CN108603122A - For by cracking by converting-plastics be gas, liquid fuel and wax method - Google Patents

For by cracking by converting-plastics be gas, liquid fuel and wax method Download PDF

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Publication number
CN108603122A
CN108603122A CN201780003036.7A CN201780003036A CN108603122A CN 108603122 A CN108603122 A CN 108603122A CN 201780003036 A CN201780003036 A CN 201780003036A CN 108603122 A CN108603122 A CN 108603122A
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China
Prior art keywords
mixture
plastics
catalyst
gas
oxygenatedchemicals
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Inventor
S.斯特雷夫
D.巴哈沙特
M.皮西尼尼
A.科马
M.塞罗-阿拉康
J.门古亚
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Solvay SA
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Solvay SA
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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
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/04—Specifically adapted fuels for turbines, planes, power generation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Abstract

The present invention relates to a kind of methods for converting the mixture comprising plastics and at least one oxygenatedchemicals to gas, liquid fuel and wax by cracking.This method includes deoxygenation step and subsequent hydrocracking step, during the hydrocracking step, so that the mixture is subjected to cracking conditions to obtain the product stream containing the gas, liquid fuel and wax.

Description

For by cracking by converting-plastics be gas, liquid fuel and wax method
This application claims the priority of the European application number EP 16306634.3 submitted on December 7th, 2016, for institute Purposefully the full content of the application is incorporated herein by quoting mode.
Technical field
The present invention relates to a kind of for will be converted comprising the mixture of plastics and at least one oxygenatedchemicals by cracking For the method for gas, liquid fuel and wax.This method includes deoxygenation step and subsequent hydrocracking step, in the hydrocracking step phase Between, so that the mixture is subjected to cracking conditions to obtain the product stream containing the gas, liquid fuel and wax.
The prior art
Importance day in view of polymer as the substitute of conventional building material (such as, glass, metal, paper and timber) Benefit increases, and perceives the non-renewable resources such as oil for needing safety and increasingly decrement can be used for filling out for disposal of wastes Buried capacitor amount, in recent years, recycling, regeneration, recycling or in some way recycle waste plastics the problem of cause sizable pass Note.
Pyrolysis or catalytic cracking waste plastics are proposed, to convert with much lower point heavy polymer to The volatile compound of son amount.According to used method, these volatile compounds can be used as fuel oil or fuel The opposite high boiling liquid hydrocarbon of oily replenishers, or can be used as the light boilings of gasoline-type fuel or other chemicals and arrive medium boiling point Carbon atom.In addition, these volatile compounds can be wax, or it at least may include wax.
The cracking of mixed waste plastic is method well known to those skilled in the art.For example, US 5,216,149 discloses use In catalyst and the temperature condition that given polymer decomposes are allowed by identification come control the pyrolysis of the complex waste stream of plastics with By such method for circulating and turning to useful high value monomer or other chemicals.
Known method for carrying out plastics depolymerization by thermal cracking or catalytic cracking is typically result in forming five kinds of main productions Object, these products can be classified according to its carbon chain lengths from length is short to：Gas, gasoline, diesel oil, kerosene and wax (or HCO=weights Recycle oil).
It was found by the inventors of the present invention that can be had the disadvantage with technology, that is, be present in the oxygenatedchemicals in raw material most It is harmful in the case of number, because it increases the oxygen content in products therefrom, to reduce its quality.Therefore, by including plastics With high-value product of the mixture of the oxygenatedchemicals production with low oxygen content by be desirable to (Pavel T.Williams, " Waste treatment and disposal [waste processing and disposition] ", the second edition, John Wiley father and son publishing company (John Wiley and Sons), strange Chester (Chichester), 2005, p 334).
