to 10 MPa, preferably 4 to 7 MPa, and a temperature of

17 between 500 ° C. and 2000 ° C., preferably from 800 ° C. to 1500 ° C.
gasification takes place in the presence of a gas containing oxygen (oxygen and / or air and / or air enriched with oxygen) and water vapor.
Gasification makes it possible to recover a mineral phase containing in all, or almost all, the metallic elements in the form of ashes and one gaseous mixture, also called synthesis gas, synthetic gas or syngas, composed mainly of carbon monoxide and hydrogen.
The mineral phase containing the metals is sent all or in part to a metal extraction step. The mineral phase can also be recycled partly in the hydroconversion unit.
The recovery of synthesis gas is described later.
Metal recovery Ashes from the gasification are sent to a stage of metals extraction in which the metals are separated from each other other in one or more substeps (s). This metal recovery is necessary, because the simple recycling of ashes in the hydroconversion stage shows a very weak catalytic activity. In general, the extraction step of the metals makes it possible to obtain, by one or more steps, several effluents containing one or more metals. Each effluent preferably contains a metal specific, for example Mo, Ni or V, usually in the form of or oxide. Each effluent containing a catalyst metal is directed to a step for preparing an aqueous or organic solution based on the identical metal at catalyst or its precursor, used in the hydroconversion stage.
The effluent containing a metal from the non-recoverable charge as a catalyst (like vanadium for example) can be valorized outside the process.
Operating conditions, fluids and / or extraction methods used to separate the different metals are considered known to the man from art and already used industrially, as for example described in Marafi et al.,

18 Resources, Conservation and Recycling 53 (2008) 1-26, US4432949, US4514369, US4544533, US4670229 or US2007 / 0025899. The different ways of extracting known metals generally include leaching by solutions acidic and / or basic, by ammonia or salts of ammonia, the bioleaching by microorganisms, low temperature heat treatment (Roasting) with sodium or potassium salts, chlorination or recovery electrolytic metals. Acid leaching can be done by of the inorganic acids (HCI, H2SO4, HNO3) or organic acids (acid oxalic, lactic acid, citric acid, glycolic acid, phthalic acid, acid malonic, succinic acid, salicylic acid, tartaric acid ...). For leaching basic generally uses ammonia, salts of ammonia, soda or Na2CO3. In both cases, oxidizing agents (H 2 O 2, Fe (NO 3) 3, Al (NO 3) 3 ...) may be present to facilitate extraction. Once the metals in solution they can be isolated by selective precipitation (at different pH and / or with agents different) and / or by extraction agents (oximes, beta-diketone ...).
Preferably, the metal extraction step according to the invention comprises leaching with at least one acidic and / or basic solution.

Preparation of catalytic solution (s) Metals recovered after the extraction stage are generally under form of salt or oxide. The preparation of catalytic solutions for produce the organic or aqueous solutions is known to those skilled in the art and has been described in the hydroconversion part. Preparation of solutions catalytic particularly concerns molybdenum and nickel metals, vanadium being generally valued as vanadium pentoxide, or in combination with the iron, for the production of ferrovanadium, outside the process.
The recovered metal recovery rate as a catalyst for the hydroconversion process in slurry or for vanadium is at least 50% wt, of preferably at least 65% by weight and more generally 70% by weight.

19 Valorization of synthesis gas The synthesis gas produced during the gasification is composed mostly carbon monoxide and hydrogen. It can be valued under form of electricity and / or in the form of hydrogen consumed preferably at Classes hydroconversion reactions and / or final hydrotreatment steps and or hydrocracking.

In the case of a valuation in the form of electricity, the synthesis gas is preferably first subjected to a washing treatment to remove mainly acid gases. The synthesis gas is then directed to gas engines or gas turbines for generating electricity.

In the case of a recovery in the form of hydrogen, the synthesis gas is preferably subjected to an impurity removal treatment, followed by conversion of gas to water and then a CO2 absorption treatment and then a hydrogen purification. Thus, the synthesis gas is washed in a unit elimination of impurities (in particular of acid gases), then introduced into a gas-to-water conversion unit (also called "water gas shift" or WGS
according to Anglo-Saxon term) to increase the hydrogen content according to the reaction (CO + H2O - CO2 + H2). The effluent is then sent to an absorption unit to remove the CO2. An absorber is generally used which uses solvents such as monoethanolamine (MEA), dimethylethanolamine (DMEA), potassium carbonate (K2CO3) or methanol. The effluent depleted in CO2 is sent to a hydrogen purification unit that is typically a unit of adsorption with regeneration by pressure variation of the adsorbent (also called "pressure swing adsorption" or "PSA" according to the English terminology Saxon) or a hydrogen membrane. The hydrogen thus produced is preferably less partially recycled in the hydroconversion stage and / or in the stages hydrotreatment and / or hydrocracking.

