DK181062B1

DK181062B1 - Method for co-processing

Info

Publication number: DK181062B1
Application number: DKPA201970766A
Authority: DK
Inventors: Aalto Pekka; Toukoniitty Blanka; Paasikallio Ville
Original assignee: Neste Oyj
Priority date: 2018-12-28
Filing date: 2019-12-12
Publication date: 2022-10-31
Also published as: DE102019133911A1; FI128635B; FR3091294A1; FI20186136A1; GB2580539B; GB2580539A; SE543084C2; ES2769963A1; BE1026853A1; GB201918837D0; SE1951472A1; FR3091294B1; DK201970766A1; ES2769963B2; NL2024523A; NL2024523B1; NO347068B1; BE1026853B1; DE102019133911B4; NO20191514A1

Abstract

The present invention relates to methods for co-processing waste plastic (WP) derived liquids and end-life-tire (ELT) derived liquids with crude oils (CO) in conventional oil refinery settings comprising desalting 10 and distilling 20.

Description

DK 181062 B1 1

FIELD The present invention relates to methods for co-processing, in particular co- processing waste plastic derived liquids and end-life-tire derived liquids with crude oils in conventional oil refinery settings.

BACKGROUND Recycled-type raw materials or reduced-carbon feedstocks are feeds created by the processing of fossil-based wastes like waste plastics (WP) or end-of-life tires (ELT). The attractive feature of these raw materials from the viewpoint of the refinery is that they are quite similar compared to traditional refinery feeds, i.e. crude oil. WP/ELT- derived oils contain primarily hydrocarbons, and their oxygen content is clearly lower compared to biomass-based oils.

WP pyrolysis derived oils contain different elemental impurities dependent mostly on the original raw material, but also on the pyrolysis technology employed. The three most relevant impurities in plastic pyrolysis oils are nitrogen, sulphur and chlorine, which have a detrimental effect on the direct utilization of the pyrolysis oil. These impurities are primarily present in organic form, which means that they are structurally associated with hydrocarbon chains of varying size and complexity. Furthermore, metal impurities originating from additives and contamination can also be detected in these oils.

ELT pyrolysis oils tend to have much lower CI content compared to WP pyrolysis oils, and therefore in co-processing of ELT pyrolysis oils this issue may be managed via simple dilution. On the other hand, ELT pyrolysis oils contain other impurities which can be detrimental in refining operations. These oils contain solid impurities mainly in the form of carbon black, which is used as a reinforcing filler in tire formulations, as well as some oil-soluble metallic impurities. ELT pyrolysis oil also contain substantial amounts of sulfur and nitrogen, both of which can be found in conventional crude oils as well.

DK 181062 B1 2 Even if the WP/ELT derived oil has very low impurity concentration and/or it is utilized in very low concentrations, the impurities can still cause various issues over time. Thus, the WP/ELT-derived oil should be introduced to the refinery in a manner that minimizes the potential effect of these impurities.

There are numerous pieces of art disclosing processes and equipment suitable for preparation, purification and cracking of waste plastic and/or ELT pyrolysis oils. For example, US2016045841 discloses a specific reactor suitable for desalting combined hydrocarbon streams including crude oils and pyrolytic oils. WO2018025103A1 discloses utilization of a ‘devolatilization’ extruder in combination with a zeolitic catalyst and a stripping for chlorine removal from hydrocarbon streams or hydrocarbon stream precursors. JP4382552 B2 discloses a method for processing plastic cracked light oil. However, it is specified that 90% of the plastic pyrolysis oil must be within a boiling point range of 100-300 °C. JPH1161148 A discloses a method for co-processing WP derived liquid with hydrocarbon oil in petroleum refining plant, the method comprising admixing the WP-derived liquid and crude oil to form an admixture and distilling the admixture. JP2002060757 A discloses thermal decomposition of WP and a production of a cracked distillate and mixing the cracked distillate with crude oil. The document discloses also refining and purifying the mixture in petroleum refining processes.

JP2005105027 A discloses a manufacturing method comprising mixing naphtha fraction with plastic cracked oil followed by subjecting the resultant mixture to hydrorefining. Accordingly, there is still need for more robust methods for processing WP and ELT derived liquids.

SUMMARY The following presents a simplified summary in order to provide a basic understanding of some aspects of various embodiments of the invention. The summary merely presents some concepts of the invention in a simplified form as a prelude to a more detailed description of exemplifying embodiments of the invention.

