HK1156654A - Additive for hydroconversion process and method for making and using same - Google Patents

Abstract

An additive for hydroconversion processes includes a solid organic material having a particle size of between about 0.1 and about 2,000 [mu]m, a bulk density of between about 500 and about 2,000 kg/m3, a skeletal density of between about 1,000 and about 2,000 kg/m3 and a humidity of between 0 and about 5 wt%. Methods for preparation and use of the additive are also provided. By the use of the additive of the present invention, the hydroconversion process can be performed

Description

Additive for hydroconversion processes and methods of making and using same

Technical Field

The present invention relates to additives used in catalytic processes for hydroconversion.

Background

Hydroconversion processes are generally known, and one example of such a process is disclosed in co-pending co-owned U.S. patent application 12/113,305 filed on 1.5.2008. In the process disclosed in this patent document, the catalyst is provided in the form of an aqueous solution or other solution, and one or more emulsions of the catalyst in oil (aqueous solution) are prepared beforehand, the emulsions are then mixed with the feedstock, and the mixture is exposed to hydroconversion conditions.

The disclosed method is generally effective in the desired conversion process. It should be noted, however, that the catalysts used may be expensive. It would be advantageous to find a way to recycle the catalyst.

In addition, foaming and the like that occurs in hydroconversion reactors can lead to a number of adverse consequences and it is therefore desirable to provide solutions to these problems.

Generally, hydroconversion processes for heavy residues with higher contents of metals, sulphur and asphaltenes do not achieve high conversions (over 80 wt.%) without recycle and without low catalyst concentrations.

Known additives that attempt to control foaming in the reactor can be expensive and can chemically degrade in the reaction zone, potentially leading to more difficult byproduct handling and the like.

Disclosure of Invention

In accordance with the present invention, an additive for use in a catalytic hydroconversion process is provided, wherein the additive scavenges catalyst metals as well as metals in the feedstock and concentrates them into a heavies stream that may be treated to recover metals, or unconverted residual material that may exit from the process reactor. The stream may be processed into a sheet material. These platelets can then be further processed to recover the catalyst metals as well as other metals in the platelets that originate from the feedstock. This advantageously allows the metal to be reused in the process or otherwise advantageously treated.

The hydroconversion process comprises the steps of: feeding a heavy feedstock containing vanadium and/or nickel, a catalyst emulsion containing at least one group 8-10 metal and at least one group 6 metal, hydrogen, and an organic additive to a hydroconversion zone under hydroconversion conditions to produce a higher hydrocarbon product and a solid carbonaceous material containing the group 8-10 metal, the group 6 metal, and the vanadium.

In addition, additives may be used to control and improve the overall fluid dynamics within the reactor. This is due to the defoaming effect created by the use of additives within the reactor, and this foam control can also provide better temperature control in this process.

The additive is preferably an organic additive, and it may preferably be selected from the group consisting of coke, carbon black, activated coke, soot (soot), and combinations thereof. Preferred sources of coke include (but are not limited to): coke derived from hard coal, and coke produced by hydrogenation or decarburization of straight run residual oil (virgin residue) and the like.

The additive can be advantageously used in a process for the liquid phase hydroconversion of a feedstock such as a heavy fraction with an initial boiling point of about 500 ℃, a typical example of which is vacuum residue.

In the hydroconversion process, the feedstock is contacted with hydrogen, one or more ultra-finely divided catalysts, a sulfur reagent (sulfur agent), and an organic additive in a reaction zone. A preferred process can be carried out in an upflow co-current three-phase bubble column reactor (upflow co-currentthree-phase bubble column reactor), although the additives of the present invention are suitable for other applications. In this apparatus, the organic additive may be introduced into the process in an amount of about 0.5% to about 5.0% by weight of the feedstock, and preferably has a particle size of about 0.1 μm to about 2,000 μm.

The process described herein is carried out using the organic additive of the present invention which scavenges catalyst metals in the process (e.g., which includes nickel and molybdenum catalyst metals) and also scavenges metals in the feedstock (vanadium being a typical example). Thus, the products of the process include higher hydrocarbon products as well as unconverted residuum containing metals. These unconverted residues can be processed into solids (e.g., into flake materials) containing heavy hydrocarbons, organic additives, and concentrated catalyst and feed metals. These flakes are a valuable source of metals for recovery as described above.

