BE1026853B1 - SIMULTANEOUS TREATMENT PROCESS - Google Patents

Abstract

The present invention relates to methods of simultaneously treating liquids derived from plastic waste (DP) and liquids derived from non-reusable waste tires (PUNR) with crude oils (PB) in conventional petroleum refinery settings comprising desalination. 10 and distillation 20.

Description

FIELD OF THE INVENTION The present invention relates to simultaneous treatment methods, in particular for the simultaneous treatment of liquids derived from plastic waste and of liquids derived from non-reusable used tires with crude oils in refinery settings. conventional oil.

PRIOR ART Raw materials of the recycled type or raw materials with a reduced carbon content are raw materials created by the treatment of fossil-based waste such as plastic waste (DP) or non-reusable used tires (PUNR). The attractive feature of these raw materials from a refinery point of view is that they are quite similar compared to conventional refinery raw materials, i.e. crude oil. Oils derived from DP / PUNR mainly contain hydrocarbons, and their oxygen content is significantly lower compared to oils based on biomass.

The oils derived from the pyrolysis of DP contain different elemental impurities depending mainly on the original raw material, but also on the pyrolysis technology used. The three most important impurities in plastic pyrolysis oils are nitrogen, sulfur and chlorine, which have an adverse effect on the direct use of pyrolysis oil. These impurities are essentially present in organic form, which means that they are structurally associated with hydrocarbon chains of varying size and complexity. In addition, metallic impurities from additives and contamination can also be detected in these oils.

PUNR pyrolysis oils tend to have a much lower CI content compared to DP pyrolysis oils and therefore in the simultaneous processing of ELT pyrolysis oils this problem can be managed through 'a simple dilution. On the other hand, ELT pyrolysis oils contain other impurities which can be harmful in refining operations. These oils contain solid impurities, primarily in the form of carbon black, which is used as a reinforcing filler in tire formulations, as well as certain oil soluble metal impurities. PUNR pyrolysis oil also contains considerable amounts of sulfur and nitrogen, both of which can also be found in conventional crude oils.

Even though oil derived from DP / PUNR has a very low concentration of impurities and / or is used in very low concentrations, impurities can still cause various problems over time. Thus, oil derived from DP / PUNR should be introduced into the refinery in a manner that minimizes the potential effect of these impurities.

There are many works of art revealing suitable processes and materials for the preparation, purification and cracking of oils from waste plastic pyrolysis and / or ELT. For example, US 201604545841 discloses a specific reactor suitable for the desalination of combined hydrocarbon streams, including crude oils and pyrolytic oils. WO 2018025103A1 discloses the use of a “devolatilization” extruder in combination with a zeolite catalyst and a stripper for removing chlorine from hydrocarbon streams or from hydrocarbon stream precursors. JP 4382552 B2 discloses a process for treating plastic cracked light petroleum. However, it is specified that 90% of the plastic pyrolysis oil must be in a boiling point range between 100 and 300 ° C. JPH1161148 A discloses a process for simultaneously treating DP-derived liquid with hydrocarbon oil in a petroleum refining plant, the process comprising mixing the DP-derived liquid and crude oil to form a mixture and distilling the oil. mixed. JP 2002060757 A discloses thermal decomposition of DP and production of a cracked distillate and mixing of the cracked distillate with crude oil. The document also discloses the refining and purification of the mixture in petroleum refining processes. JP 2005105027 A discloses a manufacturing process comprising mixing a fraction of naphtha with plastic cracked oil, followed by subjecting the resulting mixture to hydrorefining. As a result, even more robust methods are needed for the treatment of liquids derived from DP and PUNR.

SUMMARY The following is a simplified summary in order to provide a basic knowledge of certain aspects of various embodiments of the invention. The summary is not a complete overview of the invention. It is not intended to identify key or critical elements of the invention, nor to delimit the scope of the invention. The following summary simply presents certain concepts of the invention in a simplified form, as a prelude to a more detailed description of embodiments given by way of examples of the invention. It was observed that when liquids derived from DP / PUNR were mixed with crude oil followed by distillation, some impurities in liquids derived from DP / PUNR could be removed or concentrated into fractions where they could be more easily managed. In addition, the problems related to the reactivity of oils derived from DP / PUNR could be avoided or at least mitigated.

