CN107922851A - For by cracking by method of the converting-plastics into wax and thus obtained hydrocarbon mixture - Google Patents

Abstract

It is used to pass through method of the cracking by converting-plastics into wax the present invention relates to a kind of.This method comprises the following steps：Introduce the plastic into reactor；At least a portion plastics are allowed to be converted into wax, these waxes are a parts for the pyrolysis gas formed in the reactor；And the product stream containing the wax is removed from the reactor.The invention further relates to one kind as obtained by this method hydrocarbon mixture.

Description

For by cracking by method of the converting-plastics into wax and thus obtained hydrocarbon mixture

The U.S. Provisional Application No. 62/315949 submitted this application claims on March 31st, 2016 and December 07 in 2016 The priority for the European application number 16306635.0 that day submits, for all purposes by the whole of each of these applications Appearance is incorporated herein by quoting mode.

Technical field

It is used to pass through method of the cracking by converting-plastics into wax the present invention relates to a kind of.This method comprises the following steps：Will Plastics are introduced in reactor；At least a portion plastics are allowed to be converted into wax, these waxes are the pyrolysis formed in the reactor A part for gas；And the product stream containing the wax is removed from the reactor.

The invention further relates to one kind as obtained by this method hydrocarbon mixture.

The prior art

In view of importance day of the polymer as the substitute of conventional structure material (such as glass, metal, paper and timber) Benefit increase, fill out to the needs being aware of of the non-renewable resources (such as oil) of safety and available for the rubbish of waste product disposal The decrement of buried capacitor amount, in recent years, considerable concern are directed to recycling, regenerate, recycle or recycling in some way useless The problem of plastics.

Pyrolysis or catalytic cracking waste plastics has been proposed being converted into heavy polymer with much lower molecule The volatile compound of amount.Depending on used method, volatile compound can be used as fuel oil or fuel oil supplement The opposite higher boiling liquid hydrocarbon of agent or the light carbon atom to mid-boiling point as gasoline-type fuel or as other chemicals.In addition, Volatile compound can be or can at least include wax.

The catalytic cracking of mixed waste plastic is method well known to those skilled in the art.For example, US 5,216,149 is disclosed A kind of catalyst for being used to allow given polymer to decompose by identification and temperature conditionss control the complex waste stream of plastics Pyrolysis, the method that this circulation is melted into useful high value monomer or other chemicals.

Research has been carried out to be directed to carrying out optimization method parameter relative to the yield for improving desirable crackate.Example Such as, 2015/0247096 A1 of US describe a kind of be used for by adding hydrogen and waste plastics and hydrogen is abundant into reative cell Heat so that waste plastics thermal depolymerization is converted waste plastics with forming wax product (the wax product includes paraffin and olefin(e) compound) For the method for wax.Cracking carries out the duration of about 1 minute to about 45 minutes at a temperature of about 300 DEG C to about 500 DEG C, it is sufficient to Cause the thermal degradation of the plastic raw materials of substantially all melting.

US 6,150,577 and US 6,143,940 discloses a kind of be used for by waste plastics in subatmospheric pyrolysis zone Middle formation includes the pyrolysis zone effluent of 1- alkene and normal paraffin hydrocarbons to manufacture the method for weight Wax composition.Pyrolysis is from 500 DEG C To carrying out at a temperature of 700 DEG C.

M.Arabiourrutia et al. Journal ofAnalytical and appliedpyrolysis [analysis with Using pyrolysis magazine] characterization of the wax obtained by the pyrolysis of polyolefin plastics is described in 94 (2012) 230-237.Author grinds Influence of the cracking temperature to the wax and the yield of volatile matter that are obtained from different polyolefin is studied carefully.It was found that by cracking temperature from 450 DEG C Improving to 600 DEG C causes for example to reduce to 51wt.% from 80wt.% for LDPE (low density polyethylene (LDPE)) waxes obtained.At the same time The amount of the volatile matter of acquisition increases to 49wt.% from 20wt.%.These discoveries support it is generally understood that i.e. increase temperature is favourable In cracking rate towards the formation compared with short chain product.

It remains desirable, however, that further improve plastics cracking, especially with respect to specific product (such as wax) yield and The composition of such product.In some applications, for example, it is desirable to obtain the wax of high yield from plastics.Furthermore, it may be desirable to obtain Wax with increased average carbon number.

The content of the invention

The ladies and gentlemen inventor of the present invention is it has now been found that with above-mentioned expection on the contrary, with the raising of cracking temperature, the yield of wax Decline, if pyrolysis gas (pyrolysis gas forms in plastics cracking process and contains volatility crackate) exists Only there is the short residence time, under high cracking temperature, the yield of wax unexpectedly increases at a temperature of more than 370 DEG C Add.

In addition, the present invention's the inventors discovered that, under the conditions of ad hoc approach, obtain main novel comprising wax Hydrocarbon mixture, wherein these hydrocarbon with high carbon atom number, mainly straight-chain hydrocarbons and with uniqueness normal paraffin hydrocarbons and α-alkene The ratio of hydrocarbon.

Embodiment

Therefore, it is used to pass through method of the cracking by converting-plastics into wax the present invention relates to a kind of, this method includes：

Introduce the plastic into reactor；

At least a portion plastics are allowed to be converted into wax, these waxes are one of the pyrolysis gas formed in the reactor Point；And

The product stream containing the wax is removed from the reactor；

It is characterized in that the pyrolysis gas has the residence time less than 60 seconds at a temperature of more than 370 DEG C.

In addition, the present invention relates to a kind of hydrocarbon mixture, it is characterised in that these hydrocarbon show the accumulation of its carbon number purpose Distribution so that 20≤d20 and 50 >=d50；

The hydrocarbon of >=50mol% is straight-chain hydrocarbons；

And the molar ratio of normal paraffin hydrocarbons and alpha-olefin is in the range of 0.1 to 10 in these hydrocarbon.

In addition, the present invention relates to a kind of method for producing the mixture, wherein being used for above-mentioned by converting-plastics For in the method for wax, the mixture is obtained by removing the product stream containing wax from reactor.

In the catalytic cracking of plastics, several cuts of chemical compound are obtained.Typically, there are containing having less than The gas fraction of the lightweight chemical compound of 5 carbon atoms.Gasoline fraction contains the change with low boiling point (such as less than 150 DEG C) Compound.The cut includes the compound with 5 to 9 carbon atoms.Kerosene and diesel oil distillate have higher boiling point (such as 150 DEG C to 359 DEG C).The cut usually contains the compound with 10 to 21 carbon atoms.Usually will even more high boiling cut It is appointed as heavy-cycle oil (or HCO) and wax.In all these cuts, compound is optionally comprising hetero atom (such as N, O Deng) hydrocarbon.Therefore, " wax " in the sense of the present invention represents optionally to contain heteroatomic hydrocarbon.In most cases, they are in room For solid and with generally more than 26 DEG C of softening point under warm (23 DEG C).Following experimental section provides the cut of acquisition Definition.

Plastics are mainly made of specific polymer, and plastics are usually named by the specific polymer.Preferably, mould Material containing its gross weight by weight more than 25%, preferably by weight more than 40% and more preferably exceed by weight 50% particular polymers.Other components in plastics are such as additives, such as filler, reinforcing agent (re-enforcer), processing Auxiliary agent, plasticizer, pigment, light stabilizer, lubricant, anti-impact modifier, antistatic additive, ink, antioxidant etc..In general, Plastics include more than one additive.

Include polyolefin and polystyrene for the plastics in the method for the present invention, for example, it is high density polyethylene (HDPE) (HDPE), low Density polyethylene (LDPE), Ethylene-Propylene-Diene monomer (EPDM), polypropylene (PP) and polystyrene (PS).Mainly by polyene The mixed plastic that hydrocarbon and polystyrene are formed is preferable.

Other plastics (such as polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polyurethane (PU), third Alkene nitrile-butadiene-styrene (ABS), nylon and fluorinated polymer etc.) it is not ideal.If present in plastics, then they are excellent Choosing with the gross weight of dry weight plastics by weight less than 50%, preferably by weight less than 30%, it is more preferably few by weight In 20%, a small amount of presence even more preferably by weight less than 10%.

Preferably, plastics include one or more thermoplastic polymers and substantially free of thermosetting polymers.At this Aspect, substantially free of being intended to indicate that the content of thermosetting polymer based on the weight of plastics starting material and be less than 15%, preferably Less than 10% and even more preferably less than 5%.

In general, waste plastics contains other undesirable components, i.e. foreign material, such as paper, glass, stone, metal etc..