Synthesis gas can also be recycled directly without purification and without enrichment of hydrogen, in the unit hydroconversion and / or in the hydrotreating and / or hydrocracking units.
Some of the synthesis gas can be recovered in the form of electricity 5 while the other part of the synthesis gas can be recovered in the form of hydrogen. Preferably, the proportion of synthesis gas directed to step of hydrogen production or towards the stage of electricity production is adjusted in depending on the amount of hydrogen required by the hydroconversion step in slurry and / or by the hydrotreatment and / or hydrocracking steps.
Synthetic gas can also be upgraded as a feedstock for production of fuels and / or chemicals via the Fischer-Tropsch.

Description of figures Figure 1 shows a process for hydroconversion of heavy loads integrated with slurry technology without metal recovery (no according to the invention).
FIG. 2 describes a preferred embodiment of the invention allowing recovery metals by integrating a gasification step according to the invention. This figure

20 also describes the stages of recovery of the synthesis gas. We describe essentially the installation and the method according to the invention. We do not will not resume operating conditions described above.
In FIG. 1 describing the prior art, the load 1 feeds the section of catalytic hydroconversion in slurry A. This section of hydroconversion catalytic slurry consists of a preheating furnace for the charge 1 and hydrogen 2 and a reaction section consisting of one or more reactors arranged in series and / or in parallel, according to the required capacity. We inject also catalyst 4 or its precursor, as well as the optional additive 3. The catalyst 4 is kept in suspension in the reactor, flows from the bottom to the top of the reactor

21 with the load, and is evacuated with the effluent. The effluent 5 from hydroconversion is directed to a high pressure and high separation section temperature (HPHT) B which separates a fraction converted into the gaseous state 6, called light fraction, and a residual unconverted liquid / solid fraction.
fraction light 6 can be directed to a hydrotreatment section and / or hydrocracking C. An outer cut 7 generally derived from another process existing in the refinery or possibly out of the refinery can be brought before hydrotreatment and / or hydrocracking. The residual fraction not converted containing the catalyst and a fraction of solid particles used as prospective additive and / or formed during the reaction is directed to a step of fractionation D. Fractionation step D is preferably a distillation under vacuum to concentrate at the bottom of the column the vacuum residue 10 rich metals and to recover at the top of the column one or more effluents.
this scheme of valorization of a heavy load by a process of hydroconversion in traditionally used slurry, the metal-rich vacuum residue is valued as a very high viscosity fuel or as a solid fuel after pelletisation, for example to produce heat and electricity on site or outside or as fuel in cement works. Metals are not, a priori, not recovered. The effluent (s) 9 is / are usually directed via the line 31 for a small part to the hydroconversion unit in slurry A where they can be directly recycled in the reaction zone or else it (s) can (wind) be used for the preparation of catalytic precursors before injection into the charge 1 and for another part to the hydrotreatment unit and / or hydrocracking C via the line 30 in mixture with the effluents 6 and / or 7 in of the equal or different proportions depending on the quality of the products obtained.

In Figure 2, the steps (and reference signs) of hydroconversion, HPHT separation, hydrotreatment and / or hydrocracking and step optional of vacuum distillation are identical to FIG. 1. The vacuum residue 10 taken in Vacuum distillation foot D is directed to a gasification step E
for

22 concentrate the metals in the mineral phase 12. The gasification of the effluent 10 also produces a gaseous effluent 11. The product 12 from the gasification E is a mineral phase containing in totality, or almost all, the elements metal contained in the effluent 10, in the form of ash. A part of the effluent 12 can be recycled directly 32 to the hydroconversion stage in slurry A. The product 12 described above is sent all or in part to a step of metals F in which the metals are separated from each other.
other in one or more sub-stage (s). In the case where the catalyst is based on NiMo and the feedstock contains V, the effluent 13 from the extraction F comprises essentially molybdenum in the form of salt or oxide. This effluent 13 is then directed to a preparation step G of an organic solution or aqueous based on molybdenum 16 identical to catalyst 4 or its recycled precursor in part or all in the hydroconversion step in slurry A via the line 33.
The effluent 14 from extraction F comprises nickel in salt form or oxide.
This effluent 14 is then directed to a preparation step H of a solution organic or aqueous nickel-based 17 identical to the catalyst 4 or its precursor recycled in part or in full in the hydroconversion step in slurry A via line 34. The effluent 15 from extraction F comprises vanadium under form of salt or oxide. This effluent can be valorized for example as vanadium pentoxide, or in combination with iron, for the production of ferrovanadium.
The effluent 11 from the gasification E is the synthesis gas. After different stages, this gaseous effluent can be recovered as hydrogen 23 for catalytic hydroconversion stage in slurry A. The synthesis gas is so prewashed in an elimination unit I impurities 25 (in particular gas acids as CO2 and H2S), then introduced via line 18 into a unit of conversion water gas J ("water gas shift") to increase the hydrogen content.
The effluent 20 is then sent to an absorption unit L to remove the C02 26.
The effluent 22 depleted of CO2 is sent to a purification step M