Method for converting oxygen-containing hydrocarbon to hydrocarbon is described in US 4,308,411.This method is from solid waste (including cellulosic material) starts, and inorganic fraction is detached from the solid waste.In these examples, which is done It is dry, and be then pyrolyzed at the temperature (for example, 550 DEG C) from about 300 DEG C to about 800 DEG C.What is so obtained includes oxygen-containing hydrocarbon Steam detached, and then these oxygen-containing hydrocarbons contacted with crystalline aluminosilicate zeolitic to be converted into hydrocarbon.Although this method permits Perhaps oxygen-containing hydrocarbon is restored, but it has the disadvantage, that is, the organic fraction of solid waste must be pyrolyzed at high temperature first.Such high At a temperature of, the also depolymerization and depolymerization product may be reacted with these oxygenatedchemicals of plastics in solid waste leads to gained The undesirable elevated oxygen level of gas, liquid fuel and wax.
Therefore, the cracking for being further improved plastics is still needed to, it especially will be comprising plastics and at least one oxygenatedchemicals Mixture is converted into gas, liquid fuel and wax with low oxygen content.
Invention content
The present inventor is it has now been found that oxygenatedchemicals can be at a relatively low temperature from including plastics and these It is removed in the mixture of oxygenatedchemicals.In addition, ladies and gentlemen inventor also found, the gas stream obtained from the mixture of heating it is cold The density of condensate is the suitable marker terminated for determining deoxidation process.When the process starts, the density of condensate is high.De- During oxygen, the density of condensate reduces.Under certain density, a large amount of undesirable oxygenatedchemicals are removed from mixture, So that obtaining the product of the gas containing high-quality and low oxygen content, liquid fuel and wax during subsequent hydrocracking step Stream.
Specific implementation mode
Therefore, the present invention relates to a kind of for passing through cracking by the mixture comprising plastics and at least one oxygenatedchemicals The method for being converted into gas, liquid fuel and wax, this method include：
Deoxygenation step, the deoxygenation step are straight for a period of time by the constant temperature that the mixture is heated to at least 200 DEG C Condensate to the gas stream obtained from the mixture of the heating has about 0.94g/cm3Or lower density carries out；
And the hydrocracking step after the deoxygenation step makes the mixture be subjected to cracking item during the hydrocracking step Part is to obtain the product stream containing the gas, liquid fuel and wax.
In the cracking of plastics, several compound fractions are obtained.It typically, there are containing light compounds (having less than 5 Carbon atom) gas fraction.Gasoline fraction includes to have such as less than 150 DEG C of low-boiling compound.The fraction includes tool There is the compound of 5 to 9 carbon atoms.Kerosene and diesel oil distillate have such as 150 DEG C to 359 DEG C of higher boiling point.The fraction Generally comprise the compound with 10 to 21 carbon atoms.Usually will even more high boiling fraction be named as heavy-cycle oil (or ) and wax HCO.In all these fractions, compound is the hydrocarbon for optionally including hetero atom such as N, O etc..Therefore, meaning of the present invention On " wax " indicate optionally include heteroatomic hydrocarbon.In most cases, it is solid under room temperature (23 DEG C), and its The softening point having is usually above 26 DEG C.The definition of gained fraction is provided in following experimental section.
Plastics are made of particular polymers mostly, and the plastics are usually named by the particular polymers.Preferably, plastics It comprises more than 25 weight % of its total weight, be preferably more than the spy of 40 weight % and more preferably beyond 50 weight % Determine polymer.Other components in plastics are such as additives, such as filler, reinforcing agent, processing aid, plasticizer, pigment, light Stabilizer, lubricant, anti-impact modifier, antistatic agent, ink, antioxidant etc..In general, plastics include more than one addition Agent.
The plastics used in the method for the invention include polyolefin and polystyrene, such as high density polyethylene (HDPE) (HDPE), low density polyethylene (LDPE) (LDPE), Ethylene-Propylene-Diene monomer (EPDM), polypropylene (PP) and polystyrene (PS). The mixed plastic being mainly made of polyolefin and/or polystyrene is preferred.
Other plastics such as polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polyurethane (PU), third Alkene nitrile-butadiene-styrene (ABS), ethylene vinyl alcohol polymer (EVA), polyvinyl acetate, makrolon, polyacrylic acid Ester, polymethyl methacrylate (PMMA), nylon and fluorinated polymer are less desirable to.If there is in plastics, then they are excellent Selection of land with 50 weight % of the total weight less than dry weight plastics, preferably less than 30 weight %, more preferably less than 20 weight %, Even more preferably less than a small amount of presence of 10 weight %.
