EP3436548A1 - Process for converting plastic into waxes by cracking and a mixture of hydrocarbons obtained thereby - Google Patents
Process for converting plastic into waxes by cracking and a mixture of hydrocarbons obtained therebyInfo
- Publication number
- EP3436548A1 EP3436548A1 EP17713696.7A EP17713696A EP3436548A1 EP 3436548 A1 EP3436548 A1 EP 3436548A1 EP 17713696 A EP17713696 A EP 17713696A EP 3436548 A1 EP3436548 A1 EP 3436548A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydrocarbons
- plastic
- waxes
- reactor
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
- C08L91/06—Waxes
- C08L91/08—Mineral waxes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
Definitions
- Catalytic cracking of a mixed waste plastic is a process well-known to the person skilled in the art.
- US 5,216,149 discloses a method for controlling the pyrolysis of complex waste stream of plastics to convert such stream into useful high- value monomers or other chemicals, by identifying catalyst and temperature conditions that permit decomposition of a given polymer. Research has been conducted in an effort to optimize process parameters with respect to an increased yield of desired cracking products.
- US 2015/0247096 Al describes a method for converting a waste plastic to wax by adding hydrogen to the reaction chamber and heating the waste plastic and hydrogen sufficiently to thermally depolymerize the waste plastic to form a wax product, comprising paraffin and olefin compounds. Cracking is conducted at a temperature of about 300°C to about 500°C for a duration of about 1 minute to about 45 minutes, sufficient to cause thermal degradation of substantially all of the melted plastic feed stock.
- the present inventors now found that contrary to the above expectation that with increasing cracking temperature the yield of waxes is decreasing, the yield of waxes is surprisingly increased even at high cracking temperatures if the pyrolysis gas which is formed during the cracking of the plastic and which contains the volatile cracking products has only a short residence time at a temperature above 370°C. Furthermore, the present inventors found that under the specific process conditions a novel mixture of hydrocarbons comprising predominantly waxes is obtained wherein the hydrocarbons have a high number of carbon atoms, are predominantly linear hydrocarbons and have a unique ratio of n-paraffins to alpha-olefms.
- the pyrolysis gas has a residence time at a temperature above 370°C of less than 60 seconds.
- hydrocarbons > 50 mol % of the hydrocarbons are linear hydrocarbons
- n-paraffins to alpha-olefms among the hydrocarbons is in the range of 0.1 to 10.
- “Waxes” in the sense of the present invention therefore designate hydrocarbons which optionally contain heteroatoms. In most cases, they are solid at room temperature (23°C) and have a softening point of generally above 26°C. A definition of the obtained fractions is provided in the experimental section below.
- a plastic is mostly constituted of a particular polymer and the plastic is generally named by this particular polymer.
- a plastic contains more than 25 % by weight of its total weight of the particular polymer, preferably more than 40 % by weight and more preferably more than 50 % by weight.
- Other components in plastic are for example additives, such as fillers, re- enforcers, processing aids, plasticizers, pigments, light stabilizers, lubricants, impact modifiers, antistatic agents, inks, antioxidants, etc.
- a plastic comprises more than one additive.
- polypropylene PP
- polystyrene PS
- Mixed plastics mostly constituted of polyolefm and polystyrene are preferred.
- plastics such as polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polyurethane (PU), acrylonitrile-butadiene-styrene (ABS), nylon and fluorinated polymers are less desirable. If present in the plastic, they are preferably present in a minor 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 of the total weight of the dry weight plastic.
- the plastic used in the process of the present invention can be selected among:
- a "low content” preferably means a minor amount of less than 50 % by weight, preferably less than 20 % by weight, more preferably less than 10 % of the total weight of the dry plastic.
- the individual content of any less desirable plastic is less than 5 % by weight, more preferably less than 2 % by weight based on the total weight of the dry plastic.
- the raw material can be pretreated by a physico-chemical process including one or more operations as size reduction, grinding, shredding, screening, chipping, metal removal, foreign material removal, dust removal, drying, degasing, melting, solidifying and agglomerating.
- a physico-chemical process including one or more operations as size reduction, grinding, shredding, screening, chipping, metal removal, foreign material removal, dust removal, drying, degasing, melting, solidifying and agglomerating.
- the pretreatment can be conducted at a temperature lower or equal to 350°C, preferably lower or equal to 330°C.
- Gaseous degradation products occurring during the pretreatment are advantageously removed.
- gaseous degradation products are hydrochloric acid, hydrobromic acid, hydrofluorhydric acid, CO, C0 2 , small carbon containing molecules with no more than 4 C-atoms such as methane, ethane, butane, ethylene, acetylene, propane, propylene, butene, methanol, formic acid, formaldehyde, acetic acid, acetaldehyde, ethanol, acetone and the like.
- alkaline fillers such as PCC (precipitated calcium carbonate) or chalk, lime, soda lime, sodium carbonate, sodium bicarbonate, alumina, titanium oxide, magnesium oxide, calcium oxide, and the like.
- the present inventors surprisingly found that waxes can be obtained at high yield from the cracking of plastics even at high de-polymerization temperature if the pyrolysis reactor and the operation conditions ensure a short residence time of less than 60 second of the pyrolysis gas at a high temperature of above 370°C. This finding is particularly surprising because a high cracking temperature should favor cracking rate towards the formation of shorter-chain products. In other words, lower content of the wax mixture should be found at higher temperatures.
