Process for treating halide-containing feedstocks - Patent Application 20070122997

Abstract

1. A method for converting a hydrocarbonaceous feed containing at least 20 ppmw, at least 100 ppmw, or at least 500 ppmw and less than 1000 ppmw, 5000 ppmw, or 10000 ppmw of halides by hydrotreating in the presence of a material catalytically active in hydrotreating and an amount of hydrogen, comprising: the hydrocarbon product stream comprises an amount of ionic halides; the hydrocarbon product stream is combined with a quantity of wash water, the mass ratio of wash water to hydrocarbon product stream being greater than 1:10, greater than 1:5, or greater than 1:2, and less than 1:1, less than 2:1, or less than 10:1; wherein the combined hydrocarbon product stream and wash water are separated into a non-polar stream of hydrocarbon product and a polar stream of wash water containing ionic halides such that 50%, 90%, or 99% to 100% of the ionic halides are transferred from the hydrocarbon product stream to a polar stream of wash water containing ionic halides; An advantage associated with such a process, wherein the polar stream of wash water containing ionic halides is directed to a concentration means to provide a purified water stream and a brine stream, wherein the brine stream is characterized by having an ionic halide concentration that is more than 2 times, more than 5 times, or more than 10 times, and less than 50 times, or less than 100 times, that of the polar stream of wash water containing ionic halides, is the ability to receive a hydrocarbon mixture containing high amounts of halides and purify it into a hydrocarbon product of consistent quality while minimizing water consumption.

Description

[Technical Field]

[0001] FIELD OF THE INVENTION The present invention relates to a method and apparatus for the conversion of hydrocarbonaceous feeds containing halides, and in particular to a method and apparatus for the removal of halides from hydrocarbon streams containing one or more halides. [Background technology]

[0002] Background of the Invention Refining and petrochemical processes involve multiple treatments of hydrocarbon-rich streams to provide products or intermediates in the form of LPG, naphtha, gasoline, diesel, etc. Such treatments include hydrotreating, hydrocracking, steam cracking, fractionation and stripping, as well as intermediate heat exchange and impurity removal.

[0003] Depending on their origin, hydrocarbonaceous feedstocks may contain heteroatoms that are undesirable in downstream processing. The most abundant heteroatoms are sulfur, nitrogen, and, primarily for biogenic feedstocks, oxygen, which can be present at concentrations ranging from 1000 ppmw to 10 wt% (mass%), with oxygen even present at concentrations as high as 45 wt% in feedstocks derived from biological materials. These heteroatoms are converted to hydrogen sulfide, ammonia, water, and carbon oxides during the refining process and pose little problem in the process plant. Other heteroatoms are typically metals, which are present in small amounts (0–10 ppmw) and precipitate on catalyst pore particles, causing little problem in the process plant. However, when processing waste materials such as biomass or plastic waste, heteroatoms can be present in much higher concentrations. In pyrolyzed wastes, such as pyrolyzed plastics, the Cl content can be 1000 ppmw or more. After hydrotreating, organic Cl is converted to HCl, which can cause corrosion problems. Therefore, it is important to remove heteroatoms early in the process to minimize their impact on downstream processes. Similar problems may be observed with halide-containing biomass, for example when it comes from saltwater. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] WO2015 / 050635 Summary of the Invention [Problem to be solved by the invention]

[0005] WO2015 / 050635 relates to a process for hydrotreating and removing halides from hydrocarbon streams. The document does not address the amount of water required to remove the halides from the process or the practical aspects of the process, except that it emphasizes that the materials used must be corrosion resistant. [Means for solving the problem]

[0006] As much as 30%, or 80%, to 90%, or 100% of the organic halides in the hydrocarbon feedstock may be converted to inorganic halides in a hydrocarbon product stream according to one embodiment of the present disclosure, and the hydrocarbon product is washed with water to bind the inorganic halides and separated from the hydrocarbon stream.

