CN107922850A - Method for mixed waste plastic to be converted into liquid fuel by catalytic cracking - Google Patents
Method for mixed waste plastic to be converted into liquid fuel by catalytic cracking Download PDFInfo
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- CN107922850A CN107922850A CN201680051675.6A CN201680051675A CN107922850A CN 107922850 A CN107922850 A CN 107922850A CN 201680051675 A CN201680051675 A CN 201680051675A CN 107922850 A CN107922850 A CN 107922850A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1003—Waste materials
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/701—Use of spent catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention relates to a kind of method for being used to mixed waste plastic be converted into liquid fuel by catalytic cracking.This method comprises the following steps：Mixed waste plastic is introduced in reactor and includes the catalyst of amorphous type catalyst；At least a portion mixed waste plastic is allowed to be converted into liquid fuel in the reactor；And the product stream containing the liquid fuel is removed from the reactor.
Description
This application claims the priority of European application number 15201124.3, which carried on December 18th, 2015
Hand over, be for all purposes incorporated herein the full content of the application by quoting mode.
The present invention relates to a kind of method for being used to mixed waste plastic be converted into liquid fuel by catalytic cracking.This method
Comprise the following steps：Mixed waste plastic is introduced in reactor and includes the catalyst of amorphous type catalyst；In the reactor
Interior permission at least a portion mixed waste plastic is converted into liquid fuel；And remove from the reactor and fired containing the liquid
The product stream of material.
In view of importance day of the polymer as the substitute of conventional structure material (such as glass, metal, paper and timber)
Benefit increase, the needs being aware of for saving non-renewable resources (such as oil) and the garbage loading embeading available for waste product disposal hold
The decrement of amount, in recent years, considerable concern are directed to recycling, regenerate, recycle or recycling in some way waste plastics
The problem of.
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 light boiling point as gasoline-type fuel or as other chemicals is to mid-boiling point hydro carbons.
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
It is a kind of to be used to allow to decompose urging for given polymer in the presence of other polymers (decomposing without substantive) by identifying
Agent and temperature conditionss come control the pyrolysis of the complex waste stream of plastics with by this circulation turn to useful high value monomer or its
The method of his chemicals.
K.-H.Lee, et al. in Polymer Degradation and Stability [depolymerization and stability]
The mixture of discarded high density polyethylene (HDPE) and polystyrene is disclosed in 84 (2004) 123-127 through used FCC catalyst
Liquid-phase catalysis degraded.The influence of the mixed proportion of polyethylene and polystyrene is have studied, and ladies and gentlemen author has found reactant
The increase of middle polystyrene content shows in the gained product liquid increase of gasoline proportionality and kerosene and diesel fuel ratio
Reduce.However, at the same time, the ratio of aromatic components is sharply increased to 70% in product liquid, and more even polystyrene contains
Measure as only about 40%.This is found in K.-H.Lee in Polymer Degradation and Stability 93 (2008)
It is proved in the publication of 1284-1289, wherein the polystyrene content obtained is 40%, or even 90% aromatic hydrocarbons.Use 20g
Catalyst/200g plastics carry out the experiment reported by K.-H.Lee.
Although for some applications, increasing the ratio of the gasoline obtained from the catalytic cracking of waste plastics, it may be advantageous,
But a high proportion of aromatic compound is probably undesirable, such as the toxicity due to such compound.Accordingly, it is desirable to provide one
Method of the kind for catalytic cracking waste plastics, wherein the ratio of obtained gasoline and diesel oil distillate can be customized, without not
Hopefully increase the ratio of obtained aromatic compound.
The present invention the inventors discovered that, pass through selection in mixed waste plastic certain ratio polystyrene and polyene
Hydrocarbon and the ratio for increasing the catalyst and waste plastics in the reactor containing amorphous type catalyst, can unexpectedly solve
Certainly this problem and other problems as described below.