- the present inventors found that at short residence time of the pyrolysis gas at high temperature not only more of the wax mixture is produced but also the average carbon chain length of the wax is increased. This allows carrying out the cracking process at rather high temperatures which ensures high conversions of the raw material and a low residue of for example less than 50 g/kg plastic raw material but nevertheless allows the production of an increased amount of waxes having even an increased average carbon chain length.
- the plastic In the cracking reactor the plastic is generally present in a molten state at cracking temperature.
- the cracking reaction results in a de-polymerization of the plastic yielding lower molecular weight products.
- these lower molecular weight products evaporate forming a pyrolysis gas within the reactor.
- This gas comprises the volatile pyrolysis fractions, such as light-weight hydrocarbons, diesel, kerosene and waxes.
- the invention is based on the finding that the pyrolysis gas should be quickly removed from the hot cracking reaction zone and it was found that high yields of waxes are obtained if the pyrolysis gas has a residence time at a temperature above 370°C of less than 60 seconds, preferably less than 50 seconds, more preferably less than 40 seconds, even more preferably less than 30 seconds, furthermore preferably less than 25 seconds and most preferably less than 20 seconds, such as less than 15 or even less than 10 seconds.
- the residence time of the pyrolysis gas at a temperature above 370°C is more than 2 seconds, preferably more than 5 seconds, even more preferably more than 10 seconds, such as more than 15 or even more than 20 seconds.
- the temperature at which at least a portion of the plastic is converted to waxes is at least 370°C, preferably at least 400°C, more preferably at least 425°C, even more preferably at least 440°C.
- the temperature at which the plastic is converted can be as high as desired, for example up to 850°C, preferably up to 700°C, more preferably up to 600°C, even more preferably up to 500°C, such as up to 480°C or up to 470°C.
- the temperature at which the plastic is converted ranges from 400 to 650°C, preferably from 425 to 550°C, preferably from 440 to 520°C, even more preferable 440 to 470°C. Most preferably the temperature at which the plastic is converted ranges from 400 to less than 500°C.
- the required low residence time of the pyro lysis gas at a temperature of above 370°C can be obtained by any suitable means, such as reducing the residence time of the pyrolysis gas in the reactor by operating the reactor under vacuum, by dilution of the pyrolysis gas in the reactor itself, by design of the reactor for example by limiting the volume of the gas phase, or by increasing the percentage of the reactor volume filled by liquid and (if present) solid, or by a combination of these measures. Generally, it is preferred to combine several of these measures in order to obtain the desired low residence time.
- the reactor is operated at a pressure of less than or equal to 1200 mbar, preferably less than or equal to 1000 mbar, more preferably less than or equal to 950 mbar and even more preferably less than or equal to 900 mbar.
- the pressure in the reactor can be as low as 0.5 mbar, preferably 1 mbar, preferably 10 mbar, preferably 40 mbar, preferably 50 mbar, more preferably 60 mbar and even more preferably 80 mbar.
- the reactor can be operated at a pressure in the range of 0.5 to 1200 mbar, preferably 10 to 1100 mbar, preferably 50 to 1000 mbar, more preferably 60 to 950 mbar and even more preferably 80 to 900 mbar.
- the pyrolysis gas can be diluted with a diluent.
- a diluent is not particularly limited but should not adversely affect the pyrolysis reaction or the desired reaction products.
- the diluent should have a low oxygen (0 2 ) content as described below.
- suitable diluents are nitrogen, hydrogen, steam, carbon dioxide, combustion gas, hydrocarbon gas and mixtures thereof.
- the hydrocarbon gas preferably comprises one or more hydrocarbons having less than 5 carbon atoms. Nitrogen, carbon dioxide, combustion gas and hydrocarbon gas with less than 5 carbon atoms are preferred. Combustion gas and hydrocarbon gas with less than 5 carbon atoms are particularly preferred.
- the diluent preferably has a low oxygen (0 2 ) content, such as less than
- the dilution level is not particularly limited and can be selected according to the requirements.
- the molar ratio of diluent to pyrolysis product in the pyrolysis gas can be above 0.5, preferably above 0.7, more preferably above 0.8, and even more preferably above 1.
- a molar ratio of diluent to pyrolysis products in the pyrolysis gas of above 50 is less preferred.
- this ratio is up to 40, more preferably up to 20.
- Preferred molar ratios of diluent to pyrolysis products in the pyrolysis gas are in the range of 0.5 to 50, preferably 0.7 to 40 and more preferably 0.8 to 20, such as 1 to 10 or even 1 to 7.
- the diluent may be introduced into the reactor at any position.
- an inlet for the diluent can be positioned in the top of the reactor so that the diluent basically only comes into contact with the pyrolysis gas but not with the plastic melt under reaction conditions.
- the diluent inlet can be positioned for example in the bottom part of the reactor so that the diluent comes into contact with the plastic melt under reaction conditions.
- a combination of two or more different inlets may be used.
- At least one diluent inlet is positioned in the bottom part of the reactor. It has been found that in this case the pyrolysis gas is effectively removed from the hot plastic melt thereby effectively reducing the residence time of the pyrolysis gas at a temperature above 370°C. Most preferably a combination of a diluent inlet positioned in the top of the reactor and a diluent inlet positioned in the bottom part of the reactor is employed.
