CN106010617B - A kind of method of biomass with plastic refuse pyrolysis beam system for aromatic hydrocarbons - Google Patents
A kind of method of biomass with plastic refuse pyrolysis beam system for aromatic hydrocarbons Download PDFInfo
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- CN106010617B CN106010617B CN201610425196.8A CN201610425196A CN106010617B CN 106010617 B CN106010617 B CN 106010617B CN 201610425196 A CN201610425196 A CN 201610425196A CN 106010617 B CN106010617 B CN 106010617B
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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
-
- 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
- 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
- C10G2300/10—Feedstock materials
- C10G2300/1011—Biomass
-
- 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
- C10G2300/1011—Biomass
- C10G2300/1014—Biomass of vegetal origin
-
- 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
- C10G2400/30—Aromatics
Abstract
The invention belongs to biomass energy conversion and solid waste resource recovery to utilize field.Specifically, the present invention proposes that a kind of biomass is pyrolyzed beam system for the method for aromatic hydrocarbons with plastic refuse, and biomass is pyrolyzed respectively with plastic refuse first；Selective catalysis (one stage catalyzing) is carried out secondly by respective thermal decomposition product, relative inertness, the easily macromolecular oxygenatedchemicals of formation coking and long-chain hydrocarbons in product are selectively converted to active higher small molecule oxygenatedchemicals and short linear alkene；Then the shape selective catalytic reaction (two level catalysis) by active small molecular compound over a molecular sieve catalyst, to obtain the aromatic product of more high yield and selectivity, and the coking and deactivation speed of catalyst is effectively reduced, extends catalyst life.The present invention provides a new way for the preparation of biomass-based aromatic hydrocarbon product.
Description
Technical field
The invention belongs to biomass energy conversion and solid waste resource recovery to utilize field, in particular it relates to a kind of
Method of the biomass with plastic refuse pyrolysis beam system for aromatic hydrocarbons.
Background technology
Biomass helps to alleviate me as a kind of renewable and energy sources of neutral carbon to its reasonable development and utilization
The problems such as state's scarcity of resources and environmental pollution, the sustainable development to China's economy and society are significant.Pass through pyrolysis
Biomass can be transformed into the fuel and chemical industry raw material of high added value, and do not produced substantially in thermal conversion processes
NOx、SO2Deng pollutant, while also realize CO2Zero-emission, therefore, biomass pyrolytic is considered as a kind of to substitute fossil energy
Effective way.
Aromatic hydrocarbons chemicals, the basic material important as a kind of chemical industry, in recent years because downstream product is in great demand,
Benzene, toluene etc. is caused breach occur, the supply of dimethylbenzene (PX) is even more to be chronically at the situation that supply falls short of demand in China.And aromatic hydrocarbons
It is mainly derived from coal tar and oil refining.Therefore, the research that high-quality Research on Aromatic Chemistry product are prepared using biomass as raw material is carried out
To alleviating energy shortage, ensureing that national energy security is significant.
Single creature matter raw material prepares aromatic hydrocarbons technology still in laboratory development at present, wherein, target product yield
Low and catalyst easy in inactivation is still to limit the bottleneck problem of biomass aromatic hydrocarbons technology development.Its basic reason is biomass original
Material has the characteristics of poor hydrogen, oxygen-enriched.Research shows, effective hydrogen-carbon ratio of raw material Added with height
Correlation, effective hydrogen-carbon ratio H/C between value chemicals yield be presenteff≤ 1 catalytic material pyrolysis when easily produce a large amount of carbon distributions from
And cause rapid catalyst deactivation, it is difficult to be converted into the hydrocarbon of high-quality.And the H/C of standard biologic mattereffOnly 0.1
~0.3.Therefore, have research use " hydrogen-rich " and cheap plastic refuse as hydrogen source for " poor hydrogen " biomass pyrolytic confession
Hydrogen, catalyst deactivation prob caused by carbon distribution can be alleviated to a certain extent, and improve biomass pyrolytic liquid product structure.