Drawings

Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings, in which:

FIG. 1 schematically illustrates the method of the present invention; and is

FIG. 2 schematically illustrates a process for preparing the organic additive of the present invention; and is

FIG. 3 schematically illustrates the benefits of using the additives of the present invention;

FIG. 4 schematically shows the internal temperature profile of the reactor when using the additive according to the invention;

FIG. 5 schematically shows a pressure differential curve associated with hydrodynamic control when using the additive of the present invention.

FIG. 6 schematically shows the pressure difference curve associated with the phase distribution when using the additive according to the invention.

Detailed Description

The present invention relates to an additive for use in a process for the catalytic hydroconversion of heavy feedstocks. The additive can be used as a scavenger of catalyst metals and feedstock metals and concentrates these metals into a residual phase for subsequent extraction. In addition, the additive acts as a foam control agent and can be used to improve the overall process conditions.

A brief description of the hydroconversion process is given here with the aid of unit 200 in fig. 1. In the hydroconversion process, a vanadium and/or nickel containing feedstock is contacted with a catalyst consisting of one, two or more emulsions (water-in-oil) containing at least one group 8-10 metal and at least one group 6 metal under hydroconversion conditions (which refer to high hydrogen partial pressure and high temperature) and in the presence of an additive, one purpose of which is to concentrate the metals on its surface, thereby making the metal recovery process easier.

Conversion of the feedstock occurs in unit 200 and the effluent from unit 200 comprises a product stream comprising a higher hydrocarbon phase (which may be separated into liquid and vapor phases for further processing and/or fed to a gas recovery unit as needed), an additive-containing resid, which may be solidified or separated into a solids-rich stream for feeding to a metal recovery unit, and an unconverted vacuum resid, which may be recovered.

The feedstock for the hydroconversion process may be any heavy hydrocarbon, and one particularly good feedstock is vacuum residue, the properties of which may be shown in table 1 below:

properties of	Unit of
			Distilled LV%

ASTM D1160
			IBP	°F	600-900
Viscosity at 210 ℃ F	cst	＜80000
			API	-	1-7
Sulfur	By weight%	3-8
			Nitrogen is present in	By weight%	＜2
Asphaltenes	By weight%	15-30
			Tang's carbon residue	By weight%	15-30
Metal (V + Ni)	Weight ppm of	200-2000

Alternative feeds include (but are not limited to): a feedstock derived from tar sands and/or bitumen.

With respect to Vacuum Residue (VR) feedstocks, they may be obtained, for example, from a Vacuum Distillation Unit (VDU), or from any other suitable source. Other similar feeds, especially those that can be upgraded by hydroconversion and that contain feedstock metals such as vanadium and/or nickel, can be used.

As indicated above, the additive is preferably an organic additive such as coke, carbon black, activated coke, soot, and combinations thereof. These materials are available from any of a number of sources and are readily available at extremely low cost. The particle size of the organic additive is preferably from about 0.1 μm to about 2,000. mu.m.

The catalyst used is preferably a metal phase as disclosed in co-pending U.S. patent application US 12/113,305. Advantageously, the metallic phase contains one metal from group 8, 9 or 10 of the periodic table of the elements and another metal from group 6 of the periodic table of the elements. In earlier versions of the periodic table, these metals may also be referred to as group VIA metals and group VIIIA metals, or as group VIB metals and group VIIIB metals.

Advantageously, the metals of each type are prepared as separate emulsions and these emulsions are used as separate feeds or are fed with the feedstock into a reaction zone where the high temperature causes the emulsions to decompose and form a catalyst phase which is dispersed throughout the feedstock as desired. Although these metals may be provided in separate emulsions or in different emulsions, both of which are within the scope of the present invention, it is particularly preferred to provide these metals in separate or different emulsions.