, should present invention is accordingly directed to a kind of method for being used to mixed waste plastic be converted into liquid fuel by catalytic cracking
Method includes：
● introduce mixed waste plastic in reactor and include the catalyst of amorphous type catalyst；
● allow at least a portion mixed waste plastic to be converted into liquid fuel in the reactor；And
● the product stream containing the liquid fuel is removed from the reactor,
It is characterized in that, the mixed waste plastic contain by weight from 5% to 50% polystyrene and by weight from
50% to 95% polyolefin, is each based on the gross weight of polystyrene and polyolefin in the mixed waste plastic, and its feature
It is, the weight ratio of the catalyst reactor and mixed waste plastic is higher than 1: 10.
In the catalytic cracking of plastics, some cuts of chemical compound are obtained.It typically, there are containing having less than 5
The gas fraction of the lightweight chemical compound of a carbon atom.Gasoline fraction contains the change with low boiling point (such as less than 216 DEG C)
Compound.The cut includes the compound with 5 to 11 carbon atoms.Kerosene and diesel oil distillate have higher boiling point (such as 216
DEG C to 359 DEG C).The cut usually contains the compound with 12 to 21 carbon atoms.Generally will even more high boiling cut
It is named as wax (heavy-cycle oil or HCO).In all cuts, these compounds are hydrocarbon, optionally include hetero atom (such as N, O
Deng)." liquid fuel " in the sense of the present invention therefore it is such as gasoline and diesel oil fuel, it is valuable it is also possible to be used as other
Chemicals or solvent.
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, as filler, reinforcing agent, processing aid, plasticizer,
Pigment, light stabilizer, lubricant, anti-impact modifier, antistatic additive, ink, antioxidant etc..It is more than in general, plastics include
A kind of additive.
The plastics used in the method for the invention are polyolefin and polystyrene, such as high density polyethylene (HDPE) (HDPE),
Low density polyethylene (LDPE) (LDPE), polypropylene (PP) and polystyrene (PS).The mixing being mainly made of polyolefin and polystyrene
Plastics are preferable.In this context " main composition " should be understood so that in mixed plastic polyolefin and polystyrene
Concentration be by weight higher than 50%, more preferably by weight of from more than 75%, be each based on the gross weights of dry-mixing plastics.
The mixed plastic can be made of polyolefin and polystyrene.The gross weight of dry-mixing plastics is preferably based on, the mixed plastic
Containing being less than 99.5% by weight, 99% polyolefin and polystyrene are more preferably less than by weight.
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 waste plastics, then they
It is preferred that with the gross weight of dry waste plastics by weight less than 50%, preferably by weight less than 30%, more preferably by weight
Less than 20%, a small amount of presence even more preferably by weight less than 10%.The gross weight of dry waste plastics is preferably based on, is appointed
Why not the independent content of too desired plastics is by weight less than 5%, is more preferably less than 2% by weight.
Preferably, these plastic wastes starting materials include one or more thermoplastic polymers and substantially free of heat
Solidity polymer.15wt% is less than for composition substantially free of the content for being intended to indicate that thermosetting polymer in this respect,
Preferably less than 10wt% and even more preferably less than 5wt%.
In general, waste plastics contains other undesirable components, i.e. foreign material, such as paper, glass, stone, metal etc..
In the context of the present invention, no matter when refer to waste plastics weight or mixed waste plastic in polystyrene and poly-
The weight of alkene, the weight are directed to the weight of dry plastics, are mixed without any foreign material with plastics.However, the weight
Including any component in the plastic, such as additive described above.
The present invention's, the inventors discovered that when using the catalyst comprising amorphous type catalyst, polystyrene is added
The reaction rate for the reaction that depolymerizes for adding polyolefin is added in polyolefin raw material.However, in the presence of the depolymerization for making polyolefin
Close the ratio of rate kinetics the constant maximumlly optimal polystyrene and polyolefin of reaction.The increase of rate kinetics constant
It is important advantage for industrial process, because it allows the conversion ratio of higher and the productivity of higher.
It was found that the gross weight based on polystyrene in mixed waste plastic and polyolefin, when mixed waste plastic contains by weight
During about 20% polystyrene, the rate kinetics constant of the reaction that depolymerizes of polyolefin has maximum.If the useless modeling of mixing
Material containing by weight from 5% to 50% polystyrene, preferably by weight from 5% to 40%, more preferably by weight from
5% to 30% and even more preferably by weight from 10% to 30% polystyrene, be each based in mixed waste plastic gather
The gross weight of styrene and polyolefin, still obtains good value.Most preferably, based on polystyrene in mixed waste plastic and polyene
The gross weight of hydrocarbon, mixed waste plastic contain by weight from 15% to 25%, such as by weight about 20% polystyrene.