Preferably, plastics include one or more thermoplastic polymers, and substantially free of thermosetting polymer.With regard to this For a bit, substantially free of being intended to indicate that the 15 weight % of the content of thermosetting polymer less than plastics starting material, preferably Ground is less than 10 weight % and even more preferably less than 5 weight %.
The plastics used in the method for the invention can be selected from：
Single new plastic, mixed waste plastic, Rubber waste, debirs, the biology of single waste plastics, acceptance or rejection Matter or their mixture.Unitary plastic waste, underproof single new plastic, mixed waste plastic, Rubber waste or they Mixture is preferred.Underproof single new plastic, mixed waste plastic or their mixture are particularly preferred.Mixing modeling Material waste generally produces good result.
Before the method for the present invention, mixture can be pre-processed by physical-chemical method, the physical-chemical side Method include it is one or more operate, such as size reduction, grinding, crushing, screening, chip, melt removal, foreign matter removal, dedusting, Dry, degassing, fusing, solidification and reunion.
In general, waste plastics contains other undesirable components, that is, foreign matter, glass, stone, metal etc..As entrance Limited amount such component that can not be pyrolyzed (unpyrolizable) of contamination of raw material object is acceptable.For example, in the present invention Method in the mixture that uses may include 50 weight % less than dry mixture total weight, preferably less than 20 weight %, more Preferably less than 10 weight %'s can not pyrolyzed components.
In addition, waste plastics usually contain other undesirable components, mainly cellulosic substrates, such as timber, cardboard, Paper, paper handkerchief etc..These can pyrolyzed components be oxygenatedchemicals, such as oxygen-containing hydrocarbon mostly, cause during plastics cracking gained The undesirable increase of the oxygen content of gas, liquid fuel and wax.
However, " oxygenatedchemicals " in the sense of the present invention is not limited to organic compound, but it may also include inorganic chemical Object, these inorganic compounds contain the oxygen atom combined with other atoms but chemically unstable under cracking conditions.In this hair In the sense that bright, H2O is not considered as oxygenatedchemicals.
It is believed that these oxygenatedchemicals are difficult to remove, because the oxygenatedchemicals as proposed in US 4,308,411 is such as fine The pyrolysis of dimension cellulosic material needs high temperature, and plastics cracking can occur at these higher temperatures.
The present inventor it has now been surprisingly discovered that, in the mixing comprising plastics and at least one oxygenatedchemicals It is in object, the oxygenate conversion is at a fairly low for the temperature needed for gas.However it remains problems with：In specific item Under part, plastics may also can cracking at low temperature.It is therefore desirable to determine that parameter, the parameter were suitable in oxygenatedchemicals in its phase Between between the cracking process that the deoxidation process and plastics removed in mixture is converted into desired product during it carry out area Point.After further research, it was found by the inventors of the present invention that the density of the condensate of the gas stream obtained from the mixture of heating It is the suitable parameters distinguished between deoxygenation step and hydrocracking step.
The inventors discovered that during batch operation, start to convert in the mixture comprising plastics and oxygenatedchemicals When, the density of the condensate of the gas stream obtained from the mixture of heating is quite high.When reaction continues, density declines. It was found that when condensate reaches about 0.94g/cm3Density when, a large amount of or even substantially all of undesirable oxygenatedchemicals It is removed from mixture.Therefore remaining mixture includes the major part for the plastics being present in original mixture and significantly subtracts A small amount of undesirable oxygenatedchemicals.It therefore, can if remaining mixture is subjected to cracking conditions after making deoxygenation step It obtains comprising the product stream especially with respect to high-quality gas, liquid fuel and wax for the oxygen content of reduction.Meanwhile During the deoxygenation step, the only small amounts of plastics depolymerization being present in original mixture.Therefore, it is obtained from the mixture of heating The measurement of the density of the condensate of gas stream allows the quality for not only optimizing gained gas, liquid fuel and wax, but also optimizes it Yield.
