KR20180132740A - A process for converting plastics into wax by catalytic cracking and a process for converting the hydrocarbon mixture - Google Patents

Abstract

The present invention relates to a process for converting plastics to wax by catalytic cracking. The process comprises introducing plastic and catalyst 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 catalytic cracking and a process for converting the hydrocarbon mixture

This application claims priority to U.S. Provisional Application No. 62/315928, filed March 31, 2016, and European Application No. 16306636.8, filed on December 7, 2016, the entirety of which is incorporated by reference herein in its entirety .

The present invention relates to a process for converting plastics to wax by catalytic cracking. The process comprises introducing plastic and catalyst 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.

In view of the increasing importance of polymers 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 of the storage capacity available for waste treatment, Considerable attention has been drawn to the problem 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. Furthermore, the volatile compound may be a wax or 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 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 for the formation of shorter chain products.

M. M. del Remedio Hernandez et al. Have reported catalytic flash pyrolysis of HDPE in a fluidized bed reactor at 500 ° C to 800 ° C in Journal of Analytical and Applied Pyrolysis 78 (2007) 272-281} . According to the authors, the presence of small amounts of zeolite resulted in a significant reduction of saturated and unsaturated condensable hydrocarbons, while promoting the formation of aromatic compounds and branched paraffins.

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, a branched carbon chain, less aromatic compounds, and / or increased redness.

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 has been found that the yield of wax increases surprisingly even at temperatures and in the presence of cracking catalysts.

Moreover, the inventors have found that a novel mixture of hydrocarbons, predominantly comprising wax, is obtained under specific process conditions, wherein the hydrocarbons have a high number of carbon atoms and are predominantly branched hydrocarbons, and the inherent content of alpha-olefins .

Accordingly, the present invention relates to a process for converting plastics into wax by catalytic cracking,

Introducing plastic and catalyst 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 greater than 370 DEG C and the weight ratio of catalyst to plastics introduced into the reactor is at least 0.1: 30.

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 branched hydrocarbons;

And 20 mol% or less of the unsaturated hydrocarbons are alpha-olefins.

Moreover, 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. They are preferably present in the plastic in an amount of less than 50% by weight, preferably less than 30% by weight, more preferably less than 20% by weight, even more preferably less than 10% by weight 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" 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, based on 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 one or more operations such as size reduction, grinding, shredding, screening, chipping, metal removal, debris removal, dust removal, drying, degassing, melting, solidification, And can be pretreated by a physicochemical process that includes.

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, ethylene, acetylene, Propane, butane, 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 present inventors have found that when a pyrolysis reactor and a short residence time of less than 60 seconds of pyrolysis gas at high temperatures above 370 DEG C are guaranteed in the pyrolysis reactor and operating conditions, the waxes are obtained from the catalytic cracking of plastics in high yield even at high depolymerization temperatures . This finding is particularly surprising because of the high decomposition temperature and, in particular, in the presence of the catalyst, which is advantageous in the rate of decomposition for the formation of shorter chain products. In other words, a lower content of wax mixture should 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 enables the digestion process to be carried out at considerably high temperatures, which ensures a high conversion of the feedstock and, for example, low residues of the plastic raw material of less than 50 g / kg, even with an increased amount Of wax.

Moreover, the waxes obtained proved to be expensive waxes containing branched hydrocarbons, low aromatic content and optionally increased redness. The invention therefore also relates to a wax obtainable by the process disclosed herein.

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. The product of these smaller molecular weights 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 More preferably 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 the pyrolysis gas, a high pyrolysis temperature is allowed for the decomposition of the plastics. 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 415 占 폚, even more preferably at least 425 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, more preferably 425 to 520 占 폚, 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, by designing the reactor, for example by limiting the volume of the gas phase or by increasing the proportion of the reactor volume charged by liquid and solid, or by 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 can be operated at pressures ranging from 0.5 to 1200 mbar, preferably from 10 to 1100 mbar, more preferably from 60 to 950 mbar, and 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 1 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 to the diluent may be located at the top of the reactor so that the diluent is essentially in contact with the pyrolysis gas under reaction conditions, but not in contact with 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 plastics melt, and as a result, the residence time of the pyrolysis gas can be effectively reduced at a temperature exceeding 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.

The process of the present invention is characterized in that the weight ratio of the catalyst and the plastic introduced into the reactor is at least 0.1: 30. In a preferred embodiment, the weight ratio of catalyst and plastic introduced into the reactor is at least 1:30, preferably 2:30, more preferably 3:30, even more preferably at least 4:30, for example at least 5 : 30.