According to the invention, there is provided a novel process for the simultaneous treatment of liquids derived from plastic waste (DP) and / or liquids derived from non-reusable used tires (PUNR) with crude oil and / or desalinated crude oil. , wherein the method comprises the following steps of a) supplying crude oil, b) supplying a liquid derived from waste plastics (DP) and / or a liquid derived from a non-reusable used tire (PUNR), c) mixing the liquid DP derivative and / or ELT derivative liquid and crude oil to form a mixture, d) desalt the mixture, and e) distill the mixture.

A number of exemplary and non-limiting embodiments of the invention are described in the accompanying dependent claims.

The various embodiments given by way of non-limiting examples of the invention and of the operating methods, as well as additional objects and advantages thereof, are better understood by virtue of the following description of specific embodiments. given by way of example when read in conjunction with the accompanying figures.

The verbs "understand" and "include" are used in this document as open limitations which do not exclude or require the existence of characteristics also not listed. The characteristics listed in the dependent claims are freely combinable with each other, unless explicitly stated otherwise. In addition, it should be understood that the use of "a" or "a", ie. a singular form, throughout this document does not exclude a plurality.

BRIEF DESCRIPTION OF THE FIGURES The exemplary and non-limiting embodiments of the invention and their advantages are explained in more detail below with reference to the accompanying figures, in which Figure 1 illustrates non-exemplary methods. limiting the simultaneous treatment of liquids derived from plastic waste (DP) and / or liquids derived from non-reusable used tires (PUNR) with crude oil (PB) according to the present invention.

DESCRIPTION The present invention relates to the simultaneous treatment of liquids derived from DP and liquids derived from PUNR, preferably in a conventional petroleum refinery setting using existing treatment units. The principle of the present process is illustrated in Figure 1.

According to the embodiment illustrated in Figure 1, the process comprises the simultaneous introduction of the liquid derived from DP and / or ELT and crude oil (PB) into the petroleum refinery via a desalination unit. crude oil 10 and a subsequent crude oil distillation unit (UDP) 20. The distillation produces one or more distillates, i.e. distillation fractions and a distillation residue, i.e. a distillation bottom. According to this embodiment, the quality of the liquid derived from DP and / or PUNR is not determined, but the liquids are conveyed to the desalination unit with the crude oil.

If the quality of the crude oil is high enough, even the desalination of the crude oil can be omitted. According to a preferable embodiment, the distillates and the bottoms of the distillates are treated further. Thus, the distillates can be directed to one or more hydrodesulfurization units marked with reference numbers 30 and 40. The stills from the crude oil distillation unit 20 can be directed to a subsequent vacuum distillation unit 50. , to give rise to vacuum diesel fuel (GSV) and vacuum residue (RSV). GSV and / or RSV can be further processed using e.g. fluid catalytic cracking, hydrocracking and hydrocracking of tailings 60.

According to an exemplary embodiment, the method of simultaneously treating liquid derived from plastic waste (DP) and / or liquid derived from non-reusable waste tires (PUNR) with crude oil comprises the following steps of: a) providing a liquid derived from DP and / or liquid derived from ELT, b) mixing liquid derived from DP and / or liquid derived from ELT with the crude oil to form a mixture, c) desalt the mixture, and d) distilling the mixture .

As defined in this paragraph, liquid derived from waste plastic or oil derived from waste plastic (used in this paragraph and in the description interchangeably) should be understood to mean any liquid comprising oil derived from the conversion. thermal waste plastic, and liquid derived from non-reusable used tire or oil derived from non-reusable waste tire (used in this paragraph and in the description interchangeably) are to be understood to mean any liquid comprising derived oil thermal conversion of non-reusable used tires. It is understood that their composition may vary on the basis of the thermal conversion technology used as well as the nature of the raw materials.