It can be selected from for the plastics in the method for the present invention：

Single waste plastics, specification or substandard single original plastic, mixed waste plastic, Rubber waste, organic waste Thing, biomass or its mixture.Unitary plastic waste, substandard single original plastic, mixed waste plastic, Rubber waste or Its mixture is preferable.Substandard single original plastic, mixed waste plastic or its mixture are particularly preferred.Mixing Plastic wastes usually provide good result.

The limited amount of pollutant as entrance raw material can not pyrolyzed components (such as water, glass, stone, metal etc.) It is acceptable." low content " preferably mean the gross weight of dry plastics by weight less than 50%, it is preferably few by weight In 20%, more preferably less than 10% it is a small amount of.It is preferably based on the gross weight of dry plastics, the list of any plastics being less desirable to Only content is by weight less than 5%, more preferably by weight less than 2%.

Before pyrolysis, raw material can be pre-processed by physical-chemical method, which includes One or more operation, such as reduce size, grinding, crushing, screening, peeling, metal removings, foreign material removing, dedusting, do Dry, degassing, melting, cure and reunite.

Pretreatment can carry out at a temperature of less than or equal to 350 DEG C, preferably lower than or equal to 330 DEG C.Pre-processing During the gaseous degradation products that occur advantageously be removed.The example of gaseous degradation products is hydrochloric acid, hydrobromic acid, hydrogen fluorine Acid, CO, CO₂, there is carbon containing small molecule (such as methane, ethane, butane, ethene, acetylene, propane, third for being no more than 4 C atoms Alkene, butylene, methanol, formic acid, formaldehyde, acetic acid, acetaldehyde, ethanol, acetone etc.).

Some in these catabolites may react with other materials present in plastics and produce undesirable reaction Product.The example of such material is filler, for example, alkaline filler such as PCC (winnofil) or chalk, lime, soda lime, Sodium carbonate, sodium acid carbonate, aluminium oxide, titanium oxide, magnesia, calcium oxide etc..

In the exit of pretreatment, raw material can be solid or melting, preferred molten.It is optionally possible to add Acid capture component is used to pre-process.The example of acid capture component is filler, such as alkaline filler such as PCC (winnofil), Aluminium oxide, titanium oxide, magnesia, calcium oxide etc..

The ladies and gentlemen inventor of the present invention surprisingly it has been found that under high de-polymerization temperature, if pyrolysis reactor and Operating condition ensures the short residence time for being less than 60 seconds of the pyrolysis gas at a high temperature of more than 370 DEG C, then wax can also be from modeling The cracking of material is obtained with high yield.This discovery is especially unexpected, because high cracking temperature should be conducive to cracking rate direction Compared with the formation of short chain product.In other words, it should find that the content of wax mixture is relatively low at a higher temperature.

In addition, the present invention the inventors discovered that, at high temperature the residence time of pyrolysis gas it is short in the case of, not only More wax mixtures are generated, and the average carbon number of wax also increases.This allows to carry out cracking at relatively high temperatures Process, which ensure that the low-residual of the high conversion of raw material and raw materials for plastics production (such as less than 50g/kg), but still permit Perhaps produce the wax of incrementss (these waxes have even increased average carbon number).

In cracker, plastics usually exist under cracking temperature with molten condition.Cracking reaction causes plastics Depolymerization, so as to produce the product of lower molecular weight.At temperature in cracker, the product of these lower molecular weights steams Hair, forms pyrolysis gas in reactor.The gas includes volatility pyrolysis cut, such as light hydrocarbon, diesel oil, kerosene and wax. The present invention based on the finding that：Pyrolysis gas should be rapidly removed from heat cracking reaction area, and it was found that if pyrolysis gas Have at a temperature of more than 370 DEG C and be less than 60 seconds, preferably smaller than 50 seconds, more preferably less than 40 seconds, even more preferably less than 30 Second, it is then preferred that less than 25 seconds and more preferably less than 20 seconds (being, for example, less than 15 seconds or even less than 10 seconds) residence time, Then obtain the wax of high yield.

On the other hand, as long as temperature is sufficiently high, cracking reaction can still occur in pyrolysis gas.Therefore, if pyrolysis gas Residence time at a temperature of more than 370 DEG C is too short, then the product obtained may also have undesirable feature, such as in carbon Chain length, side chain hydrocarbon content, arene content etc..Therefore, in certain embodiments, if pyrolysis gas is more than 370 DEG C At a temperature of residence time more than 2 seconds, preferably greater than 5 seconds, even more preferably more than 10 seconds are (such as more than 15 seconds or even super Spend 20 seconds), this is probably desired.

Pyrolysis gas rapidly removes the high pyrolysis temperature for being allowed for cracking plastics.This is with further advantage, i.e., The conversion ratio of plastics can very high and undesirable residue it is very low.For example, at least a portion plastics are converted to residing for wax Temperature be at least 370 DEG C, preferably at least 400 DEG C, more preferably at least 425 DEG C, even more desirably at least 440 DEG C.Plastics are turned Changing residing temperature can be high as desired, such as up to 850 DEG C, preferably of up to 700 DEG C, more preferably up to 600 DEG C, Even more preferably it is up to 500 DEG C (such as up to 480 DEG C or up to 470 DEG C).In a preferred embodiment, plastics are converted residing Temperature from 400 DEG C to 650 DEG C, preferably from 425 DEG C to 550 DEG C, preferably from 440 DEG C to 520 DEG C, even more preferably from 440 DEG C in the range of 470 DEG C.Most preferably, plastics be converted residing temperature from 400 DEG C in the range of less than 500 DEG C.

Low residence time of the pyrolysis gas needed at a temperature of more than 370 DEG C can be obtained by any suitable means , for example, by operate under vacuo reactor, by reactor in itself it is middle dilution pyrolysis gas, pass through reactor design (such as by limiting the volume of gas phase or by increasing the reactor volume filled by liquid and solid (if present) Percentage) or the residence time of pyrolysis gas in the reactor reduced by the combination of these measures.Generally, it is preferred to will Several combination in these measures is to obtain the desirable low residence time.

In one embodiment, reactor less than or equal to 1200 millibars, preferably lower than or equal to 1000 millibars, it is more excellent Choosing is operated less than or equal to 950 millibars and under even more preferably less than or equal to 900 millibars of pressure.Pressure in reactor Can as low as 0.5 millibar, preferably 1 millibar, preferably 10 millibars, preferably 40 millibars, preferably 50 millibars, more preferably 60 millibars and even More preferably 80 millibars.For example, reactor can be in 0.5 to 1200 millibar, preferably 10 to 1100 millibars, preferably 50 to 1000 millis Bar, operate under the pressure in the range of more preferably 60 to 950 millibars and even more preferably 80 to 900 millibars.

In alternative or further embodiment, pyrolysis gas can use dilution dilution agent.This diluent is without spy Do not limit, but should not have a negative impact to pyrolytic reaction or desirable reaction product.Specifically, as described below, dilute Agent should have low oxygen (O₂) content.The example of suitable diluent be nitrogen, hydrogen, steam, carbon dioxide, burning gases, Appropriate hydrocarbon gas and its mixture.Appropriate hydrocarbon gas preferably comprises one or more hydrocarbon having less than 5 carbon atoms.Nitrogen, carbon dioxide, Burning gases and appropriate hydrocarbon gas having less than 5 carbon atoms are preferable.Burning gases and the hydrocarbon gas having less than 5 carbon atoms Body is particularly preferred.

Diluent preferably has low oxygen (O₂) content, it is, for example, less than 4% volume, preferably smaller than 2% volume, more preferably small In 1% volume, the volume of dry gas is each based on.Combustion gas with the oxygen for being less than 0.1% volume based on dry gas Body provides particularly preferred result.

Dilution level has no particular limits, and can make choice as requested.For example, diluent in pyrolysis gas Molar ratio with thermal decomposition product can be more than 0.5, preferably greater than 0.7, more preferably above 0.8 and even more preferably more than 1. The molar ratio of diluent and thermal decomposition product is less preferred more than 50 in pyrolysis gas.Advantageously, which is up to 40, more Preferably of up to 20.The preferred molar ratio of diluent and thermal decomposition product is 0.5 to 50, preferably 0.7 to 40 and more in pyrolysis gas It is preferred that in the range of 0.8 to 20 (such as 1 to 10 or even 1 to 7).

Diluent can be introduced into reactor at any position.For example, the entrance of diluent can be located at reactor Top so that diluent is contacted substantially only under reaction condition with pyrolysis gas, but is not contacted with plastic melt.Alternative Embodiment in, diluent inlet can be for example positioned at the base section of reactor so that diluent at reaction conditions with modeling Expect melt contacts.The combination of two or more different entrances can be used.Preferably at least a diluent inlet is positioned at reaction The base section of device.It has been found that in this case, pyrolysis gas is effectively removed from thermoplastic material melt, so as to have Effect ground reduces residence time of the pyrolysis gas at a temperature of more than 370 DEG C.Most preferably using the dilution positioned at reactor head The combination of agent entrance and diluent inlet positioned at reactor bottom part.

