BE1026831B1 - Process for upgrading waste oil - Google Patents

Abstract

The present invention relates to a method comprising subjecting a feedstock having an oxygen content of at most 5.0% by weight (on a dry basis) to heat treatment, separating solids from the heat-treated material to produce a metal-depleted feedstock the metal-depleted feedstock, optionally together with an additional feedstock, a hydrocracking and recovery of at least one hydrocarbon fraction boiling in the liquid fuel range from the hydrocracked material.

Description

Procedure for upgrading AItôl

DESCRIPTION Technical Field The present invention relates to a method for producing fuel components from waste oil, a fuel component obtainable by the method, and the use of the fuel component. Technical background Mobility and logistics are essential parts of life, the economy and today's society. In order to meet the increasing energy demands of traffic and transportation, it is important to strive for sustainable fuel solutions. Decarbonising the transportation sector (or avoiding carbon-based techniques in the transportation sector) is an overwhelming task and fossil fuels should slowly be replaced by more sustainable ones. A liquid fuel has advantages over gases and electricity in transport solutions due to the existing infrastructure and fuel logistics. The energy content of liquid fuels is also superior, which is essential as the energy has to be carried in the vehicles. In addition to biofuels, there is growing interest in the use of recycled (reused) fossil-based materials, such as used lubricant oils (ULO) or other waste oils for the production of transport fuels. Unlike most biomass-derived fluids, ULO and other fossil waste oils have a distinguished advantage in that they contain very little oxygen.

In contrast, ULO and other waste oils contain a large number of other impurities (metals, phosphorus, silicon, chlorine), which mainly result from additives that have been used in the production process.

However, the hydrocarbons contained in the recycled fossil-based materials, such as ULO and other waste oils, are largely paraffinic and fall within a boiling point range suitable for catalytic cracking.

Waste oils like these therefore offer an alternative to conventional crack raw materials such as vacuum gas oil (VGO). In addition, from 2020 in the European Union, the new Renewable Energy Directive (RED II) may contain some type of incentive for transport fuels made from fossil-based recycled feedstock.

Thus, while ULO and other waste oils are a highly challenging feedstock for purification, they are viewed as an alternative refinery feedstock with good potential.

One method of purifying used oils is distillation; it simultaneously separates most of the metallic impurities / phosphorus and the heaviest hydrocarbons into the still bottoms, resulting in distillates that take on a more usable form.

An alternative approach to upgrading waste oils, such as ULO, is to re-refine the hydrocarbons into their base oil components, for example by hydrotreating (hydrogenation treatment), and then use these in the formulation of new lubricants.

With this approach, it is essential to avoid cracking the base oil hydrocarbon chains during purification and hydrotreating.

Therefore, distillation techniques, which are particularly suitable for thermally unstable materials, are often used to fractionate ULO.

In addition, US Pat. No. 4,512,878 A discloses a method for recycling used oils, which comprises a heat impregnation step, a distillation step and a hydro refining step.

US 4411774 A discloses heat treatment of ULO in the presence of a pretreatment chemical to remove contaminants, followed by filtration and reuse of the thus treated liquids as lubricating oils.

US 3980551 A discloses the demetallization of ULO in an ebullated bed reactor, followed by vacuum distillation to produce a clean fraction and heavy fractions containing slag and metals.

Summary of the Invention It is an object of the present invention to provide an improved method for treating waste oils.

The inventors of the present invention surprisingly found that a heat treatment step is suitable to reduce the metal content of a waste oil material to such a degree that the heat-treated material, after removal of solid matter that is formed during the heat treatment, a metal-tolerant hydrocracking process without any further purification, such as distillation, can be subjected. More specifically, the inventors found that a heat-treated starting material (or a heat-treated raw material) has suitable properties that would allow it to be passed directly into hydrocracking without further need for distillation, thus significantly increasing the yield of the purification process before cracking as well as the total yield to improve.

That is, a particular disadvantage of distillation is the significant loss of hydrocarbon material to the still bottoms, even though it provides fairly pure material. In addition, although the majority of the metals are fractionated in the distillation bottoms, the resulting distillates do not necessarily meet the stringent contamination specifications of fixed bed hydrotreating / hydrocracking units (hydrogenation / hydrocracking). In practice, this means that a secondary cleaning agent must be used in order to further reduce the contamination concentrations of the used oil distillates. Depending on the distillation characteristics of the used oil sample and the distillation methodology, the hydrocarbons separated in the distillation bottoms can, for example, correspond to a vacuum residue (VR) type material that has a boiling point of> 550 ° C and contains significant amounts of metal impurities. Since an adequate level of metal removal can be achieved without distillation, the present invention thus provides a process which achieves extremely high yield compared to conventional techniques that employ distillation to provide a feed suitable for hydrotreating. The present invention is defined in the independent claims. Further preferred embodiments are set out in the dependent claims. In particular, the present invention relates to one or more of the following:

A method comprising the steps of: subjecting a raw material to a heat treatment (heat treatment step) to produce a heat-treated material containing liquid components and 5 solid components, separating solids from the heat-treated material to preparing a metal-depleted feed, subjecting the metal-depleted feed, optionally together with an additional feed, to hydrocracking (hydrocracking step) to form a hydrocracked material, recovering at least one hydrocarbon fraction boiling in the liquid fuel range from the hydrocracked material; wherein the starting material has an oxygen content of at most 5.0% by weight on a dry basis.

