KR20180132741A - A process for converting plastics into wax by decomposition and a process for converting the hydrocarbon mixture - Google Patents

Abstract

The present invention relates to a process for converting plastics into wax by decomposition. The process comprises introducing plastic into the reactor; Allowing at least a portion of the plastic to convert to wax, wherein the wax is part of a pyrolysis gas formed in the reactor; And removing the wax-containing product stream from the reactor. The present invention also relates to a hydrocarbon mixture obtainable by such a process.

Description

A process for converting plastics into wax by decomposition and a process for converting the hydrocarbon mixture

This application claims priority to U.S. Provisional Application No. 62/315949, filed March 31, 2016, and European Application No. 16306635.0, filed on December 7, 2016, the entirety of which is incorporated by reference herein in its entirety .

Technical field

The present invention relates to a process for converting plastics into wax by cracking. The process comprises introducing plastic into the reactor; Allowing at least a portion of the plastic to convert to wax, wherein the wax is part of a pyrolysis gas formed in the reactor; And removing the wax-containing product stream from the reactor.

The present invention also relates to a hydrocarbon mixture obtainable by such a process.

Considering the increase in polymer importance as a substitute for conventional building materials such as glass, metal, paper and wood, the recognition of the need for safe and non-renewable resources such as petroleum, and the reduction in the available storage capacity for waste treatment, There is considerable interest in the issue of recycling, reclaiming, recycling, or in some ways reusing waste plastics.

Thermal decomposition or catalytic decomposition of waste plastics has been proposed to convert high molecular weight polymers into volatile compounds having much smaller molecular weights. Depending on the process used, volatile compounds may be relatively high boiling liquid hydrocarbons useful as fuel oils or fuel oil supplements, or may be low to moderate boiling carbon atoms useful as gasoline type fuels or other chemicals. Moreover, the volatile compound may be a wax, or may comprise at least a wax.

Catalytic cracking of mixed waste plastics is a process well known to those skilled in the art. For example, US 5,216,149 discloses a process for controlling pyrolysis of such a stream to convert a composite waste stream of plastics into valuable useful monomers or other chemicals by identifying catalysts and temperature conditions that enable the degradation of a given polymer .

A study was conducted to optimize the process parameters for the yield increase of the desired degradation product. For example, in US 2015/0247096 A1 hydrogen is added to a reaction chamber and the waste plastics are heated to a temperature sufficient to thermally de-polymerize the waste plastic to form a wax product comprising paraffin and olefin compounds, The method comprising: The decomposition is carried out at a temperature of from about 300 DEG C to about 500 DEG C for a period of from about 1 minute to about 45 minutes sufficient to cause thermal degradation of substantially all of the molten plastic feedstock.

US 6,150,577 and US 6,143,940 disclose methods for preparing heavy wax compositions from waste plastics in pyrolysis zones at subatmospheric pressures, wherein a pyrolysis zone effluent comprising 1-olefin and n-paraffin is formed. Pyrolysis is carried out at a temperature of 500 to 700 ° C.

M. M. Arabiourrutia et al. Disclose the characterization of waxes obtained by pyrolysis of polyolefin plastics in the Journal of Analytical and Applied Pyrolysis 94 (2012) 230-237. The authors investigated the effect of decomposition temperature on the yield of waxes and volatiles obtained from different polyolefins. It has been found that increasing the decomposition temperature from 450 占 폚 to 600 占 폚 reduces the wax obtained, for example, in the case of LDPE (low density polyethylene) from 80% to 51% by weight. The amount of volatile material obtained at the same time increases from 20 wt% to 49 wt%. This finding supports the general understanding that increasing the temperature is beneficial to the rate of decomposition towards the formation of shorter chain products.

However, there is still a need to further improve the degradation of plastics, particularly with regard to the yield of certain products such as waxes and compositions of such products. In certain applications, it is desirable to obtain a high yield of wax from, for example, plastics. Moreover, it may be desirable to obtain a wax having an increased average carbon chain length.

The present inventors have found that, unlike the above-mentioned expectation that the yield of wax decreases when the decomposition temperature is increased, the pyrolysis gas formed during the decomposition of the plastic and containing the volatile decomposition product has a high residence time It was found that the yield of wax unexpectedly increased even at the temperature.

Moreover, the inventors have found that a novel mixture of hydrocarbons, predominantly comprising wax, is obtained under certain process conditions, wherein the hydrocarbons have a high number of carbon atoms, predominantly linear hydrocarbons, and the inherent properties of n-paraffins and alpha-olefins Ratio.

Accordingly, the present invention relates to a process for converting a plastic into a wax by decomposition,

Introducing plastic into the reactor;

Allowing at least a portion of the plastic to convert to wax, wherein the wax is part of a pyrolysis gas formed in the reactor; And

And removing the wax-containing product stream from the reactor,

The pyrolysis gas has a residence time of less than 60 seconds at a temperature of more than 370 ° C.

The present invention also relates to a hydrocarbon mixture wherein the hydrocarbons exhibit a cumulative distribution of the number of carbon atoms such that d20 is greater than or equal to 20 and d50 is less than or equal to 50;

At least 50 mole% of the hydrocarbons are linear hydrocarbons;

The molar ratio of n-paraffin to alpha-olefin in the hydrocarbon is in the range of 0.1 to 10.

Furthermore, the present invention relates to a process for producing the mixture, wherein the mixture is obtained by removing the wax-containing product stream from the reactor in the process described above for converting plastics to wax.

In the catalytic cracking of plastics, several fractions of the compound are obtained. There is usually a gas fraction containing a lightweight compound having less than 5 carbon atoms. The gasoline fraction contains a compound having a low boiling point, for example below 150 ° C. Such fractions include compounds having from 5 to 9 carbon atoms. The kerosene and diesel fractions have a higher boiling point, for example from 150 ° C to 359 ° C. Such fractions generally contain compounds having from 10 to 21 carbon atoms. Even higher boiling fractions are generally designated as heavy duty circulating oil (or HCO) and wax. In all these fractions, the compounds are hydrocarbons optionally containing heteroatoms such as N, O, and the like. Thus, in the sense of the present invention, "wax " refers to hydrocarbons optionally containing heteroatoms. In most cases, they are solid at room temperature (23 占 폚) and generally have a softening point of greater than 26 占 폚. The following experimental section provides definitions for the fractions obtained.

Plastics are mainly composed of specific polymers, and plastics are generally named by these specific polymers. Preferably, the plastic accounts for more than 25% by weight, preferably more than 40% by weight, more preferably more than 50% by weight, based on the total weight of the particular polymer. Other components in the plastics are additives such as fillers, reinforcing agents, processing aids, plasticizers, pigments, light stabilizers, lubricants, impact modifiers, antistatic agents, inks, antioxidants and the like. Generally, plastics contain more than one additive.

Plastics used in the process of the present invention include polyolefins and polystyrenes such as high density polyethylene (HDPE), low density polyethylene (LDPE), ethylene-propylene-diene monomer (EPDM), polypropylene (PP) and polystyrene do. A mixed plastic mainly composed of polyolefin and polystyrene is preferable.

Other plastics such as polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polyurethane (PU), acrylonitrile-butadiene-styrene (ABS), nylon and fluorinated polymers are less preferred. Preferably less than 30% by weight, more preferably less than 20% by weight, even more preferably less than 10% by weight, based on the total weight of dry weight plastic, when they are present in the plastic It is present in small amounts.

Preferably, the plastics comprise at least one thermoplastic polymer, and essentially no thermosetting polymer. In this context, 'essentially free of' is intended to indicate a content of thermosetting polymer of less than 15, preferably less than 10, even more preferably less than 5% by weight, for the plastic starting material.

Typically, waste plastic contains other unwanted components, such as paper, glass, stone, metal, and the like.

The plastic used in the process of the present invention may be a single waste plastic, a single virgin plastic on spec or off spec, mixed waste plastic, rubber waste, organic waste, biomass, ≪ / RTI > Single plastic waste, single virgin plastic offspec, mixed waste plastic, rubber waste, or mixtures thereof is preferred. Single virgin plastic offspec, mixed waste plastics or mixtures thereof are particularly preferred. Mixed plastics waste usually provides good results.

As a contaminant of the incoming raw material, a limited amount of non-pyrolyzable components such as water, glass, stone, metal, etc. is tolerated. "Low content" preferably means a minor amount of less than 50 wt%, preferably less than 20 wt%, more preferably less than 10 wt%, based on the total weight of the dry plastic. Preferably, the individual content of any less preferred plastics is less than 5% by weight, more preferably less than 2% by weight, based on the total weight of the dry plastic.

Prior to pyrolysis, the raw materials may be subjected to any one of the following methods: size reduction, grinding, shredding, screening, chipping, metal removal, debris removal, dust removal, drying, degasing, melting, solidification, Can be pretreated by a physicochemical process including the above work.