DK 181062 B1 3 It was observed that when WP/ELT-derived liquids were admixed with crude oil followed by distillation, certain impurities of the WP/ELT-derived liquids could be removed or concentrated to fractions where they could be more easily managed. Also, the problems related to reactivity of WP/ELT-derived oils could be avoided or atleast alleviated.

In accordance with the invention, there is provided a new method for co-processing waste plastic (WP) derived liquids and/or end-life-tire (ELT) derived liquids with crude oil, wherein the method comprises following steps a) providing waste plastic (WP) derived liquid and/or end-life-tire (ELT) liquid, b) providing crude oil, c) admixing 1 part by weight WP-derived liquid and/or ELT-derived liquid and 1- 1000 parts by weight crude oil to form an admixture, d) desalting the admixture, wherein the desalting comprises treating with water, e) distilling the admixture to produce one or more distillates and a distillate bottom, f) subjecting at least one of the one or more distillates to hydrodesulfurization reaction, wherein the subjecting is at 280-320 °C in 20-35 bar in the presence of hydrogen and a hydrodesulfurization catalyst, such as CoMo/Al203 or NiMo/Al203, or wherein the subjecting is at 320-380 °C in 35-80 bar in the presence of hydrogen and a hydrodesulfurization catalyst, such as CoMo/Al203 or NiMo/Al203, and g) subjecting the distillate bottom to vacuum distillation, wherein the vacuum distillation produces vacuum gas oil and/or vacuum residue, wherein the vacuum gas oil and/or the vacuum residue is subjected to one or more of fluid catalytic cracking, hydrocracking, and residue hydrocracking. Various exemplifying embodiments of the invention and methods of operation, together with additional objects and advantages thereof, are best understood from the following description of specific exemplifying embodiments when read in connection with the accompanying figures.

DK 181062 B1 4 The verbs “to comprise” and “to include” are used in this document as open limitations that neither exclude nor require the existence of also unrecited features. Furthermore, it is to be understood that the use of "a" or "an", i.e. a singular form, throughout this document does not exclude a plurality.

BRIEF DESCRIPTION OF FIGURES The exemplifying embodiments of the invention and their advantages are explained in greater detail below with reference to the accompanying figures, in which figures 1-3 show exemplary methods for co-processing waste plastic (WP) derived liquids and/or end-life-tire (ELT) derived liquids with crude oil (CO), and figure 4 shows an exemplary flow chart for co-processing waste plastic (WP) derived liquids and/or end-life-tire (ELT) derived liquids with crude oil (CO).

DESCRIPTION The present invention is related to co-processing of WP derived liquids and ELT- derived liquids preferably in conventional oil refinery setting using existing — processing units. The principle of the present method is shown in figures 1-4. According to the embodiment shown in figure 1, the process comprises co- introducing the WP and/or ELT-derived liquid and crude oil (CO) into the oil refinery via a crude oil desalting unit 10, and a subsequent crude oil distillation unit (CDU)

20. The distillation produces one or more distillates, i.e. distillation fractions and a distillation residue, i.e. a distillation bottom. According to this embodiment, the quality of the WP and/or ELT-derived liquid is not determined, but the liquids are fed to the desalting unit together with the crude oil. According to the embodiment, which is not part of the invention, shown in figure 2, the crude oil is desalted in the crude oil desalting unit 10, and co-distilled with the WP- and/or ELT-derived liquid in the crude oil distillation unit 20. This is possible if the quality of the WP-derived liquid- and the ELT-derived liquid is so good that their desalting step can be omitted.

DK 181062 B1 According to the method shown in figure 3, the quality of the ELT-derived liquid is high enough for omitting the desalting step, but the WP-derived liquid needs the desalting. Thus, a route a) is selected. When the quality of the WP-derived liquid is high enough for omitting the desalting step, but the ELT-derived liquid needs the 5 desalting, route b) is selected.

If the quality of the crude oil is high enough, even desalting of the crude oil can be omitted. This embodiment is not part of the invention.

According to the invention, the distillates and distillate bottoms are processed further. Thus, the distillates are directed into one or more hydrodesulfurization units marked with reference numbers 30 and 40. The distillation bottom from the distillation unit 20 is directed to a subsequent vacuum distillation unit 50, to give rise to vacuum gas oil (VGO) and vacuum residue (VR). The VGO and/or the VR is further processed utilizing e.g. fluid catalytic cracking, hydrocracking and residue hydrocracking processes 60.