- the reactor is operated at a reduced pressure and diluent is used.
- the molar ratio D of diluent to pyrolysis products in the pyrolysis gas and the absolute pressure P at which the reactor is operated can be adjusted such that D/P is in the range of 2 to 50 mol/mol/bar, particularly in the range of 3 to 30 mol/mol/bar, more particularly in the range of
- the carrier may be a catalyst for the cracking of the plastic.
- the heat carrier is, however, not a catalyst for gas-phase cracking of hydrocarbons.
- the heat carrier has a particle size higher than the particle size of the filler used in the plastic.
- the heat carrier comprises particles, preferably free- flowing particles, for instance granular round particles, near spherical particles, full balls, hollow balls, and the like.
- the heat carrier particles have a higher particle size than standard US mesh 632, preferably higher than standard US mesh 400.
- the heat carrier particles have a particle size lower or equal to about 5 cm, preferably lower or equal to about 2.5 cm.
- the heat carrier particles are advantageously fine or medium sand according to ISO 14688-1 :2002.
- the heat carrier particles are fine sand.
- the heat carrier is metal, such as iron or steel, they are preferably in the form of full balls.
- the particle size can be between 1 and 50 mm, preferably between 10 and 30 mm.
- the particles are advantageously glass bead or glass balls having a size of between 0.5 and 20 mm, preferably of between 0.6 and 6 mm.
- the heat carrier is gravel
- it is preferably fine or medium gravel according to ISO 14688-1 :2002, preferably fine gravel.
- the residence time of the pyrolysis gas in the reactor is expressed as the gas hold-up of the reactor (in other words, the volume of the reactor occupied by the gaseous material and expressed in m 3 ) divided by the flow of gas exiting the reactor and expressed in m 3 /min.
- gases are considered to be at the same temperature of the pyrolysis reactor. If used, gas exiting the reactor comprise the diluent.
- the residence time of the condensed material in the reactor is expressed as the condensed material hold-up of the reactor (in other words, the volume of the reactor occupied by the condensed material and expressed in m 3 ) divided by the outlet condensed material flow expressed in m 3 /min. Temperature expansion of condensed material is neglected.
- This residence time is not particularly limited but usually is in the range of 1 to 600 minutes, preferably in the range of 2 to 400 minutes, more preferably in the range of 3 to 250 minutes.
- condensed material the total amount of unconverted raw material in the liquid or solid form, liquid and solid products obtained from the reactions (such as for example coke, ashes) and, if used, the heat carrier is understood.
- the process of the present invention can be conducted batchwise or continuously. Conducting the process continuously is preferred.
- reactor types are fluidized bed, entrained bed, spouted bed, downcomer, fixed bed, rotating drum, rotating cone, screw cone, screw auger, extruder, molecular distillation, thin film evaporator, kneader, cyclone and the like.
- Fluidized bed, entrained bed, spouted bed, screw auger and rotating drum are preferred.
- Screw auger and rotating drum are particularly preferred. Rotating drum gives good results.
- Gas exiting the pyrolysis reactor may be cleaned from dust in any de-dusting device.
- de-dusting devices are cyclone, multi-cyclone, helical separator, grid separator, swirl tube, electrostatic filter, settling chamber, scroll collector, shutter collector, wet washer and the like. Cyclone, multi- cyclone, helical separator and swirl tube are preferred. Multi-cyclone is particularly preferred.
- Separation of the incondensable gas is realized by any ways known by a person skilled in the art.
- Incondensable gas are meant here as component not condensed at the operating pressure at a temperature of 25°C.
- separation devices are quench, organic quench, aqueous quench, spray column, fractionation column, cyclone and the like.
- Organic quench is preferred.
- Organic quench operated at a temperature between 110 and 250°C is preferred, between 125 and 220°C being particularly preferred. Between 140 and 180°C being even more preferred.
- Vacuum can be provided by any device known by the man skilled in the art.
- Examples of vacuum devices are liquid ring pump, dry vacuum pump, steam ejector, gas ejector, water ejector and any combination. Combustion is made in any device known by the man skilled in the art.
- Separation of the waxes from the fuel is made by any method known by the man skilled in the art. Examples are evaporation, distillation, crystallization, liquid extraction or a combination. Combination of evaporation and solvent extraction gives good results.
- Example of solvent are hexane, benzene, toluene, methylethylketone (MEK), methylisobutylketone (MIBK). MEK and MIBK are preferred.
- the condensate material separate at the outlet of the reactor may be extracted by any means known by the man skilled in the art. Examples of means are screw, rotating valve and the like. Screw is preferred.
- the condensated material may be extracted in an atmosphere with low oxygen content. Less than 2 % 0 2 in the gas phase surrounding the condensed material is preferred.
- the condensate material may be cooled down by any means known to the man skilled in the art. Examples are double wall screw conveyor, screw conveyor with water injection, extruder, screw auger and the like. Screw conveyor with water injection is preferred.
- the condensed material may be sent to a burner to burn the combustible unconverted raw material and the coke.
- the ashes and the heat carrier are heated in a furnace at a temperature between 500 and 1000°C, preferably between 600 and 800°C.
- at least a portion of the hot ashes and heat carrier is sent to the pyrolysis reactor.
- at least a portion of the ashes are separated from the heat carrier.