The pretreatment can be carried out at a temperature of 350 DEG C or less, preferably 330 DEG C or less. It is advantageous to remove gas decomposition products that occur during the pretreatment. Examples of the gas decomposition products include hydrochloric acid, hydrobromic acid, hydrofluorhydric acid, CO, CO ₂ , small carbon-containing molecules having 4 or fewer carbon atoms such as methane, ethane, butane, ethylene, Acetylene, propane, propylene, butene, methanol, formic acid, formaldehyde, acetic acid, acetaldehyde, ethanol and acetone.

Some of these decomposition products may react with other materials present in the plastics to produce undesired reaction products. Examples of such materials include fillers such as alkaline fillers such as PCC (precipitated calcium carbonate) or chalk, lime, soda lime, sodium carbonate, sodium bicarbonate, alumina, titanium oxide, magnesium oxide, calcium oxide, .

In the outlet of the pretreatment, the raw material can be solid or melted, and preferably melted. Optionally, an acid capturing component may be added for pretreatment. Examples of acid trapping components include fillers, for example, alkaline fillers such as PCC (precipitated calcium carbonate), alumina, titanium oxide, magnesium oxide, calcium oxide, and the like.

Surprisingly, the inventors have found that wax can be obtained in high yield from the decomposition of plastics even at high de-polymerisation temperatures, when a short residence time of less than 60 seconds of pyrolysis gas is ensured in the pyrolysis reactor and at high temperatures above 370 & ≪ / RTI > This finding is particularly surprising since it is advantageous in the rate of decomposition for the formation of shorter chain products due to the higher decomposition temperature. In other words, a lower content of wax mixture will appear at higher temperatures.

In addition, the present inventors have found that not only a wax mixture is produced in a short residence time of pyrolysis gas at high temperature but also an average carbon chain length of the wax is increased. This makes it possible to carry out the cracking process at considerably high temperatures, which ensures a high conversion of the raw materials and even a low residue of the plastic raw material, for example less than 50 g / kg, Thereby enabling an increase in production.

In the cracking reactor, plastics generally remain in a molten state at the decomposition temperature. The decomposition reaction causes depolymerization of the plastic, resulting in products of smaller molecular weight. This lower molecular weight product at the temperature in the cracking reactor evaporates to form pyrolysis gas in the reactor. These gases include volatile thermal decomposition fractions such as light hydrocarbons, diesel, kerosene and wax. The present invention is based on the discovery that the pyrolysis gas must be quickly removed from the hot decomposition reaction zone and the pyrolysis gas is heated at a temperature of greater than 370 DEG C for less than 60 seconds, preferably less than 50 seconds, more preferably less than 40 Wax has a high residence time of less than 30 seconds, even more preferably less than 25 seconds, most preferably less than 20 seconds, such as less than 15 seconds or even less than 10 seconds, Yield. ≪ / RTI >

On the other hand, the decomposition reaction still occurs in pyrolysis gas as long as the temperature is high enough. Therefore, when the residence time of pyrolysis gas is very short at a temperature exceeding 370 DEG C, the obtained product may also have undesirable characteristics, for example, on the carbon chain length, the content of the branched hydrocarbon, the content of the aromatic material and the like . Thus, in certain embodiments, at a temperature greater than 370 DEG C, the residence time of the pyrolysis gas is greater than 2 seconds, preferably greater than 5 seconds, even more preferably greater than 10 seconds, such as greater than 15 seconds, or even greater than 20 seconds May be preferred.

Due to the rapid removal of pyrolysis gas, a high pyrolysis temperature for the decomposition of plastics is permitted. This has the additional advantage that the conversion of plastics can be high and less unwanted residues. For example, the temperature at which at least a portion of the plastic is converted to wax is at least 370 占 폚, preferably at least 400 占 폚, more preferably at least 425 占 폚, even more preferably at least 440 占 폚. The temperature at which the plastic is switched may be as high as necessary, for example up to 850 캜, preferably up to 700 캜, more preferably up to 600 캜, even more preferably up to 500 캜, It can be up to 470 ° C. In a preferred embodiment, the temperature at which the plastic is switched is in the range of 400 to 650 占 폚, preferably 425 to 550 占 폚, preferably 440 to 520 占 폚, and even more preferably 440 to 470 占 폚. Most preferably, the temperature at which the plastic is switched is in the range of less than 400 to 500 占 폚.

The low residence time required for the pyrolysis gas at temperatures above 370 DEG C is achieved by any suitable means, such as by reducing the residence time of the pyrolysis gas in the reactor by operating the reactor under vacuum, By dilution, for example, by limiting the volume of the gas phase or by designing the reactor by increasing the ratio of liquid and (if present) the volume of the reactor charged by the solid, or a combination of these methods. In general, it is desirable to combine some of these methods to achieve the desired low residence time.

In one embodiment, the reactor is operated at pressures below 1200 mbar, preferably below 1000 mbar, more preferably below 950 mbar, even more preferably below 900 mbar. The pressure in the reactor may be as low as 0.5 mbar, preferably 1 mbar, preferably 10 mbar, preferably 40 mbar, preferably 50 mbar, more preferably 60 mbar, even more preferably 80 mbar. For example, the reactor may be operated at pressures ranging from 0.5 to 1200 mbar, preferably from 10 to 1100 mbar, preferably from 50 to 1000 mbar, more preferably from 60 to 950 mbar, even more preferably from 80 to 900 mbar .

In an alternative or additional embodiment, the pyrolysis gas may be diluted with a diluent. Such diluents are not particularly limited, but should not adversely affect the pyrolysis reaction or the desired reaction product. In particular, the diluent should have a low oxygen (O ₂ ) content, as described below. Examples of suitable diluents include nitrogen, hydrogen, steam, carbon dioxide, combustion gases, hydrocarbon gases, and mixtures thereof. The hydrocarbon gas preferably comprises one or more hydrocarbons having less than 5 carbon atoms. Nitrogen, carbon dioxide, combustion gases and hydrocarbon gases having fewer than 5 carbon atoms are preferred. Particularly preferred is a combustion gas and a hydrocarbon gas having less than 5 carbon atoms.

The diluent is preferably a low oxygen (O ₂₎ content, for example less than 4% by volume, preferably 2% by volume or less, more preferably one having an oxygen (O ₂₎ content of less than% by volume, each of which Based on the volume of dry gas. Combustion gases with less than 0.1% by volume of oxygen based on dry gas provide particularly good results.

The dilution level is not particularly limited and may be selected according to the requirements. For example, the molar ratio of the diluent and pyrolysis product in the pyrolysis gas may be greater than 0.5, preferably greater than 0.7, more preferably greater than 0.8, and even more preferably greater than 1. It is less preferable that the molar ratio of the diluting agent and the pyrolysis product in the pyrolysis gas exceeds 50. Advantageously, this ratio is up to 40, more preferably up to 20. The preferred molar ratio of the diluent and pyrolysis product in the pyrolysis gas ranges from 0.5 to 50, preferably from 0.7 to 40, more preferably from 0.8 to 20, for example from 1 to 10 or even from 1 to 7. [

The diluent may be introduced into the reactor at any location. For example, the inlet for the diluent may be located at the top of the reactor such that the diluent basically only contacts the pyrolysis gas under reaction conditions and does not contact the plastic melt. In an alternative embodiment, the diluent inlet may be located at the bottom of the reactor, for example, so that the diluent contacts the plastic melt under reaction conditions. Combinations of two or more different inflows may be used. Preferably, at least one diluent inlet is located at the bottom of the reactor. In this case, it has been found that the pyrolysis gas is effectively removed from the hot melt of the plastic, and as a result, the residence time of the pyrolysis gas can be effectively reduced at temperatures above 370 ° C. Most preferably, a combination of a diluent inlet located at the top of the reactor and a diluent inlet located at the bottom of the reactor is used.

In a particularly preferred embodiment, the reactor is operated under reduced pressure, and a diluent is used. In this case, the molar ratio (D) of the diluent and the pyrolysis product in the pyrolysis gas and the absolute pressure (P) at which the reactor is operated are in the range of 2 to 50 mol / mol / bar, / bar, more specifically in the range of 5 to 20 mol / mol / bar.

In one embodiment of the process of the present invention, converting at least a portion of the plastic to a wax is performed in the presence of a heat carrier. Examples of suitable heating media include sand (e.g., silica), stone, gravel, metal, metal oxide, glass, ceramic, and the like. Any metal having a melting point higher than the temperature at which decomposition of the plastic occurs can be used. Suitable metals include, for example, forgings and steels such as refractory steels. Metals such as sand, steel or iron, gravel and glass are preferred. Sand and steel are particularly preferred.