[0007] The water wash removes inorganic halides from the hydrocarbon stream from the product, and these inorganic halides removed from the hydrocarbon stream are removed from the system by regenerating the wash water, for example, by evaporation, membrane separation, reverse osmosis, or other methods that concentrate the impurities in brine.

[0008] In one embodiment, a make-up hydrogen stream is added to the hydrogen-rich gas phase prior to recycle to the hydrotreating reactor to ensure the necessary hydrogen is present in the hydrotreating reactor for further reactions such as conversion of organic halides to inorganic halides and possibly olefin saturation.

[0009] Throughout this text, the term "material catalytically active in the conversion of organic halides to inorganic halides" means a catalytic material positioned and / or suitable for catalyzing the conversion.

[0010] An "organohalide" is a chemical compound in which one or more carbon atoms are covalently bonded to one or more halogen atoms (fluorine, chlorine, bromine, iodine, or astatine - Group 17 in the current IUPAC terminology).

[0011] An "inorganic halide" is a compound between a halogen atom and an element or radical that is less electronegative (or more electronegative) than the halogen, producing a fluoride, chloride, bromide, iodide, or astatide compound, with the further restriction that carbon is not part of the compound. A typical example of a catalytically active material would be a classic refinery hydroprocessing catalyst, such as one or more base metal sulfides on a refractive support.

[0012] The term "removing halide" is meant to include situations in which some or all of the halide present is converted to an inorganic halide and then removed. Thus, the term is not limited to situations in which a certain percentage of the halide present is removed.

[0013] The term "reacting a stream in the presence of a catalytically active material" is meant to cover contacting a stream with a catalytically active material under conditions relevant for catalysis to occur. Such conditions typically relate to temperature, pressure, and stream composition.

[0014] The term "pyrolysis" is used broadly to refer to any decomposition process in which a substance is partially decomposed at high temperatures (typically 250-800°C or perhaps up to 1000°C) in the presence of substoichiometric amounts of oxygen (including no oxygen). The products will typically be a mixed stream of liquid and gas, as well as amounts of solid charcoal. The term is intended to include processes known as pyrolysis, partial combustion, or hydrothermal liquefaction.

[0015] Summary of the Invention A broad aspect of the present disclosure relates to a method for converting a hydrocarbonaceous feed containing at least 20 ppmw, at least 100 ppmw, or at least 500 ppmw and less than 1000 ppmw, 5000 ppmw, or less than 10000 ppmw, of halides to a hydrocarbon product stream by hydrotreating in the presence of a material catalytically active in hydrotreating and an amount of hydrogen, comprising: the hydrocarbon product stream comprises an amount of ionic halides; the hydrocarbon product stream is combined with a quantity of wash water, the mass ratio of wash water to hydrocarbon product stream being greater than 1:10, greater than 1:5, or greater than 1:2, and less than 1:1, less than 2:1, or less than 10:1; wherein the combined hydrocarbon product stream and wash water are separated into a non-polar stream of hydrocarbon product and a polar stream of wash water containing ionic halides such that 50%, 90%, or 99% to 100% of the ionic halides are transferred from the hydrocarbon product stream to a polar stream of wash water containing ionic halides; directing said polar stream of wash water containing ionic halides to a concentrating means to provide a purified water stream and a brine stream, wherein said brine stream is characterized by having a concentration of ionic halides that is more than 2 times, more than 5 times, or more than 10 times, and less than 50 times, or less than 100 times, that of said polar stream of wash water containing ionic halides; An advantage associated with such a process is the ability to receive a hydrocarbon mixture containing a high amount of halides and refine it into a hydrocarbon product of consistent quality while minimizing water consumption. DETAILED DESCRIPTION OF THE INVENTION

[0016] In a further embodiment, the concentrating means is an evaporator, where a polar stream of wash water containing ionic halides is heated to evaporate a quantity of water that makes up the purified water stream, an advantage associated with the evaporator is that it is an efficient concentrating means, particularly in a refinery environment where energy is available.