Surprisingly, it has further been found that there is a certain maximum ratio in which the selectivity to wax is undesirably reduced even though the overall conversion of plastics is increased as the ratio of catalyst to plastic introduced into the reactor increases. It has thus been found that there are two contradictory effects of the catalyst. The present invention optimizes these two contradictory effects by providing an upper limit on the weight ratio of catalyst and plastic introduced into the reactor when high selectivity to wax is required. In such a case, the weight ratio of the catalyst and the plastic introduced into the reactor is preferably 7: 1 or less, preferably 6: 1 or less, more preferably 5.5: 1 or less.

When both high total conversion and high selectivity for wax are required, the weight ratio of catalyst to plastic introduced into the reactor is, for example, in the range of from 2:30 to 12:30, more preferably from 5:30 to 10: Lt; / RTI >

The catalyst used in the process of the present invention may be any suitable catalyst. Preferred catalysts include those used in FCC operations such as fresh FCC catalysts, used FCC catalysts, equilibrated FCC catalysts, BCA (bottom cracking additive), or any mixture thereof.

For example, the catalyst may comprise a zeolite-type catalyst. Such catalysts can be selected from crystalline microporous zeolites known and commercially available to those skilled in the art. A preferred example for a zeolitic catalyst is disclosed in WO 2010/135273, the disclosure of which is incorporated herein by reference. Specific examples of suitable zeolitic catalysts include ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, TS- 1, NU-10, silicalite-1, silicalite-2, boralite-3, ITC-2, MCM-49, FU-9, PSH- -C), boralite-D, BCA, and mixtures thereof. Alternatively or additionally, the catalyst may comprise an amorphous catalyst, which may comprise, for example, silica, alumina, kaolin or any mixture thereof. Silica, especially silica in the form of sand, is well known for FCC catalyst applications.

In one embodiment of the process of the present invention, converting at least a portion of the plastic to wax is carried out 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 heating 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 or catalyst has a particle size greater than the particle size of the filler used in the plastic.

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

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

When the heating medium or catalyst 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 or catalyst is glass, the particles are advantageously glass beads or glass balls having a size of from 0.5 to 20 mm, preferably from 0.6 to 6 mm.

When the heating medium or catalyst 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 present in the reactor, i.e. the volume of the reactor filled with gaseous material (expressed in m 3) Is displayed. To account for thermal gas expansion, the gas is considered to be at the same temperature as in 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)) of the reactor divided by the flow of 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 solid product (eg, coke, ash, etc.) obtained from the unconverted feedstock, liquid, catalyst and reaction in liquid or solid form 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. Less than 2% O ₂ is preferred in the gaseous phase surrounding the condensate. The condensation material may be cooled by any means known to those skilled in the art. Examples include double wall screw conveyors, screw conveyors with water injection, extruders, screw augers and the like. A screw conveyor with a water jetting portion is preferred.

Optionally, the condensate can be sent to the 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, at least a portion of the hot ash and the heating medium (catalyst) is 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 carrier flow to the feed flow usually amounts to 0.1 to 10, preferably 0.2 to 8, by weight. Ratios higher than 0.25 provide 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 waxes and hydrocarbon mixtures obtained in the present invention have the advantage of having somewhat long chain lengths, especially branched carbon chains.

Accordingly, the present invention 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 branched hydrocarbons;

And 20 mol% or less of the unsaturated hydrocarbons are alpha-olefins.

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. In the rest of 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 branched hydrocarbons. Preferably, at least 60 mol%, more preferably at least 70 mol%, of the total amount of hydrocarbons in the hydrocarbon mixture is a branched hydrocarbon.

