Process for producing a hydroprocessed fluid having reduced chlorine content

Abstract

A process for producing a hydroprocessed fluid having a reduced chlorine content, the process comprising: (i) providing a feed fluid which comprises a content of chlorine-containing contaminants, and (ii) subjecting the feed fluid to a hydroprocessing reaction in the presence of a hydrogen-rich gas stream, wherein the hydroprocessing reaction is carried out in a moving bed reactor which contains an alumina-based hydrodemetallization catalyst, to produce a hydroprocessed fluid having a reduced chlorine content. In a preferred embodiment of the present invention, the feed fluid comprises a waste plastics pyrolysis oil.

Description

[0001] SP3165

[0002] - 1 -

[0003] PROCESS FOR PRODUCING A HYDROPROCESSED FLUID HAVING REDUCED CHLORINE CONTENT

[0004] Field of the Invention

[0005] The present disclosure relates to a process for generating a hydroprocessed fluid from the hydroprocessing of a feed fluid (e.g., crude feed fluid, bio feed fluid, waste plastics feed fluid, and combinations thereof), wherein the hydroprocessed fluid has a reduced chlorine content compared with the feed fluid.

[0006] Background of the Invention

[0007] Hydroprocessing systems are used to refine raw feed fluids (e.g., fossil fuels, bio feed stocks, waste plastics feedstocks, and combinations thereof) in order to transform hydrocarbons contained therein into more desirable hydrocarbons through hydrogenation, hydrocracking, hydrotreating, and other reactions. However, some contaminants in the feed treated in the hydroprocessing systems can rapidly degrade system components, thereby reducing the commercial and / or environmental feasibility of using such systems. In particular, since the feed fluid can contain chlorine-containing compounds, such as chloride compounds (e.g., inorganic chlorides, sodium or calcium chloride, and / or organic chlorides), a hydroprocessing reactor that performs this process also generates and contains concentrated levels of hydrogen chloride originating from a chemical reaction of chlorides with hydrogen. If the feed contains nitrogen, the hydrogen chloride can deposit as an ammonium chloride salt in hydroprocessing system components, leading to pressure drop, fouling, and corrosion, which lead to a need for costly system shut-downs, repairs, and replacements.

[0008] Existing methods for dealing with chlorides include pretreating feed fluids with aqueous washes to remove water soluble salts (e.g., NaCl). However, aqueous washes only remove water soluble chlorides (e.g., NaCl, KC1) while leaving behind water insoluble organic chlorides (e.g., benzyl chloride). In addition, such pretreatment steps to remove SP3165

[0009] - 2 -

[0010] chlorine-containing compounds from the feed tend to be expensive. Within the hydroprocessing reactor, the remaining chlorides are transformed into hydrogen chloride (HC1), which accumulates in the system. Ammonia (NH3) may also be formed in the hydroprocessing reactor from a chemical reaction of the nitrogen compounds present in the raw feed with hydrogen. As the reactor effluent stream is cooled from the temperature required in the hydroprocessing reactor down to low temperatures that are close to ambient temperatures (e.g., 50 °C), ammonium chloride (NH4CI) salt can form and deposit in the reactor effluent circuit causing fouling and plugging. The deposition temperature of NH4CI salt increases with the concentration of HC1 and NH3 in the reactor effluent stream. If the concentration is too high, the deposition of ammonium chloride salt occurs before water washing can be applied to remove the salt precursors (NH3, HC1) from the reactor effluent. If a wash water is mixed with the reactor effluent at too high of a temperature, the wash water fully vaporizes and cannot remove or dilute the chloride salt precursors.

[0011] Other attempts to reduce chlorides in hydroprocessing systems involves the stripping of chlorides from the hydroprocessing effluent. This is the approach taken in W02022 / 079051.