[0017] In a further embodiment, the evaporator is a falling film evaporator configured to cause a polar stream of wash water containing ionic halides to flow over a heated surface and further configured to collect the evaporated water and direct it as a purified water stream, an advantage associated with falling film evaporators is that they are very effective in providing an evaporator with a high evaporation surface and a small footprint.

[0018] In a further embodiment, the concentration means is a membrane separator or reverse osmosis separator, which has the associated advantage of providing a separation that requires the input of thermal energy.

[0019] In a further embodiment, the pH of said polar stream of wash water containing ionic halide is adjusted to a value between 6.5 and 9 by the addition of an amount of base or acid to either the wash water stream or the polar stream of wash water containing ionic halide, which has the associated advantage that the concentrating means can be constructed from inexpensive materials.

[0020] A further aspect of the present disclosure is a method for the conversion of a raw material feedstream rich in molecules containing C, H and halides, and optionally O, N, Si, and other elements, such as a mixture rich in plastics, lignin, straw, lignocellulosic biomass, or aquatic biological matter, comprising: a. pyrolyzing the raw material feed stream to provide a hydrocarbonaceous feed precursor or hydrocarbonaceous feed; b. An optional pre-processing step in which a precursor of the hydrocarbonaceous feed is purified to provide the hydrocarbonaceous feed; c. Hydrotreating a hydrocarbonaceous feed in the presence of hydrogen to convert the feed, according to any one of claims 1 to 5, to provide a hydrocarbonaceous product stream. and such methods have the related advantage of being suitable for converting feedstocks such as plastics, lignin, straw, lignocellulosic biomass, or mixtures rich in aquatic biological materials containing halides into purified hydrocarbons.

[0021] In a further embodiment, the process includes directing the hydrocarbon product stream to a steam cracking process following the above process for conversion of the raw material feed, with the associated advantages of providing feedstock for petrochemical processes from waste, biological materials, or low cost sources.

[0022] In a further aspect of the present disclosure, there is provided an apparatus for hydrotreating a hydrocarbonaceous stream comprising: (a) a hydroprocessing reactor containing a material catalytically active in hydroprocessing, the reactor including an inlet for receiving a hydrogen-rich hydrocarbon stream and an outlet for discharging a first product stream; (b) a mixing means having two inlets and one outlet; (c) phase separation means having an inlet and a liquid polar phase outlet, a liquid non-polar phase outlet, and a gas phase outlet; (d) a concentrating means having an inlet, a concentrated brine outlet, and a purified water outlet for discharging a first product stream, said outlet being in fluid communication with the first inlet of said mixing means; Including, an outlet of said mixing means in fluid communication with an inlet of said phase separation means, and a liquid polar phase outlet of said phase separation means in fluid communication with an inlet of said concentration means; a purified water outlet of said concentrating means, optionally in combination with a further source of purified water, in fluid communication with a second inlet of said mixing means; and The liquid non-polar phase outlet of the phase separation means is configured to provide a hydrocarbon product, and an advantage associated with such an apparatus is the conversion of waste, biological material or low cost resources into valuable hydrocarbon products with minimal consumption of purified water.

[0023] The disclosed method and apparatus prove useful when the feed to the hydrotreating process contains halides, particularly when temperatures must be kept moderate, for example, to avoid side reactions of olefins and diolefins. Examples of such methods include the direct hydrotreating of waste plastics or the direct hydrotreating of products from the pyrolysis of halide-rich materials, such as PVC or other halides containing plastics, as well as biological materials with high halide content, such as straw and algae, and other products of pyrolysis or hydrothermal processes, kerogenic feeds such as coal tar or shale oil. The feed can also be derived from non-pyrolyzed renewable sources, such as algal lipids, or other biological feeds containing hydrocarbons and chlorine, especially when grown in saltwater.

