ES2773398B2 - Method to improve used oils - Google Patents

Description

DESCRIPTION

Method to improve used oils

Technical field

The present invention relates to a method for the production of fuel components from used oils, to a fuel component obtainable by the method, and to the use of the fuel component.

Technical background

Mobility and logistics are an essential part of life, the economy and today's society. To meet the growing energy needs of traffic and transportation, it is important to seek sustainable fuel solutions. Decarbonization of the transport sector is a major challenge and fossil fuels should be slowly replaced by more sustainable fuels. Liquid fuel has benefits compared to gases and electricity in traffic solutions due to the existing infrastructure and logistics of the fuel. The energy content of liquid fuels is also higher, which is essential since energy must be transported on board in vehicles.

In addition to biofuels, there is growing interest in the use of recycled fossil materials, such as used lubricating oils (ULO) or other used oils for the production of transportation fuels. Unlike most liquids made from biomass, ULO and other fossil waste oils have the distinctive benefit of containing very little oxygen. On the other hand, ULO and the other used oils contain a plurality of other impurities (metals, phosphorus, silicon, chlorine) that mainly originate from the additives that have been used in the production process. However, the hydrocarbons that are contained in fossil fuel based recycled materials such as ULO and other waste oils are largely paraffinic, and fall within a boiling point range that is suitable for catalytic cracking. Waste oils such as these therefore offer an alternative to conventional cracking feeds such as vacuum gas oil (VGO).

In addition, as of 2020 in the European Union, the new directive on renewable energies (RED II) may include some type of incentive for transport fuels prepared from recycled food based on fossil materials. Therefore, even though ULO and the other waste oils are a highly challenging feedstock in terms of purification, they are considered an alternative refinery feed with good potential. One method for the purification of used oils is distillation; Most of the metallic / phosphorous impurities and the heavier hydrocarbons are simultaneously removed in the still bottoms, converting the resulting distillates into a more easily usable form.

An alternative approach to improving used oils, such as ULO, is to re-refine the hydrocarbons into base oil components, for example by hydrotreating, and use them later in the formulation of new lubricants. In this approach, it is essential to avoid cracking of the base oil hydrocarbon chains during purification and hydrotreating. Because of this, distillation technologies that are particularly suitable for thermally unstable materials are often used for the fractionation of ULO.

Furthermore, US Patent 4,512,878 A discloses a method for recycling used oils comprising a heat soaking stage, a distillation stage and a hydrorefining stage.

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

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

Summary of the invention

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

The inventors of the present invention have surprisingly discovered that a heat treatment step is suitable for reducing the metal content of a waste oil material to such an extent that the heat treated material, after removal of the solid substance formed during heat treatment, can be subjected to a tolerant hydrocracking process to metals without any further purification, such as distillation. More specifically, the inventors have discovered that a heat-treated feedstock possesses suitable properties that would allow it to be returned directly to hydrocracking without the additional need for distillation, thereby significantly improving the performance of the pre-cracking purification process, as well as the overall performance.

That is, a distinctive disadvantage of distillation, while providing fairly pure material, is the significant loss of hydrocarbon material to the distillation bottoms. Additionally, although most metals are fractionated in the bottoms, the resulting distillates do not necessarily meet the strict contaminant specification of fixed bed hydro-treating / hydrocracking units. In practice, this means that a secondary means of purification must be employed to further reduce contaminant concentrations in used oil distillates. Depending on the distillation characteristics of the waste oil sample and the distillation methodology, the hydrocarbons that separate in the distillation bottoms may correspond to, for example, vacuum residue (VR) type material that has a boiling point > 550 ° C and contains significant amounts of metallic impurities.

Therefore, since an adequate level of metal removal can be achieved without distillation, the present invention provides a process that achieves exceptionally high yields compared to conventional techniques that employ distillation to provide a suitable feed for hydrotreating.

The present invention is defined in the independent claims. Other beneficial embodiments are set forth in the dependent claims. Specifically, the present invention relates to one or more of the following elements:

1. A method comprising the following steps:

subjecting a raw material to a heat treatment (heat treatment step) to produce a heat treated material comprising liquid components and solid components,

separate solids from heat treated material to produce a feed reduced in metal,

subjecting the reduced metal feed, optionally together with a co-feed, to hydrocracking (hydrocracking step) to form a hydrocracked material,

recovering at least a fraction of hydrocarbon boiling in the liquid fuel range of the hydrocracked material;

in which

The raw 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 raw material has an oxygen content, on a dry basis, in the range of 0.1% by weight to 5.0% by weight, preferably maximum 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.

