CN104974779A - Pyrolysis process and apparatus used for generating more amounts of aromatic compounds - Google Patents

Abstract

The invention provides a plurality of embodiments for a process of thermally decomposing hydrocarbons. In one of the embodiments, the process for thermally decomposing the hydrocarbons comprises the following steps: inputting raw materials containing hydrocarbons into a reactor; heating the raw materials; and collecting liquid phase products from an anaerobic reactor, wherein at least 5% of organic carbon atoms originally absent in the aromatic rings of the raw material compounds appear in the aromatic rings of the compounds of the liquid phase part of the products.

Description

For generation of pyrolytic process and the device of more aromatic substance

The divisional application of the application for a patent for invention that the application to be Chinese Patent Application No. be 200480044584.7 (PCT/US2004/033796) submitted to October 13 2004 (world) applying date.The denomination of invention of original application is " pyrolytic process and device for generation of more aromatic substance ".

Background technology

As everyone knows, pyrolytic process heats shred waste of polymeric exactly, and such as thermoplastic material, tire etc. are to produce the product of such as liquid oils, gas and carbon black.But when the productive rate of benzene-toluene-xylene recovery is very low, such as, the cost that Product recycling spends is higher than this product when directly obtaining spent cost from oil, this technique is difficult to obtain business success.

English Patent UK1481352 discloses a kind of hydro carbons thermolysis process, and it is with high-temperature gas indirect contact hydro carbons at least in part.The gaseous product that this gas produces relative to thermolysis after heat exchange completes is discharged separately.Tire is then undertaken heating by the high-temperature gas flowed between pipe in pipe.In another embodiment, in pipe, there is grid region, combustion gases to be passed in this region thus to help carbonization by the direct heating of grid carbon interface gas.Steam or CO2 can be passed in grid to form water-gas or to reduce gas to help burning.

No. 7302 report of survey of U.S. Bureau discloses a kind of destructive distillating method of tire debris.This report makes after the test of a series of condition.Wherein produce, reclaim and analyze solid, liquids and gases.This report shows, different product number depend on probe temperature, wherein also report that the component in liquids and gases products also can change because of temperature variation.

The US Patent No. 4746406 of Timmann discloses the technique of the pyrolysis reprocessing of a kind of plastics, rubber or other hydrocarbons, and wherein produced pyrolysis gas is just higher than the freezing point of water and pressure is about the cooling stages that 0.8-1.4 clings to (bar) malleation obtains in temperature.Then formed condensate separation is heated normal storing temp, and the high pressure of condensation product is reduced to normal pressure.Thus, the gas including C1-C4 hydrocarbon compound produced just is fed in pyrolytic process as special product gas.The ratio wherein also disclosing aromatic substance in pyrolysis gas has substantial increase.

Although existing pyrolytic process can produce the product of recycling, the result productive rate of useful products makes these techniques not possess economic feasibility.When assigning to sieve raw material based on one-tenth, the cost of these techniques can be increased further.

Summary of the invention

Embodiments of the present invention provide the thermal decomposition process of hydrocarbons, containing more aromatic substance in the product liquid that this technique produces.In one embodiment, this hydrocarbons pyrolytic process comprises: be input in reactor by the raw material comprising hydro carbons, heats this raw material, collects the product from oxygen free operation reactor.Have at least the organic carbon atoms of 5% to be present on the aromatic ring of the compound of product liquid phase part, organic carbon atoms wherein was not originally present on the aromatic ring of raw material.

In another embodiment, being used for the technique of pyrolyzing hydrocarbonaceous material comprises: the raw material including carbonaceous material is input to volume and is at least in the reactor of 1.7 cubic metres, with about 7 × 10 ^-4kW.m ²/ kg ²to about 3.0kW.m ²/ kg ²initial rate of heat flow heats described raw material, collects the product of oxygen free operation reactor.

An embodiment of the invention additionally provide a kind of reaction unit for pyrolyzing hydrocarbonaceous material, this reaction unit comprises: a upper area, this region comprises a upper inside wall conduit tilted and an external wall of upper portion conduit, upper inside wall conduit wherein has the material inlet on a top and the material outlet of a bottom, external wall of upper portion conduit wherein has the pneumatic outlet on a top and the gas inlet of a bottom, and this external wall of upper portion conduit is round this intrawall conduits, between this intrawall conduits and this outer walled vessel, so just sandwich formation gas transfer space, a lower region, this region comprises a lower inner wall vessel tilted and a lower outer walled vessel, wherein lower inner wall vessel has a top material inlet and a bottom material outlet be connected with the bottom material outlet of upper inside wall conduit, lower outer walled vessel wherein has a upper gas and exports and the lower gas entrance being connected to external wall of upper portion conduit, this lower outer walled vessel is round this lower inner wall vessel simultaneously, thus between described intrawall conduits and described outer walled vessel, sandwich out a gas transfer space, and the well heater be arranged in lower region.This reactor assembly can comprise by multiple unit be made up of above-mentioned upper and lower unit, and it becomes reactor with stacked or stepped arrangement.Well heater alternately can be arranged in the reactor, such as, can separately add a well heater at one or more middle repeating unit place.

Accompanying drawing explanation

Embodiments of the invention can be understood with reference to following accompanying drawing.In figure, parts not draw in proportion.

Fig. 1 is the schematic diagram of the Multistage continuous reactor assembly according to one embodiment of the present invention.

Detailed Description Of The Invention

Embodiment of the present invention comprises technique for hydrocarbons in pyrolysis waste material and system, this hydrocarbons can be such as thermoplastic polymer, thermosetting polymer and composition thereof, this hydrocarbons can be converted into the useful products that can produce more polyaromatic compound thus.