According to one embodiment, the liquid derived from DP is mixed with crude oil, and the mixture desalted and distilled. According to this embodiment, the concurrent processing does not include ELT-derived liquid, and the quality of the DP-derived liquid is not determined.

According to another embodiment, the liquid derived from ELT is mixed with crude oil, and the mixture is desalted and distilled. According to this embodiment, the concurrent processing does not include liquid derived from DP, and the quality of the liquid derived from ELT is not determined.

According to another embodiment, the liquid derived from DP and ELT is mixed with crude oil, and the mixture is desalted and distilled. According to this embodiment, the quality of the liquid derived from DP and PUNR is not determined.

According to another embodiment, the quality of the liquid derived from DP is analyzed, and its quality has been observed to be less than a predetermined value. According to this embodiment, the concurrent treatment does not include a liquid derived from PUNR. Thus, the liquid derived from DP is mixed with crude oil to form a mixture which is desalted and distilled.

According to another embodiment, the quality of the liquid derived from PUNR is analyzed, and its quality is observed to be less than a predetermined value. According to this embodiment, the concurrent treatment does not include a liquid derived from DP. Thus, the liquid derived from ELT is mixed with crude oil to form a mixture which is desalted and distilled.

According to another embodiment, the quality of the ELT-derived liquid and the DP-derived liquid is analyzed, and the quality of the PUNR-derived liquid and the quality of the DP-derived liquid are observed to be less than a predetermined value. Thus, the ELT derivative liquid and the DP derivative liquid are mixed with crude oil to form a mixture which is desalted and distilled.

According to another embodiment, the quality of the ELT-derived liquid and the DP-derived liquid is determined, and the quality of the DP-derived liquid and the quality of the ELT-derived liquid have been observed to be above and below a value. predetermined, respectively. Thus, the ELT derivative liquid is mixed with crude oil to form a mixture which is desalted, and the desalted mixture is distilled with the DP derivative liquid.

According to another embodiment, the quality of the ELT-derived liquid and the DP-derived liquid is analyzed, and the quality of the PUNR-derived liquid and the quality of the DP-derived liquid are observed to be above a predetermined level. Thus, ELT derivative liquid and DP derivative liquid are distilled with the desalinated crude oil.

The quality of liquids derived from PUNR and DP can be determined using methods known in the art. Exemplary methods are titration and gas chromatography. Exemplary impurities to be determined include one or more of: inorganic halogen compounds, inorganic sulfur compounds, water soluble oxygenates. An exemplary impurity is inorganic chlorine, in the form of HCl. According to an exemplary embodiment, the impurity is inorganic chlorine and it is determined by titration with AgNO :.

The predetermined quality level can be specified as needed. According to an exemplary embodiment, the liquid derived from DP and / or ELT is desalted simultaneously with crude oil if its CI content is 200 mg / kg or more. According to one embodiment, the liquid derived from DP and / or ELT is mixed with crude oil to form a mixture. According to a particular embodiment, the mixture is produced by mixing 1 part by weight of a liquid derived from DP and / or a liquid derived from ELT and from 1 to 1000 parts by weight of crude oil. According to an exemplary embodiment, the mixture comprises a 1:10 mixture by weight of liquid derived from DP and / or ELT and crude oil.

It is obvious to a skilled person that different ratios of liquid derived from DP and / or ELT and crude oil may also be used. Other exemplary DP / PUNR: PB ratios are 1: 1, 1: 2.1: 3.1: 5.1 25.1: 50.1: 100, 1: 500 and 1: 1000 by weight.

Desalination can be carried out by any of the desalination methods known in the art. Exemplary desalination processes include chemical and electrostatic separation, chemical desalination, and electrical desalination.

In chemical and electrostatic separation, washing of the salt from the mixture is carried out using water. The oil and water phases are separated in a settling basin by adding chemicals to help break up the emulsion, by applying an electrostatic field to collapse the saltwater droplets faster, or by a combination of the two aforementioned techniques.