3. The method according to item 1 or 2, wherein the total content of hydrogen (H) and carbon (C) in the raw 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 previous points, further comprising a dehydration pretreatment step of a raw feed to prepare the raw material.

5. The method according to any one of the above, wherein the reduced metal feed is hydrocracked together with a co-feed.

6. The method according to any one of the above elements, in which the joint diet is a fossil-based diet, a renewable diet or a combination of both.

7. The method according to item 6, where the fossil feed is a fraction of crude oil and / or the renewable feed is a material obtained by deoxygenation of a renewable material.

8. The method according to any one of the above, wherein the metal content of the reduced metal feed is less than the metal content of the raw material.

9. The method according to any one of the above, wherein the metal content of the reduced metal feed is at most 60% by weight of the metal content of the raw material, preferably at most 50% by weight, maximum 40% by weight, maximum 30% by weight, maximum 20% by weight, maximum 15% by weight, maximum 10% by weight, maximum 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 raw material.

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

13. The method according to any one of the above 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, at least 80 minutes, or at least 100 minutes.

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

15. The method according to any one of the preceding points, in which the raw material contains a maximum of 20.0% by weight of water, preferably a maximum of 15.0% by weight, and a maximum of 12.0 % by weight, not more than 10.0% by weight, not more than 8.0% by weight, not more than 7.0% by weight, not more than 6.0% by weight, not more than 5.0 % by weight, maximum 4.0% by weight, maximum 3.0% by weight, maximum 2.0% by weight, maximum 1.5% by weight, maximum 1.0 % by weight, not more than 0.7% by weight or not more than 0.5% by weight of water.

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

17. The method according to any one of the above 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 maximum 490 ° C, maximum 480 ° C, maximum 470 ° C, maximum 460 ° C, maximum 450 ° C, maximum 440 ° C or maximum 430 ° C.

18. The method according to any one of the above, wherein the reduced metal feed is hydrocracked in the presence of a solid catalyst.

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

20. The method according to item 19, wherein the carrier comprises silica, alumina or clay.

21. The method according to item 18 or 19, wherein the vehicle comprises the Bronsted acid component.

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

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

24. The method according to 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 above points, wherein the partial pressure of hydrogen in the hydrocracking step is in the range of 70 to 200 bar.

26. The method according to any one of the above points, wherein the hydrocracking step is carried out in a boiling bed reactor, slurry reactor or a fixed bed reactor.

27. The method according to any one of the above points, wherein the total content of metals and phosphorus in the raw material is in the range of 500 mg / kg to 10000 mg / kg, preferably 1000 mg / kg to 8000 mg / kg.

28. The method according to any one of the previous points, in which the raw material is liquid at 25 ° C.

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

30. The method according to any one of the preceding points, in which the step of removing insoluble components (the step of separating the solids from the heat-treated material) comprises at least one of centrifugation, filtration and sedimentation, preferably at least centrifugation .

31. The method according to any one of the above 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 one of the previous points, in which a metal removal additive is mixed with the raw material before or during the step of heat treatment, 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, calcium, aluminum sulfate and sodium sulfate.

33. A fuel component obtainable by the method according to any one of the preceding items.

34. The fuel component according to item 33, comprising the recovered hydrocarbon fraction, wherein the fraction is preferably a fraction that boils in the range of gasoline, or a fraction that boils in the range of the middle distillate .

35. A use of the recovered hydrocarbon fraction obtained by the method according to any one of items 1 to 32 for the production of a fuel or a fuel component.

The oxygen content in the raw material can be determined by elemental analysis. In the present invention, the oxygen content is determined on the dry basis of the raw material (excluding water, if present in the raw material).

Brief description of the drawing

Figure 1 is a schematic illustration of the process according to the present invention.