23 hydrogen, for example of the PSA type. Hydrogen 23 is recycled in the stage of hydroconversion in slurry A (and / or in the stages hydrocracking / hydrotreating, not shown), the impurities are evacuated by line 24.
The purified syngas mixture can also be valued as electricity 21 after treatment in an impurity removal step I and a step of electricity generation by turbine K via line 19. The proportion of gases of synthesis 18 directed to the hydrogen production steps J, L and M or towards the K electricity production steps can be adjusted according to the quantity of hydrogen required by the catalytic hydroconversion step in slurry A
and / or by the hydrocracking or hydrotreating step C.

Example 1 (Comparative): Hydroconversion process in non-upgraded slurry of the metals This example illustrates the industrial valorization of a heavy load by a slurry hydroconversion process using a finely divided catalyst dispersed nickel and molybdenum type with a concentration of 100 ppm and 400 ppm under hydrogen pressure (Figure 1). In this example 1, no valuation of the metals is envisaged at the end of the charge conversion step.
Considering that the industrial unit has a capacity of 75,000 barrels per day and a utilization rate of 90% per year, the amount of nickel and molybdenum consumed per year is therefore 0.4 and 1.6 kT / year respectively. Considering a cost of nickel at $ 25k / t and molybdenum at $ 60k / t, representative of average costs observed in the metals market over the last 5 years, the cost operative is $ 110 million a year.

24 Example 2 (According to the Invention) Hydroconversion Process with Valuation of the metals and syngas in the form of electricity In Example 2, the process sequences presented in Figure 2 are considered. The residual fraction resulting from the vacuum distillation is submitted gasification to recover ashes containing metals and synthesis gas. The metals are extracted and a catalytic solution is prepared and recycled in the hydroconversion process.
The method according to the invention allows a valuation of a large part of the metals, nickel and molybdenum, present in the unconverted fraction of effluent derived from the hydroconversion into slurry. The metal recovery rate valued as a catalyst for the slurry hydroconversion process is at least 50%
wt, preferably at least 65 wt%, and more generally 70 wt%. This recycling metals can reduce the operating cost of 110 million dollars by year at $ 33 million a year. The savings thus achieved is 77 millions of dollar allows in the first place to pay the investments additional necessary for the recovery of these metals. On the other hand, present vanadium in the heavy load at 400 ppm wt can be valued as ferrovanadium. In whereas a recovery rate of 65% wt. to 70% wt., the sale of vanadium estimated at an average observed cost of $ 40K / t in the metals over the last 5 years, at $ 12 million a year. This sale will also allow in a first time to pay the investments necessary for the recovery of these metals.
Recovery of these metals in the unconverted residual fraction reduces the overall amount of nickel and molybdenum used and reduce thus the environmental impact of the hydroconversion process in slurry. In considering a recovery of 70% by weight of metals present at the entrance of the reaction zone, the amount of additional catalyst is reduced to 0.1 t / year for the nickel and 0.5 Van for molybdenum versus 0.4 t / year and 1.6 t / year without recycle.

On the other hand the valorization of synthesis gas for the production power according to the methods known to those skilled in the art generates a power of about 600 MW.

Example 3 (according to the invention) Hydroconversion process and recovery of metals and synthesis gas in the form of hydrogen and electricity Example 2 including the recovery of metals Mo, Ni and V is repeated. The synthesis gas produced in this example is partly used for the production 10 of hydrogen required in the hydroconversion unit. Surplus gas synthesis is valued for the production of electricity.
Thus, optimization of the synthesis gas valorization chain allows to adjust the amount of hydrogen to produce to compensate for the hydrogen consumption of the catalytic hydroconversion unit in slurry and 15 use the surplus synthesis gas for the production of electricity.
A review material made on the data presented in Example 1 indicates that the 10 t / h of hydrogen consumed (approximately 2% by weight) by the unit hydroconversion allow to produce in addition 300 MW of electricity according to the known methods of the skilled person.