In one embodiment, have a kind of technique being used for pyrolyzing hydrocarbonaceous material, it comprises and is input in reactor by the raw material comprising hydro carbons, heats this raw material, collects the product of oxygen free operation reactor.Here, term " anaerobic " refers to, at initial heating phase, based on the internal volume of reactor, containing the oxygen lower than 3% volume in reactor, be the oxygen lower than 2% volume in an alternate embodiment, be the oxygen lower than 1% volume in another alternate embodiment, in another alternate embodiment, for about 0.01% volume is to the oxygen of about 1% volume.This technique makes original organic carbon atoms be not present on starting compound aromatic ring of at least 5% appear on the aromatic ring of product liquid phase part compound, in an alternate embodiment, percentage ratio is wherein about 10%--90%, be about 15%-about 70% in another alternate embodiment, be about 20%-about 60% in another alternate embodiment.Term " aromatic ring " should be readily understood by the ordinarily skilled the ring that six carbon atom bonding is formed, and the carbon atom on aromatic ring does not comprise and is bonded in the chain sling on aromatic ring and the carbon atom on functional group.That is the quantity of aromatic ring is greater than the quantity of aromatic ring in raw material in product.Pyrolytic process in each embodiment described here shows: any mixing raw material containing hydro carbons all can produce new aromatic ring.

Those inversion quantities of organic carbon atoms that originally organic carbon atoms be not present on raw material aromatic ring changed on product liquid phase part compound aromatic ring depend on the quantity not being present in the organic carbon atoms on aromatic ring in raw material.Such as, if the organic carbon atoms contained by raw material has 80% not to be present on aromatic ring, so pyrolytic process at least can by wherein 4% carbon atom be converted into carbon atom in product on liquid phase part compound aromatic ring.In another embodiment, if the organic carbon atoms in raw material has 35% not to be present on aromatic ring, so pyrolytic process at least can by wherein 1.75% carbon atom be converted into carbon atom in product on liquid phase part compound aromatic ring.Carbon atom 13NMR known in the art can be utilized to test and to measure organic carbon atoms quantity that is on aromatic ring and that be not present on aromatic ring.In above-mentioned different embodiments, have at least the organic carbon atoms of 20% not to be present on the aromatic ring of raw material in raw material, it is at least 40% in certain embodiments, and in further embodiments, it is at least 50%.That is at least the bonding pattern of the organic carbon atoms of half is different from aromatic ring bonding arrangement in raw material.Can comprise arbitrary chips mixture in raw material, this mixture comprises at least about 70% weight, or at least about 80%, or at least about 90% hydrocarbons, wherein this hydrocarbons comprises at least two kinds of different components.In another embodiment, this raw material can also comprise the metal up to about 25% weight.This metal can be used to the thermal conductivity increasing whole thermal decomposition material, and it can increase rate of heating thus reduce the time needed for complete pyrolysis.

Hydrocarbons can comprise thermoplastic polymer, such as, polyethylene, polypropylene, polyester, acrylonitrile-butadiene-styrene (ABS) (ABS) multipolymer, polyamine, urethane, polyethers, PC, poly-(oxide compound), poly-(sulfide), poly-arylide, polyetherketone, polyethers ammonia, polysulfones, polyurethanes, the polymkeric substance that polyvinyl alcohol and monomer polymerization produce, this monomer is such as diene, alkene, vinylbenzene, CALCIUM ACRYLATE, vinyl cyanide, methacrylate, methacrylonitrile, diacid and glycols, lactone, diacid and diamines, lactan, vinyl halide, vinyl ester, and its segmented copolymer and its alloy type.Such as, polyvinyl chloride, tetrafluoroethylene and its halogenated copolymers can produce halogenide in pyrolysis, and it has corrodibility but can stand.

Hydrocarbons can also comprise thermosetting polymer, such as, and epoxy resin; Phenolic resin; Melamine resin; Synolac; Vinyl ester resin; Unsaturated polyester resin; Cross-linked polyurethane; Poly-chlorinated isocyanurates; Cross-linked elastomer, includes but not limited to, poly-rubber matrix, polyhutadiene, styrene butadiene, styrene-isoprene, Ethylene-Propylene-Diene monomer-polymer; With its mixture.

The hydrocarbons of shred can be the mixture of thermoplasticity and thermoset copolymer, such as, be tire, coating, tackiness agent, automatic cutting machine waste material (fluffing) etc., these can be used as the raw material in the different embodiment of thermal decomposition process described here.Other hydrocarbons utilizable comprise coal, shale oil and pitch.Also a small amount of carbon hydroxide may be there is in hydrocarbon material; But as preferably, these are not as the major portion of main hydrocarbons.Usually, carbon and hydrogen atom at least account for 55% of hydrocarbons gross weight, and in some cases, at least 65% weight, as alternative, at least accounts for 70% of the hydrocarbons gross weight in the raw material of the process of entering.

The amount adding the raw material of reactor is usually very large.Such as, in one embodiment, charging is about 25 to 635 kilograms per cubic meter [being about 100 to 2500 pounds every 64 cubic feet], in another embodiment, be about 50 to 500 kilograms per cubic meter [being about 100 to 2000 pounds every 64 cubic feet], about from 75 to about 375 kilograms per cubic meter [about 300 to about 1500 pounds every 64 cubic feet] in the selectable embodiment of another kind.In the technique stirred raw material, such as, when the diameter of reactor size is about 2.44 meters [8 feet], the raw material of reactor unit volume can be more.The raw material adding this reactor can from about 50 to about 750 kilograms per cubic meter [about 200 to about 3000 pounds every 64 cubic feet], alternatively from about 50 to about 625 kilograms per cubic meter [about 200 to about 2500 pounds every 64 cubic feet], also alternatively from about 75 to about 500 kilograms per cubic meter [from about 300 to about 2000 pounds every 64 cubic feet].Usually, the optimum quantity adding the raw material of reactor becomes according to the kind of added material and stirring, and these are all relevant with the heating rate of feeding in raw material.