In a preferred embodiment of the invention, deoxygenation step is carried out, until the gas stream that is obtained from the mixture of heating The density that condensate has is in 0.90g/cm3To 0.93g/cm3In the range of, preferably in 0.91g/cm3To 0.93g/cm3's In range, more preferably in 0.920g/cm3To 0.928g/cm3In the range of, even more preferably in 0.923g/cm3Extremely 0.927g/cm3In the range of, and most preferably about 0.925g/cm3。
In the context of the present invention, " condensate of the gas stream obtained from the mixture of heating " is interpreted as from being added For heat to the fraction of the gaseous products of at least 200 DEG C of mixture acquisition, which obtained when hot gas stream is cooled to 40 DEG C .It is discharged in those of 40 DEG C of incoagulable gas streams component.Then condensate is cooled further to 25 DEG C of temperature. At this temperature, the density of condensate is measured.Possibly, condensate can split into aqueous fraction and oil distillate.Therefore, condensate Density be defined as the ratio of example weight and sample volume, without considering any possible liquid phase division.This measurement can It is carried out by simply using the apparent weight and apparent volume of " mixing " condensate.
In order to measure the density of condensate, the condensate of certain volume is needed.If what is obtained during deoxygenation step is cold The flow of condensate is sufficiently high, then can density that is continuous or at least semi-continuously measuring condensate.However, it is possible to preferably exist The condensate of certain volume is collected before measuring its density.For example, especially in batch process, may be selected relative to being introduced into The suitable volumes of the amount of plastic in starting mixt in reactor.In this case, the volume can 0.1 to 250cm3/ kg plastics, preferably 0.15 to 100cm3/ kg plastics, more preferably 0.2 to 20cm3In the range of/kg plastics.Another In one embodiment, suitable volume can be such as 0.5 to 10cm3, preferably 0.5 to 5cm3, more preferably from 0.5 to 4cm3In the range of.The volume for being collected for measuring density is smaller, then determines when to terminate deoxygenation step and start cracking step Rapid precision can be higher.Alternatively, condensate certain time can be collected, then measures and is received during this time The density of the condensate of collection.The time interval for collecting during it condensate depends on for example comprising plastics and oxygenatedchemicals The flow etc. of the composition and amount of mixture, the size of reactor, catalyst, heating power, condensate, and can be such as 1 To 120 minutes, preferably 1 to 90 minute, more preferably 1 to 60 minute, such as in the range of 2 to 30 minutes. In addition, it is shorter with the time interval for measuring its density to collect condensate during it, it is determined that deoxygenation step terminates to walk with cracking Suddenly the precision started is higher.
Therefore, during deoxygenation step, the collecting condensation obtained is continued into certain period of time, or until obtaining Certain volume.The density of the condensate so obtained is measured, and if density is greater than about 0.94g/cm3, then continue deoxidation Step, and other condensate sample is collected for next density measure.When continuing certain to each sample collection Between section, or until obtaining certain volume.
Up to the present, the present invention is described about batch operation.However, the present invention method can also continuously into Row, such as by using reactor, such as rotary drum type reactor or screw reactor, wherein oxygen-containing comprising plastics and at least one The mixture of compound is continuously moved to next reaction zone from a reaction zone.Gas stream is collected from each reaction zone, and The density of the condensate of the gas stream is measured as described above.As long as the density that the gas stream obtained from given reaction zone has is higher than About 0.94g/cm3, which will run under deoxygenation conditions.Once mixture is moved in reaction zone, obtained in The density of condensate of gas stream be about 0.94g/cm3Or it is lower, the reaction zone and subsequent reaction zone will be in cracking items It is run under part to obtain the product stream for including desired gas, liquid fuel and wax.
The gas stream obtained during deoxygenation step contains the gaseous products that oxygenatedchemicals is converted to.By from heating Mixture in remove the gas stream, removing oxygenatedchemicals and obtaining mainly (and optionally above-mentioned can not be pyrolyzed group by plastics Point and a small amount of plasticity thermal decomposition product) composition residue.The residue is then subjected to cracking conditions.