[0024] Ammonia and halides react to form salts, such as ammonium chloride, at temperatures below the precipitation temperature. The precipitation of such salts can cause potential corrosion as well as partial or complete blockage of the process line and must be avoided. Therefore, it is also important to keep this aspect in mind when defining the process conditions.

[0025] After hydrotreating a halide-containing hydrocarbon feedstock, a halide-rich intermediate stream exists. Depending on the boiling point and temperature, this stream can be a one-phase gas stream or a two-phase stream consisting of a gas stream rich in hydrogen and hydrogenated heteroatoms such as chlorides and ammonia, and a liquid stream consisting mainly of hydrocarbons. Because the hydrogenated heteroatoms are water-soluble, adding a certain amount of wash water and cooling the stream results in a three-phase stream consisting of a gas phase, an organic non-polar phase, and an aqueous polar phase, which can be separated in a so-called three-phase separator, possibly in combination with a cascade of separators with intermediate cooling and pressure relief.

[0026] Conventional refinery processes also include such water wash process steps, where nitrogen-rich hydrocarbons are converted to ammonia, which is highly soluble in water, and the hydrogen sulfide in the wash water can be extracted as ammonium sulfide. The concentration of nitrogen heteroatoms can be 1% by weight or higher, and the mass ratio of consumed water to hydrocarbons is typically 1:20 or 1:10, resulting in a concentration of ammonia salts in the water in the region of 1% to 5% by weight. The design is limited by the concentration of ammonium sulfide, which can be tolerated up to 2% to 5% by weight before corrosion becomes a problem.

[0027] In processes where the hydrocarbon feed's heteroatoms are halides and they are present at levels greater than 100 ppmw, the amount of water used in the wash step must be increased to achieve quantitative removal of the halides from the polar phase while avoiding corrosion problems due to increased halide concentrations in the aqueous phase. Typical design limits require keeping Cl levels in the water below 500 ppmw, equivalent to the requirements for carbon steel and conventional stainless steels. For a feedstock containing 500 ppm Cl and a refined hydrocarbon containing less than 1 ppm Cl, the water to hydrocarbon mass ratio should be approximately 1:1. This amount of water represents 10 to 20 times the amount typically used in the refinery industry.

[0028] Such a large amount naturally poses economic and environmental challenges, and therefore, it is desirable to reduce the amount of water consumed. This can be achieved by providing a means of concentrating the used wash water so that it is separated into purified wash water and concentrated brine, which is rich in impurities such as halides. Several methods exist for this purpose, including membrane filtration, reverse osmosis, or evaporation, including falling film evaporation. Because the equipment used in the evaporation process can be much more expensive if it requires special grades of steel, it is also beneficial to consider reducing the corrosiveness of the used wash water, such as by neutralizing it. Wash water in the presence of halides is typically acidic—for example, a pH of 2 for low-nitrogen hydrocarbon feedstocks—so the addition of ammonia or sodium hydroxide can be used to bring the pH to a range of 6.5 to 9.0.

[0029] The products of the process may be directed to further processing for the production of hydrocarbon transportation fuels for petrochemical processes, i.e. steam crackers. [Brief explanation of the drawings]

[0030] Brief description of the diagram FIG. 1 discloses an apparatus for treating a hydrocarbon stream.

[0031] Detailed explanation of the diagram Figure 1 discloses an apparatus for processing hydrocarbons. Although several heat exchange units, pumps, and compressors are shown in Figure 1, additional pumps, heaters, valves, and other process equipment may be part of the apparatus of Figure 1.

[0032] The apparatus of Figure 1 includes a sub-unit for removing halides from the hydrocarbon stream before it enters the stripper and / or fractionation section.