A further advantage of the hydrocarbon mixture according to the invention is that the unsaturated hydrocarbons contain only small amounts of alpha-olefins. Preferably, not more than 15 mol%, more preferably not more than 10 mol% 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 hydrocarbons in the hydrocarbon mixture according to the invention is that the mixture can have a relatively high red point, for example above 25 ° C, preferably above 40 ° C, more preferably above 50 ° 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.
Figure 3 shows the reaction times (x) for different N ₂ influent flow rates, i.e. 150 ml / min (lines marked with triangles), 1 l / min (lines indicated with empty circles) and 4 l / min Axis (expressed in%) as a function of time (expressed in minutes).
Figure 4 shows the conversion rates for different N ₂ influent flow rates, namely 150 ml / min (lines marked with triangles), 1 t / min (lines indicated with empty circles) and 4 t / min : Expressed in%) as a function of the wax yield (y-axis: expressed in% by weight).
Figure 5 shows the wax yield (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 carbon chain length (x) for different N ₂ influent flow rates, ie 150 ml / min (lines marked with triangles), 1 l / min (lines indicated with empty circles) and 4 l / min (% By weight: y-axis) as a function of the axis (expressed by the number of carbon atoms).
Fig. 7 is a graph showing the catalyst / plastic ratios at different catalyst / plastic ratios, i.e., the absence of the catalyst (indicated by rhombus), 1/30 (indicated by hollow triangles), 5/30 (indicated by filled triangles), 20/30 (Y-axis: expressed as a percentage) as a function of reaction time (x-axis: expressed in hours (minutes)) for 10/30 (line indicated by squares).
Figure 8 shows the cumulative selectivity (y-axis: expressed in%) of different reaction products (listed in the x-axis) at different catalyst / plastic ratios. Legend: For each product, the color of the bar starting from the left to the right refers to the ratio of 20/30, 10/30, 5/30, 1/30.
9 shows the carbon number distribution of the wax. The charts show different catalyst / plastic ratios: 20/30 (lines marked with squares), 10/30 (lines marked with triangles), 5/30 (lines indicated with empty circles), and 1/30 (lines marked with filled diamonds) (Weight%, y-axis) as a function of the carbon chain length (x-axis: expressed in terms of carbon number).
Figure 10 shows the time to reach 65% conversion of plastics (y axis: expressed in hours (minutes)) as a function of catalyst initial concentration (x axis: expressed in weight%).

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 fed to a suitable heat transfer device 8 and recovered at the outlet as stream 9, without departing from the scope of the present invention. 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 a combination of the effluent stream 53 and the physico-chemical treatment 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 that is fed to a suitable heat transfer device 58 and recovered at the outlet as stream 59, without departing from the scope of the present invention. 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, the 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 the extent that the term is unclear, the description of the present invention will prevail.

Example

General description of the experiment process

In each catalytic run into the semi-batch mode, 30 g of plastic (20% polypropylene, 80% polyethylene) was loaded into the reactor and a predetermined amount of catalyst (approximately 20 g) was stored in the catalyst storage tank 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 catalyst storage tank containing the catalyst 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, the catalyst was introduced into the reactor. According to the experiment, the nitrogen gas flow rate was set to 150 ml / min or adjusted to a predetermined value, 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: either on top of the vessel or by bubbling 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 catalyst). 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.

The simulated distillation (SIM-DIS) GC method allowed the measurement of different fractions in the liquid sample (according to the selected cutoff) and in the detailed hydrocarbon analysis (DHA) GC method the PIONAU of 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-alcohols 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 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 bp (boiling point) below 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 at GC are related to the boiling 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 Integrate. 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 branched hydrocarbons

The amount of branched hydrocarbons in the hydrocarbon mixture according to the 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 a 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 presumed 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, CDCl ₃ as a 1-alkene solvent 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.

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 BCA-105, a 20 wt% decomposition additive purchased from Johnson Matthey, using 80 wt% HDPE and 20 wt% PP as raw materials. The reaction temperature was set at 450 ° C and the N ₂ flow rate varied from 0.15 l / min to 4 l / min. The weight ratio of catalyst to plastic was equal to 20/30 by weight.

Experimental results are shown in Figs. FIG. 3 shows the remarkable effect of increasing the total conversion and increasing the wax yield (FIG. 4) by reducing the residence time of the pyrolysis gas by increasing the flow rate of the diluent. Dependence between the residence time of the gas phase and the yield of the wax is also shown in Fig. According to the results shown in Fig. 6, when the retention time of pyrolysis gas is reduced by increasing the diluent flow rate, it has surprisingly been shown that the carbon chain distribution shifts to a longer chain compound. At a gas flow rate of 150 ml / min, the hydrocarbon mixture had a cumulative distribution of the number of carbon atoms d20 = 20 and d50 = 23. At a gas flow rate of 1 L / min, the cumulative distribution of the number of carbon atoms was d20 = 22 and d50 = 27. At a gas flow rate of 4 l / min, cumulative distributions of carbon atoms were d20 = 22 and d50 = 29.