Additionally, it is observed that increase polystyrene content allows the selectivity for changing product.Increase polyphenyl second in mixed waste plastic
Alkene content causes the selectivity to the higher of gasoline and the more low selectivity to gas and diesel oil.
However, with the report by K.-H.Lee (referring to bibliography cited above) on the contrary, the inventors discovered that increasing
The weight ratio for being added in catalyst reactor and mixed waste plastic is not only resulted on rate kinetics constant and method choice
Above-mentioned benefit, and additionally result in the low-yield of aromatic compound.It is up to by weight in mixed waste plastic
Under 50% polystyrene concentrations, the concentration of aromatic compound is very low in gasoline and diesel oil distillate.The even discovery present invention
The quality of diesel oil that obtains of method meet EN 590：2009+A1 (versions of 2 months 2010) specification.Especially, diesel oil distillate
The concentration of middle multi-aromatic compound is very low.
As the other benefit of the method for the present invention, the inventors discovered that polyolefin is pressed especially in mixed waste plastic
Quality of gasoline under the concentration of weight meter about 20% is in terms of research octane number (RON) (RON) and motor octane number (MON)
Increase be improve.
Therefore, method of the invention is further characterized in that the weight ratio of catalyst reactor and mixed waste plastic is higher than 1:
10.Preferably, the weight ratio of catalyst and mixed waste plastic is higher than 1: 9, more preferably above 1: 8 in the reactor, more preferably
Ground is higher than 1: 7, more preferably above 1: 6, more preferably above 1: 5, is more preferably above 1: 4, and even more preferably still high
In 1: 3, such as higher than 1: 2.The weight ratio of particularly preferred catalyst in the reactor and mixed waste plastic is about 1: 1.5.
The weight ratio of catalyst and mixed waste plastic can be less than 10: 1 in the reactor, be preferably lower than 7: 1.Therefore,
In the reactor the weight ratio of catalyst and mixed waste plastic can be for example from 1: 9 to 10: 1, preferably from 1: 8 to 10: 1,
It is preferred that from 1: 7 to 10: 1, preferably from 1: 6 to 10: 1, preferably from 1: 5 to 10: 1, preferably from 1: 4 to 10: 1, preferably from 1: 3 to 10
: 1, and even more preferably from 1: 2 to 10: 1 or in the range of 1: 2 to 7: 1.
The catalyst used in the method for the invention includes amorphous type catalyst.In one embodiment, the catalysis
Agent is mainly amorphous type catalyst.In a further embodiment, which is made of amorphous type catalyst.At the 3rd
In embodiment, which includes other catalyst in addition, particularly zeolite catalyst.
In the context of the present invention, " amorphous type catalyst " is understood to amorphous solid, such as amorphous powder.
Such amorphous solid is known for technical staff.Amorphous solid lacks the long-range orderly feature of crystallinity, i.e. crystal.
Via X-ray diffraction analysis by lacking sharp Bragg reflection (sharp Bragg reflexes) it is observed that this is special
Sign.
However, amorphous type catalyst can include a certain amount of crystalline solid.Preferably, the amorphous type catalyst bag
Containing being less than 50% by weight, 25% is more preferably less than by weight, is even more preferably less than 10% by weight, such as by weight
Gauge is less than 5% or is less than 2% or the crystalline solid even less than 1% by weight, is each based on the gross weight of catalyst.
The embodiment that wherein catalyst is mainly amorphous type catalyst is preferable.In this context, term is " main
Ground " defines the catalysis for the mixture for being amorphous type catalyst and non-amorphous type catalyst (such as zeolite catalyst)
Agent, but the wherein gross weight based on catalyst, the catalyst include the amorphous type catalyst by weight more than 50%.It is preferred that
Ground, which, which includes, is more than 60%, more preferably more than 70%, is still more preferably greater than 80% and is most preferably more than
90% amorphous type catalyst.The catalyst can include single amorphous type catalyst or two or more amorphous types
The mixture of catalyst.