[0033] FIG. 1 shows a chlorine-containing hydrocarbon stream 2. This stream is optionally preheated before being combined with a hydrogen-rich gas stream 6 and a hydrogen-rich hydrocarbon stream 10 to ensure the supply of hydrogen necessary for the hydrogenation of diolefins. The hydrogen-rich hydrocarbon stream 10 is heated in a heat exchanger 12, and optionally further heated, such as by a heated heater, to form a heated hydrogen-rich hydrocarbon stream 14. A first reactor 16 can optionally have operating conditions suitable for the hydrogenation of diolefins, at a pressure of about 30 Barg and a temperature of about 180° C. The first reactor 16 contains a material catalytically active in olefin saturation and hydrogen (hydro)dehalogenation. In the first reactor 16, the heated hydrogen-rich hydrocarbon stream 14 reacts in the presence of a catalytically active material to produce a first hydrogenation product stream 18.

[0034] The first hydrogenation product stream 18 is heated, for example, in a fired heater 20, and transferred as heated first hydrogenation product stream 22 to a second reactor 24, where it reacts in the presence of a second catalytically active material. Quench gas 26 is often provided to the second reactor to control the temperature. The first and second catalytically active materials may be the same or different and typically comprise a combination of sulfide-based metals, such as molybdenum or tungsten, promoted by nickel or cobalt supported on a refractory support, such as alumina or silica. Typically, the reaction over the first catalytically active material is dominated by saturation of di-olefins, while the reaction over the second catalytically active material is dominated by saturation of mono-olefins and hydro-dehalogenation of halide-hydrocarbons. Hydrodesulfurization, hydro-denitrogenation, and hydro-deoxygenation may also occur in the second reactor 24 (depending on the feed composition). Thus, the hot product stream 28 may contain hydrocarbons, HO, HS, NH, and HCl, which may be removed by scrubbing and separation. The hot product stream 28 is cooled to form a cooled product stream 30 in a heat exchanger 32. The cooled product 30 is directed to a thermal stripper 40, where separation is assisted by a stripping medium 42, and the cooled product 30 is divided into a gas product fraction 44 and a liquid product fraction 46. The gas product fraction 44 is combined with a purified water stream 50 to provide a mixed stream 52, which is cooled in a cooler 54 and separated in a three-phase separator 58 to provide a three-phase stream 56 into a light hydrocarbon stream 60, a contaminated water stream 62, and a hydrogen-rich gas stream 66. The hydrogen-rich gas stream 66 is directed to a recycle compressor 68 and is directed as a quench gas 26 for the second reactor 24, as a stripping medium 42 for the thermal stripper 40, and as recycle gas 8, where it combines with makeup hydrogen gas 4 to form a hydrogen-rich gas 6.