The hydrocarbon mixture obtained using BCA as catalyst was analyzed. The results of this analysis are summarized in Table 2 below.

rough Blocking points below C ₂₀ C ₂₀ to C ₃₀ interception points Above C ₃₀ ~ C ₄₀ blocking point C ₃₀ to less than C ₄₀₀ cutoff point Melting point 109 8 30 114 114 Iodine 56 60 64 31 32 Red dot 109.0 Not detected Not detected 115.5 116.0 C, H 82.1 / 13.3 85.7 / 14.1 85.7 / 13.9 84.8 / 13.9 66.9 / 11.6 1-olefins / internal olefins 4.3 / 95.6 4.1 / 95.9 1.8 / 98.2 100 Pb mode Dough solid meteor Dough solid solid solid

Example 2

Experiments were performed according to the general procedure described above. Using 80 wt% HDPE and 20 wt% PP as raw materials and 20 g of a zeolitic catalyst (Equilibrium fluidized catalytic cracking catalyst provided by Equilibrium Catalyst Inc. (labeled ECAT-DC )). &Lt; / RTI &gt; The reaction temperature was set at 425 ℃, and the N ₂ flow rate is set to 0.15ℓ / min. The weight ratio of catalyst to plastic varied from 20:30 to 1:30. To emphasize the effect of strong catalyst addition on the kinetics of the reaction, a comparative example without added catalyst was included. The residence time of pyrolysis gas is estimated to be in the range of 40 to 46 seconds.

The results of the experiment are shown in Figs. 7 to 10. Figure 7 shows that the kinetics is affected by the amount of catalyst used, and in particular the minimum ratio of 5/30 appears to be desirable to show a significant increase in conversion. On the other hand, the HCO yield is greatly increased when the ratio is 10/30 or less (Fig. 8). Figure 9 shows that the quality of the wax obtained by varying the amount of catalyst is unchanged and approximately the same carbon chain distribution is obtained in all cases. The cumulative distribution of carbon atoms in the hydrocarbon mixture obtained according to the catalyst to plastic weight ratio is summarized in Table 3 below.

Catalyst / plastic 20/30 10/30 5/30 1/30 d20 20 20 20 20 d50 22 23 24 22

Figure 10 shows the advantageous effect of using a catalyst on the kinetics of the reaction. Indeed, the same plastic transformation can be achieved in a much shorter time.

Example 3: Mass balance according to the present invention

In this and in the following examples, post-consumer plastics are named from their main plastic components, and on average the recycled plastics considered contain 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 1500 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 contain 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 an absolute pressure of 218 mbar at 465 DEG C as well as at 1500 kg / hr for the heating medium, wherein the heating medium was a fine sand and 750 kg FCC catalyst, INTERCAT _JM Debris decomposition additive BCA-105 (both supplied at 700 ° C). The gas holdup in the blast furnace is estimated to be 5.3 m3 and the retention of the condensed phase is estimated to be 2.4 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 to be 10.2 kmol / hr, corresponding to 1189 kg / hr.

The residence time of the gas product in the gas phase above 370 ° C was calculated to be 8 seconds. The calculated flow rate is shown in Table 4 below along with the numbering of FIG.

The heat duty of the reaction was estimated at 449 kW and the heat supplied by the heating medium and catalyst was estimated to be 139 kW which corresponded to 47% of the heat available by combustion of the coke, The heat is assumed to be 310 kW, which corresponds to 20% 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 196 ° C It reached.

The residence time of the condensate in the furnace was estimated to be 79 minutes. The overall yield of the wax was calculated to be 40.2% based on the plastic content of the mixed plastic waste (including additives). The wax was mainly branched.

Example 4: 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 950 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 contain 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 350 mbar as well as 950 kg / hr for heating medium and 560 kg / hr for nitrogen at 25 ° C, where the heating medium had a diameter of 20 Mm and a 750 kg FCC catalyst, Johnson Matthey's INTERCAT _JM Sorbitol Degradation Additive BCA-105 (both supplied at 700 ° C). The gas holdup in the blast furnace is estimated to be 6.6 m3 and the retention of the condensed phase is estimated to be 1.1 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 26.2 kmol / hr, corresponding to 1283 kg / hr.

The residence time of the gas product in the gas phase above 370 ° C was calculated to be 5.9 seconds. The calculated flow rate is shown in Table 5 together with the numbering in FIG.