In the especially preferred embodiments, reactor operates and uses diluent under reduced pressure.In this case, may be used Residing absolute pressure P during adjusting the molar ratio D and reactor of diluent and thermal decomposition product operations in pyrolysis gas so that D/ P in the range of 2 to 50mol/mol/ bars, particularly in the range of 3 to 30mol/mol/ bars, more particularly 5 to In the range of 20mol/mol/ bars.

In one embodiment of the method for the present invention, it is the presence in heat carrier that at least a portion plastics, which are converted into wax, Lower progress.The example of suitable heat carrier be sand (such as silica), stone, gravel, metal, metal oxide, glass, Ceramics etc..Any metal with the fusing point for exceeding the temperature residing for the cracking for carrying out plastics can be used.Suitable metal is Such as iron and steel, such as forged steel and heat resisting steel.Sand, metal (such as steel or iron), gravel and glass are preferable.Sand and steel are special It is not preferable.

Carrier can be the catalyst of the cracking for plastics.However, in a preferred embodiment, heat carrier is not intended to The catalyst of the cracking in vapour phase of hydrocarbon.

Preferably, heat carrier has the granularity of the granularity higher of the filler than being used in plastics.

In one embodiment, heat carrier includes particle, preferably free flowing granule, such as granular rounded grain, subsphaeroidal Particle, medicine ball, hollow ball etc..Preferably, heat carrier particle has the granularity than 632 higher of Standard U.S. Mesh, preferably high In Standard U.S. Mesh 400.It is further preferred that heat carrier particle has less than or equal to about 5cm, preferably less than or equal to about The granularity of 2.5cm.

When heat carrier is sand, according to ISO 14688-1:2002, it is fine sand or middle sand heat carrier particles benefit.It is preferred that Heat carrier particle is fine sand.

When heat carrier is metal (such as iron or steel), they are preferably in the form of medicine ball.Granularity can be in 1 and 50mm Between, preferably between 10 and 30mm.When heat carrier is glass, particles benefit be between 0.5 and 20mm, preferably The bead or glass marble of size between 0.6 and 6mm.

When heat carrier is gravel, according to ISO 14688-1:2002, it is preferably bird's-eye gravel or cobble-stone, preferably granule Stone.

The residence time of pyrolysis gas in the reactor is expressed as gas reserved (in other words, the reactor of reactor In the volume that is occupied by gaseous material and with m³Represent) divided by leave reactor gas flow and with m³/ min is represented.Consider To hot gas expander, it is believed that gas is in the mutually synthermal of pyrolysis reactor.If used, the gas of reactor is left comprising dilute Release agent.

(in other words, anti-the residence time of condensed material in the reactor is expressed as the condensed material reserved of reactor Answer the volume that is occupied in device by condensed material and with m³Represent) divided by outlet condensed material flow, with m³/ min is represented.Condense material The temperature expansion of material is ignored.The residence time has no particular limits, but usually in the range of 1 to 600 minute, preferably exists In the range of 2 to 400 minutes, more preferably in the range of 3 to 250 minutes.By " condensed material ", understanding is in liquid or solid The unconverted raw material of form, the liquid and solid product (such as coke, ash content) and heat carrier obtained from reaction (if you are using) total amount.

The method of the present invention in batches or can be carried out continuously.It is preferable continuously to carry out this method.

Technical staff knows the suitable instrument and equipment for carrying out the method according to the invention, and he will be based on him Professional experiences select suitable system, so further extensive details need not be provided herein.

The example of suitable type of reactor is fluid bed, entrainment bed, spouted bed, downspout, fixed bed, going barrel, rotation Turn cone, screw conic, auger, extruder, molecular distillation, thin film evaporator, kneader, cyclone separator etc..Fluid bed, entrainment Bed, spouted bed, auger and going barrel are preferable.Auger and going barrel are particularly preferred.Going barrel gives well Result.

Leaving the gas of pyrolysis reactor can be removed in any dust-extraction unit from dust.The example of dust-extraction unit Be cyclone separator, multi-cyclone, spiral shape separator, grid separator, cyclone pipe, electrostatic filter, expansion chamber, Vortex collector, shutter collector (shutter collector), wet scrubber etc..Cyclone separator, multistage cyclone Separator, spiral shape separator and cyclone pipe are preferable.Multi-cyclone is particularly preferred.

The separation of non-condensable gas is realized by any mode well known by persons skilled in the art.Non-condensable gas Referred to herein as the component not being condensed under operating pressure at a temperature of 25 DEG C.The example of separator be quenched, You Jicui Go out, water quenching is gone out, spray tower, fractionating column, cyclone separator etc..Organic be quenched is preferable.Temperature between 110 DEG C and 250 DEG C Organic quenching of the lower operation of degree is preferable, is particularly preferred between 125 DEG C and 220 DEG C.Between 140 DEG C and 180 DEG C It is even more preferably.

Vacuum can be provided by any device well known by persons skilled in the art.The example of vacuum plant is liquid rotary pump, does Formula vacuum pump, steam jet ejector, gas ejector, water ejector and any combinations.

Burn in any device well known by persons skilled in the art.

Wax is separated from fuel by any method known to those skilled in the art.Example be evaporation, distillation, crystallization, Liquid extraction or combination.The combination of evaporation and solvent extraction gives good result.The example of solvent be hexane, benzene, toluene, Methyl ethyl ketone (MEK), methyl iso-butyl ketone (MIBK) (MIBK).MEK and MIBK is preferable.

It can be extracted in the separated condensed material of reactor exit by any means well known by persons skilled in the art. The example of means is screw rod, rotary valve etc..Screw rod is preferable.

In order to avoid spontaneous combustion, condensed material can be extracted in the atmosphere with low oxygen content.Around the gas of condensed material O in phase₂It is preferable less than 2%.Condensed material can be cooled down by any means well known by persons skilled in the art.Example is Double-walled screw conveyor, band water filling screw conveyor, extruder, auger etc..Band water filling screw conveyor is preferable.

Optionally, condensed material can be sent to burner with the unconverted raw material and coke of burn combustible.Particularly In the case of with heat carrier.Optionally, ash content and heat carrier are between 500 DEG C and 1000 DEG C, preferably at 600 DEG C and 800 Heated at a temperature of between DEG C in stove.Optionally, the hot ash content of at least a portion and heat carrier are sent to pyrolysis reactor.It is preferred that Ground, at least a portion ash content are separated with heat carrier.Separation is carried out in any method known to one skilled in the art.Method Example is cyclonic separation, elutriation, screening, screening, centrifugation etc..The ratio of heat carrier flow and raw material streams is typically included in by weight Between meter 0.1 and 10.It is preferred that between 0.2 and 8.Ratio higher than 0.25 gives particularly preferred result.

The method of the present invention produces the wax of high value and mainly includes the hydrocarbon mixtures of these waxes, for such as candle, Adhesive, packaging, rubber, cosmetics, log of igniting (fire log), asphalt mixture, surface wearable coating, pitch, sealing In the application such as coating.

Therefore, the invention further relates to wax or hydrocarbon mixture obtained by the method as the present invention.

Wax and hydrocarbon mixture have the following advantages：With quite high chain length (especially linear carbon chain).In addition, obtain Wax be typically the wax mixture for mainly containing normal paraffin hydrocarbons and alpha-olefin.In wax the percentage of alpha-olefin can be from about 25 to 75wt.%, preferably from about 40 to 60wt.%, more preferably from about 50wt.%, are each based on the gross weight of wax.

Therefore, the invention further relates to a kind of hydrocarbon mixture, it is characterised in that these hydrocarbon show its carbon number purpose and tire out Integrate cloth so that 20≤d20 and 50 >=d50；

The hydrocarbon of >=50mol% is straight-chain hydrocarbons；

And the molar ratio of normal paraffin hydrocarbons and alpha-olefin is in the range of 0.1 to 10 in these hydrocarbon.

Hydrocarbon mixture according to the present invention mainly includes wax, the i.e. hydrocarbon with 20 or more carbon atoms.However, this is mixed Compound can also contain the hydrocarbon on a small quantity having less than 20 carbon atoms.Preferably, which includes less than 5mol%, more preferably Less than 3mol%, the even more preferably less than hydrocarbon having less than 20 carbon atoms of 2mol% and most preferably in less than 1mol%. Through the application herein with other Anywhere " mol% " of hydrocarbon refers to the total amount of hydrocarbon in hydrocarbon mixture.