Detailed description of the invention

The invention is explained in detail below by reference to specific embodiments. It is to be noted that any feature of the embodiments can be combined with any feature of another embodiment as long as 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 stage is a stage of subjecting a raw material to a heat treatment to produce a heat-treated material comprising liquid components and solid components. The raw material has an oxygen content of at most 5.0% by weight on a dry basis (ie excluding water). The solids separation step is a step of separating solids from the material heat treated to produce a reduced metal feed. The hydrocracking step is a step of subjecting the reduced metal feed, optionally together with a co-feed, to hydrocracking to form a hydrocracked material. The recovery step is a step of recovering at least a boiling hydrocarbon fraction in the liquid fuel range of the hydrocracked material.

The present inventors have surprisingly found that the heat treatment of the raw material and the subsequent removal of solids is sufficient to provide a suitable feed for metal tolerant hydrocracking units, such as residue hydrocracking units (RHC). Specifically, the inventors have found that distillation of heat-treated material is not necessary and, therefore, significant loss of valuable hydrocarbon material in distillation bottoms can be avoided.

Furthermore, the heat treatment can reduce the clogging tendencies of the cracking catalyst and thereby increase the useful life of the catalyst. Although not wishing to be bound by theory, it is assumed that the heat treatment causes the reactive components in the raw material to undergo a reaction and thus end up as a solid material that can be removed, for example, by filtration or centrifugation. . These reactive components are assumed to be responsible for the formation of coke (scale) in the hydrocracking stage.

The raw material of the present invention includes any material of fossil or renewable origin (based on biomass) that has an oxygen content of at most 5% by weight on a dry basis. In a preferred embodiment, the raw material is used oil or dehydrated waste oil. The use of a waste material (previously used material) in the present invention provides a sustainable process of reintroducing carbon material of fossil or renewable origin in the value chain and, therefore, reduces the need to exploit natural resources . Since the raw material has an oxygen content of at most 5% by weight, unprocessed bio-based oils such as crude vegetable oil, fats and the like are not included, as these materials have a high oxygen content. Rather, the invention relates to a material that contains primarily hydrocarbons, as well as contaminants, eg, contaminants included as a result of the method of production of the material or as a result of the primary use of the material.

In the present invention, the total content of metals (not including metalloids, such as Si) and phosphorus in the raw material is preferably in the range of 500 mg / kg to 10000 mg / kg, preferably 1000 mg / kg to 8000 mg. / kg. In other words, the raw material of the present invention is preferably a contaminated material, such as a waste material. The metal content in the raw material can be determined using, for example, inductively coupled plasma atomic emission spectrometry based on ASTM D5185. For the cinemas of the present invention, the total metal content preferably refers to the total (added) 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 under the assumption that all the water is removed prior to the content determination. The dry oxygen content can be determined by drying the raw material and determining the oxygen content (eg by elemental analysis). Alternatively, the dry oxygen content can be determined from a wet raw material as follows:

oxygen content (dry basis) = 100% * {(total oxygen content of wet raw material, for example by elemental analysis) - (oxygen content of wet raw material in the form of water)} / {(mass of wet raw material) - (mass of water in the wet raw material)}

The content (mass) of water contained in the wet raw material can be determined by any suitable means (for example, Karl-Fisher titration according to ASTM D6304, or distillation according to ASTM D95).

The raw material can comprise used oils, such as used lubricating oil (ULO). Specifically, the oils used in accordance with the present invention include any fossil (mineral-based) or renewable (biomass-based) lubricating or industrial oil that has become unsuitable for the use for which it was originally intended, and in particular used combustion engine oils and oils for gearboxes and also mineral lubricating oils, turbine oils and hydraulic oils.

The raw material is preferably liquid at 25 ° C. Therefore, the raw material can be easily handled and does not require excessive heating during storage and / or transportation.

In the method of the present invention, the raw material preferably has an oxygen content, on a dry basis, in the range of 0.1% by weight to 5.0% by weight, more 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 one 0.4% by weight or at least 0.5% by weight.

In other words, it is preferred that the raw material is 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 raw 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 raw material, on a dry basis, is at least 90% by weight. The hydrogen and carbon content in the raw material can be determined by elemental analysis using, for example, ASTM D5291.

That is, the raw material of the present invention is mainly composed of hydrocarbon material (consisting of C and H) with low contents of heteroatoms that can be contained as inorganic impurities and / or in the form of organic material that is not hydrocarbon.