- the separation is made by any method known by the man skilled in the art. Examples of methods are cycloning, elutriation, screening, sieving, centrifuging and the like.
- the ratio of the heat carrier flow to the raw material flow is usually comprised 0.1 and 10 in weight. Preferably between 0.2 and 8. A ratio higher than 0.25 gives particularly good results.
- the process of the present invention yields high- value waxes and mixtures of hydrocarbons comprising predominantly these waxes to be used for example in applications such as candles, adhesives, packaging, rubber, cosmetics, fire logs, bituminous mixtures, superficial wear coatings, asphalt, sealing coatings, etc.
- the present invention therefore also relates to a wax or a mixture of hydrocarbons obtainable by the invented process.
- the waxes and mixtures of hydrocarbons have the advantage of having a rather high chain length, in particular a linear carbon chain.
- the obtained waxes are generally a wax mixture mainly containing n-paraffins and alpha-olefins.
- the percentage of alpha-olefins in the wax can be from about 25 to 75 wt. %, preferably from about 40 to 60 wt. %, more preferably about 50 wt. %, each based on the total weight of the wax.
- the present invention therefore also relates to a mixture of hydrocarbons, characterized in that the hydrocarbons exhibit a cumulative distribution of their number of carbon atoms such that 20 ⁇ d20 and 50 > d50;
- hydrocarbons > 50 mol % of the hydrocarbons are linear hydrocarbons
- n-paraffins to alpha-olefins among the hydrocarbons is in the range of 0.1 to 10.
- the mixture of hydrocarbons according to the invention predominantly comprises waxes, i.e. hydrocarbons having 20 or more carbon atoms.
- the mixture may, however, also contain a small amount of hydrocarbons having less than 20 carbon atoms.
- 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.
- mol % of the hydrocarbons refers to the total amount of hydrocarbons in the mixture of hydrocarbons.
- hydrocarbons exhibit a cumulative distribution of their number of carbon atoms such that 22 ⁇ d20, preferably 25 ⁇ d20.
- the hydrocarbons in the mixture of hydrocarbons exhibit a cumulative distribution of their number of carbon atoms such that d20 ⁇ 40, more preferably d20 ⁇ 35, even more preferably d20 ⁇ 30.
- the hydrocarbons in the mixture of hydrocarbons exhibit a cumulative distribution of their number of carbon atoms such that 20 ⁇ d20 ⁇ 40, preferably 22 ⁇ d20 ⁇ 35, more preferably 25 ⁇ d20 ⁇ 30.
- the hydrocarbons in the mixture of hydrocarbons exhibit a cumulative distribution of their number of carbon atoms such that 45 > d50, preferably 40 > d50.
- the hydrocarbons in the mixture of hydrocarbons exhibit a cumulative distribution of their number of carbon atoms such that 50 > d50 > 20, preferably 40 > d50 > 22.
- hydrocarbons exhibit a cumulative distribution of their number of carbon atoms such that 20 ⁇ d20 ⁇ 40 and 50 > d50 > 20, more preferably 22 ⁇ d20 ⁇ 25 and 40 > d50 > 22.
- the hydrocarbons in the mixture of hydrocarbons according to the invention have the advantage that they comprise a high molar amount of linear hydrocarbons.
- > 60 mol %, more preferably > 70 mol % of the total amount of hydrocarbons in the mixture of hydrocarbons are linear hydrocarbons.
- a further advantage of the hydrocarbons in the mixture of hydrocarbons according to the invention is that they have a certain molar ratio of n-paraffins to alpha-olefms in the range of 0.1 to 10, preferably in the range of 0.2 to 5, more preferably in the range of 0.5 to 2.
- n-paraffins are linear saturated hydrocarbons while alpha-olefms are linear and branched hydrocarbons, which contain at least one alpha-double bond.
- a further advantage of the hydrocarbons in the mixture of hydrocarbons according to the invention is that the unsaturated hydrocarbons comprise a high amount of alpha-olefms.
- > 40 mol %, more preferably > 45 mol %, even more preferably > 50 mol % of the total amount of the unsaturated hydrocarbons are alpha-olefms.
- the mixture of hydrocarbons has a iodine number of > 10, preferably of > 25, more preferably of > 40.
- the mixture of hydrocarbons has a iodine number of ⁇ 150, preferably of ⁇ 100, more preferably of ⁇ 70.
- the mixture of hydrocarbons has a 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 mixture of hydrocarbons according to the invention is that the mixture can have a relatively high drop point of for example > 25°C, preferably of > 40°C, more preferably of > 50°C.
- the mixture of hydrocarbons according to the invention can consist of hydrocarbons which do not contain any heteroatoms. However, depending on the plastic from which the mixture of hydrocarbons is produced, it is well possible that at least a portion of the hydrocarbons contains one or more heteroatoms, such as oxygen, sulfur, nitrogen or halogen, such as fluorine, chlorine, bromine or iodine. Other heteroatoms are possible as well.
- the mixture of hydrocarbons according to the invention can be obtained by the above described process by catalytic cracking of plastic. If the product stream removed from the reactor is selected such that it contains only hydrocarbons with at least 20 carbon atoms, waxes are obtained. However, in practice and in particular on a technical scale, the product stream will usually contain minor amounts of hydrocarbons having less than 20 carbon atoms. In this case, the above described mixture of hydrocarbons 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 evolution of conversion (as %, y-axis) as function of reaction time (expressed in minutes, x-axis) at different temperatures: 425°C (square-marked line), 450°C (circle-marked line) and 465°C (triangular-marked line).