Advantageously, the group 8-10 metal may be nickel, cobalt, iron, and combinations thereof, while the group 6 metal may advantageously be molybdenum, tungsten, and combinations thereof. A particularly preferred combination of these metals is nickel and molybdenum.

One embodiment of a suitable hydroconversion process is disclosed in a concurrently filed U.S. patent application having attorney docket number 09-289-2, the contents of which are incorporated herein by reference. In this process, more than the two listed metals may be used. For example, the catalyst phase of the emulsion may contain two or more metals selected from group 8, group 9, or group 10 metals.

The catalyst emulsion and heavy feedstock are preferably fed to the reactor in an amount sufficient to provide a weight ratio of catalyst metal to heavy feedstock of from about 50 ppm to about 1,000 ppm by weight.

Hydrogen from any suitable source may be fed to the process.

The reaction conditions can be listed in table 2 below:

TABLE 2

Reactor pressure	130-210 bar
		Reactor temperature	430℃-470℃
Conversion rate	Greater than or equal to 80 percent

In accordance with the present invention, unit 200 receives Vacuum Residuum (VR) in a slurry feed process. Additive particles can be added to VR and stirred, wherein the concentration of the additive particles is between 0.5% and 5% by weight of the feedstock. Preferably, the agitated slurry is pressurised to a high pressure, preferably above 200 bar, by a high pressure slurry pump. The slurry is additionally heated to an elevated temperature, preferably to above 400 ℃. Upstream, the catalyst emulsion, sulfur reagent, and hydrogen are injected into the slurry feed. After the slurry is heated by the slurry furnace, more hydrogen can be added as needed.

The total mixture of VR, organic additives, catalyst emulsion, sulfur reagent and hydrogen is introduced into the reactor and undergoes deep hydroconversion to yield the desired light materials. In the high pressure high temperature separator, most of the hydroconverted material is separated into vapors and, if desired, the vapors can be sent to subsequent units for hydrotreating and further hydrocracking.

At the same time, the separator bottoms in the form of a heavy slurry liquid can be sent to a vacuum distillation unit to recover any remaining light materials under vacuum, and the final remaining bottoms (which is unconverted bottoms) can be sent to a different type of process where it can be converted to solid materials.

Typical yields obtained from specific starting materials are listed in table 3 below:

TABLE 3

Raw materials	Weight (D)
		Vacuum residuum catalyst emulsion + coke additive flushing oil (HGO) hydrogen	1008-102.6-3.61.8-3
Total feed	112.4-116.6
		Product of

C1-C4H2OH2S+NH3Naphtha middle distillate VGO	7-91-23.4-4.016-2028-3440-45
		Total product (without tablets)	95.4-114
Unconverted residues or flakes	17-9

One of the units that can convert the bottom residue into a solid material may be a flaker unit. The resulting sheet may advantageously have the following composition:

TABLE 4

These flakes, which contain the remaining organic additives and the catalyst metals and metals in the feedstock that are scavenged by the additives according to the process of the present invention, can themselves be provided to the consumer as a source of useful metals, or the flakes can be used as fuel, or the flakes can be treated and the metals extracted to reuse the metals as process catalysts, etc.

Of course, the metals to be recovered include not only the catalyst metals used in the process, but also certain metals (e.g. vanadium) inherent in the feedstock.

As noted above, organic additives are an important aspect of the hydroconversion process disclosed in the concurrently filed U.S. patent application having attorney docket number 09-289-2. Such additives are available from a wide variety of sources, such as coke from a variety of sources including hard coal, carbon black, activated coke, soot from gasifiers, coke produced by hydrogenation or decarbonation reactions, straight run slag oil, and the like. It should be recognized that due to the existence of such a wide variety of sources, additives can be prepared from readily available and sustainable raw materials. The following discussion of the process for preparing the additive from this feedstock, the end result for use as the additive of the present invention is: a particle size of about 0.1 μm to about 2,000 μm and a bulk density of about 500kg/m³To about 2,000kg/m³Skeleton density of about 1,000kg/m³To about 2,000kg/m³And a humidity of 0 to about 5 wt%. More preferably, the particle size is from about 20 μm to about 1,000 μm.