The method of the present invention may further comprise a dewatering pretreatment step of a raw feed to provide the raw material. In view of efficiency, the dewatering step does not need to be carried out if the material being processed already contains a low amount of water, and therefore the material can be used directly as a raw material.

Dehydration can be achieved by any suitable chemical and / or physical method. For example, a water absorbent or adsorbent can be contacted with the raw feed or the water can be thermally removed by evaporation (distillation). The temperature during dehydration is usually lower than in the heat treatment stage. The dewatering step is preferably carried out at a temperature of less than 150 ° C, preferably 130 ° C or less. Furthermore, it is preferred that the dehydration is carried out at ambient pressure to keep the processing equipment simple.

Dewatering of the raw feed allows for better performance in later stages, especially in the heat treatment stage. In particular, stable pressure conditions can be achieved by removal of water (and optionally other light components) prior to the heat treatment step.

On the other hand, a certain amount of water may be present in the raw material of the present invention. Depending on the circumstances, it may be favorable to use a raw material that contains water without subjecting it to a water removal step. In any case, the raw material of the present invention preferably contains at most 20.0% by weight of water, more preferably at most 15.0% by weight, at most 12.0% by weight, at most 10.0% by weight, or at most 8.0% by weight. Even smaller amounts of water are desirable, but can cause additional efforts to remove the water. However, the raw material can have a water content of maximum 7.0% by weight, maximum 6.0% by weight, maximum 5.0% by weight, maximum 4.0% by weight, not more than 3.0% by weight, not more than 2.0% by weight, not more than 1.5% by weight, not more than 1.0% by weight, not more than 0.7% by weight or at most 0.5% by weight water.

The method of the present invention comprises a step of removing solids (insoluble components) before carrying out the hydrocracking. Insoluble components include any material that is insoluble in the liquid phase that has undergone heat treatment. More specifically, insoluble components include particulate solids, precipitates, sludge, including (highly) viscous liquids that are immiscible with the liquid phase (which becomes metal reduced feed). By reducing the content of insoluble components (or completely removing solids) prior to hydrocracking, the tendency to clogging can be reduced and handling properties can be improved. The right methods for removing solids includes, but is not limited to, centrifugation, filtration and sedimentation, and it is preferred that the process of the present invention comprises at least centrifugation as the sole solids removal step or as at least one of multiple solids removal steps. .

In the present invention, the metal content of the reduced metal feed is less than the metal content of the raw material. In other words, the metals in the raw material accumulate in the solids and are separated after heat treatment. As a result, the metal content is reduced. In the present invention, "metal content " does not include metalloid content (eg, Si, B). At this time, the content of other pollutants (such as metalloids, phosphorus, sulfur, and chlorine) can also be reduced.

The metal content of the reduced metal feed is preferably at most 60% by weight of the metal content of the raw material, preferably at most 50% by weight, at most 40% by weight, at most 30% by weight, maximum 20% by weight, maximum 15% by weight, maximum 10% by weight, maximum 8% by weight, maximum 7% by weight, maximum 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 raw material. Metal content can be determined by any suitable means, such as atomic spectroscopy (eg, AAS, AES, AFS, ICP-MS), eg inductively coupled plasma atomic emission spectrometry based on ASTM D5185.

The more the metal content is reduced by heat treatment and subsequent solids removal, the more reduced metal feed can be employed in the subsequent hydrocracking step without concern for catalyst poisoning or other negative effects of metal impurities.

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

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

It is particularly preferred that the heat treatment temperature is the highest temperature among all the temperatures of the method of the present invention that precedes the hydrocracking step.

In the present invention, the heat treatment temperature refers to the temperature of the material being treated (that is, the raw material).

If the heat treatment temperature is at least 290 ° C, considerable metal reduction can be achieved. In this regard, although a reduction of the metal content can be achieved even at lower temperatures, this requires very long heating times which are therefore not preferred. On the other hand, heat treatment temperatures of much more than 400 ° C are not generally necessary to achieve the aim of the present invention, so that the heat treatment temperature is preferably 450 ° C or less, more preferably 440 ° C or less. The heat treatment temperature can also 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, 350 ° C or less, 340 ° C or less, or 335 ° C or less.