The internal volume of reactor can be greater than 0.0283 cubic metre [1 cubic feet], in an alternate embodiment, internal volume from about 0.0850 cubic metre [3 cubic feet] to about 84.95 cubic metres [3000 cubic feet], in another alternate embodiment, internal volume from about 0.2265 cubic metre [8 cubic feet] to about 56.63 cubic metres [2000 cubic feet].If wherein have employed agitator in certain, so this internal volume should arrive greatly about 0.0850 cubic metre to about 113.27 cubic metres [from 3 cubic feet to about 4000 cubic feet] usually, and it is often [10 to about 2500 cubic feet] from about 0.2832 cubic metre to about 70.79 cubic metres.Although can use larger size, due to the problem etc. of manufacturing cost, engineering factor and heat transfer, it is also unrealistic.Certainly, the structure of stir speed (S.S.) and stirrer is all the factor affecting reactor optimum design.In general, stir light and slowly and thermolysis bed can be made to produce less disorder, this can reduce carbon granule and/or other fluid bed granulate are entrained to pyrolysis gas and the probability in the phlegma obtained.

Although reactor shape can change, reactor preferably has larger loading table area ratio, such as cubes, rectangular parallelepiped and spherical reactor.In another embodiment, reactor is ellipsoid of revolution or tubulose.Because hot-fluid and temperature are all very high, therefore reactor is usually by the material that fusing point is very high, such as steel, stainless steel or superalloy, and such as inconel (Inconel) is made.

The Heating temperature from about 426 DEG C [800 °F] to about 1371 DEG C [2500 °F] of reactor, in an alternate embodiment, from about 649 DEG C [1200 °F] to about 1260 DEG C [2300 °F], in another alternate embodiment, be then from about 815 DEG C [1500 °F] to about 1093 DEG C [2000 °F].Thermal source can be the thermal source that can produce above-mentioned high temperature that any one is traditional, and it such as comprises, Sweet natural gas, electric heating, coke etc.Heating rate is such as constant, variable, or interval.

Have been found that the product to a large amount of raw materials adopts the heating rate of low input to produce includes alkylated aromatic hydrocarbons, this alkylated aromatic hydrocarbons is the raw material needed in many commercial applications.The hot input rate of unit mass raw material is from about 0.232MJ/kg/hr[100BTU/lb/hr] to about 116.2MJ/kg/hr[50000BTU/lb/hr], in another embodiment, for about 11.62MJ/kg/hr[5000BTU/lb/hr] or lower, in another embodiment, be about 4.65MJ/kg/hr[2000BTU/lb/hr] or lower, in another alternate embodiment, be about 1.16MJ/kg/hr[500BTU/lb/hr] or lower.Have now found that, along with the speed of low_input_power falls in the formation of thermolysis material or the formation of " pyrolysis fluidized-bed ", more a high proportion of product up to now can be produced.But if the heating rate used is too low, what economic worth is this process may not have because the time of thoroughly pyrolysis exceeded the actual limit that can bear.

During initial heating, reactor heating surface carries the average area of raw material from about 9.0kg/m ²to about 400kg/m ², in an alternate embodiment, this scope is then from about 20kg/m ²to about 375kg/m ², in another embodiment, this scope is then from about 30kg/m ²to about 250kg/m ².The degree of depth of fluidized-bed, or along the raw thickness of reactor heating surface, can be determined by the average area carrying raw material in load-reaction device.The average area of carrying raw material will consider the change of fluidized bed deep with reactor geometrical dimension.

In embodiment described above, reactor has enough degree of depth could form char layer in pyrolytic process, and on raw material, have enough headspaces thus product can be spun off with airflow pattern, at least part of condensation becomes the liquid portion of product.The internal volume of reactor is consumed (reactor internal volume=raw material volume+clearance volume+headspace) by " headspace " on the clearance volume between raw material volume, feed particles and top container or raw material.Larger headspace can provide suitable surge space, and reduces the risk that product blocks in systems in which." freeboard " refer to clearance volume and headspace and (freeboard=clearance volume+headspace).This freeboard is along with the continuation of thermal decomposition process, and the continuous consumption of raw material generates product and increases.When initial heating, clearance volume and can be disintegrated and reduce because of the fusing of raw material in heat-processed under normal circumstances.Such as, if the raw material loaded is whole tire, it likely can disintegrate thus greatly increase headspace in heat-processed, can also reduce clearance volume simultaneously.Reactor at least has the free volume of 25% when initial heating, in certain embodiments, at least have the free volume of 40% during heating, and in other alternative, heating then at least has the free volume of 50%.

This clearance volume can be depending on the particle size of raw material.If raw material is the particle of bulk, as broken tire etc., bulk, spherical or pellet form can be chopped into.Its advantage is applicable to flow reactor feed.The bulk material forming thermolysis bed also has advantage, in some cases as the clearance volume in this block stock can form thermal conduction in thermolysis load.The thermoplastic portions of melting in load and the spilling steam of high temperature can improve the heat transfer of block material, though the contact area of these block material and reactor heating surface less be also like this.But generally, if feedstock Particle size is reduced to about less than 5 millimeters, so it is not worth technological process.

Heating rate can by formally providing effectively:

The time of heating rate effectively=[(BTU/hr/lbs)]/thermolysis completely

Such as, the time thermolysis of X is needed with the thermoplastic material of given speed heating 1000lbs.The thermoset raw material so adopting identical conditions to heat 1000lbs in same reactor then needs the time thermolysis longer than the X time.The range test of example 9 shows that thermally conductive material (i.e. metal wire)+thermosetting material can at the time pyrolyze of similar X below.The time of complete thermolysis reduce to some extent be because good thermal conductor as bead tire metal silk the raising of heating rate that brings.

The time of complete thermolysis terminates to the basic pyrolysis completely of condensability pyrolysis product from the change of pyrolysis product.Terminal is infeasible based on not condensability.These are all relative control accuracy or standard.Although in theory and imperfect, this precision and other similar precision still can provide a practicable standard of comparison.