As catalyst, all types of FCC catalysts can be used.FCC catalyst is for those skilled in the art
It is well known.For example, amorphous type catalyst can include silica, aluminium oxide, kaolin or its mixture.Silica
(especially in the form of sand) is well known for FCC catalytic applications.Preferable amorphous type catalyst includes by weight
Meter at least 60%, preferably by weight at least 70% and even more preferably by weight at least 80% oxidation based on silicon
Compound (such as silica (SiO2), kaolin etc.) silica equivalent.
If catalyst additionally comprises zeolite catalyst, it can be selected from well known by persons skilled in the art and can business
The crystalline microporous zeolite of purchase.The preferred embodiment of zeolite catalyst is described in WO 2010/135273, its content is by quoting
Mode is incorporated herein.The instantiation of suitable zeolite catalyst includes but not limited to：ZSM-5、ZSM-11、ZSM-22、
ZSM-23、ZSM-35、ZSM-48、ZSM-50、TS-1、TS-2、SSZ-46、MCM-22、MCM-49、FU-9、PSH-3、ITO-1、
EU-1, NU-10, Silicalite-1, silicone zeolite -2, borosilicate zeolite-C, borosilicate zeolite-D, BCA and its mixture.
The catalyst can be fresh catalyst, equilibrium catalyst (such as used catalyst) or its mixture.
Mixed waste plastic and catalyst containing amorphous type catalyst can be subsequently or simultaneously introduced in reactor.This
Outside, by mixed waste plastic and catalyst in increments containing amorphous type catalyst or can be introduced continuously into reactor.
Technical staff knows the suitable instrument and equipment for carrying out the method according to the invention, and by based on his
Professional experiences select suitable system, so further extensive details need not be provided herein.It is not intended, however, that by theoretical beam
Tie up, stirring reactor, rotary kiln, bubble flow can be included effective for some examples for the reactor technology for carrying out the present invention
Fluidized bed reactor and circulating fluid bed reactor lifter or drop device.Rotary kiln is cylindrical vessel, is slightly slanted in level
Face, the rotary kiln are slowly rotated around its axis.Pending material is dosed to the upper end of cylinder.As kiln rotates, material
Moved down progressively towards lower end, and a certain amount of stirring and mixing may be undergone.In bubbling fluidized bed reactor, fluid
(gas or liquid) is with sufficiently high speed by catalyst granules so that it is fluid one that catalyst, which suspends and appears as it,
Sample.In recirculating fluidized bed (also known as transmitting reactor), catalyst and fluid are flowed with high speed cocurrent.Usually by whirlwind point
The fluid of downstream processes can be undergone by being used for the separation from the solid for be recycled to reactor from device system.These reactors can be with
It is the upstream for lifter, or flowing down for drop device.
Preferably, they are introduced continuously into.In one embodiment, whole process continuously carries out.In the reactor,
In the presence of a catalyst, at least one of mixed waste plastic is converted into liquid fuel.This conversion is preferably elevated
At a temperature of, such as higher than 350 DEG C, be preferably higher than 400 DEG C, occur at more preferably above 410 DEG C.Compatibly, which exists
Higher than 410 DEG C to 500 DEG C in the range of, more preferably occur at a temperature of from 420 DEG C to 470 DEG C (e.g., from about 450 DEG C).
The Gao Chong of catalyst in the reactor and mixed waste plastic is explained in greater detail referring now to following instance and attached drawing
The influence than polystyrene content in lower mixed waste plastic is measured, attached drawing is shown below：
● Fig. 1 is always to accumulate differentiation of the conversion ratio with the time for different polystyrene loading capacities,
● Fig. 2 is the differentiation with the time for the HDPE accumulation conversion ratios that different polystyrene loading capacities correct.In order to true
Surely the HDPE conversion ratios corrected, are contributed without PS, it is assumed that the pyrolytic process of two kinds of different plastics is independent.Based on this premise,
PS conversion ratios can be subtracted from total conversion, so that HDPE conversion ratios are obtained,
● Fig. 3 is the relative value for the Kinetics Rate Constants By Using of different polystyrene loading capacities,
● Fig. 4 is influence of the polystyrene loading capacity to selectivity,
● Fig. 5 is influence of the polystyrene loading capacity to the quality of gasoline fraction, and
● Fig. 6 is influence of the polystyrene loading capacity to the quality of diesel oil distillate.