The duration of the heat treatment (heat treatment time / residence time) also influences the effectiveness 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 to achieve sufficient metal reduction (solids formation) and further allow 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 can further 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. However, in view of the efficiency of the process, the heat treatment time is, if preferably not 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.

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

Preferably, the heat treatment step is carried out 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, 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. Elevated pressure during the heat treatment step can reduce the tendency for evaporation and therefore ensure effective heat treatment. The pressure should be 200 bar or less, preferably 100 bar or less, more preferably 50 bar or less to keep technical equipment simple.

Unless otherwise stated, the pressure referred to in the present invention means absolute pressure. The pressure values indicated above refer to the highest pressure that occurs in the heat treatment stage, that is, measured at the point / time of the highest pressure. In particular, it is preferred that the heat treatment is not carried out under reduced pressure, but instead under ambient pressure or elevated pressure. Specifically, a higher pressure reduces the tendency to volatilization and therefore possible loss of product or boiling effects (eg in continuous processes).

A metal removal additive may be present during the heat treatment step. The metal removal additive can be added before starting the heat treatment and / or it can be added during the heat treatment. Suitable metal removal additives are those mentioned in US Pat. No. 4411774 A, but not limited to them. Specifically, the metal removal additive in the present invention may be selected from one or more of the group consisting of ammonium sulfate, ammonium bisulfate, diammonium phosphate, ammonium dihydrogen phosphate, calcium hydrogen phosphate, phosphoric acid, and sulfate. magnesium and / or one or more selected from the group consisting of calcium sulfate, aluminum sulfate, and sodium sulfate. The total added amount of the metal removal additive is preferably at least 0.1% by weight, more preferably at least 0.5% by weight or at least 1.0% by weight relative to the dry weight of the raw material (total dry weight). The total amount added refers to the summed amount of all added metal removal additives (but not including solvents, if any, that are added together with the metal removal additives). If the metal removal additive is one or more selected from the group consisting of calcium sulfate, aluminum sulfate, and sulfate of sodium, the amount added is preferably at least 2.0% by weight, more preferably at least 3.0% by weight, and even more preferably at least 4.0% by weight to improve filterability. However, metal removal efficiency improves with any (even low) amount of metal removal additive compared to a process that does not employ any additive.

In the present invention, the type of hydrocracking is not particularly limited as long as it can tolerate the metal content of the metal-reduced feed (optionally in a mixture with a co-feed). A conventional hydrocracking process can be employed and applicable hydrocracking process types include fixed-bed hydrocracking, boiling-bed hydrocracking, and suspension hydrocracking.

Hydrocracking can be carried out in the presence of a solid catalyst. The solid catalyst can be a difunctional catalyst. When using a catalyst, 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 carrier. Preferably, both the Group VIII non-noble metal and the at least one Group VIB metal are supported on a support. Any suitable support can be used and a support comprising silica, alumina or clay is preferred. Furthermore, a support comprising a Bronsted acid component is preferred. The Bronsted acid component may preferably be amorphous zeolite or silica-alumina. A suitable zeolite is zeolite Y, zeolite beta, or any other zeolite with a 12-membered ring. The group VIII non-noble metal is preferably Co or Ni. The metal of group VIB is preferably Mo or W. Specifically, the following types of catalysts are preferred, especially when supported on a support as mentioned above: Co-Mo, Co-W, Ni-Mo, Ni -W.

The cracking temperature is not particularly limited and any suitable temperature can be employed. Specifically, a temperature within the range of 300 ° C to 500 ° C can be employed. 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. Cracking temperature can be 490 ° C maximum, 480 ° C maximum, 470 ° C maximum, 460 ° C maximum, 450 ° C maximum, 440 ° C maximum, or 430 ° C maximum.

In the hydrocracking stage, the partial pressure of hydrogen in the hydrocracking stage is preferably in the range of 70 to 200 bar.

The hydrocracking step can be carried out in any suitable reactor and a boiling bed reactor, a slurry reactor or a fixed bed reactor is preferred.

The hydrocracking step feed may comprise one or more simultaneous feeds in addition to the reduced metal feed of the present invention. The joint diet can be a fossil-based diet, a renewable diet, or a combination of both.