Thermal decomposition process also can be alternative the form of hot-fluid describe.Therefore, in one embodiment, the initial heat flux of the unit surface load raw material of this heating raw materials is about less than 3.0kW.m ²/ kg ²just, in another alternative embodiment, be then approximately from 7 × 10 ^-4kW.m ²/ kg ²to 3.0kW.m ²/ kg ², in another alternative embodiment, be then approximately from 0.001kW.m ²/ kg ²to 1.5kW.m ²/ kg ², remaining in another alternative embodiment, is then approximately from 0.005kW.m ²/ kg ²to 0.5kW.m ²/ kg ².

Above-mentioned thermal decomposition process can carry out at ambient pressure or under low pressure, such as approximately be less than 550kPa [about 80psig], be then approximately be less than 350kPa [about 50psig] in another alternative embodiment, remaining is then approximately be less than 100kPa [about 14.7psig] in another alternative embodiment.This pressure is generated in inside by gas, and it can carrying out and change with pyrolysis.

Time of complete thermolysis decomposes end substantially completely to condensability pyrolysis products from the change of pyrolysis products.Just represent when condition below occurs and reached complete thermolysis: the hurried decline of amount of the liquid product produced, and vapour temperature conforms to substantive temperature drop usually, temperature drop is wherein such as the temperature drop of within the time of 10 to 15 minutes at least 56 DEG C [100 °F], and heating rate keeps constant simultaneously.In the above-described embodiment, complete thermolysis reaches after being after eight hours or less time, in another embodiment, be approximately 3 hours or less, be then from 15 minutes to about 2 hours in another embodiment, and be from about 30 minutes to about 1.5 hours in another embodiment.When complete thermolysis, gather organic carbon atoms number in the liquid phase part of product in aromatic nucleus at least than the number about many 5% of organic carbon atoms in raw material aromatic nucleus.

In another embodiment of thermal decomposition process, reactor does not have catalyzer.But raw material can find the catalyzer of deposition, as found in thermoplastic polymer, thermosetting polymer and their mixture.

In each embodiment of above-mentioned thermolysis, in reactor, do not add carrier gas and diluent gas.In reactor is by the purge before heating, also can to add carrier gas as helium, argon gas, nitrogen, carbonic acid gas etc. reduces to trace, such as, less than the oxygen of reactor volume 1% by the amount of oxygen.The carrier gas deposited in reactor can be thermal decomposited the product air-flow of releasing in process and discharge reactor.

In another embodiment, this thermal decomposition process comprises further: collect in reactor the air-flow produced, and this condensation is obtained the product of liquid phase part.Such as, this reactor can comprise one and discharge air-flow, and it has a condenser or other suitable equipment this condensation is become one liquid stream.Also can in the downstream of reactor other equipment integrated, as heat exchanger, plant and instrument, catalyticreactor, stripping rectifying tower etc.Such as, this air-flow can be cooled to 80 DEG C or lower thus be condensed, and in another alternative embodiment, this temperature can be low to 30 DEG C or lower.In addition, the compound produced by air-flow, such as, wherein also can be used as a thermal source containing one to the air-flow of four carbon atom and carry out reactor heating.

The pyrolytic process of above-described embodiment also can carry out in production version reactor or flow reactor.When pyrolytic process be carry out in flow reactor time, raw material transmits gradually along reaction bed, this transmission bed can be divided into multiple reaction member, wherein when raw material advances along reaction bed, each unit can be seen as independent entity, and each independent unit is all within foregoing reactor volume size.Such as, the internal volume of reactor can from 1.7 cubic metres to 113.27 cubic metres.

As preheating, predrying, recirculation etc., these not easily obtain the mode that maybe can not occur at production version reactor and all can be used in continous way process Ancillary heat transfer methods.Obviously, those skilled in the art know that the heat demand of flow reactor can change along with the change of section, namely the raw material loaded in original sections compared with back section needs to add more heat when being full load, because some raw material of the section at rear portion is thermal decomposited, therefore on reactor heating surface, the raw material average load of unit surface is existing reduced, and required heat is also less.Equally, in production version reactor, although can adopt constant heating rate, the hot-fluid being added to load also can improve along with the reduction of feed material area average load in the appearance of thermolysis and reactor heating surface.

Pyrolysis/char layer or bed can because the high warm in a certain surface of conduit thus make raw material be decomposed to produce various pyrolysis product and formed.The thickness of the pyrolysis bed formed in a certain specific pyrolysis reaction process can along with the kind of heating rate, charge capacity, support materials, pressure, whether stir isoparametric change and change.In general, the thickness of the char layer part of thermal decomposition material is approximately 10cm [about 4 inches] or less, and it also can be thicker certainly.

Have now found that, for given stable heating rate, the speed of pyrolysis, namely decomposing the speed producing gas products is not constant usually.Different pyrolysis rates and/or different types of product may be there is in pyrolysis vessel.For a given pyrolysis system, on its initial activation temperature, each stable output platform of throughput rate and product temperature can be seen.

In general, the present invention tends to produce more unsaturated organic compound compared to traditional pyrolytic process, as cycloalkanes and aromatic compound.Final product, no matter it is solid-state, liquid or gaseous state, all can be used for common routine application.Such as, Jiao produced in process is suitable for the fuel being used as boiler together with coal, and has the condensable liquids of quite a few to can be used as petrochemical material.