Following instance is carried out according to following General experimental program.
In each catalysis operation under half point batch mode, by 30g plastics (high density polyethylene (HDPE) (HDPE) and variable
Polystyrene (PS)) and limited amount amorphous type catalyst (SiO2) be loaded into reactor.Reactor is closed, and 20
Reactor is heated to 200 DEG C from room temperature in minute, and is purged at the same time with 150mL/min nitrogen flows.When internal temperature reaches
During the fusing point of plastics, start to stir and be slowly increase until 690rpm.Keep the temperature at 200 DEG C and continue 25-30 minutes.
During the heating process, the nitrogen come out from reactor is not collected.
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, the circulation of gaseous products
It is replaced by another pair glass trap and corresponding gas sampling bag.This was considered as zero reaction time.
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 catalyst 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.
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 PIONA (alkane, different alkane
Hydrocarbon, alkene, cycloalkane, aromatic hydrocarbons) component, and GCxGC allows the diesel oil distillate (C12- of the definite fluid sample finally taken out
C21；216.1 DEG C of 359 DEG C of ＜ BP ＜) in saturate (not being the whole of aromatic hydrocarbons), single aromatic, two aromatic hydrocarbons and three aromatic hydrocarbons.
In order to determine the HDPE conversion ratios of correction, contributed without PS, it is assumed that the pyrolytic process of two kinds of different plastics is independent
's.Based on this premise, PS conversion ratios can be subtracted from total conversion, so as to obtain HDPE conversion ratios.
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 1
Follow general program described above and carry out the experiment.In this example, raw material are that pure HDPE (is labeled as
0%PS).Reaction temperature is arranged on 450 DEG C.In this example, using 20g silica.The weight ratio of catalyst and plastics
Equal to 20/30.
Example 2
Follow general program described above and carry out the experiment.In this example, raw material be containing 95wt.%HDPE and
The mixture (being labeled as 5%PS) of 5wt.%PS.Reaction temperature is arranged on 450 DEG C.In this example, it is used for 20g
Silica.The weight ratio of catalyst and plastics is equal to 20/30.
Example 3
Follow general program described above and carry out the experiment.In this example, raw material be containing 90wt.%HDPE and
The mixture (being labeled as 10%PS) of 10wt.%PS.Reaction temperature is arranged on 450 DEG C.In this example, using 20g dioxies
SiClx.The weight ratio of catalyst and plastics is equal to 20/30.
Example 4
Follow general program described above and carry out the experiment.In this example, raw material be containing 80wt.%HDPE and
The mixture (being labeled as 20%PS) of 20wt.%PS.Reaction temperature is arranged on 450 DEG C.In this example, using 20g dioxies
SiClx.The weight ratio of catalyst and plastics is equal to 20/30.
Example 5
Follow general program described above and carry out the experiment.In this example, raw material be containing 50wt.%HDPE and
The mixture (being labeled as 50%PS) of 50wt.%PS.Reaction temperature is arranged on 450 DEG C.In this example, using 20g dioxies
SiClx.The weight ratio of catalyst and plastics is equal to 20/30.
Example 6
Follow general program described above and carry out the experiment.In this example, raw material are that pure PS (is labeled as
100%PS).Reaction temperature is arranged on 450 DEG C.In this example, using 20g silica.The weight of catalyst and plastics
Than equal to 20/30.
Shown in Fig. 1 and accumulate differentiation of the conversion ratio with the time for the total of different polystyrene loading capacities.As existed above
As being explained in the general description of experimental arrangement, PS conversion ratios are then subtracted from total conversion, therefore obtain shown in Fig. 2
For different polystyrene loading capacities HDPE accumulate conversion ratio.According to these values, calculate in HDPE pyrolysis for difference
The relative value of the Kinetics Rate Constants By Using of polystyrene loading capacity.As a result it is showed in Fig. 3.It is obvious that converted for polyolefin
Kinetics Rate Constants By Using polystyrene present in mixed waste plastic by weight about 20% at there is maximum.