In chemical desalination, water and chemical surfactants (demulsifiers) are added to the mixture, and the mixture is heated so that salts and other impurities dissolve in water or attach to water, and are then retained in a tank where they are deposited.

Electrical desalination involves treating the mixture under load conditions so that polar molecules orient and separate. Desalination can also be carried out by extraction with water or a fluid containing water. Desalination with water removes or at least decreases the amounts of water soluble impurities in the mixture. An exemplary water / oil ratio in extraction is 1: 1. Of course, the impurities which are removed are not necessarily actual salts.

According to one embodiment, a desalted mixture comprising the liquid derived from DP and / or PUNR is distilled to give rise to one or more distillation fractions, i.e. distillates, and usually also to a distillation residue, i.e. a distillation bottom. According to an exemplary embodiment, the distillation provides two distillates and a distillate bottom. In another exemplary embodiment, the distillation provides eight distillates and one distillate bottom.

In an exemplary embodiment, the distillation provides three fractions, namely a first distillation fraction, a second distillation fraction and a distillation residue. The distillates can be further divided into sub-distillates, which can be removed from the still column as separate products.

According to one embodiment, the distillation is carried out at atmospheric pressure. According to a particular embodiment, the distillation is carried out at atmospheric pressure producing a first distillation fraction, a second distillation fraction and a third distillation fraction. According to an exemplary embodiment, at least 90% by weight of the first distillation fraction is brought to a boil at a temperature of 170 ° C. under atmospheric pressure. According to the same exemplary embodiment, at least 80% by weight of the second distillation fraction is brought to a boil at a temperature range of between 170 and 360 ° C at atmospheric pressure. Further, according to the same exemplary embodiment, at least 90% by weight of the third distillation fraction is boiled at a temperature above 360 ° C at atmospheric pressure.

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

According to a particular embodiment, the first distillate or one or more of its sub-fractions, and / or the second distillate or one or more of its sub-fractions is brought to a hydrodesulfurization unit in which a hydrodesulfurization reaction is done. Hydrodesulfurization (HDS) is a catalytic chemical process used to remove sulfur from distillates. The goal of removing sulfur and creating products like ultra low sulfur diesel is to reduce sulfur dioxide emissions that result from the use of these fuels in motor vehicles, airplanes , railway locomotives, ships, gas or oil-fired power stations, domestic and industrial furnaces and other forms of fuel combustion.

For hydrodesulfurization, different types of catalysts are used. In general, these are different combinations of oxides and sulfides of cobalt, molybdenum, nickel, iron and wolfram on a γ-alumina or alumina / silica / zeolite support, or on their mixture.

According to one embodiment, the hydrodesulfurization of the first distillate or one or more of its subfractions produces a gasoline component or an intermediate suitable for further processing into a gasoline component.

In another embodiment, the hydrodesulfurization of the second distillate or one or more of its subfractions produces a diesel component, or an intermediate suitable for further processing into a diesel component. Exemplary HDS catalysts are CoMo / Al2O3, NiMo / Al2O3, and CoMoNi / Al2O3.

According to an exemplary embodiment, the hydrodesulfurization is carried out at between 280 and 320 ° C at between 20 and 35 bars in the presence of hydrogen and of a hydrodesulfurization catalyst such as CoMo / Al2O3 or NiMo / Al2Os.

Exemplary process parameters for the middle distillate are temperature: 320 to 380 ° C; pressure: from 35 to 80 bar in the presence of hydrogen and a hydrodesulfurization catalyst such as CoMo / Al2O3 or NiMo / Al2O3. The LHSV is preferably 1.5 to 3.0 hrs and the Hz / feed ratio is preferably 300 to 450 N m 3 / m 3.

Exemplary process parameters for the naphtha fraction are catalyst CoMo / Al203 or NiMo / Al203 at temperature 280-320 ° C, pressure 20-35 bar, liquid hourly space velocity (LHSV: material flow raw in m3 at 1 m ° of catalyst for 1 h of catalyst at 20 ° C and 101.3 kPa) from 3.0 to 5.0 h "and a hydrogen / hydrocarbon ratio of 100 to 250 N m3 / m3.