[0012] Still further attempts to reduce chlorides in hydroprocessing systems involving waste plastics feedstocks are known from the prior art. WO2022 / 084433 relates to methods for producing a hydrocarbon fluid from waste plastics feedstocks in which a first hydrocarbon feed stream is provided, comprising material obtained from the pyrolysis of plastic waste, and contaminants are removed from the first hydrocarbon stream by subjecting at least a portion of the first hydrocarbon stream to a washing step with a polar solvent and / or contacting at least a portion of the first hydrocarbon feed stream with one or more adsorbents. US2023 / 0272292 (equivalent to WO2022 / 023262) relates to a process for treating a plastics SP3165

[0013] - 3 -

[0014] pyrolysis oil so as to at least partly remove impurities, notably olefins, metals and halogens. The process involves a fixed first hydrodemetallization (HDM) bed operating at a temperature of less than 280°C. This makes it possible to upgrade the plastics pyrolysis oils while at the same time reducing coke formation and the risks of clogging and corrosion in the steam cracking unit. Further, WO2024 / 088793 relates to a method for the fixed-bed treatment of a heavy fossil-based feedstock comprising a fraction of plastics pyrolysis oil.

[0015] Further processes and systems are needed that not only reduce the chlorine content of feed fluids going into a hydroprocessing system, but also treat chlorine-containing waste products from the reactor effluent to produce a hydrocarbon fluid with a reduced content of chlorine-containing compounds and achieve a reliable operation of a system so that maintenance based shut-downs are prevented. Further, it would be desirable to reduce chlorine-containing compounds in hydroprocessing processes without requiring expensive pretreatment steps to reduce chlorine in the reactor feed and / or without requiring extra equipment to remove chlorine from the reactor effluent before ammonium chloride deposits are formed.

[0016] Summary of the Invention

[0017] According to the present invention there is provided a process for producing a hydroprocessed fluid having a reduced chlorine content, the process comprising:

[0018] (i) providing a feed fluid which comprises a content of chlorine-containing contaminants, preferably comprising a mixture of waste plastics pyrolysis oil and a heavy hydrocarbon feed; and

[0019] (ii) subjecting the feed fluid to a hydroprocessing reaction in the presence of a hydrogenrich gas stream, wherein the hydroprocessing reaction is carried out in a moving SP3165

[0020] - 4 -

[0021] bed reactor which contains an alumina-based hydrodemetallization catalyst, to produce a hydroprocessed fluid having a reduced chlorine content.

[0022] It has been found that the process of the present invention provides a hydroprocessed fluid having a significantly reduced chlorine content compared with the starting feed fluid. The process of the present invention advantageously does not require an expensive pretreatment step to remove chlorine from the feed and / or does not necessitate extra equipment to remove Cl from reactor effluent before NH4C1 may deposit.

[0023] Brief Description of the Drawings

[0024] Figure 1 shows a process line-up for a preferred embodiment of the present invention.

[0025] Detailed Description of the Invention

[0026] A first step in the process involves providing a suitable feed fluid. The feed fluid for use herein may be any feed fluid suitable for use in a hydroprocessing reaction and which contains a certain amount of chlorine-containing contaminants. The main components of the feed fluid comprise carbon and hydrogen. In addition, fossil feeds may contain more than 1% wt sulphur and biofeeds may contain more than lwt% oxygen. Contaminants in the feed each represent less than l%wt of the feed and may comprise chlorine, nitrogen and metals, etc. Examples of suitable feed fluids include a crude oil (e.g., comprising hydrocarbons), a bio feedstock (e.g., a vegetable oil, an animal fat), a waste plastics pyrolysis oil, and any combination thereof. In one embodiment herein, the feed fluid comprises a combination of a heavy hydrocarbon feed originating from crude oil and a waste plastics pyrolysis oil.

[0027] The feed fluid for use herein comprises a certain level of chlorine and may contain a relatively high concentration of chlorines, such as greater than 1 weight parts per million SP3165

[0028] - 5 -

[0029] (wppm) of chlorine. In one embodiment, a feed fluid may contain a chlorine content ranging from 0.1 wppm to 200 wppm (ppm by weight). In some embodiments, a feed fluid may contain a chlorine content ranging from 0.1 wppm to 0.5 wppm, or 0.25 wppm to 0.75 wppm, or 0.5 wppm to 1.0 wppm, or 0.75 wppm to 1.25 wppm. In other embodiments, a feed fluid may contain a chlorine content ranging from 1.0 wppm to 5.0 wppm, or 2.5 wppm to 7.5 wppm, or 5.0 wppm to 10.0 wppm, or 7.5 wppm to 12.5 wppm, or 10.0 wppm to 15.0 wppm, or 12.5 wppm to 17.5 wppm, or 15.0 wppm to 20.0 wppm. By way of example, a feed fluid may contain a chlorine content of 0.1 wppm, or 0.5 wppm, or 1.0 wppm, or 1.5 wppm, or 2.0 wppm, or 2.5 wppm, or 3.0 wppm, or 3.5 wppm, or 4.0 wppm, or 4.5 wppm, or 5.0 wppm, or 7.5 wppm, or 10.0 wppm, or 12.5 wppm, or 15.0 wppm, or 17.5 wppm, or 20.0 wppm.