Referring to fig. 2, a process for preparing the additive of the present invention is shown. The starting materials may generally be as described above, and may be, for example: the bulk density was about 500kg/m³To about 2,000kg/m³A moisture content of about 5 wt.% to about 20 wt.%, a hardness of about 20HGI to about 100HGI, and a maximum particle size of about 5cm to about 10 cm. The feedstock is preferably first fed to a primary milling station 61 where the feedstock is milled and preferably reduced in particle size by an order of magnitude of about 10. These pre-milled particles typically have a particle size of about 20mm to about 20 μm and are fed into the drying zone 62. In the drying zone, the particles are exposed to a stream of air, which preferably reduces the humidity of the particles to less than about 5% by weight. The resulting dried granules are subsequently fedA primary classification zone 63 to classify the particles into a first group that meets a desired particle size criteria (e.g., less than or equal to about 1000um) and a second group that does not meet the criteria. As shown, a first group of materials having an acceptable particle size is fed to the secondary classification zone 66 while a second group is still being subjected to additional milling, and preferably a second group of materials is fed to the second milling station 64 for further milling or other processing to reduce the particle size thereof. The further milled product is fed into a further classifying zone 65, in which classifying zone 65 the particles which now meet the criteria are returned and mixed with the particles which initially meet the criteria, and the particles which still do not meet the criteria are recycled to the second milling station 64 as required.

Some granular material that does not meet the required criteria can be found from the secondary classification station 66, separated and fed to an aggregation station 70, where the granules are granulated by means of a mixture of chemicals to obtain granules with a larger diameter in the aggregation station 70. At the same time, the now-met-standard particles are fed in a classification station 66 to a heat treatment station (67), where the particles are exposed to a stream of heated air, thereby raising their temperature to about 300 ℃ to about 1,000 ℃, under which conditions a process of pore generation occurs. The heated granules are subsequently fed to a cooling station (68) for cooling them, in which case the granules are cooled by means of a water-cooled air flow. The temperature of the resulting particles should be below about 80 ℃.

The heated and cooled particles can now be fed into a further classification zone 69 to again separate out any particles that do not meet the desired size criteria. Such off-spec particles can be fed to the agglomeration zone 70 and on-spec particles can be used as the additive of the present invention.

Desirably, the organic additive may be used in an amount of from about 0.5% to about 5% by weight of the feedstock, at which level the organic additive is capable of both scavenging catalyst metals and feedstock metals and controlling foaming within the reactor, thereby providing more stable and effective conditions in the reactor.

In the reactor, when the additive of the invention is used, the reaction may advantageously be carried out at a gas velocity of greater than or equal to about 4 cm/sec.

These favorable process conditions can result in an asphaltene conversion of at least about 75 wt% and a Down's carbon residue conversion of at least about 70 wt% in hydroconversion, which is difficult or impossible to achieve using conventional techniques.

Referring now to fig. 3, two diagrams of a reactor for carrying out the hydroconversion process are shown. In the left-hand diagram such a reactor is shown, in which the hydroconversion process carried out does not use any additive according to the invention. As shown in the figure, the reaction is a two-phase reaction having a lower portion that is liquid only and an upper portion comprised of foam and gas that is about 60% to 70% by volume. The right-hand diagram in fig. 3 shows a similar reactor when using the additive according to the invention and it shows that the foam is now better controlled, wherein 70 to 80% by volume of the reactor is filled with liquid and solid phases and the upper part of the reactor (20 to 30% by volume) contains gas.

The collapse of the bubbles reduces the foam and provides better contact between the gas and the liquid, thus reducing the problem of diffusion. These conditions, obtained by using the additives of the present invention, allow more efficient conversion, better temperature control and reduction of undesirable hot spots.

During the hydroconversion reaction in unit 200, the heaviest components of the feedstock tend to be insoluble in the light fraction produced by the reaction itself. The high temperature causes the aromatic clusters to polymerize and condense, and when the difference in the solubility crude parameters between these two virtual components (asphaltenes and maltenes) reaches a critical value, the system produces precipitates, which result in the precipitation of asphaltenes and the formation of coke. The loss of residue stability at very high conversions can be controlled by coke and asphaltene scavengers with organic additives. Thus, the highest conversion was obtained. The effect of this scavenger is shown in example 1.