2. The method according to item 1, wherein the starting material has an oxygen content, on a dry basis, in the range from 0.1% by weight to 5.0% by weight, preferably at most 4.0% by weight, at most 3.5 % By weight or at most 3.0% by weight, and / or at least 0.2% by weight, at least 0.3% by weight, at least 0.4% by weight or at least 0.5% by weight. -% having.

3. The method according to item 1 or 2, wherein the total content of hydrogen (H) and carbon (C) in the base material, on a dry basis, is at least 80% by weight, preferably at least 85% by weight, at least 90% by weight. -%, at least 92% by weight, at least 94% by weight, at least 95% by weight, at least 96% by weight, at least 97% by weight, at least 98% by weight or at least 99% by weight %.

4. The method of any preceding item, further comprising a pretreatment step of dewatering a raw feedstock to produce the feedstock.

5. The method according to any one of the preceding points, wherein the metal-depleted feedstock (or the metal-depleted feed) is subjected to hydrocracking together with an additional feedstock (or an additional feed).

6. The method according to any one of the preceding points, wherein the additional feedstock is a fossil-based feedstock, a renewable feedstock, or a combination of both.

7. The method of item 6, wherein the fossil-based feedstock is a fraction of crude oil and / or the renewable feedstock is a material derived from deoxygenation of a renewable material.

8. The method according to any one of the preceding points, wherein the metal content of the metal-depleted feedstock is less than the metal content of the feedstock.

9. The method according to any one of the preceding points, wherein the metal content of the metal-depleted feedstock is at most 60% by weight of the metal content of the starting material, preferably at most 50% by weight, at most 40% by weight, at most 30% by weight, at most 20 wt%, at most 15 wt%, at most 10 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, at most 4 Wt .-% or at most 3 wt .-% of the metal content of the starting material.

10. The method according to any one of the preceding points, wherein the heat treatment is carried out at a temperature of at least 290 ° C, preferably at least 300 ° C or at least 310 ° C.

11. The method according to any one of the preceding points, wherein the heat treatment is carried out at a temperature of at least 320 ° C or at least 330 ° C.

12. The method according to one of the preceding points, wherein the heat treatment is carried out at a temperature of at most 450 ° C, preferably at most 400 ° C, at most 380 ° C, at most 370 ° C, at most 360 ° C, at most 350 ° C, at most 340 ° C or a maximum of 335 ° C.

13. The method according to one of the preceding points, wherein the heat treatment is carried out for at least 1 minute, preferably at least 2 minutes, at least 5 minutes, at least 10 minutes, at least 20 minutes, at least 30 minutes, at least 40 minutes, at least 50 minutes, at least 60 minutes Minutes, at least 80 minutes, or at least 100 minutes.

14. The method according to any one of the preceding points, wherein the heat treatment is carried out at a pressure of 1.0 bar or more, preferably 1.2 bar or more, 1.5 bar or more, 2.0 bar or more or 3.0 cash or more.

15. The method according to one of the preceding points, wherein the starting material contains at most 20.0% by weight of water, preferably at most 15.0% by weight, at most 12.0% by weight, at most 10.0% by weight , at most 8.0% by weight, at most 7.0% by weight, at most 6.0% by weight, at most 5.0% by weight, at most 4.0% by weight, at most 3.0 Weight

%, at most 2.0% by weight, at most 1.5% by weight, at most 1.0% by weight, at most 0.7% by weight or at most 0.5% by weight of water.

16. The method according to any one of the preceding points, wherein the hydrocracking step is carried out at a temperature in the range from 300 ° C to 500 ° C.

17. The method according to any one of the preceding points, wherein the hydrocracking step is carried out at a temperature of at least 310 ° C, at least 320 ° C, at least 330 ° C, at least 340 ° C, or at least 350 ° C, and / or at most 490 ° C, max 480 ° C, max 470 ° C, max 460 ° C, max 450 ° C, max 440 ° C or max 430 ° C.

18. The process of any preceding item, wherein the metal-depleted feed is subjected to hydrocracking in the presence of a solid catalyst.

19. The method of item 18, wherein the solid catalyst contains at least one Group VIII non-noble metal and at least one Group VIB metal and a carrier.

20. The method of item 19, wherein the carrier contains silica, alumina or clay.

21. The method of items 18 or 19, wherein the carrier comprises a Bronsted acid component.

22. The method of item 21 wherein the Bronsted acid component is zeolite or amorphous silica-alumina.

23. The method of item 22, wherein the zeolite is Y zeolite, beta zeolite or any other zeolite having a 12-membered ring.

24. The method of items 19 to 23, wherein the Group VIII non-noble metal is Co or Ni and the Group VIB metal is Mo or W.

25. The method according to any one of the preceding points, wherein the hydrogen partial pressure in the hydrocracking step is in the range from 70 to 200 bar.