[0030] In existing systems, chlorides contained within feed fluids are converted during hydroprocessing operations to either hydrogen chloride (HC1) or ammonium chloride (NH4CI), which may contribute to corrosion, fouling, or plugging of system components and increased system down time. Accumulation of chlorides may occur as they desublimate onto various system components. In existing systems, the concentration of chlorine in the feed fluid is preferred to be very low (e.g., < 1 wppm) to minimize fouling and plugging of system components.

[0031] In a preferred embodiment herein, the feed fluid comprises a waste plastics pyrolysis oil. A typical waste plastics pyrolysis oil contains about 20 ppmw chlorine. In another preferred embodiment herein, the feed fluid comprises a combination of a crude heavy hydrocarbon feed (typically containing about 50 ppmw metals) and a waste plastics pyrolysis oil. The hydroconversion products from such a feed (e.g. naphtha and light DAO hydrowax) can be used as ethylene cracker feed to produce ethylene. The produced ethylene can then be polymerized to plastic and in this way plastics circularity is achieved. SP3165

[0032] - 6 -

[0033] In one embodiment of the present invention, the feed fluid comprises from 1% wt to 10%wt of a waste plastics pyrolysis oil. The level of waste plastics pyrolysis oil in the feed fluid will be limited to about 10 wt% of the total feed fluid since the metals uptake capacity of the moving bed catalyst is substantially higher than its chlorine uptake capacity.

[0034] The process herein comprises a step of subjecting the feed fluid to a hydroprocessing reaction in the presence of hydrogen-rich gas, wherein the hydroprocessing reaction is carried out in a moving bed reactor which contains an alumina-based hydrodemetallization catalyst. Such a moving bed hydrodemetallization catalyst is suitably applied when the feed fluid contains from 4 ppmw to 250 ppmw metals (e.g. Ni, V). Preferably, a moving bed hydrodemetallization catalyst is applied when the feed fluid contains from 10 ppmw to 120 ppmw metals (e.g. Ni, V). This step produces a hydroprocessed fluid having a reduced chlorine content compared with the starting feed fluid. As used herein, a hydroprocessed fluid is a fluid that has been processed through one or more of the following steps: hydrodemetallization, hydrotreatment, hydrogenation, hydroisomerization, and / or hydrocracking. As used herein, the term ‘hydrotreatment’ includes one or more of hydrodesulfurization, hydrodeoxygenation, hydrodechlorination and / or hydrodenitrogenation.

[0035] The hydroprocessing step is preferably carried out at a temperature in the range from 200°C to 450°C, more preferably from 280°C to 435°C. The hydroprocessing step is preferably carried out at a hydrogen partial pressure in the range from 0.5 MPa to 30 MPa, more preferably from 1 MPa to 25 MPa. The hydroprocessing step is preferably carried out at a Weight Hourly Space Velocity (WHSV) in the range from 0.05 kg / liter / hour to 10 kg / liter / hour, more preferably from 0.1 kg / liter / hour to 6 kg / liter / hour. The hydroprocessing step is preferably carried out at a hydrogen to feed ratio of 50 Nliter / kg to 3000 Nliter / kg, more preferably from 100 Nliter / kg to 2000 Nliter / kg. In a preferred embodiment, the SP3165

[0036] - 7 -

[0037] hydroprocessing step is preferably carried out at a temperature in the range from 280°C to 435°C, a pressure in the range from 5 MPa to 20 MPa, a WHSV in the range from 0.2 kg / liter / hour to 5 kg / liter / hour and a hydrogen to feed ratio of 150 Nliter / kg to 1800 Nliter / kg. The hydroprocessing step is carried out in the presence of a hydrogen-rich gas.