Fig. 1 schematically illustrates a set of reactor assembly, and it is used for realizing the pyrolytic process of one embodiment of the invention.Hopper 10 is used for polymer scrap being supplied an inclined belt conveyer 12, and particle is delivered in a worm conveyor 14 by the upper end of this travelling belt 12, and particle is again from being sent to one here with the rotatory drier 16 of flue gas exit pipe 18.Raw material is sent in a multistage double-walled conduit 22 by one spiral/air lock 20 again.Container 22 comprises a upper inside wall conduit 24 and an external wall of upper portion conduit 26.Vertical connecting tube 28 on one is had between upper inside wall conduit 24 and lower inner wall vessel 30.Wherein lower inner wall vessel 30 hold by the lower outer walled vessel 32, and have a lower vent pipe 34 from lower inner wall vessel through lower outer walled vessel extend to a horizontal circular pipes with air lock 36, coke 38 is discharged by this air lock 36.Pipeline 40 extends to heat exchanger 42 here from upper inside wall conduit 24 through external wall of upper portion conduit, and then extends to valve 44 and liquid pipe 46 to be deposited by product, and circulating gas pipe 48 extends to the valve 50 of lower outer walled vessel 32 here.Pipeline 52 passes external wall of upper portion conduit 26 from upper inside wall conduit 24 and extends to heat exchanger 54.Pipeline 56 passes lower outer walled vessel 32 from lower inner wall vessel 30 and extends to heat exchanger 58, pipeline 52 and 56 extends to valve 60 here from heat exchanger 54 and 58 respectively, circulation is changed to liquid line 62 by valve 60, and pipeline 62 extends to product storing device there.Circulating gas pipe 64 extends to valve 50 thus gas is injected to burner 51 here to returning, and this gas is guided in the space between lower outer walled vessel 32 and lower inner wall vessel 30 by burner 51.High-temperature gas after burning continues upwards to flow between upper inside wall conduit 24 and external wall of upper portion conduit 26, then flows through spiral of air lock 20 thus heats the raw material being downward through spiral of air lock 20.Then, high-temperature flue gas flows through 16 again and discharges here from 18, carries out preheating to the raw material of coming in.

The present invention can be understood better see example below.

Example

reactor and thermal source describe:

SCH40 type 304 stainless steel tube of reactor I to be long 60.96cm diameter be 5.08cm [24 inches long, and diameter is 2 inches], end cap is sealed up at its two ends.This reactor one propane burner heats, and wherein the flame temperature of propane burner is approximately 982 DEG C [1800 °F], and burner dimensions is approximately long 60.96cm diameter 5.08cm [24 inches long, and diameter is 2 inches].This reactor is made up of two pipeline sections, and these two pipeline sections are connected on a central T-shaped pipe, and one, the effective work of this T-shaped connects pyrolysis gas is delivered to condenser.Accommodate the raw material of 0.455kg [1 pound] in this reactor, and heated with the speed of 26.42kW/kg [41000BTU every pound is per hour].

SCH40 type 304 stainless steel tube of reactor II to be long 91.44cm diameter be 10.16cm [36 inches long, and diameter is 4 inches], its two ends with two 150# flanges, and cover 150# blind plate.The sidewall that a 5.08cm [2 inches] is long on the center weld of 10.16cm [4 inches] long tube, thus provide one to connect pyrolysis gas is delivered to condenser.Accommodate the raw material of 4.545kg [10 pounds] in this reactor, and heat with the speed that reactor I is identical, namely heating rate is 26.42kW/kg [41000BTU every pound raw material is per hour].

Reactor III is the stainless steel reactor of 1514 liters [400 gallons], and it has the hemispherical nose of a 1.22m [4 feet], and the diameter parts of this head is radius 1.22m [4 feet] thick 0.9525cm [3/8 inch].The housing of reactor is thick 0.635cm, long 1.22m, diameter 1.22m [1/4 inch, 4 feet long and diameter is 4 feet].This reactor propane thermal source heats with the speed of about 117.15kW [400000BTU is per hour], and temperature is approximately 982 DEG C [1800 °F].

By the conventional equipment of standard as heat exchanger (condenser), buffer tank and be used for the pressure-regulator of vented gasses and be connected to reactor thus extract product and gather.In pyrolytic process, the internal pressure of reactor is very low, it typically is 0 to 35kPa [0 to about 5psig].

All reactors all used CO before carrying out pyrolysis operations ₂be pressurized to about 100kPa [15psig] and then be discharged in air, purging three times so like this.

the pyrolysis of polyisoprene/polystyrene blends

The mixture of 50/50 (by weight) is below added in each reactor: polyisoprene be (Goodyear company rubber), it contains the Isosorbide-5-Nitrae-polyisoprene of the synthetic of 96+% (weight); And the polystyrene spheres of bussiness class.

The observed result summary of example 1-4

The induction time of pyrolysis and the time length of pyrolysis

¹pyrolysis terminate to be defined as in constant heating process steam after 10 minutes temperature drop be-56 DEG C [100 °F] or more and/or be the generation of liquid time when obviously declining.

Example 1

Reactor I loads the said mixture of 0.455kg [1lb].Total heat-up time to complete pyrolysis is 30 minutes.

Example 2

Reactor II loads the said mixture of 4.545kg [10lb].Total heat-up time to complete pyrolysis is 1 hour 55 minutes.

Example 3

Reactor III loads the said mixture of 45.45kg [100lb], and heating rate is 2.58kW/kg [4000BTU every pound raw material is per hour].Total heat-up time to complete pyrolysis is 2 hours.

Example 4

Reactor III loads the said mixture of 454.5kg [1000lb], and the heating rate of generation is 0.258kW/kg [400BTU every pound raw material is per hour].Complete pyrolysis is reached after about 6 hours 10 minutes.

Table I gives the compound in each liquid product that experiment produces.Experiment 1,2,3 is relative to each other along with control with 4, and pyrolysis and products thereof that what it was shown is is how along with the change of dimensional parameters and heating rate changes.The preparation process of the bright the application of scale of the aromatic compound produced is significantly improved compared to existing preparation process.Experiment 3 illustrates aromatic compound and generates peak value place or the processing condition near it.