In a preferred embodiment, the hydrocarbon in hydrocarbon mixture shows its carbon number purpose cumulative distribution so that 22≤ D20, preferably 25≤d20.

In another embodiment, the hydrocarbon in hydrocarbon mixture shows its carbon number purpose cumulative distribution so that and d20≤ 40th, more preferably d20≤35, even more preferably d20≤30.

In another embodiment, the hydrocarbon in hydrocarbon mixture shows its carbon number purpose cumulative distribution so that 20≤ D20≤40, preferably 22≤d20≤35, more preferably 25≤d20≤30.

In another embodiment, the hydrocarbon in hydrocarbon mixture shows its carbon number purpose cumulative distribution so that 45 >= D50, preferably 40 >=d50.

In another embodiment, the hydrocarbon in hydrocarbon mixture shows its carbon number purpose cumulative distribution so that 50 >= D50 >=20, preferably 40 >=d50 >=22.

In a preferred embodiment, the hydrocarbon in hydrocarbon mixture shows its carbon number purpose cumulative distribution so that 20≤ D20≤40 and 50 >=d50 >=20, more preferably 22≤d20≤25 and 40 >=d50 >=22.

In addition to high carbon atom number, the hydrocarbon in hydrocarbon mixture according to the present invention has the following advantages：They are wrapped Straight-chain hydrocarbons containing high mole.Preferably, in hydrocarbon mixture hydrocarbon total amount >=60mol%, more preferably >=70mol% be straight chain Hydrocarbon.

Hydrocarbon in hydrocarbon mixture according to the present invention is further advantages in that they have in the range of 0.1 to 10, is excellent It is selected in the range of 0.2 to 5, some molar ratios of the normal paraffin hydrocarbons more preferably in the range of 0.5 to 2 and alpha-olefin.At this In the context of invention, normal paraffin hydrocarbons is straight chain saturation alkane, and alpha-olefin is straight chain and side chain containing at least one α-double bond Hydrocarbon.

It is hydrocarbon further advantages in that unsaturated hydrocarbons includes the alpha-olefin of a large amount in hydrocarbon mixture according to the present invention.It is preferred that Ground, unsaturated hydrocarbons total amount>40mol%, more preferably>45mol%, even more preferably>50mol% is alpha-olefin.

In another embodiment, hydrocarbon mixture has >=10, iodine number preferably >=25, more preferably >=40.

In another embodiment, hydrocarbon mixture has≤150, iodine number preferably≤100, more preferably≤70.

In a preferred embodiment, hydrocarbon mixture have in the range of 1 to 150, more preferably 25 to 100 scope Iodine numbers interior and even more preferably in the range of 40 to 70.

Hydrocarbon mixture according to the present invention further advantage is that the mixture can have for example>25 DEG C, preferably>40 DEG C, more preferably>50 DEG C of relatively high dropping point.

Hydrocarbon mixture according to the present invention can be by forming without any heteroatomic hydrocarbon.However, depending on production hydrocarbon mixes The plastics of compound, it is likely that at least a portion hydrocarbon contains one or more hetero atoms, such as oxygen, sulphur, nitrogen or halogen (such as fluorine, Chlorine, bromine or iodine).Other hetero atoms are also possible.

Hydrocarbon mixture according to the present invention can be obtained by the above method by the catalytic cracking of plastics.If selection The product stream removed from reactor causes it only to contain the hydrocarbon with least 20 carbon atoms, then obtains wax.However, putting into practice In and especially at industrial scale, product stream will usually contain a small amount of hydrocarbon having less than 20 carbon atoms.This In the case of, obtain above-mentioned hydrocarbon mixture.

Attached drawing

Fig. 1 schematically shows the first embodiment of the method for the present invention.

Fig. 2 schematically shows the second embodiment of the method for the present invention.

Fig. 3 is shown at different temperatures：425 DEG C (lines of square indicia), 450 DEG C (lines of circle mark) and 465 DEG C (line of triangular marker), conversion ratio (in terms of %, y-axis) as the function in reaction time (being represented with minute, x-axis) are drilled Become.

Fig. 4 is shown at different temperatures：425 DEG C (white bars), 450 DEG C (black and white pattern packings) and 465 DEG C of (black Bar), the accumulation selectivity (being represented with %, y-axis) of differential responses product (being listed in x-axis).

Fig. 5 shows that the wax accumulation as the function of pyrolysis gas residence time (being represented with the second, x-axis) is selective (with % Represent, y-axis).

Fig. 6 shows the carbon number distribution of wax.Curve is shown for different reaction temperatures：425 DEG C of (square marks The line of note), 450 DEG C (lines of circle mark) and 465 DEG C (lines of triangular marker), as carbon chain lengths (numerically, x-axis) Function percentage by weight (wt%, y-axis).

Fig. 7 is shown for different temperature and entrance N₂Flow：450 DEG C and 150mL/min N₂(open circle markers Line), 465 DEG C and 150mL/min N₂(lines of open triangular markers), 450 DEG C and 1L/min N₂(line of filled circle marker), 465 DEG C and 1L/minN₂(line of black triangle mark), 465 DEG C and 2L/minN₂The line of mark (open diamonds), 465 DEG C and 4L/minN₂The line of mark (hollow square), as the function in reaction time (being represented with minute) conversion ratio (represented with %, Y-axis).

Fig. 8 is shown in different temperature and N₂The accumulation selectivity of differential responses product (being listed in x-axis) under flow (being represented with %, y-axis).Legend：For every kind of product, to the right side since left, the color of bar refer to 450 DEG C and 150mL/min, 450 DEG C and 1L/min, 465 DEG C and 150mL/min, 465 DEG C and 1L/min, 465 DEG C and 2L/min, 465 DEG C and 4L/min.

Fig. 9 is shown for two reaction temperatures：450 DEG C (lines of circle mark) and 465 DEG C (lines of square indicia), make For the wax accumulation selectivity (being represented with %, y-axis) of the function of pyrolysis gas residence time (being represented with the second, x-axis).

Figure 10 shows the carbon number distribution of wax.Curve is shown for different reaction temperature and N₂Inlet flow rate： 450 DEG C and 150mL/min (line of circle mark), 465 DEG C and 150mL/min (line of triangular marker), 450 DEG C and 1L/min (x The line of mark), 465 DEG C and 1L/min (line of+mark), 465 DEG C and 2L/min (line of diamond indicia), 465 DEG C and 4L/min (line of square indicia), the percentage by weight as the function of carbon chain lengths (numerically, x-axis) (are represented, y with wt% Axis).

Figure 11 is shown for different N₂Entrance feed type and flow：150mL/min upward (line of circle mark), 1L/min upwards (line of diamond indicia), 1L/min downwards (line of triangular marker) and 4L/min up/downs (1L/min to Upper and 3L/min is downward, the line of square indicia), as the reaction time (being represented with minute) function conversion ratio (with % tables Show, y-axis).

Figure 12 is shown for different N₂Entrance feed type and flow, differential responses product (being listed in x-axis) Accumulation selectivity (being represented with %, y-axis).Legend：For every kind of product, refer to 150mL/min to the right side, the color of bar since left Upwards, 1L/min is upward, 1L/min is downward, 4L/min up/downs (1L/min is upwards and 3L/min is downward).

Figure 13 shows that the wax accumulation as the function of pyrolysis gas residence time (being represented with the second, x-axis) is selective (with % Represent, y-axis).

Figure 14 shows the carbon number distribution of wax.Curve is shown for different N₂Entrance feed type and flow： (line of diamond indicia), 1L/min are downward (line of triangular marker) upwards by (line of circle mark), 1L/min upwards by 150mL/min With 4L/min up/downs (1L/min upwards and 3L/min it is downward, the line of square indicia), as carbon chain lengths (with numeral Represent, x-axis) function percentage by weight (wt%, y-axis).

Illustrate the method for the present invention by way of example referring now to Fig. 1 and 2.