[0038] Preferably, the hydroprocessing reactor is charged with a hydrogen rich gas at a hydrogen rich gas pressure ranging from 1.03 Mpa (150 psi) to 20.68 MPa (3,000 psi). A hydrogen rich gas pressure may include a range from 1.03 MPa (150 psi) to 1.72 MPa (250 psi), or 1.72 MPa (250 psi) to 3.45 MPa (500 psi), or 5.17 MPa (750 psi), or 5.17 MPa (750 psi) to 6.89 MPa (1,000 psi), 7.24 MPa (1,050 psi) to 8.62 MPa (1,250 psi), or 8.62 MPa (1,250 psi) to 10.34 MPa (1,500 psi), or 12.06 MPa (1,750 psi), or 12.06 MPa (1,750 psi) to 13.79 MPa (2,000 psi), (14.13 MPa) 2,050 psi to 15.51 MPa (2,250 psi), or 15.51 MPa (2,250 psi) to 17.24 MPa (2,500 psi), or 18.96 MPa (2,750 psi), or 18.96 MPa (2,750 psi) to 20.68 MPa (3,000 psi).

[0039] A hydrogen rich gas may include a hydrogen and a hydrocarbon. A hydrocarbon of a hydrogen rich gas is preferably a C1-C5 alkane. In some embodiments, a hydrocarbon of a hydrogen rich gas may include mostly C1-C5 alkanes. A hydrogen rich gas can also include water, C6 alkanes, CO, and H2S. Preferably, the hydrogen-rich gas comprises hydrogen at a concentration ranging from about 50 % to 99.9 % hydrogen, by volume of the hydrogen-rich gas. A hydrogen rich gas may have a hydrogen content of from 50 % to 60 %, or 60 % to 70 %, or 70 % to 80 %, or 80 % to 90 %, or 90 % to 99.9 %, by volume of the hydrogen rich gas. A hydrogen rich gas may have an alkane content of from 1 % to 10 %, or 10 % to 20 %, or 20 % to 30 %, or 30 % to 40 %, or 50 % to 60 %, or 60 % to 70 %, or 70 % to 80 %, or 80 % to 90 %, or 90 % to 99 %, by volume of the hydrogen rich gas. A hydrogen rich gas may SP3165

[0040] - 8 -

[0041] include an alkane including, but not limited to, methane, ethane, propane, butane, pentane, mixtures thereof, and isomers thereof.

[0042] The hydroprocessing reaction is carried out in a bunker flow or moving bed reactor. The hydroprocessing reaction is carried out in the presence of a hydrodemetallization catalyst. Suitable hydrodemetallization catalysts for use in the present invention comprise alumina-based oxidic carriers such as alumina or silica-alumina. One or more Group VIB or Group VIII metals or metal compounds may be deposited on the carrier. Suitable hydrodemetallization catalysts are commercially available from many catalyst suppliers. Particularly suitable hydrodemetallization catalysts are those having as the active agent one of the combinations nickel / molybdenum (NiMo) or cobalt / molybdenum (CoMo), optionally promoted with phosphorus (P), or an alumina carrier. Spherical catalysts are particularly preferred herein. Examples of particularly suitable catalysts include CoMo / AhOs, CoMoP / AhOs and NiMo / AhCh and NiMoP / AhCh catalysts.

[0043] The hydroprocessed fluid produced by the process of the present invention comprises a lower chlorine content than the starting feed fluid. The hydroprocessed fluid may include at least 2%, preferably at least 5%, more preferably at least 10% less chlorine than the feed fluid. In one embodiment, the hydroprocessed fluid may include at least 50 % less chlorine than the feed fluid, more preferably at least 75 % less chlorine than the feed fluid. In one embodiment, the hydroprocessed fluid may have from about 10 wt. % to about 99 wt. % less chlorine than the starting feed fluid. By way of example, the hydroprocessed fluid may have 10 wt. %, or 20 wt. %, or 30 wt. %, or 40 wt. %, or 50 wt. %, or 60 wt. %, or 70 wt. %, or 80 wt. %, or 90 wt. %, or 99 wt. % less chlorine than the starting feed fluid.