Example 1 Coke/asphaltene scavenger Capacity

This example illustrates the capture capacity of carbonaceous additives for asphaltenes, coke, and/or condensed cyclic aromatic compounds.

In this example, Petrozuata petroleum coke was used to produce a carbonaceous additive, the coke being obtained from a delayed coking process. The coke is heat treated by a moderate combustion process (pore formation) with air to create a degree of porosity and surface area. After the scheme shown in fig. 2 was performed, the particle size was adjusted to 200 to 900 μm, thereby producing a carbonaceous additive, and the following experiment was performed.

Table 5 shows the composition of Petrozuata coke.

TABLE 5

Element(s)	By weight%
		Carbon (C)	86.6-88.9
Hydrogen	4.2-4.7
		Sulfur	4.4-4.8
Vanadium oxide	0.20-0.22
		Nickel (II)	0.30-0.54
Iron	0.106
		Ash content	0.21-0.52
Volatile substance	9.9-12.0

Mixing 10g Merey/Mesa Vacuum Residue (VR) with 100ml toluene; the mixture was stirred to dissolve the VR. 120ml of n-heptane were subsequently added and stirred for 10 minutes. Then, a carbonaceous additive was added in an amount of 1.5 wt% of VR. Followed by stirring for 24 hours. The sample was finally filtered, washed with n-heptane and the carbonaceous additive was oven dried for 4 hours. Subsequently, the solid obtained after cooling was weighed. The amount of asphaltenes retained per gram of additive used is calculated from the initial weight of additive used.

Table 6 shows the pore size, surface area and asphaltene removal capacity of the carbonaceous additives.

TABLE 6

Example 2 Metal scavenger

This example shows the metal scavenging ability of the carbonaceous additive.

In this example, a flake material containing unconverted vacuum residue and residual organic additives was used to quantify the metal content and metal mass balance (metal mass balance) of the hydroconversion process.

In this example, toluene was used as a solvent, and the residual organic additive was separated out by a desolidification (desolidification) process. After performing the protocol shown in fig. 1, sheets were produced and the following experiment was performed.

50.00g of the flakes were dissolved in 350ml of hot toluene and the mixture was centrifuged at 1500rpm for 20 minutes in order to separate the unconverted additive residue. The solid is transferred and washed by soxhlet extraction with toluene (a continuous extraction method allowing a continuous flow of fresh solvent through the compound to be extracted). Subsequently, the solid was dried in a vacuum oven at 130 ℃ for 2 hours. The unconverted vacuum residue is recovered by evaporation of toluene. In this example, the amount of dry solids was 4.9 g.

Finally, the metal content of the solid and of the unconverted vacuum residue was determined by Inductively Coupled Plasma (ICP) -emission spectroscopy.

Table 7 shows the Mo, Ni and V contents in the flakes, additives and unconverted vacuum residue.

TABLE 7

^(a)Calculated metal in the dried solid ═ dried solid analysis ═ measured dried solid (g)/measured flakes (g).^(b)Some yields exceed 100% -are within experimental error

Example 3 fluid dynamics control and temperature control

After performing the protocol shown in fig. 1, the following experiment was performed.

The test was performed using a Vacuum Residue (VR) sample of canadian petroleum (manufactured by Athabasca Crude).

This VR was fed to a slurry bubble column reactor with a total capacity of 10BPD without any internal equipment, with a temperature controller based on a preheater system and cooling gas injector.

For this test, at 0.42T/m³h operating the reactor. Three vertical slurry reactors in series were used in this test. These conditions were maintained for 11 days.

These conditions are summarized in Table 8.

In this test, the internal temperature of the first reactor was measured at 12 different heights, resulting in the curve shown in fig. 4.

The effect of the additive on temperature can be observed in fig. 4. At the start of the test, the curve varied in the range 2 ℃ to 4 ℃ at intervals of 10 hours, and it showed unstable behavior for the same height. When the additive in the reactor reaches a stable concentration, the curve changes in a range of at most less than 2 ℃, and the behavior is extremely stable.