And synergy be present in biomass and plastic refuse altogether catalytic conversion process, it can pass through phase interaction between its thermal decomposition product
With new aromatic product is formed, aromatics yield and selectivity are further improved, such as：In biomass pyrolysis product furans with
Diene synthesis reaction (Diels-Alder condensation reactions) shape occurs between small-numerator olefin class compound caused by polyene hydrocarbon pyrolysis
Into aromatic hydrocarbons (Li X, et al.Improving the aromatic production in catalytic fast
pyrolysis of cellulose by co-feeding low-density polyethylene.Applied
Catalysis A-General 2013,455:114-21.)；The small molecule such as aldehyde, ketone, alcohols is oxygen-containing caused by biomass pyrolytic
Compound can react the formation for participating in aromatic hydrocarbons with plastic refuse pyrolysis olefin product on molecular sieve catalyst surface by hydrocarbon pond,
Be advantageous to improve aromatics yield and selectivity (Dorado C, et al.Origin of carbon in aromatic and
olefin products derived from HZSM-5catalyzed co-pyrolysis of cellulose and
plastics via isotopic labeling.Applied Catalysis B:Environmental 2015,162:
338-45.)。
But above-mentioned biomass generally uses raw material with physical admixture with plastic refuse copyrolysis aromatic hydrocarbons technology
Reacted.Following drawback be present in this traditional method：(1) common catalysis pyrolysis (including the original of biomass and plastic refuse
Direct catalysis pyrolysis and copyrolysis of the material with catalyst blending produce the catalytic pyrolysis of pyrolysis oil) concentrate on the flourishing molecule of micropore
Direct conversion on sieve catalyst, because catalyst aperture is too small, biomass contains with macromolecular in polymer primary thermal decomposition product
Oxygen compound and long chain hydrocarbons or macrocyclic compound are easier to form coking, blocking or covering catalyst surface acid in catalyst surface
Property site and reduce catalyst activity, even result in rapid catalyst deactivation；(2) on the other hand, it is big in primary pyrolysis products
Molecular components, which are difficult to enter inside microporous molecular sieve catalyst vestibule, to be reacted, and is stranded to the transfer tape of raw material and product molecule
Difficulty, conversion ratio and reaction rate is caused to reduce；(3) biomass and plastic refuse are in raw material mix, pyrolysis characteristicses and product group
Differed greatly into aspect, but the common catalysis pyrolysis of conventional physical mixing can only carry out identical pyrolytic reaction (such as biology to raw material
The parameter such as matter and the pyrolysis temperature of plastics, residence time) and catalytic reaction (such as biomass and plastics thermal decomposition product carry out catalysis and split
Solve the catalyst type and the parameter such as dosage of reaction) under the conditions of conversion, the adjustable denaturation of process reaction parameter is poor.
" a kind of composite catalyst and its system for being catalyzed pyrolysis and preparing aromatic hydrocarbons disclosed in publication No. CN103484142A patent
Preparation Method ", it is that biomass and polyolefinic raw materials are subjected to common catalysis pyrolysis with catalyst using physical admixture, although more normal
Rule physical mixed catalytic thermal transform mode is significantly increased in aromatic product selectivity and aromatic carbon yield, obtains higher life
The catalysis pyrolysis efficiency of material, but this method further relates to catalysis in addition to still having the drawbacks of above-mentioned conventional method generally existing
The problem of agent separates with pyrolysis solid product difficulty.
The content of the invention
Such as urged it is an object of the present invention to be catalyzed altogether with plastic refuse existing for pyrolytic process for current biomass
The easy coking of agent, target product yield is relatively low, response parameter is adjustable denaturation it is poor the problems such as, propose that a kind of biomass is discarded with plastics
Thing is pyrolyzed method of the beam system for aromatic hydrocarbons, and this method can obtain the aromatic product of higher conversion and selectivity, realize biomass
Converted with plastic refuse to the orientation of high added value fuels and chemicals.
To achieve these goals, the invention provides following technical scheme：
A kind of method of the biomass proposed by the present invention with plastic refuse pyrolysis beam system for aromatic hydrocarbons, as shown in Figure 1.