Thus, the present invention concerns a method for co-processing waste plastic (WP) derived liquid and/or end-life-tire (ELT) derived liquid with crude oil comprising the steps characterised in the claim.

In connection with the method for co-processing waste plastic (WP) derived liquid and/or end-life-tire (ELT) derived liquid with crude oil, and before forming the admixture, the quality of the WP-derived liquid and/or ELT-derived liquid may be determined to decide if the quality of WP-derived liquid and/or ELT-derived liquid is above a predetermined level.

As defined herein the waste plastic derived liquid or waste plastic derived oil (used herein and throughout the description interchangeably) should be understood as meaning any liquid comprising oil derived from thermal conversion of waste plastics, and the end-life-tire derived liquid or end-life-tire derived oil (used herein and throughout the description interchangeably) should be understood as meaning any liquid comprising oil derived from thermal conversion of end-life-tires. It is

DK 181062 B1 6 understood that their composition may vary based on the thermal conversion technology used as well as on the nature of the raw materials. An exemplary flow chart for co-processing of WP- and/or ELT-derived liquid with crude oil is shown in figure 4.

According to one embodiment, WP-derived liquid is admixed with crude oil, and the admixture desalted and distilled. According to this embodiment, the co-processing does not include ELT-derived liquid, and the quality of the WP-derived liquid is not determined.

According to another embodiment, ELT-derived liquid is admixed with crude oil, and the admixture is desalted and distilled. According to this embodiment, the co- processing does not include WP-derived liquid, and the quality of the ELT-derived liquid is not determined.

According to another embodiment, WP- and ELT-derived liquid is admixed with crude oil, and the admixture is desalted and distilled. According to this embodiment, — the quality of the WP- and ELT-derived liquid is not determined.

According to another embodiment, quality of WP-derived liquid is analyzed, and its quality was observed to be below predetermined value. According to this embodiment, the co-processing does not include ELT-derived liquid. Thus, the WP- derived liquid is admixed with crude oil to form an admixture which is desalted and distilled.

According to another embodiment, quality of ELT-derived liquid is analyzed, and its quality is observed to be below predetermined value. According to this embodiment, the co-processing does not include WP-derived liquid. Thus, the ELT-derived liquid is admixed with crude oil to form an admixture which is desalted and distilled.

According to another embodiment, quality of ELT-derived liquid and WP-derived liquid is analyzed, and quality of ELT-derived liquid and quality of WP-derived liquid is observed to be below predetermined value. Thus, the ELT-derived liquid and WP- derived are admixed with crude oil to form an admixture which is desalted and distilled.

DK 181062 B1 7 According to another embodiment, quality of ELT-derived liquid and quality of WP- derived liquid is determined, and quality of the ELT-derived liquid and quality of the WP-derived is observed to be above and below predetermined value, respectively. Thus, the WP-derived liquid is admixed with crude oil to form an admixture which is desalted, and the desalted admixture is distilled with the ELT-derived liquid. According to another embodiment, quality of ELT-derived liquid and WP-derived liquid are determined, and quality of WP-derived liquid and quality of the ELT- derived was observed to be above and below predetermined value, respectively. Thus, the ELT-derived liquid is admixed with crude oil to form an admixture which is desalted, and the desalted admixture is distilled with the WP -derived liquid. According to another embodiment, quality of ELT-derived liquid and WP-derived liquid are analyzed, and quality of the ELT-derived liquid and quality of the WP- derived liquid is observed to be above a predetermined level. Thus, the ELT-derived liquid and WP-derived are distilled with the desalted crude oil.

The quality of the ELT- and WP-derived liquids can be determined using methods known in the art. Exemplary methods are titration and gas chromatography. Exemplary impurities to be determined comprise one or more of: inorganic halogen compounds, inorganic sulfur compounds, water soluble oxygen compounds. An exemplary impurity is inorganic chlorine, in form of HCI. According to an exemplary embodiment the impurity is inorganic chlorine and it is determined by titration with AgNO:s.

The predetermined level of quality can be specified as required. According to an exemplary embodiment the WP and/or ELT-derived liquid is co-desalted with crude oil if its CI content is 200 mg/kg or more.