Moreover, it has been found that oxygenate conversion, which is the temperature of gaseous products, depends on the plastics in mixture.For example, such as Fruit plastics are polyethylene, then oxygenatedchemicals is converted into gas at a temperature of slightly below 350 DEG C, and if plastics are poly- third Alkene is then converted into gas at a temperature of slightly below 300 DEG C.This shows mixed comprising plastics and at least one oxygenatedchemicals Closing the plastics in object influences the temperature that oxygenate conversion is gas.
As important step according to the method for the present invention, the gas generated during deoxygenation step is as first gas stream It is removed.The gas stream includes the product of undesirable oxygenatedchemicals, therefore is removed it before plastics cracking.This first The removal of gas stream can be for example by with above gas such as air, preferably the inert gas such as mixture of nitrogen purging heating Space carry out.Alternately or additionally, the first gas stream can be removed by applying decompression.
In a preferred embodiment of the invention, the gas stream obtained during deoxygenation step, which is removed, to be persistently enough from mixing At least one oxygenatedchemicals of at least 50 weight % is removed in object (based on being present in before deoxygenation step in the mixture At least one oxygenatedchemicals total weight) time.It is highly preferred that before hydrocracking step, removed from mixture At least 70 weight %, even more preferably at least 80 weight % and the most preferably substantially all of at least one are containing oxidation Close object.In this context, " the substantially all of at least one oxygenatedchemicals " should be understood so that based in deoxidation It is present in the total weight of at least one oxygenatedchemicals in mixture before step, at least 90 weight %, preferably at least 95 weight % and even more preferably at least 97 weight % are removed before hydrocracking step.
By removing the first gas stream from the mixture of heating, residue is obtained.The residue is included in the first temperature The plastics of non-depolymerization under degree, optionally the oxygenatedchemicals of surplus and it is optionally above-mentioned can not pyrolyzed components.If The heating of mixture is carried out in the presence of a catalyst at a temperature of one, then the catalyst is also contained in the residue.
In next step according to the method for the present invention, the residue is made to be subjected to cracking conditions.Under these conditions, Plastics cracking occurs, to generate the product stream comprising desired gas, liquid fuel and wax.By the product stream from the heating It is removed in residue.
The cracking of plastics can carry out under the usual conditions known to people in the art's spirit.For example, during plastics cracking Temperature be usually above 350 DEG C, preferably higher than 400 DEG C, more preferably at least 425 DEG C, such as higher than 400 DEG C to 650 DEG C In the range of, even more preferably in the range of 425 DEG C to 550 DEG C.
In one embodiment, cracking can carry out in the atmosphere that air exhausts.The atmosphere that air exhausts can for example containing There is one or more inert gases such as nitrogen or be made from it, or may be at decompression state.
In another embodiment, cracking can carry out in the presence of a catalyst.However, it is also possible in deoxygenation step Period, there is also catalyst.In this case, it is preferred that deoxygenation step and hydrocracking step in catalyst, preferably identical urge It is carried out in the presence of agent.However, it is also possible to the two steps carry out in the presence of two kinds of different catalysts, or will Another different catalyst is added in hydrocracking step.Finally, it may but be less desirable to, only deoxygenation step is in catalyst In the presence of carry out, however, then the catalyst must be removed before residue cracking.
The catalyst used in the method for the invention can be any suitable catalyst.Preferred catalyst be Those of used in FCC operations, such as fresh FCC catalyst, used FCC catalyst, the FCC catalyst of balance, BCA (bottoms cracking additive) or their any mixture.
For example, the catalyst may include zeolite catalyst.Such catalyst can be selected from it is known to those skilled in the art simultaneously And commercially available crystalline microporous zeolite.(its content is by quoting in WO 2010/135273 for the preferred embodiment of zeolite catalyst Mode is incorporated herein) in be described.The specific example 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, ITQ-1, EU-1, NU-10, Silicalite-1, silicone zeolite -2, borosilicate zeolite-C, borosilicate zeolite-D, BCA and they Mixture.Alternately or additionally, catalyst may include amorphous type catalyst, may include for example silica, aluminium oxide, Kaolin or their any mixture.Silica, particularly silica in the form of husky are for FCC catalyst application For be well-known.