- Figure 4 shows the cumulative selectivity (expressed as %, y-axis) of the different reaction products (listed in the x-axis) at different temperatures: 425°C (white bars), 450°C (black-white pattern fill bars) and 465°C (black bars).
- Figure 5 shows the wax cumulative selectivity (expressed as %, y-axis) as function of the pyrolysis gas residence time (expressed in seconds, x-axis).
- Figure 6 shows the carbon number distribution of the waxes.
- the plot shows the weight percentage (wt %, y-axis) as function of carbon chain length (expressed as a number, x-axis) for different reaction temperatures: 425°C (square-marked line), 450°C (circle-marked line) and 465°C (triangular-marked line).
- Figure 7 shows the conversion (expressed as %, y-axis) as function of reaction time (expressed in minutes) for different temperatures and inlet N 2 flow rates: 450°C and 150 mL/min N 2 (empty-circle-marked line), 465°C and 150 mL/min N 2 (empty-triangular-marked line), 450°C and 1 L/min N 2 (full-circle- marked line), 465°C and 1 L/min N 2 (full-triangular-marked line), 465°C and 2 L/min N 2 (empty-rhombus-marked line), 465°C and 4 L/min N 2 (empty-square- marked line).
- Figure 8 shows the cumulative selectivity (expressed as %, y-axis) of the different reaction products (listed in the x-axis) at different temperatures and N 2 flow rate. Legend: for each product, starting from left to the right the color of the bars refer to 450°C and 150mL/min, 450°C and 1 L/min, 465°C and
- Figure 9 shows the waxes cumulative selectivity (expressed as %, y-axis) as function of the pyrolysis gas residence time (expressed in seconds, x-axis) for two reaction temperatures: 450°C (circled-marked line) and 465°C (square- marked line).
- Figure 10 shows the carbon number distribution of the waxes.
- the plot shows the weight percentage (wt %, y-axis) as function of carbon chain length (expressed as a number, x-axis) for different reaction temperatures and N 2 inlet flow: 450°C and 150 mL/min (circled-marked line), 465°C and 150 mL/min
- triangular-marked line 450°C and 1 L/min (x-marked line), 465°C and 1 L/min (+-marked line), 465°C and 2 L/min (rhombus-marked line), 465°C and 4 L/min (square-marked line).
- Figure 11 shows the conversion (expressed as %, y-axis) as function of reaction time (expressed in minutes) for different type and flows of N 2 inlet feed: 150 mL/min up (circle-marked line), 1 L/min up (rhombus-marked line), 1 L/min down (triangular-marked line) and 4 L/min up/down (1 L/min up and 3 L/min down, square-marked line).
- Figure 12 shows the cumulative selectivity (expressed as %, y-axis) of the different reaction products (listed in the x-axis) for different type and flows of N 2 inlet feed. Legend: for each product, starting from left to the right the color of the bars refer to 150 mL/min up, 1 L/min up, 1 L/min down, 4 L/min up/down (1 L/min up and 3 L/min down).
- Figure 13 shows the waxes cumulative selectivity (expressed as %, y-axis) as function of the pyrolysis gas residence time (expressed in seconds, x-axis).
- Figure 14 shows the carbon number distribution of the waxes.
- the plot shows the weight percentage (wt %, y-axis) as function of carbon chain length (expressed as a number, x-axis) ) for different type and flows of N 2 inlet feed: 150 mL/min up (circle-marked line), 1 L/min up (rhombus-marked line), 1 L/min down (triangular-marked line) and 4 L/min up/down (1 L/min up and 3 L/min down, square-marked line).
- the pyrolysis of the raw material to produce waxes is realized under vacuum in an oxygen depleted atmosphere.
- the raw material 1 is pretreated by a combination of physico-chemical treatment 2 that separates an effluent stream 3 and the pretreated raw material 4.
- the pretreated raw material 4 is introduced with the help of the feeding device 5 in the pyrolysis reactor 10 through the line 6.
- the pyrolysis reactor is indirectly heated. Without limiting the scope, as example the reactor can be heated by the circulation of a hot stream 7 fed to a suitable heat transfer device 8 and recovered at the outlet as the stream 9.
- a heat carrier stream 11 is introduced in the pyrolysis reactor.
- the pyrolysis gas 12 is recovered from the pyrolysis reactor and sent to a physic-chemical treatment 20.
- the residue 13 is recovered through the device 14 where it is treated in an adequate way to produce the stream 15.
- the residue contains the unconverted raw material, by product and optionally the heat carrier introduced in the pyrolysis reactor through the stream 11.
- the pyrolysis gas is cleaned from dust and other detrimental components recovered in stream 21 and separated as a stream 22 that is sent to the treatment 25 where a incondensable stream 24 is separated from the condensate stream 23.
- the stream 24 is sent to a vacuum device 26.
- the effluent 27 from the vacuum device is sent to the combustion chamber 28 together with an adequate quantity of combustion air (29) to produce a hot stream 7.
- an auxiliary fuel 30 is added to the combustion chamber 28.
- the condensate stream 23 is sent to the separation unit 31 where the waxes stream 32 is separated from the byproducts 33.