According to the invention, the WP and/or ELT-derived liquid is admixed with crude oil to form an admixture. According to the invention, the admixture is produced by admixing 1 part by weight WP-derived liquid and/or ELT-derived liquid and 1 - 1000 parts by weight crude oil. According to an exemplary embodiment the admixture comprises a 1:10 mixture by weight WP- and/or ELT derived liquid and crude oil. It is obvious for a skilled person that also different ratios of WP- and/or ELT derived

DK 181062 B1 8 liquid and crude oil can be used. Further exemplary WP/ELT:CO ratios are 1:1, 1:2, 1:3, 1:5, 1:25, 1:50, 1:100, 1:500, and 1:1000 by weight.

The method of the present invention comprises that the admixture is desalted, and the desalting comprises treating with water. Exemplary desalting methods known in the art include chemical and electrostatic separation, chemical desalting, and electric desalting.

In chemical and electrostatic separation washing of the salt from the admixture is carried out using water. The oil and water phases are separated in a settling tank by adding chemicals to assist in breaking up emulsion, by the application of electrostatic field to collapse the droplets of saltwater more rapidly, or by a combination of the aforementioned two techniques.

In chemical desalting water and chemical surfactant (demulsifiers) are added to the admixture, and the admixture is heated so that salts and other impurities dissolve into the water or attach to the water, and then held in a tank where they settle out.

Desalting can also be done by extracting with water or water-containing fluid. Desalting with water removes or at least decreases the amounts of water-soluble impurities in the admixture. An exemplary water-to oil ration in the extraction is 1:1. Naturally, the impurities which are removed are not necessarily actual salts; According to the invention, a desalted admixture comprising the WP- and/or ELT- derived liquid is distilled to give rise to one or more distillation fractions, i.e. distillates and typically also a distillation residue, i.e. a distillation bottom. According to an exemplary embodiment the distillation provides two distillates and a distillate bottom. According to another exemplary embodiment the distillation provides eight distillates and a distillate bottom.

According to an exemplary embodiment, the distillation provides three fractions, namely a first distillation fraction, a second distillation fraction and a distillation residue. The distillates can be further divided into sub-distillates, which may be withdrawn from the distillation column as discrete products.

DK 181062 B1 9 According to one embodiment the distillation is performed at atmospheric pressure.

According to a particular embodiment the distillation is performed at atmospheric pressure producing a first distillation fraction, a second distillation fraction and a third distillation fraction.

According to an exemplary embodiment, at least 90 wt-% of the first distillation fraction boils at a temperature of 170 °C under atmospheric pressure.

According to the same exemplary embodiment, at least 80 wt-% of the second distillation fraction boils at a temperature range of 170 to 360 °C at atmospheric pressure.

Furthermore, according to the same exemplary embodiment, at least 90 wt-% of the third distillation fraction boils at a temperature of above 360 °C at atmospheric pressure.

According to a particular embodiment the one or more distillates are subjected to one or more further distillations to provide two or more sub-fractions of the one or more distillates.

According to the invention, the first distillate or one or more of its sub-fractions, and/or the second distillate or one or more of its sub-fractions is fed to a hydrodesulfurization unit wherein a hydrodesulfurization reaction is performed.

Hydrodesulfurization (HDS) is a catalytic chemical process used to remove sulfur from the distillates.

The purpose of removing the sulfur and creating products such as ultra-low-sulfur diesel, is to reduce the sulfur dioxide emissions that result from using those fuels in automotive vehicles, aircraft, railroad locomotives, ships, gas or oil burning power plants, residential and industrial furnaces, and other forms of fuel combustion.

For hydrodesulfurization, there are various types of catalysts employed.

Mostly these are different combinations of oxides and sulfides of cobalt, molybdenum, nickel, iron, and wolfram on y-alumina or alumina/silica/zeolite support, or on their mixture.

According to one embodiment the hydrodesulfurization of the first distillate or one or more of its sub-fractions produces a gasoline component or an intermediate suitable for further processing to a gasoline component.

DK 181062 B1 10 According to another embodiment the hydrodesulfurization of the second distillate or one or more of its sub-fractions produces a diesel component, or an intermediate suitable for further processing to a diesel component. Exemplary HDS catalysts are CoMo/Al203, NiMo/Al203 and CoMoNi/Al2O3.