As can be seen from Table I, there is multiple beyond thought increase or minimizing in the various compounds in liquid-phase product, and the amount of simultaneously total aromatic compound is also outside the enlightenment of prior art.Such as, the amount of toluene is approximately 4.1% to 7.6% (weight), phenethyl ester (ethyl benzene) is approximately 3.2% to 18.8%, the amount of (1-methyl ethylidene) benzene [α-methylstyrene] is approximately 3.8% to 7.7%, the amount that cinnamic amount is approximately 33.2% to 60.2%, 1-methyl-4-(1-methyl-vinyl)-cyclohexenyl [benzene alkene] is approximately 11.2% to 21.5%.Table I

The pyrolysis of polyisoprene-polystrene

Here a large amount of (l-methyl the ethylidene)-cyclopropane surprisingly produced, l-methyl-l, 3-cycloheptadiene, 1,5-dimethylcyclopentene, 2-methyl-l, 3-pentadiene, 1,2-dimethyl cyclohexane, and more uncommon is have 3,7,7-a large amount of trimethyl-bicyclo-[4.1.0]-hept-2-ene".In addition 3-methyl-2,4-hexadiene is also had, 2,3-dimethyl-l, 4-hexadiene, 2,3,6-trimethylammonium-l, 5-heptadiene and 3-methyl-l, 3,5-hexatriene (a kind of polyenoid (cumlene)); And have in all samples.These diene and triolefin are the precursors of many aromatic compounds.

Generally, each compound has all had obvious increase or minimizing here compared with existing method for pyrolysis.Different especially with prior art, the raw material of higher per-cent can be reclaimed with the form of the aromatic compound of liquid product.

Data in Table III-A obtain by mode below: the liquid of pyrolysis and coke are expressed as the weight of weight divided by raw material of salvage material in report.Gas as previously mentioned, is differ to calculate and next remainder more than material/material.

Table III-A

The pyrolysis of polyisoprene-polystrene

We can vinylbenzene in comparative example 1-4 relative to the cinnamic rate of recovery in raw material.If all polystyrene of raw material all convert the vinylbenzene in the liquid-phase product that pyrolysis reclaims to, so reclaimed cinnamic weight should equal the weight of polystyrene in raw material.For example 1, it is calculated as follows:

Weight percentage=91% (see Table III-A) of liquid-phase product

Cinnamic weight percentage=54.6% (see Table I) in liquid-phase product

Cinnamic weight percentage=91%X the 54.6%=49.686% reclaimed

Wish cinnamic weight percentage=50% reclaimed from the polystyrene of raw material

The data of example 1-4 provide in table iv.

Table IV

The vinylbenzene work output that polyisoprene-polystrene pyrolysis obtains

Vinylbenzene is as independent sample

More than the amount representing the amount charging that vinylbenzene obtains in example 3, this shows the conversion that there is isoprene.This instruction is different from prior art.

In these experiments, the increase of fragrant substance can be calculated, namely, the weight of the aromatic compound detected in the liquid-phase product of recovery is added up, then is multiplied by the weight percentage of reclaimed liquid-phase product, and then divided by the known weight of aromatic portion in raw material and polystyrene.For clarity, be calculated as follows for example 1 below:

Initial feed=0.454kg [1lb]

Weight percentage=91% of liquid-phase product in initial feed

0.454kg X 0.91＝0.413kg[0.91lb]

The weight percentage summation of product (in the Table I)=69.7% of fragrant substance in liquid-phase product

The weight of fragrant substance in liquid-phase product

0.413kg X 0.697＝0.288kg[0.6344lb]

In the increasing amount=liquid-phase product of fragrant substance fragrant substance weight-raw material in the weight of fragrant substance (i.e. polystyrene)

0.288kg-0.227kg＝0.061kg[0.13427lb]

The weight of the weight/initial of the percentage ratio=increase of fragrance increasing amount

0.061kg/0.227kg＝13.4％

The analytical results of example 1-4 is see Table V below.

If the content of whole fragrant substance in consideration liquid-phase product, so example 1-4 all shows that the weight percentage of fragrant substance in liquid-phase product is all greater than the content of polystyrene in raw material.The excess of liquid-phase product is made up of non-aromatic component.

Table V

The general output of polyisoprene-polystrene pyrolysis

The weight percentage of fragrant substance in liquid phase

Only the aromatic nucleus that in raw material, non-aromatic carbon atom generates is considered in another kind of method of the present invention.This point makes the present invention be different from aromatic nucleus alkanisation in raw material in prior art to improve the technology of aromatic compound weight percentage in pyrolysis product.In order to be described this method, be calculated as follows for the toluene reclaimed in example 1 below:

Weight=0.455kg X the 0.91=0.4136kg [0.91lb] of liquid-phase product

Weight percentage=4.31% of toluene in liquid-phase product

Weight=0.413kg X the 0.0431=0.01696kg [0.03731lb] of toluene in liquid-phase product

Reclaim toluene kilogram mole number=toluene weight/toluene molal weight=

0.01696kg/92g/mol＝1.843x 10 ^-4kg mol[4.055x 10 ^-4lb mol]

In liquid-phase product toluene benzene mole equivalent=

1.843x 10 ^-4molal weight=the 1.843x 10 of kg mol X benzene ^-4kg mol X 78=

The molar equivalent of 0.01438kg [0.0316324lb] benzene

Calculate toluene molecule amount 92

Polyisoprene-polystrene pyrolysis

Can all carry out similar calculating (see Table II) to each aromatic compound, result sum is the molar equivalent of benzene.As selection, the summation of all E is exactly the molar equivalent of benzene.The example 1 that just wherein can contain 0.2272kg polystyrene calculates the molar equivalent value of desired benzene:

0.2272kg polystyrene/104g/mol=2.185x 10 ^-3kmol vinylbenzene

[4.808x 10 " 3lb mol vinylbenzene]

2.185x 10 ^-3kmol vinylbenzene x 78g/mol benzene=0.1704kg [0.375lb]

Benzene mole equivalent

The benzene mole equivalent of the aromatic nucleus increased is exactly the percent increase between numerical value desired in such as example 1 and actual test value:

The increment of 100%X (0.47202 ÷ 0.375-1)=25.872%

Table VI

Benzol equivalent number

The increase of aromatoising substance weight is not generally because the result of existing aromatic nucleus alkanisation, but produced by the increase of aromatic nucleus quantity.Will inevitably be there are some alkanisation/reconstruct/destructions in existing aromatic nucleus, but undeniable, and isoprene is formed new aromatic nucleus as starting material by whole being characterised in that of the present invention.The percentage ratio that aromatic nucleus increases is basically by reaching 43% (weight), its numerical value reported significantly more than prior art.This is because the increase of aromatic nucleus number, instead of the alkanisation of existing ring, this enlightenment is different from existing known technology completely.

the pyrolysis of broken tire

By shown in Table VIII, the broken tire of difference amount is joined in each reactor.Wherein size, Heating temperature, the speed of heating, the CO of reactor ₂elementary purging etc. with above with reference to reactor I-III mention identical.Reactor in example 5-8 adds the tire of chopping, does not knit line in the tire of these choppings containing tire.What the reactor III in example 9 loaded is whole tire.The filler of reactor requires that the rim size of tire is less than 14 inches.Experimental result is shown in Table VIII.