Influence of the polystyrene loading capacity to the selectivity of this method is shown in Fig. 4.It is obvious that the selectivity to gasoline
Increase with the increase of polystyrene loading capacity, and the selectivity of gas, diesel oil and wax is reduced.
However, it is opposite with the expection of technical staff and with described in the prior art on the contrary, method of the invention carries
The gasoline fraction and diesel oil distillate for having supplied the two all to include only a small amount of aromatic compound.Only in 100% polystyrene conduct
In the case of originating plastics (not according to the present invention), the amount increase of aromatic compound in gasoline and diesel oil distillate.By this
It is a little to find to summarize in figs. 5 and 6.
Fig. 5 shows polystyrene loading capacity to gasoline fraction (P：Alkane, I：Isoparaffin, O：Alkene, N：Cycloalkanes
Hydrocarbon, A：Aromatic hydrocarbons, U：Do not identify) quality influence.In addition Fig. 5 shows the gasoline obtained with different polystyrene loading capacities
The RON and MON of cut.Unexpectedly, if in mixed waste plastic polystyrene amount from 0% increase to 20%, RON and
Both MON increases.
Fig. 6 shows polystyrene loading capacity to diesel oil distillate (S：Saturation, MA：Single aromatic, DA：Two aromatic series
, TA：Three is aromatic, PA：It is more aromatic) quality influence.It is obvious that the aromatic compound in diesel oil distillate
Total amount keeps very low, even if the polystyrene content in mixed waste plastic increases to by weight up to 50%.Only when polyphenyl second
When alkene content increases to 100% (not according to the present invention), the amount of aromatic compound dramatically increases in diesel oil distillate.
Claims (14)
1. a kind of method for mixed waste plastic to be converted into liquid fuel by catalytic cracking, this method includes：
Mixed waste plastic is introduced in reactor and includes the catalyst of amorphous type catalyst；
At least a portion mixed waste plastic is allowed to be converted into liquid fuel in the reactor；And
The product stream containing the liquid fuel is removed from the reactor,
It is characterized in that, the mixed waste plastic contain by weight from 5% to 50% polystyrene and by weight from 50%
To 95% polyolefin, the gross weight of polystyrene and polyolefin in the mixed waste plastic is each based on, and it is characterized in that,
The weight ratio of the catalyst reactor and mixed waste plastic is higher than 1: 10.
2. according to the method described in claim 1, wherein based on the gross weight of polystyrene and polyolefin in the mixed waste plastic,
The mixed waste plastic contains by weight from 5% to 40%, preferably by weight from 5% to 30%, more preferably by weight from
10% to 30% polystyrene.
3. method according to claim 1 or 2, wherein the weight ratio of catalyst and mixed waste plastic is high in the reactor
In 1: 8,1: 5, more preferably above 1: 3 are preferably higher than.
4. according to any method of the preceding claims, wherein catalyst and mixed waste plastic in the reactor
Weight ratio is less than 10: 1, is preferably lower than 7: 1.
5. according to any method of the preceding claims, wherein the catalyst is mainly amorphous type catalyst.
6. method according to any one of claim 1 to 4, the wherein catalyst are made of amorphous type catalyst.
7. method according to any one of claim 1 to 5, the wherein catalyst additionally include zeolite catalyst.
8. according to any method of the preceding claims, wherein the amorphous type catalyst includes silica, oxygen
Change aluminium, kaolin or its mixture.
9. according to any method of the preceding claims, wherein the catalyst be fresh catalyst, equilibrium catalyst,
Or its mixture.
10. according to any method of the preceding claims, wherein at least a portion mixes useless modeling in the reactor
The temperature that material is converted into residing for liquid fuel is higher than 350 DEG C, 410 DEG C is preferably higher than, more preferably higher than 410 DEG C extremely
In the range of 500 DEG C, even more preferably still in the range of from 420 DEG C to 470 DEG C.