The medium may be a catalyst for the decomposition of plastics. However, in a preferred embodiment, the heating medium is not a catalyst for the gas phase decomposition of hydrocarbons.

Preferably, the heating medium has a particle size larger than the particle size of the filler used in the plastic.

In one embodiment, the heating medium comprises particles, preferably free-flowing particles, such as granular round particles, approximate-spherical particles, full balls, hollow balls, and the like. Preferably, the heating medium particles have a particle size greater than a standard US mesh 632, preferably a standard US mesh 400. Also preferably, the heat carrier particles have a particle size of about 5 cm or less, preferably about 2.5 cm or less.

If the heating medium is a sand, the heating medium particles are advantageously fine or medium size sand according to ISO 14688-1: 2002. Preferably, the heating medium particles are fine sand.

When the heating medium is a metal such as iron or steel, they are preferably in the form of a full-ball. The particle size may be from 1 to 50 mm, preferably from 10 to 30 mm. When the heating medium is glass, the particles are advantageously glass beads or glass balls having a size of 0.5 to 20 mm, preferably 0.6 to 6 mm.

When the heating medium is gravel, it is preferably fine or medium sized gravel, preferably fine gravel, according to ISO 14688-1: 2002.

The residence time of the pyrolysis gas in the reactor is expressed as the gas hold-up of the reactor divided by the gas flow rate present in the reactor, that is, the volume of the reactor filled with the gaseous material (expressed in m 3) Is displayed. To account for the thermal gas expansion, the gas is considered to be equal to the temperature of the pyrolysis reactor. When a gas present in the reactor is used, it includes a diluent.

The residence time of the condensate in the reactor is expressed as the condensate retention (i.e., the volume of the reactor filled with condensate (expressed in m3)) divided by the flow rate of the outflow condensate, expressed in m3 / min. The temperature expansion of the condensate is ignored. Such a residence time is not particularly limited, but is usually in the range of 1 to 600 minutes, preferably in the range of 2 to 400 minutes, and more preferably in the range of 3 to 250 minutes. "Condensate" is understood to mean the total amount of unconverted feedstock in liquid or solid form, the liquid and solid product obtained from the reaction (e.g., coke, ash, etc.) and, if used, the heat medium.

The process of the present invention may be performed batchwise or continuously. It is preferable to carry out the process continuously.

Those skilled in the art are aware of suitable apparatus and equipment for carrying out the process according to the present invention and will select a suitable system based on their professional experience so as not to provide additional and broad details herein.

Examples of suitable reactor types include, but are not limited to, a fluidized bed, an entrained bed, a spouted bed, a downcomer, a fixed bed, a rotating drum, a rotating cone, a screw cone, screw auger, extruder, molecular distillation, thin film evaporator, kneader, cyclone and the like. The fluidized bed, fractionation bed, jetted bed, screw auger and rotary drum are preferred. Screw augers and rotary drums are particularly preferred. The rotary drum provides good results.

The gas present in the pyrolysis reactor can be cleaned from dust in any de-dusting device. Examples of draining apparatuses include cyclones, multicycons, spiral separators, grid separators, swirl tubes, electrostatic filters, settling chambers, scroll collectors, shutter collectors, wet washer, and the like. Cyclones, multicycons, helical separators and swirl tubes are preferred. Multicylons are particularly preferred.

The separation of the non-condensing gases is implemented in any manner known to those skilled in the art. The refractory gases herein are referred to as components that do not condense at operating temperatures at a temperature of 25 캜. Examples of separation devices include quench, organic quench, aqueous quench, spray column, fractionation column, cyclone, and the like. Organic quench is preferred. An organic quench which is operated at a temperature of 110 to 250 캜 is preferred, and a temperature of 125 to 220 캜 is particularly preferred. Even more preferably from 140 to 180 占 폚.

Vacuum may be provided by any device known to those skilled in the art. Examples of vacuum devices include a liquid ring pump, a dry vacuum pump, a steam ejector, a gas ejector, a water ejector and any combination thereof.

Combustion occurs in any device known to those skilled in the art.

The separation of the wax from the fuel is accomplished by any method known to those skilled in the art. Examples are evaporation, distillation, crystallization, liquid extraction or a combination. The combination of evaporation and solvent extraction provides good results. Examples of the solvent include hexane, benzene, toluene, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK). MEK and MIBK are preferred.

Condensate materials separated at the reactor outlet can be extracted by any means known to those skilled in the art. Examples of means include screws, rotary valves and the like. Screws are preferred.

To avoid spontaneous ignition, condensate can be extracted from the atmosphere with low oxygen content. O ₂ in the gas phase surrounding the condensate is preferably less than 2%. The condensation material may be cooled by any means known to those skilled in the art. Examples include a double wall screw conveyor, a screw conveyor equipped with a water injection part, an extruder, and a screw auger. A screw conveyor provided with a water injection part is preferable.

Optionally, the condensable material may be sent to a burner to burn the flammable unconverted feedstock and the coke. Especially when equipped with a heating medium. Optionally, the ash and the heating medium are heated in a furnace to a temperature of 500 to 1000 캜, preferably 600 to 800 캜. Optionally, the hot ash and at least a portion of the heating medium are sent to the pyrolysis reactor. Preferably, at least a portion of the ash is separated from the heating medium. Separation is accomplished by any method known to those skilled in the art. Examples of methods include cycloning, elutriation, screening, sieving, centrifugation, and the like. The ratio of the heat medium flow rate to the feed flow rate usually accounts for 0.1 to 10, preferably 0.2 to 8 on a weight basis. A ratio of 0.25 or more provides particularly good results.

According to the process of the present invention, expensive waxes, such as for example candles, adhesives, packaging materials, rubber, cosmetics, fire logs, bituminous mixtures, surface abrasion coatings, asphalt, And a hydrocarbon mixture mainly comprising these waxes are obtained.

The invention therefore also relates to waxes or hydrocarbon mixtures obtainable by the process of the invention.

The wax and hydrocarbon mixtures have the advantage of having rather large chain lengths, especially linear carbon chains. Moreover, the wax obtained is generally a wax mixture which mainly contains n-paraffins and alpha-olefins. The percentage of alpha-olefin in the wax may be about 25 to 75 wt%, preferably about 40 to 60 wt%, more preferably about 50 wt%, each based on the total weight of the wax .

Thus, the present invention also relates to a hydrocarbon mixture, wherein the hydrocarbons exhibit a cumulative distribution of the number of carbon atoms such that d20 is greater than or equal to 20 and d50 is less than or equal to 50;

At least 50 mole% of the hydrocarbons are linear hydrocarbons;

The molar ratio of n-paraffin to alpha-olefin in the hydrocarbon is in the range of 0.1 to 10.

The hydrocarbon mixture according to the invention comprises mainly waxes, i. E. Hydrocarbons having at least 20 carbon atoms. However, the mixture may also contain small amounts of hydrocarbons having fewer than 20 carbon atoms. Preferably, the mixture comprises less than 5 mol%, more preferably less than 3 mol%, even more preferably less than 2 mol%, and most preferably less than 1 mol% of hydrocarbons having less than 20 carbon atoms do. Throughout this application and elsewhere, "mol% of hydrocarbons" refers to the total amount of hydrocarbons in the hydrocarbon mixture.

In a preferred embodiment, the hydrocarbons in the hydrocarbon mixture exhibit a cumulative distribution of the number of these carbon atoms such that d20 is at least 22, preferably d20 at least 25.

In a further embodiment, the hydrocarbons in the hydrocarbon mixture exhibit a cumulative distribution of the number of these carbon atoms such that d20 is less than 40, more preferably d20 is less than 35, and still more preferably d20 is less than 30.

In a further embodiment, the hydrocarbons in the hydrocarbon mixture have a cumulative number of carbon atoms of d20 ranging from 20 or more to 40 or less, preferably d20 ranging from 22 or more to 35 or less, and more preferably d20 ranging from 25 or more to 30 or less. Distribution.

In a further embodiment, the hydrocarbons in the hydrocarbon mixture exhibit a cumulative distribution of the number of these carbon atoms such that the d50 is 45 or less, preferably d50 is 40 or less.

In a further embodiment, the hydrocarbons in the hydrocarbon mixture exhibit a cumulative distribution of the number of these carbon atoms such that the d50 is from 50 or less to 20 or more, preferably from d50 to 40 or less to 22 or more.

In a preferred embodiment, the hydrocarbons in the hydrocarbon mixture have a d20 of not less than 20 and not more than 40, d50 of not more than 50 and not less than 20, more preferably d20 of not less than 22 and not more than 25, and d50 not less than 40 and not less than 22, The cumulative distribution of the number of atoms is shown.