26. The method according to any one of the preceding items, wherein the hydrocracking step is carried out in an ebullated bed reactor, a slurry reactor or a fixed bed reactor.

27. The method according to any one of the preceding points, wherein the total content of metals and phosphorus in the starting material is in the range from 500 mg / kg to 10,000 mg / kg, preferably 1,000 mg / kg to 8,000 mg / kg.

28. The method according to any one of the preceding points, wherein the starting material is liquid at 25 ° C.

29. The method according to any one of the preceding points, wherein the temperature during the dewatering is lower than the (highest) temperature in the heat treatment step.

30. The method according to any one of the preceding points, wherein the step of removing insoluble constituents from the heat-treated material (the step of removing solids)

comprises at least one of centrifugation, filtration and sedimentation, preferably at least centrifugation.

31. The method according to any one of the preceding points, wherein the heat treatment step is carried out for 100 hours or less, preferably 50 hours or less, 40 hours or less, 30 hours or less, 20 hours or less, 10 hours or less or 5 hours or less .

32. The method according to any of the preceding points, wherein a metal removal additive is added to the starting material before or during the heat treatment step, the metal removal additive preferably being at least one selected from the group consisting of ammonium sulfate, ammonium bisulfate, diammonium phosphate, ammonium dihydrogen phosphate, calcium hydrogen phosphate, phosphoric acid, magnesium sulfate , Aluminum sulfate and sodium sulfate.

33. Fuel component obtainable by the method according to one of the preceding points.

34. Fuel component according to item 33, comprising the recovered hydrocarbon fraction, the fraction preferably being a fraction which boils in the gasoline range or a fraction which boils in the middle distillate range.

35. Use of the recovered hydrocarbon fraction, which is obtained by the method according to any one of items 1 to 32, for producing a fuel or a fuel component.

The oxygen content in the starting material can be determined by elemental analysis. In the present invention, the oxygen content is determined on a dry basis of the starting material (excluding water if it is present in the starting material). Brief Description of the Drawing Figure 1 is a schematic illustration of the process in accordance with the present invention.

Detailed Description of the Invention The invention will now be described in detail with reference to specific embodiments. It should be noted that any feature of the embodiments can be combined with any feature of another embodiment, provided that such combination does not result in a contradiction.

The present invention relates to a method comprising a heat treatment step, a solids separation step, a hydrocracking step and a recovery step. The heat treatment step is a step of subjecting a raw material to heat treatment to produce a heat-treated material comprising liquid components and solid components. The starting material has an oxygen content of at most 5.0% by weight on a dry basis (i.e. excluding water). The solids separation step is a step of separating solids from the heat treated material to produce a metal-depleted feedstock. The hydrocracking step is a step of subjecting the metal-depleted feedstock, optionally along with an additional feedstock, to hydrocracking to form a hydrocracked material. The recovering step is a step of recovering at least one hydrocarbon fraction boiling in the liquid fuel region from the hydrocracked material.

The inventors of the present invention surprisingly found that heat treatment of the feedstock and subsequent removal of solids is sufficient to provide a feedstock that is suitable for metal tolerant hydrocracking units, such as residue hydrocracking (RHC) units. In particular, the inventors have found that distillation of the heat-treated material is not necessary and thus the significant loss of valuable hydrocarbon material in the distillation bottoms can be avoided. In addition, the heat treatment can reduce the slagging tendency (fouling tendency) of the cracking catalyst and thus increase the catalyst life. While not wishing to be bound by theory, it is believed that the heat treatment causes reactive components in the starting material to undergo a reaction and thus end up as a solid material which can be removed, for example, by filtration or centrifugation . It is believed that such reactive components are responsible for coke formation (slagging or fouling) in the hydrocracking step. The starting material of the present invention includes any material of fossil or renewable (biomass-based) origin with an oxygen content of at most 5% by weight on a dry basis. In a preferred embodiment that is

The starting material is a waste oil or a dehydrated waste oil. The inclusion of waste materials (already used materials) in the present invention provides a sustainable process of reintroducing fossil or renewable carbon material into the value chain, thus reducing the need to exploit natural resources. Since the starting material has an oxygen content of at most 5% by weight, unprocessed bio-based oils such as raw vegetable oil, fats and the like are not included because these materials have a high content of oxygen. Rather, the invention relates to a material that mainly comprises hydrocarbons as well as contaminants, for example contaminants that are included as a result of the manufacturing process of the material or as a result of the first use of the material.

In the present invention, the total content of metals (not including metalloids such as Si) and phosphorus in the starting material is preferably in the range of 500 mg / kg to 10,000 mg / kg, more preferably 1,000 mg / kg to 8,000 mg / kg. In other words, the starting material of the present invention is preferably a contaminated material such as a waste material. The content of metals in the starting material can be determined, for example, using inductively coupled plasma atomic emission spectrometry based on the ASTM D5185 standard. For the purpose of the present invention, the total content of metals preferably refers to the total content (summed content) of Al, Cr, Cu, Fe, Na, Ni, Pb, Sn, V, Ba, Ca, Mg, Mn and Zn.