[0035] The light hydrocarbon stream 60 exiting the three-phase separator 58 enters the second stripper 48, where it is further separated into liquid and gaseous components with the aid of a stripping medium 72. The light ends output 78 from the second stripper 48 is cooled in a cooler 80 and directed as a cooled light ends fraction 82 to a further three-phase separator 84 configured to separate an off-gas fraction 86 from a water fraction 88 and a hydrocarbon liquid fraction 92. The hydrocarbon liquid fraction 92 from the further three-phase separator 84 is recycled to the second stripper 48, and the polar liquid fraction 88, combined with the contaminated water stream 62, can be directed to a concentration means 96, from which a concentrated brine stream 98, for example, rich in NHCl, as well as a purified water stream 50 containing minor impurities such as NHCl, are removed. The purified water can typically be added, along with a quantity of water, as pure wash water 50. The present invention includes the following items. [Item 1] 1. A method for converting a hydrocarbonaceous feed containing at least 20 ppmw, at least 100 ppmw, or at least 500 ppmw and less than 1000 ppmw, 5000 ppmw, or 10000 ppmw of halides by hydrotreating in the presence of a material catalytically active in hydrotreating and an amount of hydrogen, comprising: the hydrocarbon product stream comprises an amount of ionic halides; the hydrocarbon product stream is combined with a quantity of wash water, the mass ratio of wash water to hydrocarbon product stream being greater than 1:10, greater than 1:5, or greater than 1:2, and less than 1:1, less than 2:1, or less than 10:1; wherein the combined hydrocarbon product stream and wash water are separated into a non-polar stream of hydrocarbon product and a polar stream of wash water containing ionic halides such that 50%, 90%, or 99% to 100% of the ionic halides are transferred from the hydrocarbon product stream to a polar stream of wash water containing ionic halides; the polar stream of wash water containing ionic halides being directed to a concentrating means to provide a purified water stream and a brine stream, wherein the brine stream has a concentration of ionic halides that is more than 2 times, more than 5 times, or more than 10 times, and less than 50 times, or less than 100 times, that of the polar stream of wash water containing ionic halides. [Item 2] 2. The method of claim 1, wherein the concentrating means is an evaporator, and a polar stream of wash water containing ionic halides is heated to evaporate a quantity of water that constitutes the purified water stream. [Item 3] 3. The method according to claim 2, wherein the evaporator is a falling film evaporator configured to cause a polar stream of wash water containing ionic halides to flow over a heated surface, and further configured to collect the evaporated water and direct it as a purified water stream. [Item 4] Item 10. The method according to item 1, wherein the concentration means is a membrane separator or a reverse osmosis separator. [Item 5] 5. The method according to item 1, 2, 3 or 4, wherein the pH of said polar stream of wash water containing ionic halide is adjusted to a value between 6.5 and 9 by addition of an amount of base or acid to either the wash water stream or the polar stream of wash water containing ionic halide. [Item 6] 1. A process for the conversion of a raw material feedstream rich in molecules containing C, H and halides, and optionally O, N, Si, and other elements, such as a mixture rich in plastics, lignin, straw, lignocellulosic biomass, or aquatic biological matter, comprising: a. pyrolyzing the raw material feed stream to provide a hydrocarbonaceous feed precursor or hydrocarbonaceous feed; b. An optional pre-processing step in which a precursor of the hydrocarbonaceous feed is purified to provide the hydrocarbonaceous feed; c. Hydrotreating the hydrocarbonaceous feed in the presence of hydrogen to convert the hydrocarbonaceous feed to provide a hydrocarbonaceous product stream, according to any one of items 1 to 5. The method comprising: [Item 7] 7. The method of claim 6, further comprising the step of: subsequently directing the hydrocarbon product stream to a steam cracking step. [Item 8] a. a hydroprocessing reactor comprising a material catalytically active in hydroprocessing, the reactor comprising an inlet for receiving a hydrogen-rich hydrocarbon stream and an outlet for discharging a first product stream; b. A mixing means having two inlets and one outlet; c. a phase separation means having an inlet and a liquid polar phase outlet, a liquid non-polar phase outlet, and a gas phase outlet; d. a concentrating means having an inlet, a concentrated brine outlet, and a purified water outlet for discharging a first product stream, said outlet being in fluid communication with the first inlet of said mixing means; Including, an outlet of said mixing means in fluid communication with an inlet of said phase separation means, and a liquid polar phase outlet of said phase separation means in fluid communication with an inlet of said concentration means; a purified water outlet of said concentrating means, optionally in combination with a further source of purified water, in fluid communication with a second inlet of said mixing means; and 10. An apparatus for hydroprocessing a hydrocarbonaceous stream, wherein the liquid non-polar phase outlet of the phase separation means is configured to provide a hydrocarbon product.