In addition to the high number of carbon atoms, the hydrocarbons in the hydrocarbon mixture according to the invention have the advantage that they have a high molar amount of linear hydrocarbons. Preferably, at least 60 mol%, more preferably at least 70 mol%, of the total amount of hydrocarbons in the hydrocarbon mixture is linear hydrocarbons.

A further advantage of the unsaturated hydrocarbons in the hydrocarbon mixture according to the invention is that they have a specific molar ratio of n-paraffin to alpha-olefin ranging from 0.1 to 10, preferably from 0.2 to 5, more preferably from 0.5 to 2 . In the context of the present invention, n-paraffins are linear saturated hydrocarbons, while alpha-olefins are linear and branched hydrocarbons, where they contain at least one alpha-double bond.

A further advantage of the hydrocarbons in the hydrocarbon mixture according to the invention is that the hydrocarbons contain a large amount of alpha-olefins. Preferably, greater than 40 mole percent, more preferably greater than 45 mole percent, and even more preferably greater than 50 mole percent of the total amount of unsaturated hydrocarbons are alpha-olefins.

In a further embodiment, the hydrocarbon mixture has an iodine number of 10 or more, preferably 25 or more, more preferably 40 or more.

In a further embodiment, the hydrocarbon mixture has an iodine number of 150 or less, preferably 100 or less, more preferably 70 or less.

In a preferred embodiment, the hydrocarbon mixture has an iodine number in the range of 1 to 150, more preferably in the range of 25 to 100, and even more preferably in the range of 40 to 70.

A further advantage of the hydrocarbon mixture according to the invention is that the mixture can have a relatively high drop point, for example greater than 25 DEG C, preferably greater than 40 DEG C, more preferably greater than 50 DEG C.

The hydrocarbon mixture according to the invention may be composed of hydrocarbons containing no heteroatoms. However, it is perfectly possible that at least a portion of the hydrocarbons contain at least one heteroatom such as oxygen, sulfur, nitrogen or halogen, such as fluorine, chlorine, bromine or iodine, depending on the plastic in which the hydrocarbon mixture is produced. Other heteroatoms are also possible.

The hydrocarbon mixture according to the invention can be obtained by the process described above via catalytic cracking of plastics. When the product stream removed from the reactor is selected to contain only hydrocarbons having at least 20 carbon atoms, a wax is obtained. However, in practice, especially on a technology scale, the product stream will usually contain small amounts of hydrocarbons with fewer than 20 carbon atoms. In this case, the above-mentioned hydrocarbon mixture is obtained.

Figure 1 schematically shows a first embodiment of the process of the present invention.
Figure 2 schematically shows a second embodiment of the process of the present invention.
3 is a graph of the response time (expressed in x-axis: hours (minutes)) at different temperatures: 425 캜 (line marked with squares), 450 캜 (line marked with circles) and 465 캜 Represents the evolution of the conversion rate (y-axis: expressed in%).
Figure 4 shows the cumulative selectivity (cumulative selectivity, y-axis) of different reaction products (listed in the x-axis) at different temperatures: 425 캜 (white bars), 450 캜 : Expressed in%).
Figure 5 shows the cumulative selectivity of the wax (y axis: expressed in%) as a function of pyrolysis gas residence time (x axis: expressed in seconds).
6 shows the carbon number distribution of the wax. The plot shows the weight as a function of the carbon chain length (x-axis: expressed as carbon number) for different reaction temperatures, namely 425 캜 (line marked with squares), 450 캜 (line marked with circles) and 465 캜 (% By weight; y axis).
FIG. 7 is a graph of the temperature and inlet N ₂ flow rates at different temperatures and inlet N _{2 (} 450 ° C and 150 ml / min N ₂ (indicated by empty circles), 465 ° C and 150 ml / min N ₂ and 1 ℓ / min of N ₂ (indicated by the filled circle line), 465 ℃ and 1 ℓ / min of N ₂ (shown in line with filled triangles), 465 ℃ and 2 ℓ / min of N ₂ (blank diamonds), 465 (Expressed in%) as a function of the reaction time (expressed in hours (minutes)) and the reaction time (expressed in hours) for 4 L / min N ₂ (line indicated by an empty square).
Figure 8 shows the cumulative selectivity (y-axis: expressed in%) of different reaction products (listed in the x-axis) at different temperatures and N ₂ flow rates. Legend: For each product, the color of the bar from the left to the right is 450 ° C and 150 ml / min, 450 ° C and 1 l / min, 465 ° C and 150 ml / min, 465 ° C and 1 l / Min, 465 DEG C and 2 L / min, 465 DEG C and 4 L / min.
Figure 9 shows the accumulation of wax as a function of the residence time of the pyrolysis gas (expressed in x-axis: time in seconds) for two reaction temperatures, 450 [deg.] C (line marked in circles) and 465 [deg.] C Selectivity (y axis: expressed in%).
10 shows the carbon number distribution of the wax. The diagrams are plotted at different reaction temperatures and N ₂ influent flow rates: 450 ° C and 150 ml / min (lines marked in circles), 465 ° C and 150 ml / min Carbon chain lengths at 465 DEG C and 1 L / min (lines marked +), 465 DEG C and 2 L / min (lines indicated by rhombus), 465 DEG C and 4 L / min (weight%; y-axis) as a function of the weight (x axis: expressed in carbon number).
Figure 11 shows the results for different types and N ₂ influent feed rates: 150 ml / min rise (line marked in circles), 1 l / min rise (line marked rhombo), 1 l / min fall (y axis: expressed as a percentage) as a function of the reaction time (expressed in hours (minutes)) relative to the rise / fall (rise in 1 / min and 3 / drop in line; .
Figure 12 shows the cumulative selectivity (y axis: expressed in%) of different reaction products (listed in the x-axis) for different types and N ₂ influent feed flow rates. Legend: For each product, the color of the bar from the left to the right is 150 ml / min rise, 1 l / min rise, 1 l / min fall, 4 l / min rise / fall (1 l / Minute rise and 3 L / min fall).
Figure 13 shows the cumulative selectivity of the wax (y axis: expressed in%) as a function of pyrolysis gas residence time (x axis: expressed in seconds).
14 shows the carbon number distribution of the wax. The charts show different types and N ₂ inflow feed rates: 150 ml / min rise (lines marked in circles), 1 l / min rise (rhombus lines), 1 l / min fall (triangles) (Weight%; y axis) as a function of carbon chain length (x axis: expressed in carbon number) relative to the carbon chain length (relative to the line indicated by the square) / min rise / fall (1 L / min rise and 3 L / .

The process of the present invention will now be described by way of example with reference to Figs. 1 and 2. Fig.

In the first embodiment, shown schematically in Figure 1, the pyrolysis of the raw material to produce the wax is realized under vacuum in an oxygen-deficient atmosphere. The raw material 1 is pretreated by the combination of the effluent stream 3 and the physico-chemical treatment section 2 in which the pretreated raw material 4 is separated. The pretreated feedstock 4 is introduced into the pyrolysis reactor 10 via line 6 with the aid of a feeder 5. The pyrolysis reactor is indirectly heated. As an example, the reactor can be heated by circulation of the hot stream 7 which is fed to a suitable heat transfer device 8 and recovered as stream 9 at the outlet, unless it departs from this category. Optionally, the heating medium stream 11 is introduced into the pyrolysis reactor. The pyrolysis gas (12) is recovered from the pyrolysis reactor and sent to the physicochemical treatment section (20). The residue 13 is withdrawn via the device 14, which is treated in a suitable manner to produce the stream 15. The residue contains unconverted starting materials, by-products, and optionally a heating medium which is introduced into the pyrolysis reactor via stream (11). In the physico-chemical treatment section, the pyrolysis gas is cleaned from the dust, and other harmful components recovered in the stream 21 and separated as the stream 22 are sent to the treatment section 25 where the refractory stream 24 is recovered from the condensate stream 23). Stream 24 is sent to vacuum device 26. The effluent 27 from the vacuum device is sent to the combustion chamber 28 together with an appropriate amount of combustion air 29 to produce the hot stream 7. Optionally, an auxiliary fuel 30 is added to the combustion chamber 28. The condensation stream 23 is sent to the separation unit 31 where the wax stream 32 is separated from the byproduct 33.