According to another embodiment, the distillation residue is subjected to vacuum distillation, generally at between 370 and 410 ° C and between 1 and 10 kPa producing vacuum gas oil (GSV) and vacuum residues (RSV).

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

In the CCF process, the GSV is heated to high temperature and moderate pressure, and contacted with hot powdered catalyst. An exemplary CCF catalyst has four main components: crystalline zeolite, a matrix, a binder, and a filler.

Zeolite is the primary active component and can be in the range of about 15 to 50 percent by weight of the catalyst.

The catalyst breaks down the long chain molecules of the high boiling point hydrocarbon liquids into much shorter molecules, which are collected and then separated by distillation in the main fractionator of CCF.

The main products of the CCF process are gasoline and liquefied petroleum gas (LPG). In the HC process, the catalytic cracking of GSV is aided by the presence of added hydrogen gas.

The HC is preferably facilitated by a bifunctional catalyst which is capable of rearranging and breaking hydrocarbon chains as well as adding hydrogen to aromatics and olefins which may be present in the GSV.

HC products are saturated hydrocarbons.

The main products of hydrocracking are kerosene and diesel, but fractions of low sulfur naphtha and LPG are also produced.

All of these products are generally very low in sulfur and other contaminants.

According to another particular embodiment, the RSVs are further processed using one or more of fluid catalytic cracking, hydrocracking and tailings hydrocracking processes.

The process of the present invention alleviates problems that would arise if impure liquids derived from DP / PUNR were distilled in a stand-alone distillation unit, and the resulting distillates would be processed simultaneously directly e.g. in refinery hydrodesulfurization units.

When using the latter approach, i.e. Autonomous distillation and simultaneous processing of distillates, distillates contain varying amounts of heteroatoms such as N and CI.

During the hydrotreatment, these will be eliminated in the form of NH 3 and HCl.

This process will consume hydrogen and the resulting gases can form NH4CI deposits which are problematic eg. in heat exchangers and recirculated gas compressors. Thus, it would be advantageous to reduce the concentration of these heteroatoms before the hydrotreatment operations.

The treatment of oils derived from DP / PUNR according to the process of the present invention has the following advantages: The water-soluble impurities are removed in the desalination unit. These impurities can include, e.g. HCl, oxygenated organic molecules and some organic molecules containing nitrogen.

It is known that liquids derived from DP / PUNR can include organic chlorides. When subjected to the high temperatures used in UDP preheating units, chlorides are released as HCl. The gaseous HCl which is released during the distillation will be transported to the top of the distillation column and to the upper condenser, where it will then condense with the vapor which is introduced into the distillation column, thus forming aqueous hydrochloric acid. However, certain measures such as adding NaOH downstream of the desalination unit or using a neutralizing amine can be used to control and limit corrosion at the top of the distillation column and in the upper condenser. It is less difficult to release HCI in UDP than in a downstream hydrotreatment unit which does not exhibit a similar level of preparation for corrosion control.

If the oil derived from DP / PUNR contains non-volatile impurities such as metals, the simultaneous treatment of the oil in a UDP has the advantage of concentrating the metals into heavier hydrocarbon fractions which already have a higher metal content. high initially. Depending on the impurities that are present in the oil derived from DP / PUNR and the distillation configuration that is used, metal impurities can e.g. concentrate in vacuum gas oil or vacuum residue. These fractions can then be further processed in refining units which have a higher tolerance for metals. Such refining units can include e.g. fluid catalytic cracking or hydrocracking of tailings in a boiling bed reactor.

Oils derived from DP / PUNR are more reactive than typical crude oil. As a result, reactivity is reduced by dilution with crude oil, which allows subsequent processing of oils derived from DP / PUNR in reactors such as HDS reactors designed for crude oil.

Experimental Example 1: Removal of water-soluble impurities in liquids derived from DP The liquids derived from DP / PUNR (pyrolysis oils) which are used in these examples were purchased from Ecomation Oy (Salo, Finland).