In the present invention, the oxygen content "on a dry basis" means that the oxygen content is determined on the assumption that

that all water is removed prior to determining the content. The oxygen content on a dry basis can be determined by drying the starting material and determining the oxygen content (e.g. by elemental analysis). Alternatively, the dry basis oxygen content can be determined from a wet feedstock as follows: Oxygen content (dry basis) = 100% * {(total oxygen content of the wet feedstock, e.g. by elemental analysis) - (oxygen content present in the wet feedstock in the form of Water is contained)} / {(mass of the moist starting material) - (mass of the water in the moist starting material)} The content (mass) of the water contained in the moist starting material can be determined by suitable means (e.g. Karl- Fisher titration according to ASTM D6304, or distillation according to ASTM D95).

The feedstock may include used oil, such as used lubricant oil (ULO). In particular, waste oils according to the present invention can include any fossil (mineral oil-based) or renewable (biomass-based) lubricating or industrial oils which have become unsuitable for the originally intended use, and in particular used internal combustion engine oils and gear oils and also mineral lubricating oils, turbine oils and hydraulic oils. The starting material is preferably liquid at 25 ° C. Thus, the starting material can be handled easily and does not require excessive heating during storage and / or transport.

In the method of the present invention, the starting material preferably has an oxygen content, on a dry basis, in the range of 0.1 wt% to 5.0 wt%, more preferably at most 4.0 wt%, at most 3 , 5% by weight or at most 3.0% by weight, and / or at least 0.2% by weight, at least 0.3% by weight, at least 0.4% by weight or at least 0.5 Wt%. In other words, it is preferred that the starting material be a material that contains only small amounts of oxygen.

Furthermore, it is preferred that the total content of hydrogen (H) and carbon (C) in the starting material, on a dry basis, is at least 80% by weight, preferably at least 85% by weight, at least 90% by weight, at least 92% by weight, at least 94% by weight, at least 95% by weight, at least 96% by weight, at least 97% by weight, at least 98% by weight, or at least 99% by weight. It is preferred that the total content of hydrogen (H) and carbon (C) in the starting material, on a dry basis, be at least 90% by weight sel. The contents of hydrogen and carbon in the starting material can be determined by elemental analysis using, for example, ASTM D5291 can be determined. That is, the starting material of the present invention is preferably composed predominantly of hydrocarbon material (consisting of C and H) with low contents of heteroatoms, which may be contained as inorganic impurities and / or in the form of organic non-hydrocarbon material. The method of the present invention may further include a pretreatment step of dewatering a raw feedstock to provide the feedstock. In terms of

Efficiency, the dewatering does not have to be carried out if the material to be processed already contains small amounts of water, and thus the material can be used directly as the starting material.

Dewatering can be achieved by any suitable chemical and / or physical method. For example, an absorbent or an adsorbent for water can be brought into contact with the raw feedstock, or water can be removed thermally by evaporation (distillation). The temperature during dewatering is usually lower than that during the heat treatment step. The water removal step is preferably carried out at a temperature less than 150 ° C, preferably 130 ° C or less. It is further preferred that the dewatering is carried out at ambient pressure in order to keep the process equipment simple. The dewatering of the raw feedstock enables better performance in the subsequent steps, particularly in the heat treatment step. In particular, stable printing conditions can be achieved by removing water (and optionally other light components) before the heat treatment step. In contrast, some amount of water may be present in the starting material of the present invention. Depending on the circumstances, it may be advantageous to use a water-containing starting material without subjecting it to a water removal step. In any case, the starting material of the present invention preferably contains at most 20.0 wt% of water, more preferably at most 15.0 wt%, at most 12.0 wt%, at most 10.0 wt%, or at most 8.0% by weight. Even smaller amounts of water are desirable, but can involve additional effort to remove water.

Nevertheless, the starting material can have a water content of at most 7.0% by weight, at most 6.0% by weight, at most 5.0% by weight, at most 4.0% by weight, at most 3.0% by weight. -%, at most 2.0 wt.%, at most 1.5 wt.%, at most 1.0 wt.%, at most 0.7 wt.% or at most 0.5 wt.% water.

The method of the present invention includes a step of removing solids (insolubles) prior to performing hydrocracking.

The insoluble components include anything that is insoluble in the liquid phase that has been subjected to the heat treatment step.

In particular, the insoluble constituents include particulate solids, precipitates, slag, including (highly) viscous liquids which are immiscible with the liquid phase (which becomes the metal-depleted feedstock).

By reducing the level of insolubles (or by completely removing solids) before hydrocracking, the tendency to slagging can be reduced and the handling properties can be improved.

Suitable methods for removing solids include, but are not limited to, centrifugation, filtration, and sedimentation, and it is preferred that the process of the present invention include at least centrifugation as the single solids removal step or as one of several solids removal steps.

In the present invention, the metal content of the metal-depleted feedstock is less than the metal content of the feedstock.

In other words, metals in the raw material accumulate in the solids and are separated after the heat treatment.

As a result, the metal content is reduced.