11. according to any method of the preceding claims, wherein the gross weight based on the mixed waste plastic, the mixing
Waste plastics includes the polystyrene and polyolefin by weight more than 50%.
12. according to any method of the preceding claims, this method is carried out continuously.
13. according to any method of the preceding claims, wherein the waste plastics is selected from post-consumer plastic waste, does not conform to rule
Lattice plastics and industrial waste plastics.
14. according to any method of the preceding claims, the wherein waste plastics is substantially free of thermosetting polymer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP15201124 | 2015-12-18 | ||
| EP15201124.3 | 2015-12-18 | ||
| PCT/EP2016/081304 WO2017103015A1 (en) | 2015-12-18 | 2016-12-15 | Process for converting mixed waste plastic into liquid fuels by catalytic cracking |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107922850A true CN107922850A (en) | 2018-04-17 |
Family
ID=54936878
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680051675.6A Pending CN107922850A (en) | 2015-12-18 | 2016-12-15 | Method for mixed waste plastic to be converted into liquid fuel by catalytic cracking |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US20190002765A1 (en) |
| EP (1) | EP3390574A1 (en) |
| CN (1) | CN107922850A (en) |
| WO (1) | WO2017103015A1 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114133951B (en) * | 2021-12-14 | 2023-04-18 | 青海天创新能源科技有限公司 | Method for preparing fuel oil by depolymerizing waste plastics by using catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1150968A (en) * | 1995-11-23 | 1997-06-04 | 杨亚力 | Method and equipment for treat waste plastic hydrocarbon |
| CN102744101A (en) * | 2012-08-02 | 2012-10-24 | 新疆大学 | Catalyst used for preparing gasoline through splitting of waste plastic and preparation method and using method thereof |
| WO2014040634A1 (en) * | 2012-09-14 | 2014-03-20 | Outotec Oyj | Method and apparatus for recycling plastic wastes |
| CN104479721A (en) * | 2014-12-29 | 2015-04-01 | 江苏健神生物农化有限公司 | Fuel oil preparation technique utilizing waste plastics |
| WO2015128033A1 (en) * | 2014-02-25 | 2015-09-03 | Saudi Basic Industries Corporation | Process for converting mixed waste plastic (mwp) into valuable petrochemicals |
-
2016
- 2016-12-15 EP EP16809849.9A patent/EP3390574A1/en not_active Withdrawn
- 2016-12-15 WO PCT/EP2016/081304 patent/WO2017103015A1/en active Application Filing
- 2016-12-15 CN CN201680051675.6A patent/CN107922850A/en active Pending
- 2016-12-15 US US16/062,702 patent/US20190002765A1/en not_active Abandoned
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1150968A (en) * | 1995-11-23 | 1997-06-04 | 杨亚力 | Method and equipment for treat waste plastic hydrocarbon |
| CN102744101A (en) * | 2012-08-02 | 2012-10-24 | 新疆大学 | Catalyst used for preparing gasoline through splitting of waste plastic and preparation method and using method thereof |
| WO2014040634A1 (en) * | 2012-09-14 | 2014-03-20 | Outotec Oyj | Method and apparatus for recycling plastic wastes |
| WO2015128033A1 (en) * | 2014-02-25 | 2015-09-03 | Saudi Basic Industries Corporation | Process for converting mixed waste plastic (mwp) into valuable petrochemicals |
| CN104479721A (en) * | 2014-12-29 | 2015-04-01 | 江苏健神生物农化有限公司 | Fuel oil preparation technique utilizing waste plastics |
Non-Patent Citations (3)
| Title |
|---|
| A.G.BUEKENS，H.HUANG: "Catalytic plastics cracking for recovery of gasoline-range hydrocarbons from municipal plastic wastes", 《RESOURCES, CONSERVATION AND RECYCLING》 * |
| 刘公召: "废塑料催化裂解生成汽柴油中试工艺的研究", 《环境科学与技术》 * |
| 李国鼎: "《环境工程手册 固体污染物防治卷》", 31 December 2003, 高等教育出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| EP3390574A1 (en) | 2018-10-24 |
| WO2017103015A1 (en) | 2017-06-22 |
| US20190002765A1 (en) | 2019-01-03 |
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