Biomass is pyrolyzed respectively with plastic refuse first；Secondly by selective catalysis, (one-level is urged to thermal decomposition product
Change), by relative inertness, easily the macromolecular oxygenatedchemicals of formation coking and long-chain hydrocarbons selective conversion in thermal decomposition product
For active higher small molecule oxygenatedchemicals and short linear alkene；Then by active small molecular compound in molecular sieve catalytic
More high conversion and the shape selective catalytic reaction (two level catalysis) of selectivity occur in agent, to obtain the virtue of more high yield and selectivity
Hydrocarbon products, and effectively reduce the coking and deactivation speed of catalyst.
The technological core of the present invention is exactly that (small molecule is containing oxidation by promoting activated product to the catalytic pyrolysis of thermal decomposition product
Compound and short linear alkene) formation, strengthen be beneficial to aromatic hydrocarbons formed synergy (Diels-Alder condensation reactions and hydrocarbon pond
Reaction), and then improve the yield and selectivity of target product aromatic hydrocarbons；Meanwhile using plastic refuse be pyrolyzed caused by high hydrogen carbon
Interacted than oxygenatedchemicals in thermal decomposition product and biomass pyrolysis product, effectively prevent oxygenatedchemicals in catalyst table
Face occurs Direct Pyrolysis reaction and forms a large amount of carbon distributions, reduces the deactivation rate of catalyst, extends catalyst service life.
A kind of method of the biomass proposed by the present invention with plastic refuse pyrolysis beam system for aromatic hydrocarbons, including following step
Suddenly：
(1) by biomass at a certain temperature in carrying out pyrolysis processing in pyrolysis reactor, it is oxygen-containing that formation includes macromolecular
The biomass pyrolysis product of compound；
(2) plastic refuse is formed with long-chain hydro carbons at a certain temperature in carrying out pyrolysis processing in pyrolysis reactor
Plastics thermal decomposition product based on compound；
(3) biomass pyrolysis product that step (1) is formed is carried out one by catalyst A beds in catalytic cracking reaction device
Level catalytic pyrolysis, forms the one stage catalyzing pyrolysis product of biomass based on small molecule oxygenatedchemicals；
(4) the plastics thermal decomposition product that step (2) is formed is subjected to one-level by catalyst B beds in catalytic cracking reaction device
Catalytic pyrolysis, form the one stage catalyzing pyrolysis product of plastics based on short linear alkene；
(5) by the one stage catalyzing hot tearing product of biomass that step (3) is formed with plastics that step (4) is formed are one stage catalyzing splits
Solve and two level shape selective catalysis conversion is carried out by catalyst C beds in catalytic cracking reaction device after product is sufficiently mixed, formed with light
Target product based on matter aromatic hydrocarbons.
Long-chain hydrocarbon compound of the present invention includes the hydrocarbon compound of long linear and long-chain branch.It is prepared by the present invention
Among journey obtains and final product is：Macromolecular oxygenatedchemicals (such as carbohydrate and pyridines oxygenatedchemicals, and macromolecular
The aliphatic such as acid, alcohol, ester oxygenatedchemicals), it is long linear and long-chain branch class compound (such as more than C6 long chain hydrocarbons and paraffin wax), small
Molecular oxygen-containing compound (such as methanol, furfural, below cyclopentenone C6 small molecule oxygenatedchemicals), short linear alkene (C6
And its following short linear alkene) and light aromatics (refer generally to the arene compounds that phenyl ring number is less than or equal to 2, including benzene, first
The di pah such as the mononuclear aromatics such as benzene, dimethylbenzene and naphthalene, indenes), above major name term is that those skilled in the art is ripe
Know the compound of understanding.
According to method of the present invention, wherein, biomass pyrolytic temperature is at 300~700 DEG C in step (1)；Preferably,
Biomass pyrolytic temperature is at 350~550 DEG C.
According to method of the present invention, wherein, plastics pyrolysis temperature is at 300~900 DEG C in step (2)；Preferably, mould
Expect pyrolysis temperature at 350~650 DEG C.