Table VIII

The data of example 5-9

The induction time of pyrolysis and the time length of pyrolysis

NM=does not survey

¹pyrolysis terminates to refer to that vapour temperature declines about after 10 minutes _~100 °F, and/or the generation of liquid phase obvious slack-off time time.

²do not have the broken tire of steel ring and tire line after chopping tire refers to chopping, its mean sizes is about _~2cm.

³whole tire refers to the tire of 13 and 14 inches with complete steel ring and tire line

⁴pyrolysis refers to because the time is oversize and do not proceed to pyrolysis and terminate

Example 9 is the range tests carried out before example 8, assesses the propane amount needed for testing 454.5kg raw material with this.Reactor III loads the whole tire of 136.36kg [300lbs], and this tire includes steel ring and tire line.Rate of heating is 0.86kW/kg [1333BTU/lb*hr].Test the speed of carrying out can not expect, be approximately 2 hours.Following data do not gather: the time that the first liquid-phase product occurs, the component of the time that pyrolysis terminates and liquid phase.

Then, be test the tire of 454.5kgkg [1000lb], this tire is the shredded material not having tire line.Complete pyrolysis is not reached at rational time i.e. 10 hours build-in tests.Test end is that the liquid product now produced is 5 to 10 cc/min because run out of gas.The thermal decomposition material 324.77kg [714.5lbs] reclaimed is onion shape multilayered structure, consist of: carbonization shell 103.64kg [228lbs], centre is the melting layer 58.41kg [128.5lbs] of pitch sample, kernel wrap up by brea bed, it has 143.18kg [315lbs].The top temperature of kernel is not high, and therefore tire line does not degenerate (untiing).Do not imported to by heat in the kernel of broken tyre material of 454.5kg [1000lbs], this raw material does not have steel ring or tire silk, and unexpected be that the kernel of material has been completely wrapped.

TABLE II

The pyrolysis of tire

As shown in Table II, the pyrolysis of crumb can produce a large amount of aromatic compounds.Because broken tire is a kind of important waste product in the U.S., therefore the present invention can greatly reduce the accumulation of this kind of tire and they are converted into useful resource.

Due to tyre material accurate composition and do not know, namely in raw material fragrant compound and non-aromatic component ratio and do not know, the fragrant substance that therefore the inventive method is produced is the contrast carried out with the example of prior art.U.S. mineral office's No. 7302 report of survey shows the tire pyrolysis aromatic compound (see the 10th page, heavy oil) that can produce average 128.3 liters [33.9 gallons] per ton.Assuming that the density of perfume oil is 0.9, so can calculate roughly.Be multiplied by 8lb/gal by 0.9 and equal 7.2lb/gal, then be multiplied by 33.9gal/ton and just equal 244.08lb/ton aromatic compound.244.08 again by 2000 except just equaling 12.2%, the weight production of average fragrant substance.

Now above-mentioned similar calculating is carried out to the numerical value that example 5,6 and 7 (see Table III-B) records.These results are carried out the ultimate production can seeing the aromatic compound reported in Table III-C and the numerical value calculated by mineral office research report.The output of example of the present invention is approximately the twice of the numerical value that mineral office research report obtains.

Table III-B

Tire pyrolysis

Table III-C

Example	5	6	7	U.S. mineral office
					The weight percentage of fragrant substance	19.78％	20.27％	23.24％	12.2％

Obviously, the method for pyrolysis hydro carbons particularly plastics or rubbery chip can make the fragrant substance in output material more than the raw material of input.Obviously, the method can be used for pyrolytic polymer raw material, and this comprises many polymkeric substance, as rubber, as automobile lining hair and tire, also as plastics, as computer case, disk and circuit card and paint, ink, sticky agent and limited amount polyvinyl chloride.Therefore, so a kind of powerful method can be eliminated or reduce the process of expensive raw material and pre-sifted operation.

Although the present invention is described preferred embodiment by reference to the accompanying drawings, obviously also can adopts other similar embodiment, can modify to above-described embodiment in addition or increase thus complete the function identical with the present invention without departing from the scope of the present invention.Therefore, the present invention should not be defined in some embodiments, and its protection domain should be determined by appending claims.

D＝A/B E＝A/(B+C) G＝B/F

H＝D/G I＝E/G J＝D·G

Claims (35)

1. hydrocarbons is carried out to a method for pyrolysis, it comprises the following steps:

Be input to by raw material in reactor, wherein, described reactor has the internal volume at least about 0.0850 cubic metre;

Heat this raw material and the hot input rate of unit mass raw material lower than 11.62mJ/kg/hr; Wherein during initial heating on reactor heating surface average carrying raw material from 20kg/ ㎡ to about 250kg/ ㎡;

Collect the product from described reactor;

It is oxygen free operation in wherein said reactor;

Wherein, described raw material at least comprises the hydrocarbons containing at least two kinds of different componentss of 70% weight, and the bonding pattern of the organic carbon atoms of at least half of described raw material is different from aromatic ring bonding arrangement;

5% original organic carbon atoms be not present on starting compound aromatic ring is wherein had at least to appear on the aromatic ring of the compound of product liquid phase part.