Technical staff knows for carrying out appropriate device and equipment according to the method for the present invention, and it will be based on it specially Industry experience selects suitable system so that need not provide more details herein.
The example of suitable type of reactor is fluid bed, carries 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, carrying Bed, spouted bed, auger and going barrel are preferred.Auger and going barrel are particularly preferred.
According to one embodiment of the method for the invention, deoxygenation step and hydrocracking step are in two different reactors Middle progress.
In a further embodiment of the method in accordance with the present invention, deoxygenation step and hydrocracking step are in the same reactor It carries out.This can then be carried out in two or more different pieces of the same section of reactor or the same reactor, Such as in the going barrel or auger operated under different temperatures in wherein different piece.
According to the method for the present invention can in batches, semi-batch or be carried out continuously.In half point batch mode, any feeding flow and Spawn stream can be continuous, but at least one feeding flow or a product stream be it is discontinuous and/or it is at least one into Stream or a product stream are continuous.
The present invention additionally relates to a kind of contain for removing from the mixture comprising plastics and at least one oxygenatedchemicals The method of oxygen compound, this method include：By the mixture be heated at least 200 DEG C of constant temperature for a period of time until from this The density that the condensate for the gas stream that the mixture of heating obtains has is about 0.94g/cm3Or it is lower.In the method, preferably Embodiment is those of as described above.
If by quote the disclosure content of any patent, patent application and publication that mode is incorporated herein with The application's illustrates mutually to conflict to the degree that term may be caused unclear, then this explanation should be preferential.
The method and its effect of the present invention are explained in greater detail referring now to following instance.
Following example is carried out according to following General experimental program：
In each catalysis operation under half point batch mode, 30g plastics (20% polypropylene, 80% polyethylene) are packed into anti- It answers in device, and will determine that the catalyst (about 20g) of amount is stored in catalyst storage tank.It closes reactor and is heated to from room temperature 200 DEG C, and the purged with nitrogen flow of 150mL/min is used simultaneously.When internal temperature reaches the fusing point of plastics, start stirring and slowly Increase to 690rpm.Temperature is kept for several minutes at 200 DEG C, to carry out plastic molten melt and homogenizing.During the heating process, The nitrogen being discharged from reactor is collected in gas sampling bag, and no condensate is recovered in liquid trap.Together When, for several times with catalyst storage tank of the nitrogen purging containing catalyst.
After first pre-treatment step, temperature is risen to less than 425 DEG C with the rate of heat addition of 10 DEG C/min.At this moment Between during, the collection of gas and nitrogen completes in another gas sampling bag.Hereafter, temperature is further increased to 425 DEG C Cracking temperature.When internal temperature reaches the cracking temperature, catalyst is introduced in reactor, and by the cycle of gaseous products It is transformed into another pair glass trap and corresponding gas sampling bag.
During the selected period, product liquid and gaseous products are collected respectively in a pair of of glass trap and its phase In the gas sampling bag of pass.At the end of experiment, reactor is cooled to room temperature.During the cooling step, liquid is also had collected And gas.
Reaction product is divided into three groups：I) gas, ii) liquid hydrocarbon and iii) residue (accumulation on a catalyst wax-like Compound, ash and coke).Gas quantitatively uses nitrogen to be used as internal standard to complete by gas chromatography (GC), and liquid and residual The quantitative of excess is then completed by weighing.Glass trap claims (together with its corresponding lid) before and after collecting liquid Weight, and reactor vessel is weighed before and after each run.