In the following invention, “metal content” does not include the metalloid content (e.g. Si, B). The content of other contaminants (such as metalloids, phosphorus, sulfur and chlorine) may also be reduced.

The metal content of the metal-depleted feedstock is preferably at most 60% by weight of the metal content of the starting material, preferably at most 50% by weight, at most 40% by weight, at most 30% by weight, at most 20% by weight, at most 15% by weight %, at most 10% by weight, at most 8% by weight, at most 7% by weight, at most 6% by weight, at most 5% by weight, at most 4% by weight or at most 3% by weight. -% of the metal content of the starting material. The metal content can be determined by any suitable means such as atomic spectroscopy (e.g. AAS, AES, AFS, ICP-MS), e.g. inductively coupled plasma atomic emission spectroscopy based on the ASTM D5185 standard.

The more the metal content is reduced by the heat treatment and the subsequent solids removal, the more metal-depleted feedstock can be used in the subsequent hydrocracking step without worrying about catalyst poisoning or other negative effects of the metal contaminants.

In the present invention, the heating temperature during the heat treatment step is preferably at least 290 ° C. In this regard, the balance between heating temperature and heating time (residence time) affects the efficiency of the process of the present invention. In general, the lower the heat treatment temperature, the longer the heat treatment time should be for best results.

The heat treatment temperature is preferably at least 300 ° C, or at least 310 ° C, and can be at least 320 ° C or at least 330 ° C.

It is particularly preferred that the heat treatment temperature be the highest temperature among all temperatures of the process of the present invention that precede the hydrocracking step.

In the present invention, the heat treatment temperature refers to the temperature of the material to be treated (i.e., the raw material). When the heat treatment temperature is at least 290 ° C, remarkable metal depletion can be achieved. In this regard, although a reduction in the metal content can be achieved even at lower temperatures, this requires long heating times, which is therefore not preferred. On the other hand, heat treatment temperatures much higher than 440 ° C are usually not necessary to achieve the object of the present invention, so the heat treatment temperature is preferably 450 ° C or lower, more preferably 440 ° C or lower. Further, the heat treatment temperature may be 430 ° C or less, 420 ° C or less, 410 ° C or less, 400 ° C or less, 390 ° C or less, 380 ° C or less, 370 ° C or less, 360 ° C or less lower, 350 ° C or lower, 340 ° C or lower, or 335 ° C or lower. The heat treatment time (heat treatment time / residence time) also affects the efficiency of the method of the present invention. In general, it is preferred that the heat treatment step is carried out for at least 1 minute in order to achieve sufficient metal reduction (solidification) and also to enable good process control. The heat treatment time is preferably at least 2 minutes, at least 5 minutes, at least 10 minutes, at least 20 minutes, at least 30 minutes or at least 40 minutes. The heat treatment time may also be at least 50 minutes, at least 60 minutes, at least 80 minutes, or at least 100 minutes. In general there is no upper limit to the heat treatment time. In view of process efficiency, the heat treatment time is, although preferably without an upper limit, 100 hours or less, more preferably 50 hours or less, 40 hours or less, 30 hours or less, 20 hours or less, 10 hours or less, or 5 hours or less Less.

When the heat treatment is carried out in a batch reactor, the heat treatment time corresponds to the temperature holding time. In a continuous reactor the heat treatment time corresponds to the residence time.

Preferably the heat treatment step is at a pressure of 0.5 bar or more, more preferably 0.8 bar or more, 1.0 bar or more, 1.2 bar or more, 1.5 bar or more, 2.0 bar or more more, 3.0 bar or more, 4.0 bar or more, 5.0 bar or more, 6.0 bar or more, 8.0 bar or more, 10.0 bar or more, 12.0 bar or more or 14.0 bar or more carried out. Increased pressure during the heat treatment step can reduce the tendency to evaporate and thus ensure efficient heat treatment. The pressure should be 200 bar or less, preferably 100 bar or less, more preferably 50 bar or less, in order to keep the technical equipment simple.

Unless otherwise specified, a pressure indicated in the present invention means an absolute pressure. The pressure values above relate to the highest pressure occurring in the heat treatment step, ie measured at the point / time of the highest pressure. In particular, it is preferred that the heat treatment is not performed under reduced pressure (negative pressure), but rather under ambient pressure or increased pressure. In particular, higher pressure reduces the evaporation tendency and thus possible product loss or boiling effects (e.g. in continuous processes).

A metal removal additive may be present during the heat treatment step. The metal removal additive can be added before the start of the heat treatment and / or during the heat treatment. Suitable metal removal additives are those mentioned in US 4411774 A, but they are not limited to these. Specifically, the metal removal additive of the present invention may be one or more selected from the group consisting of ammonium sulfate, ammonium bisulfate, diammonium phosphate, ammonium dihydrogen phosphate, calcium hydrogen phosphate, phosphoric acid and magnesium sulfate and / or one or more selected from the group consisting of calcium sulfate, aluminum sulfate and sodium sulfate. The total addition amount of the metal removing additive is preferably at least 0.1 wt%, more preferably at least 0.5 wt%, or at least 1.0 wt% relative to the dry weight of the starting material (total weight on a dry basis). The total amount added relates to the total amount of all metal removal additives added (but not including solvents, if these are added together with the metal removal additives). When the metal removal additive is one or more selected from

Group consisting of calcium sulfate, aluminum sulfate and sodium sulfate, the addition amount is preferably at least 2.0% by weight, more preferably at least 3.0% by weight, and further preferably at least 4.0% by weight, so as to improve the filterability .