[0044] The hydroprocessed fluid may contain a chlorine concentration ranging from about 0.1 wppm to about 100 wppm, or greater. A hydroprocessed fluid may contain a chlorine SP3165

[0045] - 9 -

[0046] concentration from 0.1 wppm to 10 wppm, or 5 wppm to 15 wppm, or 10 wppm to 20 wppm, or 15 wppm to 25 wppm, or 20 wppm to 30 wppm, or 25 wppm to 35 wppm, or 30 wppm to 40 wppm, or 35 wppm to 45 wppm, or 40 wppm to 50 wppm, or 45 wppm to 55 wppm or 50 wppm to 60 pm, or 55 wppm to 65 wppm, or 60 wppm to 70 wppm, or 65 wppm to 75 wppm, or 70 wppm to 80 wppm, or 75 wppm to 85 wppm, or 80 wppm to 90 wppm, or 85 wppm to 95 wppm, or 90 wppm to 100 wppm. By way of example, a hydroprocessed fluid may contain a chlorine concentration of 0.1 wppm, or 2 wppm, or 3 wppm, or 4 wppm, or 5 wppm, or 6 wppm, or 7 wppm, or 8 wppm, or 9 wppm, or 10 wppm, or 20 wppm, or 30 wppm, or 40 wppm, or 50 wppm, or 60 wppm, or 70 wppm, or 80 wppm, or 90 wppm, or 100 wppm.

[0047] The process of the present invention may remove chlorine from a hydroprocessed fluid in chloride form including hydrogen chloride, ammonium chloride, sodium chloride, potassium chloride, and combinations thereof. In a preferred embodiment of the present invention, hydrogen chloride is removed from the hydroprocessed fluid by adsorption on to the hydrodemetallization catalyst.

[0048] Disclosed systems and methods operate by removing chlorides from a hydroprocessing reactor fluid so that they do not accumulate and cause system harm. A disclosed system may remove chlorides from a hydroprocessing reactor fluid at temperatures well above the deposition temperature of the chloride salt. Since the deposition temperature of a chloride increases as the concentration of the chloride in the hydroprocessing reactor fluid increases, disclosed systems that remove the chloride from the hydroprocessing reactor fluid prevent salt deposition in the systems where this hydroprocessed fluid is used.

[0049] A hydroprocessed fluid may contain a hydrocarbon including alkanes, branched alkanes, linear alkanes, alkenes, alkynes, aryls, aromatics, and combinations thereof. SP3165

[0050] - 10 -

[0051] A hydroprocessed fluid may have a sulfur concentration of 5,000 wppm or less, or less than 4,500 wppm, or less than 4,000 wppm, or less than 3,500 wppm, or less than 3,000 wppm, or less than 2,500 wppm, or less than 2,000 wppm, or less than 1,500 wppm, or less than 1,000 wppm, or less than 500 wppm, or less than 1 wppm. A hydroprocessed fluid may have a sulfur concentration of less than 100 wppm, or less than 90 wppm, or less than 80 wppm, or less than 70 wppm, or less than 60 wppm, or less than 50 wppm, or less than 40 wppm, or less than 30 wppm, or less than 20 wppm, or less than 10 wppm, or less than 1 wppm. A disclosed process may produce low sulfur hydroprocessed fluids having reduced sulfur dioxide emissions when combusted (e.g., combustion in automotive vehicles, aircraft, railroad locomotives, ships, gas or oil burning power plants, residential and industrial furnaces, and other forms of fuel combustion) as compared to hydroprocessed fuels having higher sulfur content.

[0052] The hydroprocessed fluid having a reduced chlorine content may be directly saleable, used or further refined. For example, the hydroprocessed fluid may be further refined by a fractional distillation unit. A fractional distillation unit may include a fractional distillation column and a heating element. The hydroprocessed fluid may be further refined by a hydrocracking unit, in order to convert the hydroprocessed fluid into a range of desirable hydrocarbon products, such as naphtha, light DAO hydrowax and heavy DAO hydrowax. The naphtha and light DAO hydrowax may be used as feed in an ethylene cracker for the production of ethylene, which in turn can be polymerized to plastics, hence creating the possibility for plastics circularity.

[0053] FIGURE 1 illustrates one embodiment of a disclosed system 100 that may generate a hydroprocessed fluid having reduced chlorine levels. A system 100 includes various components used to hydroprocess a feed fluid to produce a hydroprocessed fluid containing SP3165

[0054] - 11 -

[0055] reduced levels of chlorine. A system 100 may include a hydroprocessing reactor 105 configured to generate a hydroprocessed fluid that may contain hydrogen chloride (HC1) and ammonia (NH3).