The heat load of the reaction, including the nitrogen preheat, was estimated at 341 kW and the heat supplied by the heating medium was estimated to be 98 kW, corresponding to 49% of the heat available by combustion of the coke, Is estimated to be 243 kW, which corresponds to 16% of the heat available by combustion of the gas. The heat transfer surface 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 and the reaction medium used to heat the furnace reached 153 ° C.

The residence time of the condensate in the furnace was estimated to be 93 minutes. The specific dilution ratio (D / P) was calculated to be 9.3 mol / mol / bar. The overall yield of the wax was calculated to be 40.3% based on the plastic content of the mixed plastic waste (including additives). The wax was mainly branched.

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 700 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 contain gaseous products resulting from the decomposition of any constituents of the feed material. The pretreated material was introduced into the double wall rotary drum furnace at 465 ° C under an absolute pressure of 155 mbar and at a rate of 350 kg / hr for the INTERCAT _JM slag decomposition additive BCA-105 (supplied at 25 ° C) of Johnson Matthey, an FCC catalyst . The gas holdup in the blast furnace is estimated to be 6.9 m3 and the retention of the condensed phase is estimated to be 0.7 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 was estimated at 5.8 kmol / hr, corresponding to 679 kg / hr.

The residence time of the gas product in the gas phase above 370 ° C was calculated to be 15.9 seconds. The calculated flow rates are shown in Table 6 together with the numbering in FIG.

The heat load of the reaction, including nitrogen and catalyst preheating, was estimated at 307 kW, and the heat supplied by the double wall is estimated to be 307 kW, corresponding to 34% of the heat available by combustion of the gas. The heat transfer surface available in the blast furnace is estimated to be 20 m2 and the total heat transfer coefficient is estimated to be 80 W / m2K, and the algebraic temperature difference between the hot gas used to heat the furnace and the reaction medium is 194 ℃ It reached.

The retention time of the condensate in the furnace was estimated to be 108 minutes. The overall yield of the wax was calculated to be 39.8% based on the plastic content of the mixed plastic waste (including additives). The wax was mainly branched.

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

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 1100 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 contain gaseous products resulting from the decomposition of any constituents of the feed material. The pretreated material was introduced into a double-walled rotary drum furnace operating at 465 ° C under an absolute pressure of 1340 mbar, as well as 550 kg / hr for an INTERCAT _JM dip cracking additive BCA-105 (supplied at 25 ° C) of Johnson Matthey, an FCC catalyst . The gas holdup in the blast furnace is estimated to be 6.7 m3 and the retention amount of the condensed phase is estimated to be 0.7 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 was estimated at 7.8 kmol / hr, corresponding to 837 kg / hr.

The residence time of the gas product in the gas phase above 370 ° C was calculated to be 76 seconds. The calculated flow rate is shown in Table 7 together with the numbering in FIG.

The heat load of the reaction, including the preheating of the catalyst, was estimated at 334 kW, and the heat supplied by the double wall is estimated to be 334 kW, which corresponds to 40% 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 260 ° C It reached.

The retention time of the condensate in the furnace was estimated to be 110 minutes. The overall yield of the wax was calculated to be 24.7% based on the plastic content of the mixed plastic waste (including additives). The wax was mainly branched.

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

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 800 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 contain gaseous products resulting from the decomposition of any constituents of the feed material. The pretreated material was calcined at 465 &lt; 0 &gt; C under an absolute pressure of 1420 mbar as well as 56 kg / hour for nitrogen and 400 kg / hour for an INTERCAT _JM Sorbitol Decomposition Additive BCA-105 (both supplied at 25 [deg.] C) Time rotating double drum rotary drum furnace. The gas holdup in the blast furnace is estimated to be 6.9 m3 and the retention of the condensed phase is estimated to be 0.8 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 7.8 kmol / hr, corresponding to 665 kg / hr.

The residence time of the gas product in the gas phase above 370 ° C was calculated to be 83.6 seconds. The calculated flow rate is shown in Table 8 together with the numbering in FIG.

The heat load of the reaction, including nitrogen and catalyst preheat, was estimated at 311 kW, and the heat supplied by the double wall was estimated to be 311 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 19 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 196 ° C It reached.

The residence time of the condensate in the furnace was estimated to be 102 minutes. The specific dilution ratio (D / P) was calculated to be 0.24 mol / mol / bar. The overall yield of the wax was calculated to be 18.6% based on the plastic content of the mixed plastic waste (including additives). The wax was mainly branched.