The pressure difference of the three reactors was measured to obtain the graph shown in fig. 5.

The curve shows that the three reactors have a stable solids concentration near the 100 hour point of the feed, which is very noticeable because the pressure difference shows an almost linear behavior since the first hour. This is in line with the temperature profile in which there is almost a stable behaviour since the same first hour.

This indicates that the additive not only provides hydrodynamic control, but also acts as a temperature control.

Example 4 foam control and phase distribution

After performing the protocol shown in fig. 1, the following experiment was performed.

The example was carried out using Vacuum Residuum (VR) of Venezuela petroleum (Merey/Mesa).

This VR was fed to a slurry bubble column reactor with a total capacity of 10BPD without internal equipment with a temperature controller based on a preheater system and cooling gas injector.

For this test, three vertical slurry reactors in series were used at 0.4T/m³h (space velocity) the reactor is operated. The apparatus was operated continuously for 21 days.

These conditions are summarized in Table 9.

TABLE 9

In this test, the pressure differences in the three reactors were measured, resulting in the curve shown in FIG. 6.

As shown in this graph, the time to fill each reactor was about 15 hours, which is given by the time when the differential pressure measurements of the reactors were more stable. It can be seen from this curve that the first reactor reached a stable measurement at about 15 hours, that after the first reactor was filled, the second reactor continued for another 15 hours to reach a stable measurement, and that the third reactor exhibited the same behavior.

When the reactor was filled, the time taken to reach stabilization was about 75 hours.

It can be seen that the amount of liquid increases due to the concentration of solids in the reactor, with a consequent increase in the pressure difference, thus reducing the foaming.

By means of the pressure difference, the phase distribution of the first reactor can be calculated. The difference was calculated under two conditions: the results are summarized in Table 10, as well as the average values over the course of the test, i.e. after a stabilization time (75 hours).

Watch 10

As shown in table 10, the liquid holdup in the reactor using the additive was increased by a factor of 2, which is related to a higher conversion and thus an increase in the reaction volume.

The above examples demonstrate that excellent results can be obtained by using the additives in the hydroconversion process of the present invention.

The present disclosure is provided by a detailed description of the preferred embodiments. It should also be appreciated that this particular embodiment is provided for purposes of example only, and in no event should the embodiment be construed as limiting the scope of the invention, which is instead defined solely by the appended claims.

Claims (30)

1. An additive for use in a hydroconversion process comprising a solid organic material having a particle size in the range of from about 0.1 μm to about 2,000 μm and a bulk density of about 500kg/m³To about 2,000kg/m³Skeleton density of about 1,000kg/m³To about 2,000kg/m³And a moisture content of 0 to about 5 wt%.

2. The additive of claim 1, wherein the particle size is from about 20 μm to about 1,000 μm.

3. A method of making an additive for a hydroconversion process, comprising the steps of:

feeding a feedstock carbonaceous material to a primary grinding zone to produce a ground material having a particle size reduced relative to the particle size of the feedstock carbonaceous material;

drying the milled material to produce a dried milled material having a moisture content of less than about 5% by weight;

feeding the dried milled material into a classification zone to separate particles meeting a desired particle size criterion from particles not meeting the desired particle size criterion;

heating the particles meeting the desired particle size criteria to a temperature of from about 300 ℃ to about 1,000 ℃; and

cooling the particles exiting the heating step to a temperature of less than about 80 ℃ to provide the additive.

4. The method of claim 3, further comprising the steps of:

feeding particles that do not meet the required particle size criteria to a further milling step to provide a further milled material;

feeding the further milled material into a further classification zone to separate particles that meet the desired size criterion from particles that still do not meet the desired size criterion; and

recycling said particles that still do not meet the desired size criterion into said further classification zone.

5. The method of claim 4, wherein additional particles meeting desired size criteria are added to the particles meeting desired size criteria prior to the heating step.

6. The method of claim 3, wherein the heating step and the cooling step are performed by exposing the particles to a flow of air having a desired temperature.