[0056] A system 100 may be configured to transfer feed fluids from feed fluid tanks 145 and 140 to a hydroprocessing reactor 105 through a feed fluid transfer line. Preferably, feed fluid tank 145 comprises waste plastics pyrolysis oil, typically having a high chlorine content. Preferably, feed fluid tank 140 comprises a heavy hydrocarbon fossil feed, typically having a high metal content, such as deasphalted oil, or long residue. The hydroprocessing reactor 105 is a moving bed reactor. The system may comprise two or three moving bed reactors and there could also be some fixed bed reactors e.g. 107. A temperature of a feed fluid may be increased by exchanging heat with a hydroprocessing reactor effluent 108 in a first heat exchanger 110. The heat exchanger 110 is optional. In some embodiments, a fired heater may be used to preheat the feed fluid(s) up to the required temperature before it enters a hydroprocessing reactor 105. In some embodiments, a portion of feed fluid may be transferred to a hydroprocessing reactor 105 from another source instead of from feed fluid tanks 145 and / or 140. A feed fluid or fluids may enter a hydroprocessing reactor 105 at various locations including the top of the hydroprocessing reactor 105 and one or more side locations between catalyst beds contained within the hydroprocessing reactor 105. A system 100 may include a hydrogen rich gas tank 150 connected to a hydroprocessing reactor 105 through a hydrogen rich gas connector. A system 100 may be configured to transfer a hydrogen rich gas from a hydrogen rich gas tank 150 to a hydroprocessing reactor 105 through a hydrogen rich gas transfer line. A hydrogen rich gas may be transferred from a recycle gas stream produced within the system 100 or from a hydrogen source external to system 100 or a combination of both. A hydrogen rich gas 150 may be mixed with the feed SP3165

[0057] - 12 -

[0058] fluid(s) before entering the hydroprocessing reactor 105. A hydrogen rich gas may be provided by a quench hydrogen rich gas tank 150 and may be used as quench gas when transferred directly to a hydroprocessing reactor 105. According to a preferred embodiment, a hydroprocessing reactor 105 may be configured to combine a feed fluid or fluids with a hydrogen rich gas in the presence of catalyst in a hydroprocessing reactor 105 to produce a hydroprocessed fluid containing hydrocarbons, and other compounds including hydrogen chloride and ammonia.

[0059] According to some embodiments, a system 100 may be configured to combine a hydrogen rich gas with a catalyst and a feed fluid in a hydroprocessing reactor 105 to generate a hydroprocessed fluid. The hydroprocessed fluid that is generated in a system 100 may be directly used as a hydrocarbon product or further refined. A hydroprocessed fluid may be generated in a system 100 by combining a hydrogen rich gas with a catalyst and a feed fluid. A hydrogen rich gas may be supplied to a hydroprocessing reactor 105 from a hydrogen rich gas tank 150 through a hydrogen rich gas transfer line.

[0060] The hydroprocessing reactor 105 is configured to contain an alumina-containing hydrodemetallisation catalyst, as discussed above.

[0061] According to some embodiments, a system 100 may include a hydroprocessing reactor 105 containing a reactor vessel having one or more thermocouples. A thermocouple may be configured to maintain a reactor vessel temperature at a range from 250 °C to 450 °C, preferably from 280°C to 435°C.

[0062] The primary reaction occurring in reactor 105 is a hydrodemetallization reaction. The hydrodemetallized product 106 emerging from reactor 105 contains less chlorine and metals than the starting feeds. The hydrometallised product 106 emerging from reactor 105 may be transferred to a fixed bed reactor 107. All kinds of hydroprocessing reactions may occur in SP3165

[0063] - 13 -

[0064] reactor 107 including one or more of hydrodesulphurization, hydrocracking, and the like, such reactions being exothermic and creating quite a lot of heat. The product 108 emerging from reactor 107 may be passed through a heat exchanger 110 to cool it down.

[0065] In some embodiments, a hydroprocessed fluid generated by a hydroprocessing reactor 105 may be directly used or processed further (e.g., distilled). A system 100 may include a fractionation section 112 configured to distill a hydroprocessed fluid into one or more hydrocarbon fractions. A hydrocarbon fraction may include multiple fractions at a range of boiling points, for example a light fraction 114, a heavier fraction 116 and a bottoms fraction 118. In some embodiments, the bottoms fraction 118 can be recycled to the feed fluids. In some embodiments, one or more hydrocarbon fractions may be transferred from a fractional distillation unit to any collection container.