The hydrocracking step feed preferably comprises a renewable feed component (biomass-based feed component) as co-feed in addition to the reduced metal feed (component). By combining the reduced metal feed with a biomass-based feed, the method of the present invention can be even more sustainable. The raw material, and furthermore the metal reduced feed produced from it, mainly comprises hydrocarbons (compounds consisting of carbon atoms and hydrogen atoms) and therefore the oxygen content and other properties can be adjusted finely by combination of biomass based feed and reduced metal feed.

Renewable feed can be a material obtained by deoxygenation of a renewable material.

In addition, the hydrocracking step feed may comprise a fossil feed component in addition to the reduced metal feed. The fossil feed may be a suitable feed other than the reduced metal feed and may be a crude oil fraction (eg, a crude oil distillation fraction or a fraction obtained by processing crude oil). Specifically, the fossil feed can be a conventional cracking feed, such as vacuum gas oil (VGO) or vacuum residue (VR).

By combining the reduced metal feed with another feed (co-feed), the hydrocracking properties can be finely adjusted and the distribution of the desired product can be adjusted easily. Preferably, the content of the reduced metal feed in the hydrocracking step (total) feed is 50% by weight or less, more preferably 40% by weight or less, 30% by weight or less or 20%. % by weight or less. To effectively increase the use of waste oil components, the content of the reduced metal feed in the hydrocracking step feed is preferably 1% by weight or more, more preferably 2% by weight or more, a 5% by weight or more or 8% by weight or more. By limiting the content of the reduced metal feed in the hydrocracking (general) feed, the metal content can be limited while achieving a sustainable effect. The limited metal content allows the selection of less metal tolerant catalysts and / or can improve catalyst life.

The method of the present invention further comprises a step of recovering at least a fraction of hydrocarbon from the material subjected to hydrocracking (the product of the hydrocracking step / hydrocracking product). This step can be accomplished by fractionating the hydrocracked material and recovering at least a fraction. Fractionation can be carried out by any known means and preferably results in the production of at least a gasoline range fraction and / or a middle distillate range fraction.

The process of the present invention is shown schematically in Figure 1. As illustrated in Figure 1, water can be removed in a dehydration step (optional), insoluble components (precipitates) are removed, for example, in a centrifugation step. The resulting reduced metal feed is hydrocracked.

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 method of the present invention enables efficient production of fuel components, especially in the gasoline and middle distillate range, with high yield.

The present invention further relates to a use of the recovered hydrocarbon fraction for the production of a fuel or a fuel component.

Examples

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

Example 1

Used lubricating oil (ULO) was used as raw material. The ULO contained 17.0% by weight of water and had a large amount of metallic impurities (3181 mg / kg wet = 3833 mg / kg dry; metals detected: 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 (wet) and thus 101 mg / kg (dry). The oxygen content (dry) was 1.0% by weight.

The ULO was dehydrated on a rotary evaporator at 100 ° C and 80 mbar. As a consequence, water (and light ends) was removed. The dehydrated ULO was then subjected to heat treatment in a batch reactor at 320 ° C for 1 hour. The pressure at the beginning of the heat treatment was 1 bar and the pressure increased to approximately 23 bar as a result of heating in the closed container. The heat treated material was cooled to 50 ° C and centrifuged at 4300 rpm for 30 minutes and the liquid parts (excluding solids and sludge) were recovered as a reduced metal feed ready to feed to hydrocracking.

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

Table 1:

As can be seen from Table 1, the method of the present invention achieves a significant reduction in metal content (and metalloid content) suitable for feeding into a metal tolerant hydrocracking process.

Comparative example 1:

The reduced metal feed 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 (m.p. <560 ° C) decreased further to 2 mg / kg, while the Si content and the P content remained almost unchanged. On the other hand, another 6% by weight of the product (with respect to the dry basis of the raw material) was lost as distillation background.

Example 2

Another batch of used lubricating oil (ULO-2) was used as raw material. ULO-2 contained 2.6% by weight of water and had a large amount of metallic impurities (2155 mg / kg wet; metals detected: 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 (dry) was 1.0% by weight.

The ULO-2 was dehydrated on a rotary evaporator at 100 ° C and 80 mbar. As a consequence, water (and light ends) was removed. A part of the dehydrated ULO-2 was then mixed with 3000 ppm (relative to the dehydrated ULO-2) of H3PO4 at 85% by weight as a metal removal enhancer, and then subjected to heat treatment in a batch reactor at 320 ° C for 1 hour.