- the pyrolysis of the raw material to produce waxes realized under vacuum in the presence of a diluent gas is as an example schematically shown in figure 2.
- the pyrolysis of the raw material to produce waxes is realized under vacuum in an oxygen depleted atmosphere.
- the raw material 51 is pretreated by a combination of physico-chemical treatment 52 that separates an effluent stream 53 and the pretreated raw material 54.
- the pretreated raw material 54 is introduced with the help of the feeding device 55 in the pyrolysis reactor 60 through the line 56.
- the pyrolysis reactor is indirectly heated. Without limiting the scope, as example the reactor can be heated by the circulation of a hot stream 57 fed to a suitable heat transfer device 58 and recovered at the outlet as the stream 59.
- a heat carrier stream 61 is introduced in the pyrolysis reactor.
- a gaseous diluent 66 is introduced at a controlled rate in the reactor 60.
- the pyrolysis gas in mixture with the diluent 62 is recovered from the pyrolysis reactor and sent to a physic-chemical
- the residue optionally in mixture with the heat carrier 63 is recovered through the device 64 where it is treated in an adequate way to produce the stream 65.
- the residue contains the unconverted raw material, by product and optionally the heat carrier introduced in the pyrolysis reactor through the stream 61.
- the pyrolysis gas is cleaned from dust and other detrimental components recovered in stream 71 and separated as a stream 72 that is sent to the treatment 75 where an incondensable stream 74 is separated from the condensate stream 73.
- the stream 74 is sent to a vacuum device 76.
- the effluent 77 from the vacuum device is sent to the combustion chamber 78 together with an adequate quantity of combustion air (79) to produce a hot stream 57.
- an auxiliary fuel 80 is added to the combustion chamber 78.
- the condensate stream 73 is sent to the separation unit 81 where the waxes stream 82 is separated from the by-products 83.
- liquid and gaseous products were collected in a pair of glass traps and their associated gas sampling bag, respectively.
- the reactor was cooled to room temperature. During this cooling step, liquids and gases were also collected.
- reaction products were classified into 3 groups: i) gases, ii) liquid hydrocarbons and iii) residue (waxy compounds, ashes and coke accumulated on the heat carrier). Quantification of the gases was done by gas chromatography (GC) using nitrogen as the internal standard, while quantification of liquids and residue was done by weight. Glass traps (along with their corresponding caps) were weighed before and after the collection of liquids, while the reactor vessel was weighed before and after each run.
- the simulated distillation (SIM-DIS) GC method allowed determination of the different fractions in the liquid samples (according to the selected cuts), the detailed hydrocarbon analysis (DHA) GC method allowed determination of the PIONAU components in the gasoline fraction of the last withdrawn sample (C5-C11 : Boiling point ⁇ 216.1°C; what includes C5-C6 in the gas sample and C5-C1 1 in the liquid samples), and GCxGC allowed the determination of saturates, mono-, di- and tri-aromatics in the diesel fraction of the last withdrawn liquid samples (C12-C21; 216.1 ⁇ BP ⁇ 359°C).
- the residence time of the pyrolysis gas was calculated using a reactor volume of 300 mL, a raw plastic density of 0.94 g/mL, a bulk density of the silica of 1. lg/mL. This leads to a gas hold-up of 250 mL.
- HCO heavy cycle oil which is considered as hydrocarbon molecules with at least 22 carbon atoms (+C22).
- Waxes refer to hydrocarbon molecules with at least 20 carbon atoms (+C20).
- Gasolines contains C5s and C6s in gases + liquids with bp (boiling point) ⁇ 150°C (ca. C5-C9)
- Kerosene liquids with boiling point 150 ⁇ bp ⁇ 250°C (ca. C10-C14)
- the number of carbon atoms and their distribution in a mixture of hydrocarbons is measured using the ASTM-D-2887 method.
- This method is a GC method for the simulated-distillation of complex hydrocarbon mixtures.
- the method allows separation of the hydrocarbon molecules in a complex mixture according to their boiling point.
- the boiling point is then related to the carbon number according to defined cut points.
- the relationship between boiling point and carbon number as defined in table 1 below is used.
- Those fractions having a boiling point below 105.8°C are defined as hydrocarbons having a carbon number of less than 10.
- the peaks obtained in the GC are integrated according to the boiling point cuts given in table 1 so that the obtained areas under the curves relate to the relative amount of hydrocarbons having the given carbon number for each boiling point range. Normalization of all peaks to 100 % allows calculation of the distribution of the number of carbon atoms within the sample according to standard methods known to the person skilled in the art.
- the obtained distribution is a weight distribution related to the total weight of the sample.
- the amount of linear and branched hydrocarbons in the mixture of hydrocarbons according to the invention is determined according to the
- ASTM-D-6730 method Measurements are carried out in a Varian 3900 chromatograph equipped with a FID detector and a 100 m capillary column. The GC is also equipped with a back- flush that only allowed a fraction of sample to enter the column.
- the Varian DHA software (detailed hydrocarbon analysis) is used. The obtained peaks are integrated and then compared by the DHA software with its internal database to qualify and quantify the peaks.
- the families of molecules which are quantified are those with boiling points below 216.1 °C.
- the distribution that is observed in the gasolines having a boiling point below 216.1°C is identical to that in the hydrocarbons having a higher boiling point.