[0066] A fractionation section may connect to a hydroprocessing reactor 105 / 107 through a fractionation connector. A fractionation section may be configured to receive a hydroprocessed fluid from a hydroprocessing reactor 105 / 107 through a fractionation connector.

[0067] Examples

[0068] Example 1

[0069] A waste plastics pyrolysis oil feed was pretreated such that the chlorine content was below 113 ppmw. Subsequently, this pretreated feed was hydrotreated over the hydrodemetallization (HDM) catalyst RM-5030, which catalyst is commercially available from Shell Catalyst and Technologies. RM-5030 is a nickel and molybdenum based alumina catalyst promoted with phosphorus. The hydrogen partial pressure during the hydrotreatment varied between 80 and 110 bars and the catalyst bed temperature was between 335 and 370°C. The weight hourly space velocity over the RM-5030 catalyst was 0.58 kg / l / h and the SP3165

[0070] - 14 -

[0071] RM-5030 loading density was 0.426 g / ml. After 665 hours of fixed bed hydrotreating the HDM catalyst was analysed and it had accumulated 0.208 %wt of chlorine. Hence, during the test at least 2% of the chlorine entering the RM5030 catalyst was adsorbed.

[0072] Example 2

[0073] Example 1 described an experiment in which a fixed bed was applied and in which the HDM catalyst absorbed at least 0.2 wt% of chlorine. This finding can be applied to a situation in which a moving bed HDM catalyst is used on a typical heavy fossil feed containing a certain amount of metals (102 ppmw of metals (Ni + V)) and more than 1000 ppmw nitrogen whilst virtually no chlorine (<lppmw) is present. This fossil feed can be coprocessed with 2 wt% of a waste plastics pyrolysis oil containing 100 ppmw Cl, and the combined feed will contain about 2 ppmw Cl and about 100 ppmw metals. Assuming the HDM catalyst metals uptake capacity is 10% wt and the Cl uptake capacity is 0.2 wt%, a simultaneous breakthrough of metals and Cl may occur. By moving the HDM catalyst beds at such a speed that metals breakthrough is prevented, Cl breakthrough may also surprisingly be prevented in the case of co-processing of waste plastics pyrolysis oil.

Claims

CLAIMS1. A process for producing a hydroprocessed fluid having a reduced chlorine content, the process comprising:(i) providing a feed fluid which comprises a content of chlorine-containing contaminants, preferably comprising a mixture of waste plastics pyrolysis oil and a heavy hydrocarbon feed; and(ii) subjecting the feed fluid to a hydroprocessing reaction in the presence of a hydrogenrich gas stream wherein the hydroprocessing reaction, is carried out in a moving bed reactor which contains an alumina-based hydrodemetallization catalyst, to produce a hydroprocessed fluid having a reduced chlorine content.

2. The process according to Claim 1, wherein the feed fluid comprises from 0.1 ppmw to 200 ppmw of chlorine.

3. The process according to claim 1 or 2, wherein the hydroprocessed fluid comprises at least 2%, preferably at least 5%, more preferably at least 10% less chlorine than the feed fluid.

4. The process according to any of Claims 1 to 3, wherein the feed fluid comprises a waste plastics pyrolysis oil.

5. The process according to any of Claims 1 to 4, wherein the feed fluid comprises a mixture of a heavy hydrocarbon feed and a waste plastics pyrolysis oil.

6. The process according to any of claims 1 to 5, wherein the hydroprocessing reaction is carried out at a temperature in the range from 250 °C to 450 °C, preferably from 280°C to 435°C.- 16 -7. The process according to any of claims 1 to 6, wherein the hydroprocessing reaction is carried out a hydrogen-gas pressure in the range from 0.5 MPa to 30 MPa.

8. The process according to any of Claims 1 to 7, wherein the hydrogen-rich gas comprises a hydrogen concentration ranging from about 50 % to 99 % hydrogen, by volume of the hydrogen-rich gas.

9. The process according to any of Claims 1 to 8, wherein the alumina-based hydrodemetallisation catalyst comprises one or more Group VIB and / or Group VIII metals or metal compounds deposited on an alumina-based carrier.

10. The process according to Claim 9 wherein the hydrodemetallization catalyst is selected from a NiMo or CoMo catalyst, optionally promoted with phosphorus, on an alumina carrier.

Images