Simulation distillation (SIM-DIS) GC methods allow to measure the different fractions (according to selected fraction) in fluid sample, in detail Thin hydrocarbon analysis (DHA) GC methods allow the gasoline fraction (C5-C11 for measuring the sample finally taken out：216.1 DEG C of boiling point ＜；Its Including the C7-C11 in the C5-C6 and fluid sample in gaseous sample) in PIONAU (P：Paraffin, I：Iso-paraffins, O=：Alkene Hydrocarbon, N：Cycloalkane, A：Aromatic hydrocarbons, U：It is unidentified) component, and GCxGC allows the diesel oil for measuring the fluid sample finally taken out to evaporate Divide (C12-C21；216.1 DEG C of 359 DEG C of ＜ BP ＜) in saturate, single aromatic, two aromatic hydrocarbons and three aromatic hydrocarbons.
According to the source of plastics and purity, two-phase fluid sample is obtained.In this case, using THF as solvent with Just uniform fluid sample is obtained, and then carries out SIM-DIS, DHA and GCxGC.In addition, being titrated by Karl-Fischer Method carries out the measurement of the water concentration in the diluted samples of these liquid THF.
In these examples, HCO refers to being considered to have the hydrocarbon molecules of at least 22 carbon atoms (+C22) to recirculate Oil.Wax refers to the hydrocarbon molecule at least 20 carbon atoms (+C20).In general：
● gasoline：Including the C5 and C6+ of gas have the liquid (about C5-C9) of 150 DEG C of bp (boiling point) ＜
● kerosene：Liquid (about C10-C14) with 150 DEG C of 250 DEG C of ＜ bp ＜ of boiling point
● diesel oil：Liquid (about C15-C21) with 250 DEG C of 359 DEG C of ＜ bp ＜ of boiling point
●HCO：With 359 DEG C of products (C22 or more) of boiling point ＞
● wax：With 330 DEG C of products (C20 or more) of boiling point ＞
The measurement of different fractions by gas chromatography by simulate distillating method and according to ASTM-D-2887 standards come It carries out.
Example 1
It is tested according to above-mentioned general program.It is preheated using at about 105 DEG C to remove 80 weight %HDPE of moisture removal (in example 1.1, the pure plastics not comprising oxygenatedchemicals are for being compared with 20 weight %PP；And in 1.2 He of example In 1.3, from recycling factory and plastics containing impurity paper, metal foil etc. are for being compared) as raw material and 20g amorphous catalysts are (that is, SiO2) tested.The weight ratio of catalyst and dry plastic hybrid is equal to 20/30 (by weight Meter).These results are summarized in following table 1.
Example 2
It is tested according to above-mentioned general program.It is preheated using at about 105 DEG C to remove 80 weight %HDPE of moisture removal The fluidisation balanced as raw material and 20g with 20 weight %PP (from recycling factory, and containing impurity such as paper, metal foil etc.) Catalytic cracking catalyst (ECATDC) is tested, and the catalyst is by equilibrium catalyst company (Equilibrium Catalyst Inc it) provides.The weight ratio of catalyst and dry plastic hybrid is equal to 20/30 (by weight).Prepare three kinds of the HDPE and PP that gives up Mixture simultaneously carries out catalytic degradation (example 2.1 and 2.2).These results are summarized in following table 1.
Example 3
It is tested according to above-mentioned general program.It is preheated using at about 105 DEG C to remove 80 weight %HDPE of moisture removal It is used as raw material and 20g bottoms crackings with 20 weight %PP (from recycling factory, and containing impurity such as paper, metal foil etc.) Catalyst for additives BCA-105 is tested, which is provided by village letter Wan Feng companies (Johnson Matthey).Catalysis Agent and the weight ratio of dry plastic hybrid are equal to 20/30 (by weight) (example 3.1).These results are summarized in following table 1.