However, metal removal efficiency is improved with any (even small) amount of metal removal additive compared to a process that uses no additive at all.

In the present invention, the type of hydrocracking is not particularly limited as long as it can tolerate the metal content of the metal-depleted feed (optionally mixed with an additional feed).

A conventional hydrocracking process can be employed, and usable types of hydrocracking processes include fixed bed hydrocracking, fluidized bed hydrocracking, and suspension hydrocracking.

Hydrocracking can take place in the presence of a solid catalyst (resp.

Solid catalyst) are carried out.

The solid catalyst can be a bifunctional catalyst.

If a catalyst is used, the cracking effect can be achieved at a lower cracking temperature.

The solid catalyst preferably contains at least one Group VIII non-noble metal, at least one Group VIB metal and a support.

Both the non-noble metal of group VIII and the at least one metal of group VIB are preferably supported on the carrier.

A suitable carrier can be used, and a carrier comprising silica, alumina or clay is preferred.

Moreover, a carrier containing a Bronsted acid component can preferably be used.

The Bronsted acid component may preferably be a zeolite or amorphous silica-alumina.

A suitable zeolite is Y zeolite, beta zeolite, or any other 12-membered zeolite

Ring zeolite. The Group VIII non-noble metal is preferably Co or Ni. The group VIB metal is preferably Mo or W. The following types of catalysts are particularly preferred, especially when they are supported on a carrier as mentioned above: Co-Mo, Co-W, Ni-Mo, Ni-W The cracking temperature is not particularly limited, and any suitable temperature can be used. Specifically, a temperature in a range of 300 ° C to 500 ° C can be used. The cracking temperature is preferably at least 310 ° C, at least 320 ° C, at least 330 ° C, at least 340 ° C, or at least 350 ° C. The cracking temperature may be 490 ° C or less, 480 ° C or less, 470 ° C or less, 460 ° C or less, 450 ° C or less, 440 ° C or less, or 430 ° C or less.

In the hydrocracking step, the hydrogen partial pressure in the hydrocracking step is preferably in the range from 70 to 200 bar. The hydrocracking step can be carried out in any suitable reactor and preferred is a fluidized bed reactor, a slurry reactor (suspension reactor) or a fixed bed reactor. The feed to the hydrocracking step may comprise one or more additional feeds in addition to the metal depleted feed of the present invention. The additional feed (or feed) may be a fossil-based feed, a renewable feed, or a combination of both. The feedstock of the hydrocracking step preferably comprises a renewable feedstock component (biomass-based

Feedstock component) as an additional feedstock in addition to the metal-depleted feedstock (component). By combining the metal-depleted feedstock with a biomass-based feedstock, the process of the present invention can be made even more sustainable. The feedstock, and much more the metal-depleted feedstock made from it, mainly comprises hydrocarbons (compounds composed of carbon atoms and hydrogen atoms), and thus the oxygen content and other properties can be finely adjusted by combining the biomass-based feedstock and the metal-depleted feedstock. The renewable feedstock may be a material derived from deoxygenation of a renewable material.

Furthermore, the feed to the hydrocracking step may contain a fossil feed component in addition to the metal depleted feed. The fossil feed may be a suitable feed different from the metal depleted feed and may be a fraction of crude oil (e.g., a fraction from crude oil distillation or a fraction obtained from processing crude oil). In particular, the fossil feedstock may be a conventional cracking feedstock, such as vacuum gas oil (VGO) or vacuum residue (VR).

By combining the metal-depleted feedstock with a further feedstock (additional feedstock or additional feed), the hydrocracking properties can be finely adjusted and the desired product distribution can be adjusted more easily. Preferably, the content of the metal-depleted feedstock in the (total) feedstock of the hydrocracking step is 50% by weight or less, more preferably 40% by weight or less, 30% by weight or less, or 20% by weight or less.

In order to efficiently increase the use of waste oil components, the content of the metal-depleted feed in the feed of the hydrocracking step is preferably 1 wt% or more, more preferably 2 wt% or more, 5 wt% or more, or 8 wt. -% or more.

By limiting the level of metal-depleted feed in the (total) hydrocracking feed, the metal content can be limited while still having a sustained effect.

Limiting the metal content allows a selection of less metal-tolerant catalysts and / or can improve catalyst life.

The process of the present invention further comprises a step of recovering at least one hydrocarbon fraction from the hydrocracked material (the product of the hydrocracking step / hydrocracked product). This step can be accomplished by fractionating the hydrocracked material and recovering the at least one fraction.

Fractionation can be carried out by any known means and preferably results in the production of a fraction in the gasoline range and / or a fraction in the middle distillate range.