A liquid derived from plastic waste was washed with water at room temperature to remove water-soluble impurities. The washing was performed using a water / oil ratio of 1: 1 (w / w) while stirring the mixture in a separatory funnel. The oil and water were separated, and the oil was analyzed for the content of heteroatoms (N, S, Cl, Br). The results are shown in Table 1.

Table 1. Results of water washing of liquid derived from plastic waste at room temperature using a water / oil ratio of 1: 1.

Original oil Washed oil | % (TT men

Although the procedure itself may differ from an actual desalination process, the results show that a certain amount of impurities can be removed from liquids derived from waste plastic by essentially washing the sample with water.

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

One of skill in the art can also understand that the amount of water soluble impurities in the liquid derived from waste plastic will also vary depending on the raw material and the pyrolysis process.

In addition, the conditions (temperature, residence time, dilution with crude oil) that are used in the actual desalination process can also influence the removal of impurities.

Example 2: Concentration of metallic impurities in the distillation of a liquid derived from ELT The example shows that the metallic impurities are advantageously concentrated in the still bottoms when a liquid derived from ELT is distilled into three distinct fractions.

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

As shown by the results in Table 2, these two impurities were effectively concentrated in the still bottoms, which in this case are represented by the fraction with a boiling point range of> 360 ° C.

Thus, the distillate fractions, which would then be introduced eg. in fixed bed hydrotreatment reactors no longer contain Fe or Zn.

Table 2. Distillation yields and distribution of the main metallic impurities in the distillation of ELT-derived liquid.

Oil Fraction Fraction Original fraction | <170 ° C 170-360 ° C |> 360 ° C Distillation yield (% 21 52 27 by weight) In this example, the liquid derived from ELT was distilled in pure form, i.e. without conventional crude oil. In the treatment concept that was presented in Figure 1, the> 360 ° C fraction of ELT-derived liquid would exit the UDP into the atmospheric tailings stream, which would then be subjected to vacuum distillation. Thus, the contaminating metals of the ELT derived liquid could further concentrate in the still bottoms of the vacuum distillation unit, i.e. vacuum residues. In addition, all of the distillate fractions that are obtained from the liquid derived from DP / PUNR would be diluted with the crude oil being processed simultaneously.

The specific examples provided in the description given above should not be interpreted as limiting the scope and / or applicability of the appended claims.

Claims (10)

Claims A method of simultaneously treating liquid derived from waste plastics (DP) and / or liquid derived from non-reusable waste tires (PUNR) with crude oil, the method comprising the steps of a) providing a liquid derived from DP and / or ELT derived liquid, b) supplying crude oil, c) mixing the DP derived liquid and / or ELT derived liquid and crude oil to form a mixture, d) desalting the mixture, and e) distilling The mixture. 2. The method of claim 1, wherein step c) comprises mixing 1 part by weight of a liquid derived from DP and / or a liquid derived from PUNR and 1 to 1000 parts by weight of. crude oil. 3. The method of claim 1 or 2, wherein the desalination comprises treatment with water. 4. A process according to any one of claims 1 to 3, wherein the distillation produces one or more distillates and a distillate bottom. 5. The method of claim 4, comprising the step of subjecting at least one of the one or more distillates to a hydrodesulfurization reaction. 6. The method of claim 5, wherein the submission is between 280 and 320 ° C to between 20 and 35 bar in the presence of hydrogen and a hydrodesulfurization catalyst such as CoMo / Al203 or NiMo / Al2O: 3. 7. The method of claim 5, wherein the submission is between 320 and 380 ° C to between 35 and 80 bars in the presence of hydrogen and a hydrodesulfurization catalyst such as CoMo / Al203 or NiMo / Al2O: 3. 8. The method of claim 4 comprising the step of subjecting the bottom of the distillate to vacuum distillation. 9. The method of claim 8, wherein the vacuum distillation produces vacuum gas oil and / or vacuum residues. 10. The method of claim 9, wherein the vacuum gas oil and / or the vacuum residue is subjected to one or more of fluid catalytic cracking, hydrocracking and residue hydrocracking.