Claims

1. 1. A method for converting a hydrocarbonaceous feed from thermal cracking containing at least 100 ppmw or at least 500 ppmw and less than 1000 ppmw, less than 5000 ppmw or less than 10000 ppmw of halides by hydrotreating in the presence of a material catalytically active in hydrotreating and an amount of hydrogen, into a hydrocarbon product stream, comprising: the hydrocarbon product stream comprises an amount of ionic halides; the hydrocarbon product stream is combined with a quantity of wash water to produce a combined hydrocarbon product stream and wash water, wherein the mass ratio of wash water to hydrocarbon product stream is greater than 1:10, greater than 1:5, or greater than 1:2, and less than 1:1, less than 2:1, or less than 10:1; 1. A process for separating a combined hydrocarbon product stream and wash water into a non-polar stream of hydrocarbon product and a polar stream of wash water containing ionic halides, such that 50%, 90%, or 99% to 100% of said ionic halides are transferred from said hydrocarbon product stream to the polar stream of wash water containing ionic halides, in a phase separation means having an inlet and a liquid polar phase outlet, a liquid non-polar phase outlet, and a gas phase outlet; directing said polar stream of wash water containing ionic halides to a concentrating means to provide a purified water stream and a brine stream, wherein said brine stream has a concentration of ionic halides that is more than 2 times, more than 5 times, or more than 10 times, and less than 50 times, or less than 100 times, that of said polar stream of wash water containing ionic halides; The method as defined above, wherein purified water in the purified water stream is added as wash water together with the quantity of wash water.

2. 2. The method of claim 1, wherein said concentrating means is an evaporator, wherein a polar stream of wash water containing ionic halides is heated to evaporate a quantity of water comprising the purified water stream.

3. 3. The method of claim 2, wherein the evaporator is a falling film evaporator configured to flow a polar stream of wash water containing ionic halides over a heated surface and further configured to collect evaporated water and direct it as a purified water stream.

4. 10. The method of claim 1, wherein the concentration means is a membrane separator or a reverse osmosis separator.

5. 5. The method of claim 1, 2, 3 or 4, wherein the pH of said polar stream of wash water containing ionic halide is adjusted to a value of from 6.5 to 9 by the addition of an amount of base or acid to either the wash water stream or the polar stream of wash water containing ionic halide.

6. 1. A process for the conversion of a raw material feedstream rich in molecules containing C, H and halides, and optionally O, N, Si, and other elements, which is a mixture rich in plastics, lignin, straw, lignocellulosic biomass, or aquatic biological matter, the process comprising: a. pyrolyzing the raw material feed stream to provide a hydrocarbonaceous feed precursor or hydrocarbonaceous feed; b. An optional pre-processing step in which precursors of the hydrocarbonaceous feed are purified to provide the hydrocarbonaceous feed; c) hydrotreating the hydrocarbonaceous feed in the presence of hydrogen to convert the hydrocarbonaceous feed to provide a hydrocarbonaceous product stream according to any one of claims 1 to 5. The method comprising:

7. 7. The method of claim 6, further comprising the step of subsequently directing the hydrocarbon product stream to a steam cracking step.

8. a. a hydroprocessing reactor for converting a hydrocarbonaceous feed comprising a material catalytically active in hydroprocessing and comprising at least 100 ppmw or at least 500 ppmw and less than 1000 ppmw, 5000 ppmw, or 10000 ppmw of halides into a hydrocarbon product stream, the reactor comprising an inlet for receiving a hydrogen-rich hydrocarbon stream and an outlet for discharging a first product stream; b. a mixing means having two inlets and one outlet; c. a phase separation means having an inlet and a liquid polar phase outlet, a liquid non-polar phase outlet, and a gas phase outlet for separating the combined hydrocarbon product stream and wash water into a non-polar stream of hydrocarbon product and a polar stream of wash water containing ionic halides; d. a concentrating means having an inlet, a concentrated brine outlet, and a purified water outlet; Including, wherein the outlet for discharging a first product stream in a hydroprocessing reactor is in fluid communication with a first inlet of the mixing means; an outlet of said mixing means in fluid communication with an inlet of said phase separation means, and a liquid polar phase outlet of said phase separation means in fluid communication with an inlet of said concentration means; a purified water outlet of said concentrating means, optionally in combination with a further source of purified water, in fluid communication with a second inlet of said mixing means; and 10. An apparatus for hydroprocessing a hydrocarbonaceous stream, wherein the liquid non-polar phase outlet of the phase separation means is configured to provide a hydrocarbon product.

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