According to the invention, the hydrodesulfurization is performed at 280-320 °C in 20-35 bar in the presence of hydrogen and a hydrodesulfurization catalyst such as CoMo/Al203 or NiMo/Al20s.

Exemplary process parameters for the middle distillate are temperature: 320— 380 °C; pressure: 35-80 bar in the presence of hydrogen and a hydrodesulfurization catalyst such as CoMo/Al20z or NiMo/Al20z. LHSV is preferably 1.5-3.0h™" and H»/feed ratio is preferably 300-450 N m%/m?.

Exemplary process parameters for naphtha fraction are CoMo/Al203 or NiMo/Al203 catalyst at 280-320°C temperature, 20-35 bar pressure, 3.0-5.0 h”! liquid hour space velocity (LHSV: flow of feedstock in m? through 1m? catalyst during 1h catalyst at normal condition of 20°C and 101.3kPa), and 100-250 N m%m? hydrogen/hydrocarbon ratio.

According to another embodiment the distillation residue/bottom is subjected to vacuum distillation typically at 370-410 °C and 1-10 kPa producing vacuum gas oil (VGO) and vacuum residue (VR).

According to a particular embodiment the VGO is further processed utilizing one or more of fluid catalytic cracking (FCC), hydrocracking (HC) and residue hydrocracking processes.

In the FCC process, the VGO is heated to a high temperature and moderate pressure, and brought into contact with a hot, powdered catalyst. An exemplary FCC catalyst has four major components: crystalline zeolite, matrix, binder, and filler. Zeolite is the primary active component and can range from about 15 to 50 weight percent of the catalyst. The catalyst breaks the long-chain molecules of the high- boiling hydrocarbon liquids into much shorter molecules, which are collected as a

DK 181062 B1 11 are then separated via distillation in the FCC main fractionator. The main products from the FCC process are gasoline and liquefied petroleum gas (LPG).

In the HC process, catalytic cracking of the VGO is assisted by the presence of added hydrogen gas. The HC is preferably facilitated by a bifunctional catalyst that is capable of rearranging and breaking hydrocarbon chains as well as adding hydrogen to aromatics and olefins that may be present in the VGO. The products HC are saturated hydrocarbons. The major products from hydrocracking are jet fuel and diesel, but low sulphur naphtha fractions and LPG are also produced. All these products have typically very low content of sulphur and other contaminants.

According to another particular embodiment the VR is further processed utilizing one or more of fluid catalytic cracking, hydrocracking and residue hydrocracking processes.

The method of the present invention alleviates problems which would be encountered if impure WP/ELT-derived liquids were distilled in a stand-alone distillation unit, and the resulting distillates would be co-processed directly in e.g. refinery hydrodesulfurization units. When utilizing this latter approach, i.e. stand- alone distillation and co-processing of distillates, the distillates will contain varying amounts of heteroatoms such as N and Cl. Upon hydrotreating, these will be removed in the form of NHs and HCI. This process will consume hydrogen and the resulting gases can form deposits of NH4CI which are problematic e.g. in heat exchangers and recycle gas compressors. Thus, it would be beneficial to lower the concentration of these heteroatoms prior to hydrotreating operations.

Processing the WP/ELT-derived oils according to the method of the present invention has the following benefits: Water-soluble impurities are removed in the desalting unit. These impurities may include e.g. HCI, oxygenated organic molecules and certain nitrogen-containing organic molecules.

It is known that WP/ELT-derived liquids may include organic chlorides. When subjected to high temperatures used in CDU preheating units the chlorides are released as HCI. The gaseous HCI that is released in the distillation will be carried

DK 181062 B1 12 to the top of the distillation column and to the overhead condenser, where it will subsequently condense along with the steam that is fed into the distillation column, thus forming aqueous hydrochloric acid. However, certain measures such as NaOH addition downstream of the desalter unit or use of a neutralizing amine can be used — to control and limit corrosion at the top of the distillation column and in the overhead condenser. It is less challenging to have HCI released in the CDU than in a downstream hydrotreating unit which does not have similar readiness for corrosion control.

If the WP/ELT-derived oil contain non-volatile impurities such as metals, co- processing the oil in a CDU has the benefit of concentrating the metals into a heavier hydrocarbon fractions which already have higher metal content to begin with. Depending of the impurities which are present in the WP/ELT-derived oil and the distillation configuration that is utilized, the metallic impurities can e.g. concentrate in vacuum gas oil or vacuum residue. These fractions can then be further processed in refining units which have a higher tolerance for metals. Such refining units can include e.g. fluid catalytic cracking or residue hydrocracking in an ebullated bed reactor.