The procedure of the present invention is shown schematically in FIG.

As illustrated in FIG. 1, water can be removed in a dewatering step (optional), insoluble constituents (precipitates) are removed, for example, in a centrifugation step.

The resulting metal-depleted feed is then subjected to hydrocracking.

The present invention further relates to a fuel component obtainable by the method of the present invention.

As can be seen from the results of the examples, the process of the present invention makes it possible to produce fuel components, particularly in the gasoline range and in the middle distillate range, in high yield.

The present invention also relates to the use of the recovered hydrocarbon fraction in the manufacture of a fuel or a fuel component.

Examples The present invention is further illustrated by way of examples. It should be noted, however, that the invention is not intended to be limited to the exemplary embodiments shown in the examples.

Example 1 Used lubricating oil (ULO) was used as a starting material. The ULO contained 17.0 wt.% Water and had a high amount of metal impurities (3181 mg / kg on a wet basis = 3833 mg / kg on a dry basis; detected metals: Al, Cr, Cu, Fe, Na, Ni , Pb, Sn, V, Ba, Ca, Mg, Mn, Zn). The Si content was also detected and was 84 mg / kg (moist) and thus 101 mg / kg (dry). The oxygen content (on a dry basis) was 1.0 wt%.

The ULO was dehydrated in a rotary evaporator at 100 ° C. and 80 mbar.

As a result, water (and light components) were removed.

The dehydrated ULO was then subjected to a heat treatment in a batch reactor at 320 ° C. for 1 hour.

The pressure at the start of the heat treatment was 1 bar and the pressure increased to about 23 bar as a result of the heating in the closed vessel.

The heat treated material was cooled to 50 ° C and centrifuged at 4300 RPM for 30 minutes and the liquid parts (excluding solids and slag) were recovered as metal-depleted feed ready for addition to a hydrocracking process.

The yield of the respective process steps (% by weight of the original ULO) and the metal content of the starting material (ULO) and of the metal-depleted starting material (after centrifugation) are given in Table 1 below.

Table 1: Yield Yield Metals _ p {% by weight (Gem. 0e mg / kg ”‚ “Dress current moist dry {dry ma / kg mg / kg step {dry {dry starting starting basic basis} | basis } material} material) location} EE 5 | 75 | Water + light level 18.5 drainage | PRE whose parts as | # 8 | # 8 | <| 8 | 7 solids heat recovery 6.5 7.8 handiung + Schiacke} solids sea distemuns | poor 73.4 88.4 48 17 20 delivery

As can be seen from Table 1, the process of the present invention achieves a significant reduction in metal (and metalloid) content, making it suitable as a feed to a metal tolerant hydrocracking process.

Comparative Example 1 The metal-depleted feedstock from Example 1 was further subjected to thin-film evaporation at 0.1 mbar (270-281 ° C.). As a result, the total metal content of the distillate (boiling point <560 ° C.) was further reduced to 2 mg / kg, whereas the Si content and the P content remained almost unchanged. In contrast, a further 6% by weight of product (relative to the starting material on a dry basis) was lost as distillate bottoms.

Example 2 Another batch of used lubricating oil (ULO-2) was used as a starting material. The ULO-2 contained 2.6% by weight of water and had a high content of metal impurities (2155 mg / kg on a moist basis; detected metals: Al, Cr, Cu, Fe, Na, Ni, Pb, Sn, V , Ba, Ca, Mg, Mn, Zn). The Si content was 278 mg / kg (wet) and the P content was 455 mg / kg (wet). The oxygen content (on a dry basis) was 1.0 wt%.

The ULO-2 was dehydrated in a rotary evaporator at 100 ° C. and 80 mbar. As a result, water (and light components) were removed. A portion of the dehydrated ULO-2 was then mixed with 3000 ppm (relative to the dehydrated ULO-2) of 85 wt% H3PO4 as a metal removal enhancer and then became one

Subjected to heat treatment in a batch reactor at 320 ° C for 1 hour. Another part of the dehydrated ULO-2 was subjected to the heat treatment in a batch reactor at 320 ° C. for 1 hour without an additive. In each case the pressure at the beginning of the heat treatment was 1 bar and the pressure increased to about 6-7 bar as a result of the heating in the closed vessel. The heat treated material was cooled to 50 ° C and solids were removed and the liquid parts (excluding solids and slag) were recovered as a metal-depleted feed ready for hydrocracking.

Solids removal was carried out using centrifugation at 4300 rpm for 30 minutes. In another experiment, solids removal was carried out by filtration instead of centrifugation.

The yield of the respective process steps (% by weight of the original ULO) and the metal contents of the starting material (ULO-2) and of the metal-depleted starting material (after centrifugation) are shown in Table 2 below.