In a second embodiment, pyrolysis of the raw material to produce the wax, which is realized under vacuum in the presence of diluent gas, is schematically illustrated in Fig. 2 as an example. Pyrolysis of the raw material to produce the wax is achieved under vacuum in an oxygen-deficient atmosphere. The raw material 51 is pretreated by the combination of the effluent stream 53 and the physico-chemical treatment section 52 in which the pretreated raw material 54 is separated. The pretreated feedstock 54 is introduced into the pyrolysis reactor 60 via line 56 with the aid of a feeder 55. The pyrolysis reactor is indirectly heated. As an example, the reactor may be heated by circulation of the hot stream 57 supplied to the suitable heat transfer device 58 and recovered at the outlet 59 as stream 59, unless departing from the above scope. Optionally, a heating medium stream 61 is introduced into the pyrolysis reactor. A gas diluent 66 is introduced into the reactor 60 at a controlled rate. The pyrolysis gas in the mixture (62) with the diluent is recovered from the pyrolysis reactor and sent to the physico-chemical treatment section (70). Optionally, the residue in the mixture 63 with the heating medium is withdrawn via the device 64, where it is treated in an appropriate manner to produce stream 65. The residue contains unconverted feedstock, by-products, and optionally a heating medium which is introduced into the pyrolysis reactor via stream (61). In the physico-chemical treatment section, pyrolysis gas is cleaned from dust, and other harmful components recovered in stream 71 and separated as stream 72 are sent to treatment section 75 where refractory stream 74 is recovered from the condensate stream 73). Stream 74 is sent to vacuum device 76. The effluent 77 from the vacuum device is sent to the combustion chamber 78 together with an appropriate amount of combustion air 79 to produce the hot stream 57. Optionally, auxiliary fuel 80 is added to combustion chamber 78. The condensate stream 73 is sent to the separation unit 81 where the wax stream 82 is separated from the byproduct 83.

Where the disclosure of any patent, patent application, and publication included herein by reference is inconsistent with the description of the present application to such an extent that the term is unclear, the description of the present invention will prevail.

Example

General description of the experiment process

In each run in a semi-batch mode, 30 g of plastic (20% polypropylene, 80% polyethylene) are loaded into the reactor and a quantity of heating medium (SiO ₂ (approximately 20 g) Respectively. The reactor was closed, heated from room temperature to 200 DEG C over 20 minutes, and simultaneously purged at a nitrogen flow rate of 150 mL / min, which was introduced into the top of the reaction vessel. When the internal temperature reached the melting point of the plastic, stirring was started and slowly increased to 690 rpm. The temperature was maintained at 200 ° C for 25-30 minutes. Nitrogen flowing out of the reactor during this heating process was not collected. On the other hand, the heating medium storage tank containing the heating medium was purged with nitrogen several times.

After this first pretreatment step, the temperature was increased to a reaction temperature at a heating rate of 10 DEG C / min and collection of gases and nitrogen in the corresponding gas sample bags began. When the internal temperature reached the reaction temperature, a heating medium was introduced into the reactor. According to the experiment, the nitrogen gas flow rate was set to 150 ml / min or 1, 2 or 4 l / min, and the gas product circulation communicated with another pair of glass traps and corresponding gas sample bags. This was considered as zero reaction time. Experiments have shown that nitrogen can enter the reactor in two ways: by bubbling into the top of the vessel or through molten plastic.

During the selected period, the liquid and gaseous products were collected in a pair of glass traps and their associated gas sample bags, respectively. At the end of the experiment, the reactor was cooled to room temperature. Liquid and gas were also collected during this cooling step.

The reaction products were divided into three groups: i) gas, ii) liquid hydrocarbons and iii) residues (wax compounds, ash and coke that accumulate on the heating medium). Quantification of the gas was carried out by gas chromatography (GC) using nitrogen as an internal standard, while quantification of the liquid and the residue was carried out by weight. The weight of the glass trap (with their corresponding lids) was measured before and after the collection of the liquid, while the weight of the reactor vessel was measured before and after each run.

In the simulated distillation (SIM-DIS) GC method, it was possible to measure different fractions in the liquid sample (depending on the selected cut point) and in the detailed hydrocarbon analysis (DHA) GC method, PIONAU in the gasoline fraction of the last withdrawn sample (C5 to C11: boiling point below 216.1 deg. C, including C5 to C6 in the gas sample and C5 to C11 in the liquid sample), the saturation mono-isomer in the diesel fraction of the last withdrawn liquid sample in GCxGC, , Di- and tri-aromatics (C12-C21; 216.1 < BP < 359 C).

In all experimental cases, the residence time of pyrolysis gas was calculated using a reactor volume of 300 ml, a raw plastic density of 0.94 g / ml and a silica bulk density of 1.1 g / ml. As a result, the gas holdup amount was 250 ml.

In an embodiment, HCO refers to a heavy duty circulating oil that is considered as a hydrocarbon molecule (+ C22) having at least 22 carbon atoms. The wax refers to a hydrocarbon molecule (+ C20) having at least 20 carbon atoms. Generally:

Gasoline: Contains C5 and C6 in the gas + liquid with a bp (boiling point) of less than 150 ° C (approx. C5 to C9)

Kerosene: a liquid with a boiling point (bp) greater than 150 ° C but less than 250 ° C (about C10 to C14)

Diesel: A liquid with a boiling point (bp) of greater than 250 ° C but less than 359 ° C (about C15 to C21)

HCO: products (C22 and +) having a boiling point above 359 DEG C

Wax: products (C20 and +) having a boiling point above 330 &lt; 0 &

The measurement of the different fractions is carried out by gas chromatography by the simulated distillation method and according to ASTM-D-2887 standard.

A general description of the analytical method

Measurement of the number of carbon atoms

The number of carbon atoms in the hydrocarbon mixture and their distribution is measured according to the ASTM-D-2887 method. This method is a GC method for simulated distillation of a complex hydrocarbon mixture. The method allows separation of hydrocarbon molecules in the complex mixture according to their boiling point. Then, the boiling point is related to the number of carbon atoms according to the predetermined blocking point. In the present invention, the relationship between the boiling point and the number of carbon atoms is used as defined in Table 1 below.

These fractions having a boiling point of less than 105.8 DEG C are defined as hydrocarbons having less than 10 carbon atoms. To determine the carbon chain length of the molecules in a given sample, the peaks obtained in the GC are plotted against the boiling point blocking points listed in Table 1 so that the area under the curve obtained is related to the relative amount of hydrocarbons having a given number of carbon atoms for each boiling point range . Normalizing all the peaks to 100% makes it possible to calculate the distribution of the number of carbon atoms in the sample according to standard methods known to those skilled in the art. The distribution obtained is the weight distribution with respect to the total weight of the sample.

Measurement of linear and branched hydrocarbons

The amount of linear and branched hydrocarbons in the hydrocarbon mixture according to the present invention is determined according to the ASTM-D-6730 method. Measurements are performed on a Varian 3900 chromatograph equipped with an FID detector and a capillary column of 100 m size. The GC also has a back-flush that allows only the fraction of the sample to enter the column. For the determination of the composition of the mixture, Varian DHA software (detailed hydrocarbon analysis) is used. After integrating the obtained peaks, they are compared with DHA software, which has its own internal database, to qualify and quantify the peaks. By this technique, the classes of molecules quantified (paraffin, isoparaffin, olefin, naphthene and aromatics) are molecules with a boiling point below 216.1 ° C. In the present invention, the distribution observed in gasoline having a boiling point of less than 216.1 DEG C is assumed to be equal to the distribution in hydrocarbons having a higher boiling point.

Measurement of unsaturated hydrocarbons and alpha-olefins

The amount of alpha-olefins in the unsaturated hydrocarbon mixture according to the present invention is determined using conventional ¹ H and ¹³ C NMR techniques. For example, a 1-alkene as a solvent in CDCl ₃ shows a peak at 5.82 ppm, a 2-alkene shows a peak at 5.42 ppm, and a 2-methyl-1-alkene shows a peak at 4.69 ppm. Those unsaturated hydrocarbons containing both alpha-double bonds and other double bonds can be distinguished by the GC method described above for the measurement of branched hydrocarbons. Alpha-olefins containing both alpha-double bonds and other double bonds are quantified as alpha-olefins in the context of the present invention.

n-paraffins (linear saturated hydrocarbons) can be distinguished from linear unsaturated hydrocarbons and branched (saturated or unsaturated) hydrocarbons by the same methods (GC and NMR).

Iodine measurement

The iodine value of the hydrocarbon mixture according to the invention is determined by dissolving 0.1 to 0.2 g of sample in 10 ml of chloroform. To this solution is added 5 ml of a Wijs solution containing 0.1 M ICl and the mixture is allowed to react in the dark for 1 hour. Following unreacted Weiss solution is reacted with potassium iodide solution and 100 g / ℓ to convert unreacted ICl as I _2. The amount of I ₂ formed is determined by titration with a thiosulfate solution. Calculate the amount of unreacted wise solution from the amount of thiosulphate required to react with I ₂ , which indicates the number of unsaturated bonds in the hydrocarbon.

Measurement of the red dot

The ratios of the mixtures of hydrocarbons according to the invention are measured in accordance with European standard EN 1427, March 2007.