Another part of the dehydrated ULO-2 was subjected to heat treatment in a batch reactor at 320 ° C for 1 hour without 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 heating in the closed container. The heat treated material was cooled to 50 ° C and solids were removed and the liquid parts (excluding solids and sludge) were recovered as a reduced metal feed ready to feed to hydrocracking.

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

The yield of the respective process steps (wt% original ULO) and the metal content of the raw material (ULO-2) and the reduced metal feed (after centrifugation) are given below in Table 2 .

Table 2:

As can be seen from Table 2, the method of the present invention achieves a significant reduction in metal content (and metalloid content) suitable for feeding into a metal tolerant hydrocracking process. Furthermore, it can 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 step of the metal removal step or as single stage of metal removal).

Comparative Example 2

ULO-2 was subjected to heat treatment in the same manner as in Example 2 but without metal removal additive and subsequent centrifugation. The heat-treated sample was subjected to distillation under the conditions used in Comparative Example 1. The results are shown below in Table 3.

Table 3:

As can be seen from Table 3, the metal removal efficiency of the distillation is higher than when using only centrifugation or filtration after heat treatment. However, the Si content is even higher (presumably because volatile Si compounds evaporate even from the sludge) than for the technique of the present invention. Furthermore, a significant amount of product is lost as a distillation background.

Claims (14)

1. A method comprising the following steps: subjecting a raw material to a heat treatment (heat treatment step) to produce a heat treated material comprising liquid components and solid components, separate solids from heat treated material to produce reduced metal feed, subjecting the reduced metal feed, optionally together with a co-feed, to hydrocracking (hydrocracking step) to form a hydrocracked material, recovering at least a fraction of hydrocarbons that boils in the liquid fuel range of the hydrocracked material; where the raw material has an oxygen content of at most 5% by weight on a dry basis, and wherein the step of separating the solids from the heat-treated material (the step of removing insoluble components) comprises at least one of centrifugation, filtration , and sedimentation. The method according to claim 1, wherein the raw material has an oxygen content, on a dry basis, in the range of 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. The method according to claim 1 or 2, wherein the total content of hydrogen (H) and carbon (C) in the raw material, on a dry basis, is at least 80% by weight, preferably at less 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 one 97% by weight, at least 98% by weight, or at least 99% by weight. The method according to any one of the preceding claims, wherein the reduced metal feed is hydrocracked together with a co-feed, wherein the co-feed is preferably a fossil-based feed, a renewable feed or a combination of both. The method according to any one of the preceding claims, wherein the metal content of the reduced metal feed is at most 60% by weight of the metal content of the raw material, preferably at most 50% by weight, maximum 40% by weight, maximum 30% by weight, maximum 20% by weight, maximum 15% by weight, maximum 10% by weight, maximum 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 raw material. The method according to any one of the preceding claims, wherein the heat treatment is carried out at a temperature of at least 290 ° C, preferably at least 300 ° C, at least 310 ° C, at least 320 ° C, or at least 330 ° C. 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, at least 80 minutes, or at least 100 minutes. 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. The method according to any one of the preceding claims, wherein the reduced metal feed is hydrocracked in the presence of a solid catalyst and the solid catalyst preferably contains at least one group VIII non-noble metal and at least a metal from Group VIB and a support. The method according to claim 9, wherein the support comprises silica, alumina or clay and / or wherein the support comprises a Bronsted acid component, wherein the Bronsted acid component is preferably zeolite or amorphous silica. The method according to any one of the preceding claims, wherein the hydrocracking step is carried out in a boiling bed reactor, a slurry reactor or a fixed bed reactor. 12. The method according to any one of the preceding claims, wherein the total content of metals and phosphorus in the raw material is in the range of 500 mg / kg to 10000 mg / kg, preferably 1000 mg / kg to 8000 mg / kg. The method according to any one of the preceding claims, wherein the step of separating solids from the heat-treated material (removal of insoluble components) comprises at least centrifugation. 14. A use of the recovered hydrocarbon fraction obtained by the method according to any one of claims 1 to 13 for the production of a fuel or a fuel component.