7. The method of claim 3, wherein particles meeting the desired particle size criteria are fed to a secondary classification zone prior to the heating step, and wherein the secondary classification zone further separates classified particles meeting the desired particle size criteria that are fed to the heating step and particles that do not meet the desired particle size criteria that are fed to an aggregation station.

8. The method of claim 3, further comprising the steps of:

after the cooling step, the additive is fed into a final separation zone to separate additive particles that meet the desired size criteria from additive particles that do not meet the desired size criteria, and

feeding the additive particles that do not meet the desired particle size criteria to an agglomeration station.

9. The method of claim 3, wherein the additive product comprises a solid organic material having a particle size of about 0.1 μm to about 2,000 μm and a bulk density of about 500kg/m³To about 2,000kg/m³Skeleton density of about 1,000kg/m³To about 2,000kg/m³And a moisture content of 0 to about 5 wt%.

10. The method of claim 9, wherein the particle size is from about 20 μ ι η to about 1,000 μ ι η.

11. A hydroconversion process comprising feeding a heavy feedstock comprising at least one feedstock metal selected from vanadium and nickel, a catalyst emulsion comprising at least one group 8-10 metal and at least one group 6 metal, hydrogen and an organic additive under hydroconversion conditions into a hydroconversion zone to produce a higher hydrocarbon product and a solid carbonaceous material comprising the group 8-10 metal, the group 6 metal and the at least one feedstock metal, wherein the organic additiveComprising a solid organic material having a particle size of about 0.1 μm to about 2,000 μm and a bulk density of about 500kg/m³To about 2,000kg/m³Skeleton density of about 1,000kg/m³To about 2,000kg/m³And a moisture content of 0 to about 5 wt%.

12. The method of claim 11, wherein the organic additive is present in an amount of about 0.5% to about 5% by weight of the feedstock.

13. The method of claim 11, wherein the gas velocity of the method is greater than or equal to about 4 cm/sec.

14. The process of claim 11, wherein the conversion of asphaltenes in the hydroconversion is at least about 75 wt% and the conversion of Down's carbon residue is at least about 70 wt%.

15. The method of claim 11, wherein the heavy feedstock is selected from the group consisting of vacuum resids, heavy crudes, extra heavy crudes, and combinations thereof.

16. The process of claim 11, wherein the heavy feedstock is a vacuum residuum.

17. The process of claim 11, wherein the heavy feedstock has an API gravity of from about 1 to about 7.

18. The process of claim 11, wherein the heavy feedstock has a metals content of from about 200 ppm by weight to about 2,000 ppm by weight.

19. The process of claim 11, wherein the metal component of the heavy feedstock comprises vanadium and nickel.

20. The method of claim 11, wherein the catalyst emulsion comprises a first catalyst emulsion comprising a group 8-10 metal, and a second catalyst emulsion comprising a group 6 metal.

21. The method of claim 11, wherein the group 8-10 metal is selected from the group consisting of nickel, cobalt, iron, and combinations thereof.

22. The method of claim 11, wherein the group 6 metal is selected from the group consisting of molybdenum, tungsten, and combinations thereof.

23. The method of claim 11, wherein the group 6 metal is in the form of a group 6 metal sulfide salt.

24. The method of claim 11, wherein the organic additive comprises coke particles.

25. The process of claim 11, wherein the process is conducted in a continuous manner.

26. The process of claim 25, wherein the process is conducted in a single pass with the feedstock.

27. The process of claim 11, wherein the hydroconversion conditions comprise: the reactor pressure is from about 130 bar to about 210 bar and the reactor temperature is from about 430 ℃ to about 470 ℃.

28. The process of claim 11 wherein the catalyst emulsion and the heavy feedstock are fed to the reactor in amounts such that the weight ratio of catalyst metal to heavy feedstock is from about 50 ppm to about 1,000 ppm by weight.

29. The process of claim 11, wherein product yield by weight, excluding the solid carbonaceous material, is greater than the weight of the heavy feedstock.

30. The process of claim 11, wherein the hydroconversion zone comprises an upflow, co-current, three-phase bubble column reactor.