Example 1

Experiments were performed according to the general procedure described above. Experiments were conducted using 80 wt% HDPE and 20 wt% PP as raw materials and 20 g silica as a heating medium. The reaction temperature varied from 425 ° C to 465 ° C and N ₂ was introduced at the top of the reactor at 0.15 l / min. The weight ratio of heat medium to plastic was equal to 20/30 by weight.

Experimental results are shown in Figs. As expected, Figure 3 shows how the conversion rate increases as the temperature increases. On the other hand, Fig. 4 shows the remarkable effect of increasing the yield of HCO and wax when the temperature is increased. Figure 5 shows that the selectivity to wax increases as the residence time of pyrolysis gas decreases. Figure 6 further shows that the wax produced at high temperatures also has a different carbon chain distribution moving towards longer chain compounds.

The cumulative distribution of carbon atoms in the hydrocarbon mixture obtained according to the reaction temperature is summarized in Table 2 below.

Temperature 425 DEG C 450 ℃ 465 DEG C d20 20 20 21 d50 22 23 24

The hydrocarbon mixture obtained in this example was further analyzed and the results of this analysis are summarized in Table 3 below.

Raw C ₂₀ to C ₅₄ C ₂₀ to C ₃₀ interception points C ₃₀ -C ₄₀ interception point C ₄₀₊ breaking point Melting point # 45 ° C 26 ℃ 57 ℃ 72 ℃ Iodine 51 60 48 40 Freezing point 70 ℃ -> -15 ℃ TBD TBD TBD Red dot 63.2 DEG C 26.2 DEG C 53.4 DEG C 75.4 DEG C C, H, O 79.9 / 12.7 / 0.7 84.8 / 14.85 85.3 / 14 85.6 / 14.1 1-olefin / 2-olefin / isoolefin 60/27/10 68/20/5 60/29/6 52/38/7 mode Dough solid Dough solid solid solid

Example 2

Experiments were performed according to the general procedure described above. Experiments were conducted using 80 wt% HDPE and 20 wt% PP as raw materials and 20 g silica as a heating medium. The reaction temperature was set at 450 ° C or 465 ° C, and the N ₂ flow rate varied from 0.15 l / min to 4 l / min. The weight ratio of heat medium to plastic was equal to 20/30 by weight.

The experimental results are shown in Figs. As expected, Figure 7 shows how the conversion rate increases as the temperature increases from 450 캜 to 465 캜. Moreover, as expected, the reaction rate is completely independent of the N ₂ flow rate used. On the other hand, FIG. 8 shows the surprising effect that an increase in the nitrogen flow rate leads to an increase in the yield of HCO and wax. Figure 9 shows that the selectivity to wax increases as the residence time of pyrolysis gas decreases. Figure 10 additionally shows that the wax produced using higher N ₂ flow rates also has a different carbon chain distribution moving towards longer chain compounds.

The cumulative distribution of carbon atoms in the hydrocarbon mixture obtained according to the reaction temperature and N ₂ flow rate is summarized in Table 4 below.

Temperature [℃] / N ₂ flow rate [㎖ / min; 450/150 465/150 450/1000 465/1000 465/2000 465/4000 d20 20 21 21 21 23 24 d50 23 24 24 25 30 32

Example 3

Experiments were performed according to the general procedure described above. Experiments were conducted using 80 wt% HDPE and 20 wt% PP as raw materials and 20 g silica as a heating medium. The reaction temperature was set at 450 ° C and the N ₂ flow rate varied from 0.15 l / min to 4 l / min. In particular, the N ₂ flow rate was set as follows:

The N ₂ inlet was located at the top of the reactor and was not in contact with the plastic melt under the reaction conditions. This configuration is defined as &quot; up &quot; in the figure.

The N ₂ inlet is located at the bottom of the reactor and is in contact with the plastic melt under the reaction conditions. This enables a kind of "stripping (stripping) 'effects. This configuration is defined as &quot; down &quot; in the drawings.

The weight ratio of heat medium to plastic was equal to 20/30 by weight.

Experimental results are shown in Figs. 10-13. Figure 10 shows that as the flow rate increases, the conversion rate increases. In particular, by placing the N ₂ inlet at the bottom of the reactor, the N ₂ flow rate is brought into contact with the plastic melt, further increasing the conversion rate. Figure 11 shows the surprising effect of increasing the yield of HCO and wax with increasing nitrogen flow. In particular, the effect of N ₂ in bringing it into contact with the plastic melt under reaction conditions is even more pronounced. Figure 12 shows that the selectivity to wax increases as the residence time of pyrolysis gas decreases. Figure 13 additionally shows that the resulting wax also has a different carbon chain distribution moving toward longer chain compounds.

The cumulative distribution of carbon atoms in the hydrocarbon mixture obtained according to the N ₂ flow rate is summarized in Table 5 below.

N ₂ flow rate [ml / min] 150 rise 1000 rise 1000 descent 4000 rise + fall d20 20 21 22 24 d50 23 24 28 33

Example 4: Mass balance according to the present invention

In the present embodiment and the following examples, the post-consumer plastic is named on the basis of the main plastic components thereof, and on average the abovementioned reusable plastic contains 8% by weight of additives.

A unit equipped with a double wall rotary drum furnace with an internal diameter of 1.4 m and an internal length of 5 m (equipped with a gas product absorption line having a diameter of 400 mm and a length of 2 m) Mixed plastic waste was fed at 2500 kg / hr:

g / kg

PE 415.2

PP 400.0

PS 20.0

PVC 20.0

water 100.0

Food residue 20.0

Foreign matter solid 20.0

air 4.8

First, the mixed plastic waste was pretreated at 250 ° C and atmospheric pressure to melt the plastic and remove most of the air, water, food residues and foreign solids as effluent. These effluents also contained gaseous products resulting from the decomposition of any constituents of the feed material. The pretreated material was introduced into a double wall rotary drum furnace operating at 450 kg / hr for a heating medium consisting of fine sand fed at 465 ° C under an absolute pressure of 150 mbar as well as 700 ° C. The gas holdup in the blast furnace was estimated to be 4 m3 and the retention amount of the condensed phase was estimated to be 3.6 m3. It is estimated that the supplementary gas holdup amount at a temperature of 370 ° C or higher is 0.3 m 3. The total gas flow produced at the outlet of the blast furnace is estimated at 9 kmol / hr, corresponding to 1903 kg / hr.

The residence time of the gas product in the gas phase above 370 ° C was calculated to be 4.5 seconds. The calculated flow rate is shown in Table 6 below along with the numbering of FIG.

The heat duty of the reaction was estimated at 517 kW, and the heat supplied by the heating medium was estimated to be 217 kW, corresponding to 42% of the heat available by combustion of the coke, and the heat supplied by the double wall 300 kW, which corresponds to 50% of the heat available by combustion of the gas. The heat transfer surface available in the furnace is estimated to be 20 m 2 and the total heat transfer coefficient is estimated to be 80 W / ㎡ K, and the algebraic temperature difference between the hot gas used to heat the furnace and the reaction medium is 190 ° C It reached.

The residence time of the condensate in the furnace was estimated to be 80 minutes. The overall yield of the wax was calculated to be 59% based on the plastic content of the mixed plastic waste (including additives). The wax was predominantly linear.

Example 5: Mass balance according to the present invention

A unit equipped with a double-walled rotary drum furnace (having a diameter of 400 mm and a length of 5 m with a gas product absorption line) with an internal diameter of 1.4 m and an internal length of 5 m was subjected to re- Mixed plastic waste was fed at 2500 kg / hr:

g / kg

PE 415.2

PP 400.0

PS 20.0

PVC 20.0

water 100.0

Food residue 20.0

Foreign matter solid 20.0

air 4.8

First, the mixed plastic waste was pretreated at 250 ° C and atmospheric pressure to melt the plastic and remove most of the air, water, food residues and foreign solids as effluent. These effluents also contained gaseous products resulting from the decomposition of any constituents of the feed material. The pretreated material was fed to a double wall rotary drum furnace operating at 465 ° C under an absolute pressure of 355 mbar as well as at 4000 kg / hr for a heating medium consisting of fine sand fed at 700 ° C and 560 kg / hr for nitrogen at 25 ° C . The gas holdup in the blast furnace is estimated to be 6 m3 and the retention amount of the condensed phase is estimated to be 1.7 m3. It is estimated that the supplementary gas holdup amount at a temperature of 370 ° C or higher is 0.3 m 3. The total gas flow produced at the outlet of the blast furnace is estimated at 29 kmol / hr, corresponding to 2463 kg / hr.

The residence time of the gas product in the gas phase above 370 ° C was calculated to be 4.9 seconds. The calculated flow rate is shown in Table 7 together with the numbering in FIG.