Claims (14)

1. Hydroconversion process for heavy hydrocarbon feedstocks containing metals comprising:
a) a step of hydroconversion of the feedstock in at least one reactor containing a slurry catalyst based on at least one metal, and possibly containing a solid additive, b) a step of separation of the hydroconversion effluent without decompression into a so-called light fraction containing the compounds boiling at not more than 500 ° C and in a residual fraction, b ') optionally a fractionation step comprising a vacuum separation of said residual fraction as obtained at step b), and there is obtained a vacuum residue concentrated in metals, c) a gasification step in which only said residual fraction as obtained in step b) or only said vacuum residue as obtained in step b ') is subjected to a gasification which makes it possible to obtain concentrated ash of metals and synthesis gas, d) a step of extracting the metals from the ashes obtained at the step of gasification, e) a step of preparation of (s) metallic solution (s) containing at least minus the catalyst metal, solution (s) that is / are recycled to the hydroconversion stage. 2. Method according to the preceding claim wherein the step of gasification is carried out at a temperature between 500 ° C and 2000 ° C, preferably between 800 ° C and 1500 ° C, and at a pressure of between 2.5 and 10 MPa, from preferably between 4 and 7 MPa. 3. Method according to one of the preceding claims wherein said fraction said light resulting from the step of separation without decompression is subject to the at least one hydrotreatment and / or hydrocracking step. 4. Method according to one of the preceding claims wherein the fraction light is submitted directly, without additional separation steps and without decompression at least one hydrotreatment stage and / or hydrocracking. 5. Method according to one of the preceding claims wherein the gas of synthesis from the gasification stage is directed to gas engines or gas turbines to produce electricity. 6. Process according to claims 1 to 4, in which the synthesis gas resulting from of the gasification stage is recovered in the form of hydrogen by subjecting it at a treatment of elimination of the impurities, then a gas conversion with the water, then a CO2 absorption treatment, then a purification of hydrogen. 7. Method according to the preceding claim wherein the hydrogen from the gas synthesis is at least partially recycled in the hydroconversion stage and or in the hydrocracking and / or hydrotreating steps. 8. Process according to claims 5 to 7 wherein the proportion of the gas of synthesis directed to the hydrogen production step or to the step of electricity production is adjusted according to the amount of hydrogen Requirements by the hydroconversion step in slurry and / or by the hydrocracking steps and / or hydrotreatment. 9. Method according to one of the preceding claims wherein said fraction residual from the no-decompression separation step is split by vacuum distillation in at least one vacuum distillate fraction and a fraction vacuum residue, at least a part and preferably all of said fraction vacuum residue being sent to the gasification stage, at least a part and preferably all of said vacuum distillate fraction being subjected to to at least one hydrotreatment and / or hydrocracking step. 10. Method according to one of the preceding claims wherein the load heavy hydrocarbon contains at least 50% wt of product distilling above 250 ° C and at least 25% wt. distilling above 350 ° C, and contains at less than 50 ppm by weight of metals, not less than 0.5% by weight of sulfur and not less than 1% by weight asphaltenes (asphaltenes with heptane). 11. Method according to one of the preceding claims wherein the load heavy hydrocarbon is selected from petroleum residues, oils gross, headless crude oils, deasphalted oils, asphalts or pitches deasphalting, derivatives of oil conversion processes, sands bituminous materials or their derivatives, oil shales or their derivatives, coal or their derivatives, organic waste or their derivatives, residues biomass or their derivatives, or mixtures of such fillers. 12. Method according to one of the preceding claims wherein the step hydroconversion operates at a pressure of 2 to 35 MPa, preferably 10 to 25 MPa, a hydrogen partial pressure of 2 to 35 MPa, preferably 10 at 25 MPa, a temperature of between 300 ° C and 500 ° C, preference of 420 ° C to 480 ° C and a contact time of 0.1 h to 10 h, preferably from 0.5h to 5h h. 13.Procédé according to one of the preceding claims wherein the catalyst in slurry is a sulphurized catalyst containing at least one element selected from the group formed by Mo, Fe, Ni, W, Co, V, Ru. 14. Method according to one of the preceding claims wherein the additive is selected from the group consisting of mineral oxides, used catalysts supported by at least one Group VIII element and / or at least one group VIB element, low carbon solids hydrogen or mixtures of such additives, said additive having a size of particle less than 1 mm.