In the first embodiment, schematically shown in Fig. 1, the pyrolysis of raw material is under vacuo in poor oxygen to produce wax Realized under atmosphere.Raw material 1 by the combination (separation effluent stream 3 and pretreated raw material 4) of physical chemistry processing 2 into Row pretreatment.Pretreated raw material 4 are introduced into by means of the feed arrangement 5 in pyrolysis reactor 10 by pipeline 6.Heat Solution reactor is heated indirectly.In the case where not limiting scope, as example, reactor (can be fed to by hot-fluid 7 Suitable heat transfer unit (HTU) 8 and be recovered as flowing 9 in exit) circulation heat.Optionally, heat carrier flow 11 is introduced In pyrolysis reactor.Pyrolysis gas 12 is recycled from pyrolysis reactor and sent to physical chemistry processing 20.Residue 13 passes through dress Put 14 to be recovered, residue is treated to generate stream 15 by rights in the apparatus.The residue contains unconverted Raw material, accessory substance and the heat carrier being introduced into optionally by stream 11 in pyrolysis reactor.In physical chemistry processing, it will be pyrolyzed Gas is removed in the dust recycled in 21 and other harmful constituents from flowing and separated as stream 22, which is sent to processing 25 In, processing 25 in can not condensate flow 24 separated with condensate flow 23.Stream 24 is sent to vacuum plant 26.Stream from vacuum plant Go out thing 27 and combustion chamber 28 is sent to together with the combustion air (29) of sufficient amount to produce hot-fluid 7.Optionally, 30 quilt of auxiliary fuel It is added in combustion chamber 28.Condensate flow 23 is sent to separative element 31, and wax stream 32 is separated with accessory substance 33 in separative element 31.

In a second embodiment, the pyrolysis for the raw material realized under vacuo in the presence of diluent gas is to produce wax Example as shown in Figure 2 schematically.The pyrolysis of raw material is realized under vacuo under oxygen-lean atmosphere to produce wax.Raw material 51 Pre-processed by the combination (separation effluent stream 53 and pretreated raw material 54) of physical chemistry processing 52.Pretreatment The raw material 54 crossed are introduced into by means of the feed arrangement 55 in pyrolysis reactor 60 by pipeline 56.Pyrolysis reactor is by between Connect heating.In the case where not limiting scope, as example, reactor (can be fed to suitable heat transfer by hot-fluid 57 Device 58 and 59 be recovered as stream in exit) circulation heat.Optionally, heat carrier flow 61 is introduced into pyrolytic reaction In device.Gaseous diluent 66 is introduced with controllable rate in reactor 60.It is anti-from pyrolysis with the pyrolysis gas that diluent 62 mixes Answer and recycle and sent to physical chemistry processing 70 in device.Optionally it is recovered with the residue that heat carrier 63 mixes by device 64, Residue is treated to generate stream 65 by rights in device 64.The residue contains unconverted raw material, by-product Thing and the heat carrier being introduced into optionally by stream 61 in pyrolysis reactor.Physical chemistry processing in, by pyrolysis gas from stream 71 Remove in the dust of middle recycling and other harmful constituents and as the separation of stream 72, which is sent into processing 75, in processing 75 In can not condensate flow 74 separated with condensate flow 73.Stream 74 is sent to vacuum plant 76.Effluent 77 and foot from vacuum plant The combustion air (79) enough measured is sent to combustion chamber 78 to produce hot-fluid 57 together.Optionally, auxiliary fuel 80 is added to combustion Burn in room 78.Condensate flow 73 is sent to separative element 81, and wax stream 82 is separated with accessory substance 83 in separative element 81.

If the disclosure content of any patent, patent application and the publication that are incorporated herein by quoting mode with Mutually conflict is to the degree that term may be caused not know for the explanation of the application, then this explanation should be preferential.

Example

The general description of experimental arrangement

In each run under half point batch mode, 30g plastics (20% polypropylene, 80% polyethylene) are loaded into reactor It is interior, and by the heat carrier (SiO of limited amount₂, about 20g) it is stored in heat carrier storage tank.Reactor is closed and in 20 minutes 200 DEG C, while the 150mL/min nitrogen flows purging introduced used in reactor head are heated to from room temperature.When internal temperature reaches To plastics fusing point when, start to stir and be slowly increased to 690rpm.Keep the temperature at 200 DEG C and continue 25-30 minutes.At this During heating process, the nitrogen come out from reactor is not collected.Meanwhile the heat carrier storage tank containing heat carrier is blown with nitrogen Sweep several times.

After first pre-treatment step, reaction temperature is raised the temperature to the rate of heat addition of 10 DEG C/min, and open Begin to collect gas and nitrogen in corresponding gas sampling bag.When internal temperature reaches reaction temperature, heat carrier is introduced anti- Answer inside device.Depending on experiment, nitrogen flow is set as 150mL/min or is adjusted to 1,2 or 4L/min, and by gaseous products Circulation be converted to another pair glass trap and corresponding gas sampling bag.This was considered as zero reaction time.Depending on experiment, nitrogen Gas can enter reactor by two ways：In the top of container or the plastics bubbling for passing through melting.

Within the selected period, liquid and gaseous products are collected respectively and taken in a pair of of glass trap and its relevant gas In sample bag.At the end of experiment, reactor is cooled to room temperature.During this cooling step, liquids and gases are also have collected.

Reaction product is divided into 3 groups：I) gas, ii) liquid hydrocarbon and iii) (waxy compound, be accumulated in heat carrier to residue On ash content and coke).The quantitative of gas is completed by using gas chromatography (GC) of the nitrogen as internal standard compound, and liquid with Residue is quantitatively completed by weight.Glass trap (together with its corresponding lid) is weighed before and after liquid is collected, together When reactor vessel is weighed before and after each run.

Simulation distillation (SIM-DIS) GC methods allow to determine that the different fractions in fluid sample (are evaporated according to selected Point), detailed hydrocarbon analysis (DHA) GC methods allow the gasoline fraction (C5-C11 of the definite sample finally taken out：Boiling point<216.1 ℃；It includes the C5-C11 in C5-C6 and fluid sample in gaseous sample) in PIONAU components, and GCxGC allow it is true Diesel oil distillate (the C12-C21 of the fixed fluid sample finally taken out；216.1℃<BP<359 DEG C) in saturate, single aromatic, two Aromatic hydrocarbons and three aromatic hydrocarbons.

Under all experimental conditions, the reactor volume of 300mL, the former plastic density of 0.94g/mL, 1.1g/mL are used Silica bulk density calculates the residence time of pyrolysis gas.This causes gas reserved to be 250mL.

In instances, HCO refers to be considered to have the heavy-cycle oil of the hydrocarbon molecule of at least 22 carbon atoms (+C22).Wax Refer to the hydrocarbon molecule with least 20 carbon atoms (+C20).In general：

● gasoline：Containing with the C5 of gas and C6+bp (boiling point)<150 DEG C of liquid (about C5-C9)

● kerosene：150 DEG C of boiling point<bp<250 DEG C of liquid (about C10-C14)

● diesel oil：250 DEG C of boiling point<bp<359 DEG C of liquid (about C15-C21)

●HCO：Boiling point>359 DEG C of product (C22 and+)

● wax：Boiling point>330 DEG C of product (C20 and+)

The definite of different fractions is by simulating distillating method and complete according to ASTM-D-2887 standards by gas chromatography Into.

The general description of analysis method

Carbon number purpose measures

Carbon atom number and its distribution in hydrocarbon mixture are measured using ASTM-D-2887 methods.This method is to be used for The GC methods of the simulation distillation of complex hydrocarbon mixture.This method allows to separate the hydrocarbon in complex mixture according to their boiling point Molecule.Then it is according to the cut point of restriction that boiling point is related to carbon number.In the present invention, using such as the boiling defined in table 1 below Relation between point and carbon number.

There is the cut of the boiling point less than 105.8 DEG C to be defined as the hydrocarbon for being less than 10 carbon number for those.In order to true Surely the carbon chain lengths of molecule, the peak obtained in GC are incorporated into according to the boiling point fraction provided in table 1 so that obtain in given sample Area under the curve it is related to having the relative quantity of the hydrocarbon of given carbon number for each boiling spread.According to people in the art Standard method known to member, all peaks are normalized to 100% allows to calculate carbon number purpose distribution in sample.Point obtained Cloth is and the relevant distribution of weight of sample gross weight.

The measurement of straight-chain hydrocarbons and branched-chain hydrocarbons

The amount of straight-chain hydrocarbons and branched-chain hydrocarbons in hydrocarbon mixture according to the present invention is determined according to ASTM-D-6730 methods 's.Measurement carries out on 3900 chromatographs of Varian equipped with fid detector and 100m capillary columns.GC is further equipped with only A part of sample is allowed to enter the backwash of column.In order to determine the composition of mixture, Varian DHA software (detailed hydrocarbon is used Analysis).The peak obtained is integrated, and then by DHA softwares compared with interior data storehouse, with to peak into Row is qualitative and quantitative.By this technology, by the family of quantitative molecule (paraffin, isoparaffin, alkene, cycloalkane and aromatic hydrocarbons) It is those that boiling point is less than 216.1 DEG C.For the present invention, it is assumed that observed in the gasoline of the boiling point with less than 216.1 DEG C Distribution with higher boiling point hydrocarbon in it was observed that distribution it is identical.