The heat load of the reaction, including nitrogen preheating, was estimated at 585 kW, and the heat supplied by the heating medium was estimated to be 261 kW, corresponding to 50% of the heat available by combustion of the coke, Is estimated to be 324 kW, which corresponds to 53% of the heat available by combustion of the gas. The heat transfer surface available in the blast furnace is estimated to be 20 m 2 and the total heat transfer coefficient is estimated to be 80 W / ㎡K and the algebraic temperature difference between the hot gas used to heat the furnace and the reaction medium is 205 ° C It reached.

The residence time of the condensate in the furnace was estimated to be 132 minutes. The specific dilution ratio (D / P) was calculated to be 6.3 mol / mol / bar. The overall yield of the wax was calculated to be 59% based on the plastic content of the mixed plastic waste (including additives). The wax was predominantly linear.

Example 6: Mass balance according to the present invention

A unit equipped with a double-walled rotary drum furnace (having a diameter of 400 mm and a length of 5 m with a gas product absorption line) with an internal diameter of 1.4 m and an internal length of 5 m was subjected to re- Mixed plastic waste was fed at 1200 kg / hr:

g / kg

PE 415.2

PP 400.0

PS 20.0

PVC 20.0

water 100.0

Food residue 20.0

Foreign matter solid 20.0

air 4.8

First, the mixed plastic waste was pretreated at 250 ° C and atmospheric pressure to melt the plastic and remove most of the air, water, food residues and foreign solids as effluent. These effluents also contained gaseous products resulting from the decomposition of any constituents of the feed material. The pretreated material was introduced into a double wall rotary drum furnace operating at 465 ° C under an absolute pressure of 120 mbar, but also at 224 kg / hr for nitrogen at 25 ° C. The gas holdup in the blast furnace was estimated to be 7 m3 and the retention amount of the condensed phase was estimated to be 0.6 m3. It is estimated that the supplementary gas holdup amount at a temperature of 370 ° C or higher is 0.3 m 3. The total gas flow produced at the outlet of the blast furnace is estimated at 12.3 kmol / hr, corresponding to 1137 kg / hr.

The residence time of the gas product in the gas phase above 370 ° C was calculated to be 4.6 seconds. The calculated flow rate is shown in Table 8 together with the numbering in FIG.

The heat load of the reaction, including nitrogen preheating, was estimated at 275 kW, and the heat supplied by the double wall is estimated to be 275 kW, which corresponds to the heat available by the combustion of the gas. The heat transfer surface available in the blast furnace is assumed to be 20 m 2 and the total heat transfer coefficient is estimated to be 80 W / ㎡K and the algebraic temperature difference between the hot gas used to heat the furnace and the reaction medium is 174 ° C It reached.

The retention time of the condensate in the furnace was estimated to be 161 minutes. The specific dilution ratio (D / P) was calculated to be 15.4 mol / mol / bar. The overall yield of the wax was calculated to be 59% based on the plastic content of the mixed plastic waste (including additives). The wax was predominantly linear.

Reference Example 1: Mass balance for conditions deviating from the present invention

A unit equipped with a double-walled rotating drum furnace (having a diameter of 400 mm and a length of 2 m with a gas product absorption line) having an internal diameter of 1.4 m and an internal length of 8 m was subjected to re- Mixed plastic waste was fed at 2500 kg / hr:

g / kg

PE 415.2

PP 400.0

PS 20.0

PVC 20.0

water 100.0

Food residue 20.0

Foreign matter solid 20.0

air 4.8

First, the mixed plastic waste was pretreated at 250 ° C and atmospheric pressure to melt the plastic and remove most of the air, water, food residues and foreign solids as effluent. These effluents also contained gaseous products resulting from the decomposition of any constituents of the feed material. The pretreated material was introduced into a double wall rotary drum furnace operated at 450 ° C under an absolute pressure of 1320 mbar. The gas holdup in the blast furnace is estimated to be 11.1 m3 and the retention of the condensed phase is estimated to be 1.2 m3. It is estimated that the supplementary gas holdup amount at a temperature of 370 ° C or higher is 0.3 m 3. The total gas flow produced at the outlet of the blast furnace is estimated to be 15.1 kmol / hr, corresponding to 1902 kg / hr.

The residence time of the gas product in the gas phase above 370 ° C was calculated to be 64.9 seconds. The calculated flow rate is shown in Table 9 together with the numbering in FIG.

The heat load of the reaction was estimated at 668 kW, and the heat supplied by the double wall was estimated to be 668 kW, corresponding to 43% of the heat available by combustion of the gas. The heat transfer surface available in the furnace is estimated to be 32 m 2 and the total heat transfer coefficient is estimated to be 80 W / ㎡ K, and the algebraic temperature difference between the hot gas used to heat the furnace and the reaction medium is 263 ° C It reached.

The residence time of the condensate in the furnace was estimated to be 300 minutes. The overall yield of the wax was calculated to be 24% based on the plastic content of the mixed plastic waste (including additives). The wax was predominantly linear.

Reference Example 2: Mass balance for conditions deviating from the present invention

A unit equipped with a double-walled rotating drum furnace (having a diameter of 400 mm and a length of 2 m with a gas product absorption line) having an internal diameter of 1.4 m and an internal length of 8 m was subjected to re- Mixed plastic waste was fed at 2500 kg / hr:

g / kg

PE 415.2

PP 400.0

PS 20.0

PVC 20.0

water 100.0

Food residue 20.0

Foreign matter solid 20.0

air 4.8

First, the mixed plastic waste was pretreated at 250 ° C and atmospheric pressure to melt the plastic and remove most of the air, water, food residues and foreign solids as effluent. These effluents also contained gaseous products resulting from the decomposition of any constituents of the feed material. The pretreated material was introduced into a double wall rotary drum furnace operating at 450 ° C under an absolute pressure of 1400 mbar as well as at 28 kg / hr for nitrogen at 25 ° C. The gas holdup in the blast furnace is estimated to be 11.1 m3 and the retention of the condensed phase is estimated to be 1.2 m3. It is estimated that the supplementary gas holdup amount at a temperature of 370 ° C or higher is 0.3 m 3. The total gas flow produced at the outlet of the blast furnace was estimated at 16.1 kmol / hr, corresponding to 1929 kg / hr.

The residence time of the gas product in the gas phase above 370 ° C was calculated to be 64.6 seconds. The calculated flow rate is shown in Table 10 together with the numbering in FIG.

The heat load of the reaction was estimated at 670 kW, and the heat supplied by the double wall is estimated to be 670 kW, which corresponds to 43% of the heat available by combustion of the gas. The heat transfer surface available in the blast furnace is assumed to be 32 m 2 and the total heat transfer coefficient is estimated to be 80 W / ㎡K, and the algebraic temperature difference between the hot gas used to heat the furnace and the reaction medium is 265 ° C It reached.

The residence time of the condensate in the furnace was estimated to be 300 minutes. The specific dilution ratio (D / P) was calculated to be 0.05 mol / mol / bar. The overall yield of the wax was calculated to be 24% based on the plastic content of the mixed plastic waste (including additives). The wax was predominantly linear.

Waxes of the type obtained according to the process of the present invention are particularly suitable for bituminous coating compositions, more generally (i) mineral aggregates and (ii) petroleum (a mixture of bitumen or synthetic polymeric resin and oil) and / Or as an additive in coating compositions based on organic binders derived from plants (especially binders based on resins and vegetable oils). The waxes of the present invention can be applied to coatings based on bitumen based on pure or modified bitumen (especially through the addition of polymers) and bituminous mixtures and asphalt concrete as well as other organic binders, such as coatings of synthetic polymers of this type and / or vegetable resins Especially useful.

In a first embodiment, the wax according to the invention is used to facilitate the use of a binder and / or a mixture of binder and aggregate when used in a coating based on inorganic aggregates and organic binders; And / or the coating of agglomerates, and can be used in particular in heat: the presence of the wax according to the present invention typically tends to decrease by several tens degrees Celsius, Is sufficiently fluid to be used, which is manifest itself in terms of a reduction of the process cost in particular.

According to another embodiment that is compatible with and compliant with previous embodiments for the specific application of the type described below, the wax according to the invention can be used in coatings based on inorganic aggregates and organic binders to increase the curing rate of the coating during its cooling have. Waxes according to the present invention tend to have a higher "settling" rate than organic binders such as the bitumen or clear binder described above.

Thus, by way of example and not limitation, the waxes of the present invention can be advantageously used at least in the following applications:

In the so-called "warm" bitumen mixture obtained by coating aggregates with heated bitumen (pure or modified): for this application the wax is advantageously mixed with the bitumen prior to the coating of the agglomerate, Can be mixed with aggregates at much lower temperatures than in the absence (typically at temperatures of about 110 to 140 占 폚, more precisely at temperatures of 150 to 200 占 폚 as compared to 200 占 폚 in the absence of resin).