- the amount of alpha-olefins in the unsaturated hydrocarbons in the mixture according to the invention was determined using usual 1H and 13 C NMR techniques. For example, in CDC1 3 as solvent 1-alkenes show a peak
- the drop point of the mixture of hydrocarbons according to the invention is measured according to European standard EN 1427 of March 2007.
- Figure 3 shows how increasing the temperature leads to higher conversion rates.
- Figure 4 shows the surprising effect that increasing temperature results in increasing HCO and waxes yield.
- Figure 5 shows the increase in selectivity for waxes with decreasing pyrolysis gas residence time.
- Figure 6 further shows that waxes produced at high temperatures also have a different carbon chain distribution, shifted towards longer chain compounds.
- the mixed plastic waste was first pretreated at 250°C and atmospheric pressure to melt the plastic and remove most of the air, water, food residue and foreign solid as an effluent.
- This effluent contained also the gaseous product resulting from the decomposition of any component of the fed material.
- the pretreated material was introduced in the double-wall rotating drum furnace operating at 465°C under 150 mbar absolute pressure as well as 4000 kg/h of a heat carrier constituted of fine sand supplied at 700°C.
- the gas hold-up in the furnace was estimated to 4 m 3 and the condensed phase hold-up to 3.6 m 3 .
- the supplementary gas hold-up at a temperature equal or above 370°C was estimated to 0.3 m 3 .
- the total gas flow produced flow produced at the outlet of the furnace was estimated to 9 kmol/h corresponding to 1903 kg/h.
- the mixed plastic waste was first pretreated at 250°C and atmospheric pressure to melt the plastic and remove most of the air, water, food residue and foreign solid as an effluent.
- This effluent contained also the gaseous product resulting from the decomposition of any component of the fed material.
- the pretreated material was introduced in the double-wall rotating drum furnace operating at 465°C under 355 mbar absolute pressure as well as 4000 kg/h of a heat carrier constituted of fine sand supplied at 700°C and 560 kg/h of nitrogen at 25°C.
- the gas hold-up in the furnace was estimated to 6 m 3 and the condensed phase hold-up to 1.7 m 3 .
- the supplementary gas hold-up at a temperature equal or above 370°C was estimated to 0.3 m 3 .
- the total gas flow produced at the outlet of the furnace was estimated to 29 kmol/h corresponding to 2463 kg/h.
- the waxes were mostly linear.
- a unit equipped with a double-wall rotating drum furnace of 1.4 m of internal diameter and 5 m internal length equipped with a gaseous product uptake line of 400 mm of diameter and 5 m long at a temperature above 370°C was fed with 1200 kg/h of post-consumer mixed plastic waste of the following composition:
- the residence time of the gaseous products in the gas phase at or above 370°C was calculated to 4.6 s.
- the calculated flows are given in the following table 8 with the numbering of figure 2.
- the heat duty of the reaction including the preheating of the nitrogen was estimated at 275 kW and the heat supplied by the double-wall to 275 kW corresponding to the heat available by combustion of the gases.
- the heat transfer surface available in the furnace was estimated to 20 m 2
- the overall heat transfer coefficient is estimated to 80 W/m 2 K and the logarithmic difference of temperature between the hot gases used to heat up the furnace and the reaction medium reached 174°C.
- a unit equipped with a double-wall rotating drum furnace of 1.4 m of internal diameter and 8 m internal length equipped with a gaseous product uptake line of 400 mm of diameter and 2 m long at a temperature above 370°C was fed with 2500 kg/h of post-consumer mixed plastic waste of the following composition:
- the mixed plastic waste was first pretreated at 250°C and atmospheric pressure to melt the plastic and remove most of the air, water, food residue and foreign solid as an effluent.
- This effluent contained also the gaseous product resulting from the decomposition of any component of the fed material.
- the pretreated material was introduced in the double-wall rotating drum furnace operating at 450°C under 1320 mbar absolute pressure.
- the gas hold-up in the furnace was estimated to 11.1 m 3 and the condensed phase hold-up to 1.2 m 3 .
- the supplementary gas hold-up at a temperature equal or above 370°C is estimated to 0.3 m 3 .
- the total gas flow produced at the outlet of the furnace was estimated to 15.1 kmol/h corresponding to 1902 kg/h.
- the residence time of the gaseous products in the gas phase at or above 370°C is calculated to 64.9 s.
- the calculated flows are given in the following table 9 with the numbering of the figure 1.
- the heat duty of the reaction was estimated at 668 kW, and the heat supplied by the double-wall to 668 kW corresponding to 43 % of the heat available by combustion of the gases.
- the heat transfer surface available in the furnace was estimated to 32 m 2
- the overall heat transfer coefficient was estimated to 80 W/m 2 K
- the logarithmic difference of temperature between the hot gases used to heat up the furnace and the reaction medium reach 263 °C.
- the residence time of the condensed material in the furnace was estimated to 300 min.
- the waxes overall yield was calculated to 24 % based on the plastic content (including the additives) of the mixed plastic waste.
- the waxes were mostly linear.
- the mixed plastic waste was first pretreated at 250°C and atmospheric pressure to melt the plastic and remove most of the air, water, food residue and foreign solid as an effluent.
- This effluent contained also the gaseous product resulting from the decomposition of any component of the fed material.