The measurement of unsaturated hydrocarbons and alpha-olefin

Using common¹H and¹³C NMR technologies determine in mixture according to the present invention alpha-olefin in unsaturated hydrocarbons Amount.For example, in CDCl₃As in solvent, 1- alkene shows peak at 5.82ppm, and 2- alkene shows peak at 5.42ppm, and And 2- methyl isophthalic acids-alkene shows peak at 4.69ppm.Those, which include α-double bond and the unsaturated hydrocarbons of both other double bonds, to lead to Cross and be used for the GC methods for determining branched-chain hydrocarbons as described above to distinguish.In the context of the present invention, comprising α-double bond and its The alpha-olefin of both his double bonds is suitable as alpha-olefin.

Can be by identical method (GC and NMR) by normal paraffin hydrocarbons (straight chain saturation alkane) and straight chain unsaturated hydrocarbons and side chain (saturation or unsaturation) hydrocarbon distinguishes.

The measurement of iodine number

Hydrocarbon mixture according to the present invention is measured by the way that the sample between 0.1 and 0.2g is dissolved in 10ml chloroforms Iodine number.By 5ml include 0.1M ICl Wijs solution be added in solution, and make mixture react in the dark 1 it is small when.So The liquor kalii iodide of unreacted Wijs solution and 100g/l is set to react so that unreacted ICl is converted into I afterwards₂.By using Thiosulfate solution is titrated to determine the I formed₂Amount.According to I₂The amount of thiosulfate needed for reaction, calculates not anti- The amount for the Wijs solution answered, indicates the number of unsaturated bond in hydrocarbon.

The measurement of dropping point

The dropping point of hydrocarbon mixture according to the present invention is measured according to the European standard EN1427 in March, 2007.

Example 1

Tested according to above-mentioned general procedure.Raw material and 20g bis- are used as using 80wt.%HDPE and 20wt.%PP Silica is tested as heat carrier.Reaction temperature changes from 425 DEG C to 465 DEG C, and is introduced in reactor head The N of 0.15L/min₂.The weight ratio of heat carrier and plastics is equal to by weight 20/30.

Experimental result is shown in Fig. 3 into Fig. 6.As expected, Fig. 3 shows how increase temperature causes the conversion of higher Rate.On the other hand, Fig. 4 shows unexpected effect, i.e. temperature increase causes HCO and the increase of wax yield.Fig. 5 show with The reduction of pyrolysis gas residence time, the selectivity increase of wax.Fig. 6, which further illustrates the wax produced at high temperature, also to be had Different carbochain distributions (being moved to longer chain compound).

Table 2 below summarizes the cumulative distribution (depending on reaction temperature) of carbon atom in the hydrocarbon mixture of acquisition.

Table 2

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

The hydrocarbon mixture obtained in the example is further analyzed, and the result of the analysis is summarised in table 3 below.

Table 3

Example 2

Tested according to above-mentioned general procedure.Raw material and 20g bis- are used as using 80wt.%HDPE and 20wt.%PP Silica is tested as heat carrier.Reaction temperature is set as 450 DEG C or 465 DEG C, and N₂Flow from 0.15L/min to 4L/min changes.The weight ratio of heat carrier and plastics is equal to by weight 20/30.

Experimental result is shown in Fig. 7 into Figure 10.As expected, Fig. 7 is shown increases to 465 DEG C such as by temperature from 450 DEG C What causes the conversion ratio of higher.In addition, as expected, kinetics and N used₂Flow is completely irrelevant.On the other hand, scheme 8 show unexpected effect, i.e. nitrogen flow increase causes HCO and the increase of wax yield.Fig. 9 is shown with pyrolysis gas The reduction of residence time, the selectivity increase of wax.Figure 10, which is further illustrated, uses higher N₂The wax that flow produces also has Different carbochain distributions (being moved to longer chain compound).

The cumulative distribution that table 4 below summarizes carbon atom in the hydrocarbon mixture of acquisition (depends on reaction temperature and N₂Flow).

Table 4

Example 3

Tested according to above-mentioned general procedure.Raw material and 20g bis- are used as using 80wt.%HDPE and 20wt.%PP Silica is tested as heat carrier.Reaction temperature is set as 450 DEG C, and N₂Flow is from 0.15L/min to 4L/min Change.Specifically, N₂Flow set is as follows：

●N₂Entrance is located at reactor head and is not contacted at reaction conditions with plastic melt.This is arranged in figure It is defined as ' upward '

●N₂Entrance is located at the base section of reactor and is contacted at reaction conditions with plastic melt.This allows certain ' stripping ' effect.This, which is arranged in figure, is defined as ' downward '

The weight ratio of heat carrier and plastics is equal to by weight 20/30.

Experimental result is shown in Figure 10 into Figure 13.Figure 10 shows that increase flow causes the conversion ratio of higher.It is worth noting , by by N₂Entrance is arranged in reactor bottom, makes N₂Stream is contacted with plastic melt further increases conversion ratio.Figure 11 Show unexpected effect, i.e. nitrogen flow increase causes HCO and the increase of wax yield.Specifically, as permission N₂Reacting Under the conditions of when being contacted with plastic melt, its effect is even more notable.Figure 12 shown with the reduction of pyrolysis gas residence time, The selectivity increase of wax.Also there is the wax that Figure 13 further illustrates generation different carbochain distributions (to be moved to longer chain compound It is dynamic).

The cumulative distribution that table 5 below summarizes carbon atom in the hydrocarbon mixture of acquisition (depends on N₂Flow).

Table 5

Example 4：Mass balance according to the present invention

In this example and following example, Post-consumer plastic is named with their predominant plastics component；It is average For, the Post-consumer plastic considered contains the additive of 8 weight %.

To at a temperature of more than 370 DEG C, equipped with double-walled rotary drum type stove, (internal diameter of the double-walled rotary drum type stove is 1.4m and inner length are 5m, equipped with a diameter of 400mm and the gaseous products intake pipeline of long 2m) unit with Mixed plastic waste after consumption of the 2500kg/h chargings with consisting of：

Mixed plastic waste pre-processes under 250 DEG C and atmospheric pressure so as to plastic molten melt and remove most of sky first Gas and water, food waste and foreign solid are as effluent.This effluent also contains point by any component of feed material Solve the gaseous products produced.By the heat being made of fine sand of pretreated material and the 4000kg/h supplied at 700 DEG C Carrier is introduced into the double-walled rotary drum type stove operated at 465 DEG C under 150 millibars of absolute pressures.Estimate that the gas in stove retains Measure as 4m³, and condensation phase reserved is 3.6m³.Make-up gas reserved is estimated at a temperature of equaling or exceeding 370 DEG C For 0.3m³.Total gas couette caused by the stream for estimating to produce in the exit of stove is 9kmol/h, corresponding to 1903kg/h.

Gaseous products in gas phase are 4.5s at 370 DEG C or more than the residence Time Calculation at 370 DEG C.Following table 6 is given The flow calculated, and the numbering with Fig. 1 are gone out.

The thermic load of estimation reaction is 517kW, and by the heat of heat carrier supply, for 217kW, (corresponding to can by coke burning The heat of acquisition 42%), and as the heat that double-walled is supplied be 300kW (heats obtained by corresponding to gas burning 50%).Estimate that available heating surface is 20m in stove², estimation overall heat-transfer coefficient is 80W/m²K, and for the heat of heating furnace The logarithmic difference of temperature between gas and reaction medium reaches 190 DEG C.

Residence time of the condensed material in stove is estimated as 80min.Plastic content based on mixed plastic waste (including adds Add agent), the gross production rate of wax is calculated as 59%.Wax is mainly straight chain.

Example 5：Mass balance according to the present invention

To at a temperature of more than 370 DEG C, equipped with double-walled rotary drum type stove, (internal diameter of the double-walled rotary drum type stove is 1.4m and inner length are 5m, equipped with a diameter of 400mm and the gaseous products intake pipeline of long 5m) unit with Mixed plastic waste after consumption of the 2500kg/h chargings with consisting of：

Mixed plastic waste pre-processes under 250 DEG C and atmospheric pressure so as to plastic molten melt and remove most of sky first Gas and water, food waste and foreign solid are as effluent.This effluent also contains point by any component of feed material Solve the gaseous products produced.By the heat being made of fine sand of pretreated material and the 4000kg/h supplied at 700 DEG C The nitrogen of carrier and the 560kg/h at 25 DEG C introduce the double-walled going barrel operated at 465 DEG C under 355 millibars of absolute pressures In formula stove.Estimate that the gas reserved in stove is 6m³, and condensation phase reserved is 1.7m³.Equaling or exceeding 370 DEG C At a temperature of make-up gas reserved be estimated as 0.3m³.Estimate that in the total gas couette that the exit of stove produces be 29kmol/h, it is right Should be in 2463kg/h.