- in surface abrasion coatings where the wax is typically mixed with bitumen which is a flux additive of vegetable oil type, for example as disclosed in EP 1845134 in particular. This fluxed binder is for spraying on the road surface, and the aggregates are then deposited thereon. In this connection, the presence of the wax not only reduces the temperature at which the binder is sprayed, but also increases the bitumen and its agglomeration increase (curing) rate after its deposition, despite the presence of a fluxing agent.

Poured asphalt, a composition having a bituminous mixture of the type described above, but with a higher bitumen content (typically at least 10% by weight, based on the total weight of the mixed liquor, compared to 4.5 to 5.5% by weight in a conventional bituminous mixture) The wax is typically mixed with a bitumen binder whereby bitumen can be mixed with the aggregate at a temperature of about 160 to 190 DEG C compared to a temperature of above 200 DEG C (typically about 250 DEG C) in the absence of wax . The wax also gives curing properties.

- a bituminous mixture based on a "transparent binder", also referred to as a "synthetic binder", that is to say a bituminous mixture based on synthetic polymers and / or based on binders based on resins and oils of vegetable origin and / The presence of the wax in these binders causes the temperature at which the coating is made and settled to decrease.

- sealing coatings, including bitumen mixed with polymers, especially in sealing coatings for roofs: the presence of wax also reduces the temperature at which the coating is made. This also accelerates the settling of the coating after deposition, which is particularly notable in the case of deposits on inclined roofs which tend to flow when the deposited composition is not cured sufficiently fast.

Moreover, waxes of the present invention can be used to improve the rheological properties of the binder, and more specifically to increase the modulus of rigidity. In this connection, the wax of the present invention can also provide lubrication properties.

On the other hand, in at least some cases, the presence of the wax according to the present invention in the bituminous coating tends to improve the resistance to embrittlement of the coating in the face of solubilization by the hydrocarbons. In this connection it has been found that the waxes according to the invention are particularly suitable as additives in bituminous coatings, for example in bituminous coatings used in service stations, which are brought into contact with gasoline or kerosene.

Claims (33)

A process for converting plastics into wax by cracking,
Introducing plastic into the reactor;
Allowing at least a portion of the plastic to convert to wax, wherein the wax is part of a pyrolysis gas formed in the reactor; And
And removing the wax-containing product stream from the reactor,
Characterized in that the pyrolysis gas has a residence time of less than 60 seconds at a temperature of more than 370 ° C. The method of claim 1, wherein the pyrolysis gas is heated to a temperature of greater than 370 DEG C for less than 50 seconds, preferably less than 40 seconds, more preferably less than 30 seconds, even more preferably less than 25 seconds, such as less than 20 seconds Lt; RTI ID = 0.0 &gt; of: &lt; / RTI &gt; 3. The method of claim 1 or 2, wherein the temperature at which at least a portion of the plastic is converted to wax is at least 370 캜, preferably at least 400 캜, more preferably at least 425 캜, even more preferably at least 440 캜, Such as 400 to 650 占 폚, preferably 425 to 550 占 폚, and more preferably 440 to 520 占 폚. 4. The process according to any one of claims 1 to 3, wherein the reactor has a pressure of less than 1200 mbar, preferably less than 1000 mbar, more preferably less than 950 mbar, even more preferably less than 900 mbar, Is operated at a pressure in the range of 1200 mbar, preferably 10 to 1100 mbar, more preferably 60 to 950 mbar, even more preferably 80 to 900 mbar. 5. A process according to any one of claims 1 to 4, wherein the pyrolysis gas is diluted with a diluent, wherein the diluent is preferably selected from nitrogen, hydrogen, steam, carbon dioxide, a combustion gas, a hydrocarbon gas and mixtures thereof In process. 6. The method of claim 5, wherein the molar ratio of the diluent in the pyrolysis gas to the pyrolysis product is greater than 0.5, preferably greater than 0.7, more preferably greater than 0.8, even more preferably greater than 1, such as 0.5 to 50, Is in the range of 0.7 to 40, more preferably 1 to 20. 7. The process according to any one of claims 1 to 6, wherein the conversion of at least a portion of the plastic to wax is carried out in the presence of a heating medium. 8. The process according to claim 7, wherein the heating medium comprises particles, preferably free-flowing particles. The method of claim 7 or 8, wherein the heating medium is selected from a sand (e.g., silica), stone, gravel, metal, metal oxide, glass, ceramic and mixtures thereof, preferably sand or steel In process. 10. The process according to any one of claims 7 to 9, wherein the heating medium is a catalyst for decomposing plastics. 11. The process according to any one of claims 7 to 10, wherein the heating medium is not a catalyst for gas phase decomposition of hydrocarbons. 12. The process according to any one of claims 1 to 11, wherein the residence time of the condensate in the reactor is from 10 to 600 minutes, preferably from 20 to 400 minutes, more preferably from 30 to 250 minutes. 13. The process according to any one of claims 1 to 12, which is carried out continuously. 14. The process according to any one of claims 1 to 13, wherein the plastic is a waste plastic, preferably a mixed waste plastic. 15. The process of claim 14, wherein the waste plastics are selected from post-consumer waste plastics, off-spec plastics and industrial scrap plastics. As the hydrocarbon mixture,
The hydrocarbons show a cumulative distribution of the number of carbon atoms such that d20 is greater than or equal to 20 and d50 is less than or equal to 50;
At least 50 mole% of the hydrocarbons are linear hydrocarbons;
Wherein the molar ratio of n-paraffin to alpha-olefin in the hydrocarbon ranges from 0.1 to 10. 17. The mixture of claim 16, wherein the hydrocarbons exhibit a cumulative distribution of the number of carbon atoms such that d20 is greater than or equal to 22, preferably greater than or equal to 25. 18. The mixture according to claim 16 or 17, wherein the hydrocarbons exhibit a cumulative distribution of the number of carbon atoms such that d20 is 40 or less, preferably d20 is 35 or less, more preferably d20 is 30 or less. The hydrocarbon according to any one of claims 16 to 18, wherein the hydrocarbon has a d20 of 20 or more and 40 or less, preferably d20 of 22 or more and 35 or less, and more preferably d20 of 25 or more to 30 or less. Lt; RTI ID = 0.0 &gt; of carbon atoms. &Lt; / RTI &gt; 20. The mixture according to any one of claims 16 to 19, wherein the hydrocarbons exhibit a cumulative distribution of the number of carbon atoms so that d50 is 45 or less, preferably d50 is 40 or less. 21. The composition according to any one of claims 16 to 20, wherein the hydrocarbons exhibit a cumulative distribution of the number of carbon atoms such that the d50 is 50 or less to 20 or more, preferably d50 is 40 or less to 22 or more. . 22. The mixture according to any one of claims 16 to 21, wherein the molar ratio of n-paraffin to alpha-olefin in the hydrocarbon is in the range of from 0.2 to 5, preferably from 0.5 to 2. 23. The mixture according to any one of claims 16 to 22, wherein at least 60 mol%, preferably at least 70 mol%, of the hydrocarbons are linear hydrocarbons. 24. The mixture according to any one of claims 16 to 23, wherein the unsaturated hydrocarbon is more than 40 mole%, preferably more than 45 mole%, more preferably more than 50 mole% is alpha-olefins. 25. The mixture according to any one of claims 16 to 24 having an iodine number of 10 or more, preferably 25 or more, more preferably 40 or more. The mixture according to any one of claims 16 to 25, having an iodine number in the range of 10 to 150, preferably in the range of 25 to 100, more preferably in the range of 40 to 70. 27. The mixture according to any one of claims 16 to 26, having a drop point of greater than 25 DEG C, preferably greater than 40 DEG C, more preferably greater than 50 DEG C. 28. The mixture according to any one of claims 16 to 27, wherein at least a portion of the hydrocarbons contain one or more heteroatoms. A wax obtainable by a process according to any one of claims 1 to 15. 30. A wax according to claim 29, which is a mixture according to any one of claims 16 to 28. A bituminous mixture, superficial wear coating, asphalt or seal coating comprising a mixture according to any one of claims 16 to 28. 28. A process for producing a mixture according to any one of claims 16 to 28 by applying decomposition to plastics,
Introducing plastic into the reactor;
Allowing at least a portion of the plastic to convert to wax, wherein at least a portion of the wax is part of a pyrolysis gas formed in the reactor; And
Removing the product stream containing the wax that is part of the pyrolysis gas formed in the reactor from the reactor to obtain the mixture,
Wherein the pyrolysis gas has a residence time of less than 60 seconds at a temperature greater than 370 &lt; 0 &gt; C. The process according to claim 32, which is a process according to any one of claims 1 to 15.

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