Table 2:

Prazess stream yield yield metals Si p step (Gem% tea Do mg / kg mg / kg mg / kg moist dry {dry | {dry | {dry starting | starting basic foundation | basic day material) | materiaD location} e} e} me [all # water + light _ constituent AG VE parts

LO fast substances and F3 7.5 hot slag treatment with Addy + metal zentiri- ARR veramate; 88.1 30.5 111 133 69 fuglernen se © 5 Schickung Festatoffe wWärme- (us 75 7.8 treatment slag) with Additiy + | Metal filtration | Vérannts 87.8 96.1 31 71 14 Feed As can be seen from Table 2, the process of the present invention achieves a significant reduction in metal (and metalloid) content, making them suitable for feeding in a metal tolerant hydrocracking process. It can also be seen that the metal removal efficiency is significantly improved when a metal removal additive is used in combination with filtration as the solids removal step (preferably at least as the first stage of the metal removal step or as the only metal removal step).

Comparative Example 2 ULO-2 was subjected to the heat treatment in the same manner as in Example 2, but without the metal removal additive, followed by centrifugation.

The heat-treated sample was then subjected to distillation under the conditions used in Comparative Example 1.

The results are shown in Table 3 below.

Table 3

Process Stream Yield Yield Metals Si P mg / kg step {wt. 4 IGEw. wb mg / kg mg / kg {dry moist dry {dry | (dry | Srund- Grund- Crund- Basis) Basis} stock} stock} situation} EEK | =] water + light I constituent dewatering ésan parts dry 85.4 978 ULo a ’solids heat.

Lure 9.46 3.3 treated slag) without additive + metal Zenirfugleren. impoverished 85.7 88.0 soî 122 308 Ainsatz-. ’Maternal treatment + centrifugation As can be seen from Table 3, the metal removal efficiency of the distillation is higher than a case where centrifugation or filtration is carried out only after the heat treatment.

However, the Si content is even higher (presumably because volatile Si compounds themselves evaporate from the slag) than for the technique of the present invention.

In addition, a significant amount of the product is lost as distillation bottoms.

Claims (12)

PATENT CLAIMS 1. A method comprising the following steps: subjecting a starting material (or feedstock or raw material) to a heat treatment (heat treatment step) to produce a heat-treated material that contains liquid components and solid components, the heat treatment at a temperature of at least 310 ° C and is carried out at a pressure of 1.2 bar or more, separating solids from the heat-treated material to produce a metal-depleted feedstock, subjecting the metal-depleted feedstock, optionally together with an additional feedstock, to a hydrocracking (hydrocracking step) to give a hydrocracked Forming material, recovering at least one hydrocarbon fraction boiling in the liquid fuel region from the hydrocracked material; wherein the feedstock has an oxygen content of at most 5.0% by weight on a dry basis and the feedstock consists predominantly of hydrocarbon material. 2. The method of claim 1, wherein the starting material has an oxygen content, on a dry basis, in the range from 0.1 wt% to 5.0 wt%, preferably at most 4.0 wt%, at most 3.5 Wt .-% or at most 3.0 wt .-%, and / or at least 0.2 wt .-%, at least 0.3 wt .-%, at least 0.4 wt .-% or at least 0.5 wt. -% having. 3. The method according to claim 1 or 2, wherein the total content of hydrogen (H) and carbon (C) in the base material, on a dry basis, is at least 80% by weight, preferably at least 85% by weight, at least 90% by weight. -%, at least 92% by weight, at least 94% by weight, at least 95% by weight, at least 96% by weight, at least 97% by weight, at least 98% by weight or at least 99% by weight. 4. The method according to any one of the preceding claims, wherein the metal-depleted feedstock (or the metal-depleted feed) is subjected to hydrocracking together with an additional feedstock, the additional feedstock preferably being a fossil-based feedstock, a renewable feedstock or a combination of both. 5. The method according to any one of the preceding claims, wherein the heat treatment is carried out at a temperature of at least 320 ° C or at least 330 ° C. 6. The method according to any one of the preceding claims, wherein the heat treatment is carried out for at least 1 minute, preferably at least 2 minutes, at least 5 minutes, at least 10 minutes, at least 20 minutes, at least 30 minutes, at least 40 minutes, at least 50 minutes, at least 60 minutes Minutes, at least 80 minutes, or at least 100 minutes. 7. The method according to any one of the preceding claims, wherein the hydrocracking step is carried out at a temperature in the range of 300 ° C to 500 ° C. 8. The process of any preceding claim, wherein the metal-depleted feed is subjected to hydrocracking in the presence of a solid catalyst and the solid catalyst preferably contains at least one Group VIII non-noble metal and at least one Group VIB metal and a carrier. 9. The method according to claim 8, wherein the carrier comprises silica, alumina or clay and / or wherein the carrier comprises a Brönsted acid component, wherein the Brönsted acid component is preferably zeolite or amorphous silica-alumina. 10. The method according to any one of the preceding claims, wherein the hydrocracking step is carried out in a fluidized bed reactor, a slurry reactor or a fixed bed reactor. 11. The method according to any one of the preceding claims, wherein the total content of metals and phosphorus in the starting material is in the range from 500 mg / kg to 10,000 mg / kg, preferably 1,000 mg / kg to 8,000 mg / kg. 12. The method according to any one of the preceding claims, wherein the step of removing insoluble components from the heat-treated material (the step of removing solids) comprises at least one of centrifugation, filtration and sedimentation, preferably at least centrifugation.