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 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, , Which is obvious in itself in terms of the reduction of the processing cost.

In accordance with another aspect that is compatible with and complies with the prior art for a particular application of the type described below, the wax according to the present invention may be applied to a coating based on inorganic aggregates and organic binders to increase the curing rate of the coating during its cooling Can be used. 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. These fluxed binders are intended to be sprayed on the road surface, and then aggregates are 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.

In a bituminous mixture based on a "transparent binder" referred to as a "synthetic binder ", i.e. a synthetic polymer, and / or a binder of oil type and / In contrast to the mixture, the agglomerates they contain are distinguished: the presence of the wax in these binders also leads to a reduction in the temperature at which the coating is made to settle.

In sealing coatings, in particular in roofing sealing coatings, including bitumen mixed with polymers: the presence of the wax also makes it possible to reduce the temperature at which the coating is made here. This also accelerates the settling of the coating after deposition, which is particularly noteworthy in the case of deposits on sloped roofs which tend to flow when the deposited composition is not cured quickly enough.

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 bitumen coatings which come into contact with gasoline or kerosene, for example as additives in bituminous coatings used in rest areas.

Claims (32)

A process for converting plastics to wax by catalytic cracking,
Introducing plastic and catalyst 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 DEG C and the weight ratio of catalyst to plastic introduced into the reactor is at least 0.1: . 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 415 캜, even more preferably at least 425 캜, For example, in the range of 400 to 650 占 폚, preferably 425 to 550 占 폚, and more preferably 425 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 and the pyrolysis product in the pyrolysis gas 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 0.8 to 40, more preferably 1 to 20. 7. The process according to any one of claims 1 to 6, wherein the weight ratio of catalyst and plastic introduced into the reactor is at least 0.1: 30, preferably at least 1:30, more preferably at least 5:30 . 8. The process according to any one of claims 1 to 7, wherein the weight ratio of catalyst and plastic introduced into the reactor is 7: 1 or less, preferably 6: 1 or less, more preferably 5.5: 1 or less. 9. The process according to any one of claims 1 to 8, wherein the weight ratio of catalyst and plastic introduced into the reactor is in the range of 0.1:30 to 12:30, preferably 5:30 to 10:30. 10. The process according to any one of claims 1 to 9, wherein the catalyst is a zeolitic catalyst and / or an amorphous catalyst. 11. The process according to any one of claims 1 to 10, wherein the catalyst is a fresh catalyst, an equilibration catalyst, or a mixture thereof. 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. 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 branched hydrocarbons;
Wherein less than 20 mole% of the unsaturated hydrocarbons are alpha-olefins. 16. The mixture of claim 15, 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. The mixture according to claim 15 or 16, 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. 18. The method according to any one of claims 15 to 17, 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; 19. The mixture according to any one of claims 15 to 18, 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. 20. The composition according to any one of claims 15 to 19, 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. . 21. The mixture according to any one of claims 15 to 20, wherein at least 60 mol%, preferably at least 70 mol% of the hydrocarbons are branched hydrocarbons. 22. A mixture according to any one of claims 15 to 21, wherein up to 15 mol%, preferably up to 10 mol%, of the unsaturated hydrocarbons are alpha-olefins. 23. The mixture according to any one of claims 15 to 22, having an iodine number of 10 or more, preferably 25 or more, more preferably 40 or more. 24. The mixture according to any one of claims 15 to 23 having an iodine number of 150 or less, preferably 100 or less, more preferably 70 or less. 25. The mixture according to any one of claims 15 to 24, having an iodine number in the range of from 10 to 150, preferably in the range of from 25 to 100, more preferably in the range of from 40 to 70. The mixture according to any one of claims 15 to 25 having a drop point of greater than 25 ° C, preferably greater than 40 ° C, more preferably greater than 50 ° C. 27. The mixture according to any one of claims 15 to 26, 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 14. The wax according to claim 28, which is a mixture according to any one of claims 15 to 27. 27. A bituminous mixture, superficial wear coating, asphalt or seal coating comprising a mixture according to any one of claims 15 to 27. 27. A process for producing a mixture according to any one of claims 15 to 27 by applying catalytic decomposition to plastics,
Introducing plastic and catalyst 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 DEG C and wherein the weight ratio of catalyst to plastic introduced into the reactor is at least 0.1: 30. The process according to claim 31, which is a process according to any one of claims 1 to 14.

Images