WP/ELT-derived oils are more reactive than typical crude oil. Accordingly, the reactivity is reduced by diluting with crude oil which allows further processing of WP/ELT-derived oils in reactors such as HDS reactors designed for crude oil. Experimental Example 1. Removal of water-soluble impurities from WP-derived liquids The WP/ELT-derived liquids (pyrolysis oils) which are utilized in these examples were purchased from Ecomation Oy (Salo, Finland).

A waste plastic derived liquid was washed with water at ambient temperature to remove water-soluble impurities. The washing was carried out using a water-to-oil ratio of 1:1 (weight/weight) by agitating the mixture in a separation funnel. The oil and the water were separated, and the oil was analysed for heteroatom (N, S, Cl, Br) content. The results are shown in Table 1.

DK 181062 B1 13 Table 1. Results from water-washing of waste plastic derived liquid at room temperature using water-to-oil ratio of 1:1. re er Although the procedure itself may differ from an actual desalting process, the results show that a certain amount of impurities can be removed from waste plastic derived liquids by essentially washing the sample with water.

The impurities/heteroatoms which are removed are not necessarily actual salts — some of the compounds may also be water-soluble organic compounds.

One skilled in the art can also appreciate that the amount of water-soluble impurities in the waste plastic derived liquid will also vary depending of the feedstock and the pyrolysis process.

Furthermore, the conditions (temperature, residence time, diluting with crude oil) that are used in the actual desalting process can also influence the removal of impurities.

Example 2: Concentration of metallic impurities in the distillation of ELT-derived liquid

The example shows the metallic impurities beneficially concentrate into the distillation bottoms when an ELT-derived liquid is distilled into three separate fractions.

Iron (Fe) and zinc (Zn) were the most abundant impurities in the original ELT-derived liquid.

As the results in Table 2 show, both of these impurities were effectively concentrated into the distillation bottoms, which in this case is represented by the fraction with a boiling point range of >360 °C.

Thus, the distillate fractions which would be subsequently fed into e.g. fixed-bed hydrotreating reactors, no longer contain any Fe or Zn.

DK 181062 B1 14 Table 2. Distillation yields and distribution of main metallic impurities in distillation of ELT-derived liquid. ow, CELE, © raction fraction fraction Yield in distillation 21 52 27 (wt-%) In this example, the ELT-derived liquid was distilled in neat form, i.e. without any conventional crude oil.

In the processing concept that was presented in Figure 1, the >360 °C fraction of the ELT-derived liquid would exit the CDU in the atmospheric residue stream, which would then be subjected to vacuum distillation.

Thus, the contaminant metals of the ELT-derived liquid might further concentrate into the distillation bottoms of the vacuum distillation unit, i.e. vacuum residue.

Furthermore, all the distillate fractions that are obtained from the WP/ELT-derived liquid would be diluted with the co-processed crude oil.

Claims

DK 181062 B1 15 Patent claim

1. Process for co-processing liquid derived from waste plastic (WP) and/or liquid derived from end-of-life tires (ELT) with crude oil, which method comprises a) providing WP-derived liquid and/or ELT-derived liquid, b) to provide crude oil, c) to mix 1 part by weight of WP-derived liquid and/or ELT-derived liquid and 1 - 1000 parts by weight of crude oil to form an admixture, d) to desalt the admixture, where the desalination includes treatment with water, e) to distill the admixture to produce one or more distillates and a distillate bottom, f) subjecting at least one of the one or more distillates to a hydrodesulphurisation reaction, where the exposure takes place at 280-320 °C at 20-35 bar in the presence of hydrogen and a hydrodesulphurisation catalyst , such as CoMo/AlzO3 or NiMo/AlzO3, or where the exposure takes place at 320-380 °C at 35-80 bar in the presence of hydrogen and a hydrodesulfurization catalyst, such as CoMo/Al20s or NiMo/AlzO3, and g) exposing the distillate bottoms for vacuum distillation, where the vacuum distillation produces vacuum gas oil and/or vacuum residue, where the vacuum gas oil and/or vacuum residue is subjected to one or more of fluidized catalytic cracking, hydrocracking and residual hydrocracking.