Gaseous products in gas phase are 4.9s at 370 DEG C or more than the residence Time Calculation at 370 DEG C.Following table 7 is given The flow calculated, and the numbering with Fig. 2 are gone out.

The thermic load (preheating for including nitrogen) of estimation reaction is 585kW, (right for 261kW by the heat of heat carrier supply Should in coke burn obtained by heat 50%), and by double-walled supply heat for 324kW (correspond to gas burning can The heat of acquisition 53%).Estimate that available heating surface is 20m in stove², estimation overall heat-transfer coefficient is 80W/m²K, and use The logarithmic difference of temperature between the hot gas and reaction medium of heating furnace reaches 205 DEG C.

Residence time of the condensed material in stove is estimated as 132min.Specific thinner ratio D/P is calculated as 6.3mol/mol/ Bar.Plastic content (including additive) based on mixed plastic waste, the gross production rate of wax are calculated as 59%.Wax is mainly straight chain 's.

Example 6：Mass balance according to the present invention

To at a temperature of more than 370 DEG C, equipped with double-walled rotary drum type stove, (internal diameter of the double-walled rotary drum type stove is 1.4m and inner length are 5m, equipped with a diameter of 400mm and the gaseous products intake pipeline of long 5m) unit with Mixed plastic waste after consumption of the 1200kg/h chargings with consisting of：

Mixed plastic waste pre-processes under 250 DEG C and atmospheric pressure so as to plastic molten melt and remove most of sky first Gas and water, food waste and foreign solid are as effluent.This effluent also contains point by any component of feed material Solve the gaseous products produced.By the nitrogen of pretreated material and the 224kg/h at 25 DEG C introduce at 465 DEG C In the double-walled rotary drum type stove operated under 120 millibars of absolute pressures.Estimate that the gas reserved in stove is 7m³, and condense rank Section reserved is 0.6m³.Make-up gas reserved is estimated as 0.3m at a temperature of equaling or exceeding 370 DEG C³.Estimation is in stove The total gas couette that exit produces is 12.3kmol/h, corresponding to 1137kg/h.

Gaseous products in gas phase are 4.6s at 370 DEG C or more than the residence Time Calculation at 370 DEG C.Following table 8 is given The flow calculated, and the numbering with Fig. 2 are gone out.

The thermic load (preheating for including nitrogen) of estimation reaction is 275kW, and is 275kW by the heat that double-walled is supplied (corresponding to heat obtained by gas burning).Estimate that available heating surface is 20m in stove², estimate that overall heat-transfer coefficient is 80W/m²K, and reach 174 DEG C for the logarithmic difference of the temperature between the hot gas and reaction medium of heating furnace.

Residence time of the condensed material in stove is estimated as 161min.Specific thinner ratio D/P is calculated as 15.4mol/mol/ Bar.Plastic content (including additive) based on mixed plastic waste, the gross production rate of wax are calculated as 59%.Wax is mainly straight chain 's.

Reference example 1：The mass balance of situation outside the present invention

To at a temperature of more than 370 DEG C, equipped with double-walled rotary drum type stove, (internal diameter of the double-walled rotary drum type stove is 1.4m and inner length are 8m, equipped with a diameter of 400mm and the gaseous products intake pipeline of long 2m) unit with Mixed plastic waste after consumption of the 2500kg/h chargings with consisting of：

Mixed plastic waste pre-processes under 250 DEG C and atmospheric pressure so as to plastic molten melt and remove most of sky first Gas and water, food waste and foreign solid are as effluent.This effluent also contains point by any component of feed material Solve the gaseous products produced.Pretreated material is introduced to the double-walled operated at 450 DEG C under 1320 millibars of absolute pressures In rotary drum type stove.Estimate that the gas reserved in stove is 11.1m³, and condensation phase reserved is 1.2m³.It is being equal to or is surpassing Make-up gas reserved is estimated as 0.3m at a temperature of crossing 370 DEG C³.Estimate that the total gas couette in the generation of the exit of stove is 15.1kmol/h, corresponding to 1902kg/h.

Gaseous products in gas phase are 64.9s at 370 DEG C or more than the residence Time Calculation at 370 DEG C.Following table 9 is given The flow calculated, and the numbering with Fig. 1 are gone out.

The thermic load of estimation reaction is 668kW, and for 668kW, (corresponding to gas burning can by the heat of double-walled supply The heat of acquisition 43%).Estimate that available heating surface is 32m in stove², estimation overall heat-transfer coefficient is 80W/m²K, and use The logarithmic difference of temperature between the hot gas and reaction medium of heating furnace reaches 263 DEG C.

Residence time of the condensed material in stove is estimated as 300min.Based on mixed plastic waste plastic content (including Additive), the gross production rate of wax is calculated as 24%.Wax is mainly straight chain.

Reference example 2：The mass balance of situation outside the present invention

To at a temperature of more than 370 DEG C, equipped with double-walled rotary drum type stove, (internal diameter of the double-walled rotary drum type stove is 1.4m and inner length are 8m, equipped with a diameter of 400mm and the gaseous products intake pipeline of long 2m) unit with Mixed plastic waste after consumption of the 2500kg/h chargings with consisting of：

Mixed plastic waste pre-processes under 250 DEG C and atmospheric pressure so as to plastic molten melt and remove most of sky first Gas and water, food waste and foreign solid are as effluent.This effluent also contains point by any component of feed material Solve the gaseous products produced.By the nitrogen of pretreated material and the 28kg/h at 25 DEG C introduce at 450 DEG C In the double-walled rotary drum type stove operated under 1400 millibars of absolute pressures.Estimate that the gas reserved in stove is 11.1m³, and it is cold Solidifying stage reserved is 1.2m³.Make-up gas reserved is estimated as 0.3m at a temperature of equaling or exceeding 370 DEG C³.Estimation exists The total gas couette that the exit of stove produces is 16.1kmol/h, corresponding to 1929kg/h.

Gaseous products in gas phase are 64.6s at 370 DEG C or more than the residence Time Calculation at 370 DEG C.Following table 10 Give the flow of calculating, and the numbering with Fig. 2.

The thermic load of estimation reaction is 670kW, and for 670kW, (corresponding to gas burning can by the heat of double-walled supply The heat of acquisition 43%).Estimate that available heating surface is 32m in stove², estimation overall heat-transfer coefficient is 80W/m²K, and use The logarithmic difference of temperature between the hot gas and reaction medium of heating furnace reaches 265 DEG C.

Residence time of the condensed material in stove is estimated as 300min.Specific thinner ratio D/P is calculated as 0.05mol/mol/ Bar.Plastic content (including additive) based on mixed plastic waste, the gross production rate of wax are calculated as 24%.Wax is mainly straight chain 's.

The wax for the type that the method according to the invention obtains is particularly useful as bituminous coating composition and more generally Based on the additive in following coating composition：(i) mineral aggregates and (ii) organic bond (are derived from oil (pitch Or the mixture of synthetic polymer resin and oil) and/or plant (adhesive for being based particularly on resin and vegetable oil)).This hair Bright wax based on pure or modified pitch (especially by addition polymer) asphalt mixture and bituminous concrete in, and It is particularly useful in the coating based on (such as type of synthetic polymer and/or propolis) other organic bonds 's.

In a first aspect, when in for the coating based on mineral aggregates and organic bond, wax according to the present invention Available for the use for promoting adhesive and/or the mixture of adhesive and aggregation；And/or for optimizing the coating of aggregation, And particularly under heat：The presence of wax according to the present invention tends to reduction composition and flows the residing temperature of use enough (typically reducing by tens degrees Celsius), in terms of this is especially embodied in the method cost of reduction.

According on the other hand, some applications for type illustrated below with previously compatible and be complementary to, according to The wax of the present invention can be used in the coating based on mineral aggregates and organic bond to increase coating in its cooling period Setting rate.Wax according to the present invention does tend to have than organic bond (such as above-mentioned pitch or clear binder) more High " solidification " speed.

Therefore, by way of illustration and not by way of limitation, the wax of the present invention is at least being advantageously used in applying below：

- (obtained in so-called " heat " asphalt mixture by using pitch (pure or modification) coated aggregate of heating) In：For the application, wax is advantageously mixed with pitch before the coating of aggregation, thus pitch can be than there is no wax When much lower temperature under (compared to there is no 200 DEG C during resin, more precisely, 150 DEG C -200 DEG C, typically about 110 At a temperature of DEG C -140 DEG C) mixed with aggregation.