It is in upper table 1 statistics indicate that, during deoxygenation step, most of oxygenatedchemicals is removed from plastic hybrid (measuring the removal of oxygenatedchemicals by measuring the water content in sample #0).On the other hand, the sample obtained in hydrocracking step The water measured in product (sample #1-#4) is only low.This shows that the method for the present invention allows from comprising plastics and oxygen-containing chemical combination Oxygenatedchemicals is removed in the mixture of object so that seldom oxygen is only contained by gas, liquid fuel and wax that cracking obtains. Meanwhile only a small amount of plastics are cracked into during deoxygenation step so that the gas of desired low oxygen content, liquid fuel and wax it is total Body yield is still good.In addition, the product and reality that are obtained in comparison example 1.1 (using the pure plastics not comprising oxygenatedchemicals) The comparison of the product of example 1.2-3.1 shows that undesirable oxygenatedchemicals is removed before hydrocracking step will not significantly change product Distribution.

Claims (15)

1. for by cracking by the mixture comprising plastics and at least one oxygenatedchemicals be converted into gas, liquid fuel and The method of wax, this method include：
Deoxygenation step, the deoxygenation step by the mixture is heated at least 200 DEG C of constant temperature for a period of time until from The density that the condensate for the gas stream that the mixture of the heating obtains has is about 0.94g/cm3Or it lower carries out；
And the hydrocracking step after the deoxygenation step, during the hydrocracking step, make the mixture be subjected to cracking conditions with Obtain the product stream containing the gas, liquid fuel and wax.
2. according to the method described in claim 1, the deoxygenation step is wherein carried out, until what is obtained from the mixture of the heating is somebody's turn to do The density that the condensate of gas stream has is in 0.90g/cm3To 0.93g/cm3In the range of, preferably in 0.91g/cm3Extremely 0.93g/cm3In the range of, more preferably in 0.920g/cm3To 0.928g/cm3In the range of, even more preferably exist 0.923g/cm3To 0.927g/cm3In the range of, and most preferably about 0.925g/cm3。
3. method according to claim 1 or 2, range of the temperature wherein in the deoxygenation step at 250 DEG C to 400 DEG C It is interior, preferably in the range of 250 DEG C to 380 DEG C, more preferably in the range of 270 DEG C to 350 DEG C.
4. according to the method in any one of claims 1 to 3, wherein the gas stream obtained during the deoxygenation step with The product stream is held apart at each other.
5. according to any method of the preceding claims, wherein the gas stream obtained in the deoxygenation step is gone Contained based on at least one being present in before the deoxygenation step in the mixture except the removal from the mixture is persistently enough At least 50 weight % of the total weight of oxygen compound, preferably at least 70 weight %, more preferably at least 80 weight %, even more The preferably substantially time of whole at least one oxygenatedchemicals.
6. according to any method of the preceding claims, wherein the plastics include waste plastics, such as mixed waste plastic, Preferably post-consumer plastic waste, unqualified plastics and/or industrial waste plastics.
7. according to any method of the preceding claims, wherein the total weight based on plastics, the plastics include to be more than The polystyrene and/or polyolefin of 50 weight %.
8. according to any method of the preceding claims, wherein the hydrocracking step carries out in the presence of a catalyst.
9. according to the method described in claim 8, wherein deoxygenation step and the hydrocracking step carries out in the presence of a catalyst.
It is catalyzed 10. method according to claim 8 or claim 9, the wherein catalyst are zeolite catalyst and/or amorphous type Agent, such as silica, aluminium oxide, kaolin or their mixture.
11. the method according to any one of claim 8 to 10, the wherein catalyst are fresh catalyst, balance Catalyst or their mixture.
12. according to any method of the preceding claims, wherein the deoxygenation step and the hydrocracking step at two not It is carried out in same reactor.
13. method according to any one of claim 1 to 11, the wherein deoxygenation step and the hydrocracking step are same It is carried out in reactor.
14. according to any method of the preceding claims, this method in batches, semi-batch or continuously carry out.
15. the method for removing oxygenatedchemicals from the mixture comprising plastics and at least one oxygenatedchemicals, the party Method includes：
The mixture is heated at least 200 DEG C of the constant temperature gas until being obtained from the mixture of the heating for a period of time The density that the condensate of stream has is about 0.94g/cm3Or it is lower.
CN201780003036.7A 2016-12-07 2017-12-06 For by cracking by converting-plastics be gas, liquid fuel and wax method Pending CN108603122A (en)

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