2. method for pyrolysis as claimed in claim 1, wherein the hot input rate of unit mass raw material is from 0.232MJ/kg/hr to 11.62MJ/kg/hr.

3. method for pyrolysis as claimed in claim 1, wherein during initial heating on reactor heating surface average carrying raw material from 30kg/ ㎡ to about 250kg/ ㎡.

4. method for pyrolysis as claimed in claim 1, wherein said reactor has the internal volume from 1.7 cubic metres to 113.27 cubic metres.

5. method for pyrolysis as claimed in claim 1, its Raw is from 0.001kW.m by the initial heat flux of the unit surface load raw material heated ²/ kg ²to about 1.5kW.m ²/ kg ².

6. method for pyrolysis as claimed in claim 1, its Raw is from 0.005kW.m by the initial heat flux of the unit surface load raw material heated ²/ kg ²to about 0.5kW.m ²/ kg ².

7. method for pyrolysis as claimed in claim 1, has at least the organic carbon atoms of 40% to be carbon atom not on aromatic ring in its Raw.

8. method for pyrolysis as claimed in claim 1, wherein reactor has the free volume of about 25% at least when initial heating.

9. method for pyrolysis as claimed in claim 1, does not wherein add catalyzer or diluent gas in the reactor.

10. method for pyrolysis as claimed in claim 1, does not wherein add carrier gas in the reactor.

11. method for pyrolysis as claimed in claim 1, the time being wherein used for heating is 6 hours or less.

12. method for pyrolysis as claimed in claim 1, hydrocarbons wherein comprises the compound being selected from a group below: thermoplastic polymer, thermosetting polymer and their mixture.

13. method for pyrolysis as claimed in claim 1, wherein hydrocarbons comprises at least two kinds of different compounds being selected from a group below: polyethylene, polypropylene, polyester, acrylonitrile-butadiene-styrene (ABS) (ABS) multipolymer, polyamine, urethane, polyethers, PC, poly-(oxide compound), poly-(sulfide), poly-arylide, polyetherketone, polyethers ammonia, polysulfones, polyurethanes, polyvinyl alcohol, diene, alkene, vinylbenzene, CALCIUM ACRYLATE, vinyl cyanide, methacrylate, methacrylonitrile, diacid and glycols, lactone, diacid, diamines, lactan, vinyl halide, vinyl ester, epoxy resin, phenolic resin, melamine resin, Synolac, vinyl ester resin, unsaturated polyester resin, cross-linked polyurethane, poly-chlorinated isocyanurates, poly-rubber matrix, polyhutadiene, styrene butadiene, styrene-isoprene, Ethylene-Propylene-Diene monomer-polymer, with its mixture and segmented copolymer thereof.

14. method for pyrolysis as claimed in claim 1, wherein raw material comprises the metal of the highest 25% weight.

15. method for pyrolysis as claimed in claim 1, it comprises further: in heat-processed, stir raw material.

16. method for pyrolysis as claimed in claim 1, wherein the thickness of the char layer part of pyrolytic process is 10cm or less.

17. method for pyrolysis as claimed in claim 1, wherein pyrolytic process is continuous print.

18. method for pyrolysis as claimed in claim 1, wherein reactor comprises multiple reactor unit, and each reactor unit all has the internal volume of 1.7 cubic metres to 113.27 cubic metres.

19. method for pyrolysis as claimed in claim 1, reactor unit wherein has the freeboard of 40% at least when initial heating when including raw material.

20. method for pyrolysis as claimed in claim 1, the average particle size particle size of its Raw is approximately 15cm or less.

21. method for pyrolysis as claimed in claim 1, it comprises further: collect the product of airflow pattern from reactor, and this air-flow of condensation thus obtain the liquid phase part of product.

22. as the method for pyrolysis of claim 21, and it comprises further: this liquid stream is cooled to about 80 DEG C or lower temperature.

23. method for pyrolysis as claimed in claim 1, wherein have at least 10% original organic carbon atoms be not present on starting compound aromatic ring to appear on the aromatic ring of the compound of product liquid phase part.

24. method for pyrolysis as claimed in claim 1, wherein said process is continuous print batch feed process.

25. as the method for pyrolysis of claim 24, and reactor wherein comprises multiple reactor unit, and each reactor unit all has the internal volume of 1.7 cubic metres to 114 cubic metres.

26. method for pyrolysis as claimed in claim 1, wherein the hot input rate of unit mass raw material is from 0.3kW/kg to 25kW/kg.

27. method for pyrolysis as claimed in claim 1, wherein the hot input rate of unit mass raw material is from 0.232MJ/kg/hr to 4.65MJ/kg/hr.

28. method for pyrolysis as claimed in claim 1, raw materials by weight wherein comprises the thermosetting polymer of 5% to 95% and the thermoplastic polymer of 95% to 5%.

29. method for pyrolysis as claimed in claim 1, wherein the interior pressure of reactor is approximately less than 550kPa.

30. method for pyrolysis as claimed in claim 1, wherein reactor is oxygen free operation; And this reactor of internal volume based on reactor comprises the oxygen lower than 3% volume when initial heating.

31. method for pyrolysis as claimed in claim 1, wherein reactor is oxygen free operation; And this reactor of internal volume based on reactor comprises the oxygen lower than 2% volume when initial heating.

32. method for pyrolysis as claimed in claim 1, wherein reactor is oxygen free operation; And this reactor of internal volume based on reactor comprises the oxygen lower than 1% volume when initial heating.

33. as the method for pyrolysis of claim 30, wherein during initial heating the volume of oxygen by purging carrier gas or diluent gas reaches in reactor.

34. as the method for pyrolysis of claim 33, and wherein carrier gas or diluent gas are selected from following group: helium, argon gas, nitrogen and carbonic acid gas.

35. as the method for pyrolysis of claim 30, and wherein during initial heating, the volume of oxygen, by purging three carrier gas or diluent gas reaches in reactor, and then to be discharged in air.