- in surface wearable coating (wherein typically mixing wax with pitch), the flux additives of vegetable oil type (for example, especially as described in EP 1845134).This fluxing agent adhesive is intended to spray on road surface, then aggregation meeting It is deposited on road surface.In this context, the presence of wax not only allows for reducing temperature when spraying, and it is heavy at it to increase pitch Cohesive force increase (solidification) speed after product, and despite the presence of fluxing agent when is also such.

- pitch paying (composition of i.e. above-mentioned asphalt mixture type, but with higher bitumen content (typically For the gross weight based on mixture by weight at least 10%, to impinge upon in conventional pitch mixture for by weight 4.5% to 5.5%) in)：Typically wax is mixed with bituminous cement, thus in the case of there is no wax, with more than 200 DEG C (typical cases About 250 DEG C of ground) temperature compare, pitch can mix at a temperature of about 160 DEG C to 190 DEG C with aggregation.Wax also assigns solid Change characteristic.

- in the asphalt mixture based on " clear binder " (also referred to as " composite adhesives "), i.e., based on transparent type Adhesive (adhesive is based on synthetic polymer and/or resin and oily (petroleum resources and/or plant origin), is mixed with pitch Compound is opposite, it is allowed to which the aggregation that they are included is distinguished：The presence of wax in these adhesives allows to reduce system again Make and temperature during depositing coating.

- in the seal coating comprising the pitch with mixed with polymers, especially for roof：The presence of wax is also permitted herein Perhaps temperature during manufacture coating is reduced.It also allows the solidification for accelerating coating after deposition, this deposition in inclined roof The feelings of thing (if the composition of deposition does not harden fast enough, the composition deposited tends to flow in inclined roof) It is particularly apparent under condition.

In addition, the wax of the present invention can be used for the rheological behavior for improving adhesive, and it is more specifically for increase rigidity Modulus.In this context, in addition wax of the invention can provide lubrication property.

On the other hand, at least in some cases, presence of the wax according to the present invention in bituminous coating is tended to improve Coating by hydrocarbon when being dissolved to brittle resistance.Find in this context wax according to the present invention be particularly suitable as being intended to Additive in gasoline or the bituminous coating (such as bituminous coating for gas station) of kerosene contact.

Claims (33)

1. a kind of be used to pass through method of the cracking by converting-plastics into wax, this method includes：

Introduce the plastic into reactor；

At least a portion plastics are allowed to be converted into wax, these waxes are a parts for the pyrolysis gas formed in the reactor； And

The product stream containing the wax is removed from the reactor；

It is characterized in that the pyrolysis gas has the residence time less than 60 seconds at a temperature of more than 370 DEG C.

2. according to the method described in claim 1, wherein the pyrolysis gas at a temperature of more than 370 DEG C have less than 50 seconds, Preferably smaller than 40 seconds, more preferably less than 30 seconds, even more preferably less than 25 seconds, be, for example, less than residence time of 20 seconds.

3. method according to claim 1 or 2, the temperature that wherein at least a part of plastics are converted into residing for wax is at least 370 DEG C, preferably at least 400 DEG C, more preferably at least 425 DEG C, even more desirably at least 440 DEG C, for example, 400 DEG C to 650 DEG C, it is excellent Select in the range of 425 DEG C to 550 DEG C, more preferably 440 DEG C to 520 DEG C.

4. according to any method of the preceding claims, the wherein reactor is excellent less than or equal to 1200 millibars Choosing is less than or equal to 1000 millibars, more preferably lower than or equal to 950 millibars, even more preferably less than or equal to 900 millibars, such as At 0.5 to 1200 millibar, preferably 10 to 1100 millibars, more preferably 60 to 950 millibars and even more preferably 80 to 900 millibars In the range of pressure under operate.

5. according to any method of the preceding claims, wherein the pyrolysis gas is with dilution agent is diluted, wherein this is dilute Release agent and be preferably selected from nitrogen, hydrogen, steam, carbon dioxide, burning gases, appropriate hydrocarbon gas and its mixture.

6. according to the method described in claim 5, wherein the molar ratio of diluent and thermal decomposition product is more than in the pyrolysis gas 0.5, preferably greater than 0.7, more preferably greater than 0.8, even more preferably greater than 1, for example, 0.5 to 50, preferably 0.7 to 40, it is more excellent Select in the range of 1 to 20.

7. according to any method of the preceding claims, wherein at least a part of plastics, which are converted into wax, is carried in heat Carried out in the presence of body.

8. according to the method described in claim 7, wherein the heat carrier includes particle, preferably free flowing granule.

9. the method according to claim 7 or 8, the wherein heat carrier be selected from sand (such as silica), stone, gravel, Metal, metal oxide, glass, ceramics and its mixture, preferably sand or steel.

10. the method according to any one of claim 7 to 9, the wherein heat carrier are the catalysis of the cracking for plastics Agent.

11. the method according to any one of claim 7 to 10, the wherein heat carrier are not intended to the cracking in vapour phase of hydrocarbon Catalyst.

12. according to any method of the preceding claims, wherein during the stop of condensed material in the reactor Between be between 10 and 600min, preferably between 20 and 400min, more preferably between 30 and 250min.

13. according to any method of the preceding claims, this method is carried out continuously.

14. according to any method of the preceding claims, wherein the plastics are waste plastics, preferably mixed waste plastic.

15. according to the method for claim 14, wherein the waste plastics is selected from post-consumer plastic waste, substandard plastics and work Industry waste plastics.

16. a kind of hydrocarbon mixture, it is characterised in that these hydrocarbon show its carbon number purpose cumulative distribution so that 20≤d20 And 50 >=d50；

The hydrocarbon of >=50mol% is straight-chain hydrocarbons；

And the molar ratio of normal paraffin hydrocarbons and alpha-olefin is in the range of 0.1 to 10 in these hydrocarbon.

17. mixture according to claim 16, wherein these hydrocarbon show its carbon number purpose cumulative distribution so that 22≤d20, preferably 25≤d20.

18. the mixture according to claim 16 or 17, wherein these hydrocarbon show its carbon number purpose cumulative distribution, So that d20≤40, preferably d20≤35, more preferably d20≤30.

19. the mixture according to any one of claim 16 to 18, wherein these hydrocarbon show its carbon number purpose Cumulative distribution so that 20≤d20≤40, preferably 22≤d20≤35, more preferably 25≤d20≤30.

20. the mixture according to any one of claim 16 to 19, wherein these hydrocarbon show its carbon number purpose Cumulative distribution so that 45 >=d50, preferably 40 >=d50.

21. the mixture according to any one of claim 16 to 20, wherein these hydrocarbon show its carbon number purpose Cumulative distribution so that 50 >=d50 >=20, preferably 40 >=d50 >=22.

22. normal paraffin hydrocarbons and alpha-olefin in the mixture according to any one of claim 16 to 21, wherein these hydrocarbon Molar ratio is in the range of 0.2 to 5, preferably in the range of 0.5 to 2.

23. the mixture according to any one of claim 16 to 22, wherein this of >=60mol%, preferably >=70mol% A little hydrocarbon are straight-chain hydrocarbons.

24. the mixture according to any one of claim 16 to 23, wherein>40mol%, preferably>It is 45mol%, more excellent Choosing>The unsaturated hydrocarbons of 50mol% is alpha-olefin.

25. the mixture according to any one of claim 16 to 24, which has >=10, preferably >=25, it is more excellent The iodine number of choosing >=40.

26. the mixture according to any one of claim 16 to 25, which has in the range of 10 to 150, It is preferred that the iodine number in the range of 25 to 100, more preferably in the range of 40 to 70.

27. the mixture according to any one of claim 16 to 26, which has>25 DEG C, preferably>40 DEG C, more It is preferred that>50 DEG C of dropping point.

28. at least a portion of the mixture according to any one of claim 16 to 27, wherein these hydrocarbon contains one Or multiple hetero atoms.

29. a kind of wax, which is as obtained by the method according to any one of claim 1 to 15.

30. wax according to claim 29, which is the mixture according to any one of claim 16 to 28.

31. a kind of asphalt mixture, surface wearable coating, pitch or seal coating, the asphalt mixture, surface wearable coating, Pitch or seal coating include the mixture according to any one of claim 16 to 28.

32. a kind of be used to produce the mixture according to any one of claim 16 to 28 by making plastics carry out cracking Method, this method includes：

Introduce the plastic into reactor；

At least a portion plastics are allowed to be converted into wax, at least a portion of these waxes is the pyrolysis gas formed in the reactor A part for body；And

The product stream containing the wax is removed from the reactor to obtain the mixture, the wax is the shape in the reactor Into pyrolysis gas a part；

It is characterized in that the pyrolysis gas has the residence time less than 60 seconds at a temperature of more than 370 DEG C.

33. according to the method for claim 32, this method is the method according to any one of claim 1 to 15.