- the pretreated material was introduced in the double-wall rotating drum furnace operating at 450°C under 1400 mbar absolute pressure as well as 28 kg/h of nitrogen at 25°C.
- the gas hold-up in the furnace was estimated to 11.1 m 3 and the condensed phase hold-up to 1.2 m 3 .
- the supplementary gas hold-up at a temperature equal or above 370°C was estimated to 0.3 m 3 .
- Waxes of the type obtained according to the process of the invention may, inter alia, be used as additives in bituminous coating compositions, and more generally in coating compositions on the basis (i) of mineral aggregates and (ii) of organic binders derived from petroleum (bitumen or mixtures of synthetic polymeric resins and oil) and/or from plants (in particular binders on the basis of resins and plant oils).
- Waxes of the invention are especially useful in bituminous mixtures and asphalt concretes, based on pure or modified bitumen (in particular through addition of polymers), as well as in coatings based on other organic binders, for example of the type of synthetic polymers and/or plant resins.
- the waxes according to the invention when used in coatings on the basis of mineral aggregates and organic binders, can be employed to facilitate the use of the binder and/or the mixture of binder and aggregate; and/or to optimize the coating of the aggregates, and particularly in the heat: the presence of waxes according to the invention tends to decrease, typically by several tens of degrees Celsius, the temperature at which the compositions are sufficiently fluid to be used, which manifests itself especially in terms of reduced process costs.
- the waxes according to the invention may be used in a coating based on mineral aggregates and organic binders to increase hardening speed of the coating during its cooling.
- the waxes according to the invention indeed tend to have a "setting" speed higher than organic binders such as bitumen or clear binders mentioned above.
- a wax of the invention may be advantageously used at least in the following applications:
- so-called "warm” bituminous mixtures obtained by coating aggregates with heated bitumen (pure or modified): for this application, the wax is advantageously mixed with the bitumen before the coating of the aggregates, whereby the bitumen can be mixed with aggregates at a much lower temperature than in the absence of wax (typically at a temperature of about 110-140°C compared to 200°C in the absence of resin, more precisely, 150-200°C).
- a flux additive of the plant oil type for example as described, inter alia, in EP 1845134.
- This fluxed binder is intended to be sprayed onto a road surface on which aggregates are then deposited.
- the presence of waxes allows in this context not only to reduce the temperature at which it is sprayed, but also to increase the speed of cohesion increase (setting) of the bitumen after its deposition and this despite the presence of fluxing agents.
- the wax is typically mixed with the bituminous binder, whereby the bitumen can be mixed with the aggregates at a temperature of about 160 to 190°C, compared to a temperature above 200°C (typically about 250°C) in the absence of wax.
- the wax also imparts curing properties.
- the presence of wax also here allows reducing the temperature at which the coatings are manufactured. It also allows an acceleration of the setting of the coating after deposition, which is particularly appreciable in the case of deposits on pitched roofs where the deposited composition tends to flow if it does not harden sufficiently rapidly.
- a wax of the invention may be used to improve the rheological properties of binders and more specifically, to increase the modulus of rigidity.
- a wax of the invention may, in this context, additionally provide lubricating properties.
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
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Abstract
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US201662315949P | 2016-03-31 | 2016-03-31 | |
EP16306635 | 2016-12-07 | ||
PCT/EP2017/057654 WO2017167948A1 (en) | 2016-03-31 | 2017-03-31 | Process for converting plastic into waxes by cracking and a mixture of hydrocarbons obtained thereby |
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KR (1) | KR20180132741A (en) |
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AR110493A1 (en) | 2016-12-08 | 2019-04-03 | Shell Int Research | A METHOD FOR PRE-TREAT AND CONVERT HYDROCARBONS |
BR112021020625A2 (en) | 2019-04-18 | 2021-12-21 | Shell Int Research | Recovery of aliphatic hydrocarbons |
US20220403264A1 (en) | 2019-12-10 | 2022-12-22 | Shell Oil Company | Recovery of aliphatic hydrocarbons |
EP4370628A2 (en) * | 2021-07-13 | 2024-05-22 | Indaver Plastics2chemicals | Method for producing purified fractions of a liquid crude pyrolysis oil from a hydrocarbon based waste plastic |
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SG43674A1 (en) * | 1991-03-05 | 1997-11-14 | Bp Chem Int Ltd | Polymer cracking |
US5216149A (en) | 1991-06-07 | 1993-06-01 | Midwest Research Institute | Controlled catalytic and thermal sequential pyrolysis and hydrolysis of mixed polymer waste streams to sequentially recover monomers or other high value products |
DE69323125T2 (en) * | 1992-06-29 | 1999-08-19 | Mortimer Technology Holdings Ltd. | Process for the conversion of polymers |
US6143940A (en) | 1998-12-30 | 2000-11-07 | Chevron U.S.A. Inc. | Method for making a heavy wax composition |
US6150577A (en) | 1998-12-30 | 2000-11-21 | Chevron U.S.A., Inc. | Method for conversion of waste plastics to lube oil |
FR2898604B1 (en) | 2006-03-17 | 2008-05-30 | Colas Sa | ROAD BINDERS BASED ON BITUMEN, FUNCTIONALIZED NATURAL FLOWERS AND WAX |
US20150247096A1 (en) | 2014-02-28 | 2015-09-03 | Honeywell International Inc. | Methods for converting plastic to wax |
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