According to method of the present invention, wherein, the one stage catalyzing cracking reaction temperature of biomass pyrolysis product in step (3)
Scope is spent at 300~700 DEG C, it is preferable that one stage catalyzing cracking reaction temperature range is at 350~550 DEG C；Catalyst A selections pair
Macromolecular oxygenatedchemicals is big with reinforcing breakpoint effect and anti-carbon solid super acid catalyst of good performance or with
The cheap catalyst of pore structure, it is preferable that using ZrO2、TiO2、Fe2O3And ZnO2One or more in base solid super-strong acid,
Or using SiO2·Al2O3、γ-Al2O3There are the one or more in the cheap catalyst of middle macroporous structure with CaO.Wherein,
Catalyst is reacted with biomass material by any mass ratio, it is preferable that catalyst：Biomass material=1:10~10:1
(mass ratio).
According to method of the present invention, wherein, the one stage catalyzing cracking reaction temperature of plastics thermal decomposition product in step (4)
Scope is at 300~800 DEG C, it is preferable that one stage catalyzing cracking reaction temperature range is at 350~650 DEG C；Catalyst B is selected to length
Catenanes material has the cheap catalyst for strengthening breakpoint effect and anti-carbon middle macroporous structure of good performance, including SiO2·
Al2O3、γ-Al2O3With the one or more in the cheap catalyst of macroporous structure in CaO etc..Wherein, catalyst and plastic waste
Gurry raw material is reacted by any mass ratio, it is preferable that catalyst：Plastic refuse raw material=1:10~10:1 (quality
Than).
According to method of the present invention, wherein, in step (5) two level shape selective catalytic reaction temperature at 300~800 DEG C,
Preferably, shape selective catalytic reaction temperature is at 350~650 DEG C；Catalyst C is using the high ZSM-5 micro porous molecular sieves of selective activization.
Wherein, catalyst is reacted with raw material (biomass+plastic refuse) by any mass ratio, it is preferable that catalyst：Raw material
(biomass+plastic refuse)=1:10~10:1 (mass ratio).
Pressure condition in each step reaction of the invention meets the conventional pressure that pyrolysis reactor or catalytic cracking reaction device use
Power scope, is not particularly limited.
According to method of the present invention, wherein preferably, step (1) biomass and step (2) described plastic waste
The charge ratio of gurry raw material is biomass：Plastic refuse=1:10~10:1 (mass ratio).
The method according to invention, as supplement, described biomass is standard biologic matter raw material, as stalk, rice husk,
Wood chip etc.；Described plastic refuse is effective hydrogen-carbon ratio H/Ceff>=1 hydrogen-rich plastic material, such as polyethylene, polypropylene, gather
Vinyl chloride and polystyrene etc..
Pyrolysis reactor of the present invention can use conventional pyrolysis reactor, such as fixed bed, moving bed, fluidized-bed reaction
Device or helical reactors etc..The catalytic cracking reaction device can use Conventional catalytic cracking reactor, can be fixed bed, move
Dynamic bed or fluidized-bed reactor or Cyclonic reactor etc..
Technical advantage is specific as follows caused by the present invention：
(1) present invention prepares high added value aromatic hydrocarbon product using biomass and plastic refuse as raw material, realizes biomass
The utilization of the energy, and minimizing, the recycling of plastic solidification discarded object, can produce good environmental benefit and economy
Benefit.
(2) a kind of biomass provided by the invention is pyrolyzed beam system for the method for aromatic hydrocarbons, more single life with plastic refuse
Catalysis pyrolysis way can obtain the aromatic product of more high yield and selectivity altogether for the catalysis pyrolysis of material or tradition, and effectively reduce
Catalyst coking rate, extend catalyst life.Macromolecular in biomass pyrolysis product is contained by selective catalysis cracking reaction
Long-chain hydrocarbons caused by oxygen compound and polyene hydrocarbon pyrolysis are converted into the higher small molecule oxygenatedchemicals of activity and short straight
Olefine, high oxygen-bearing organic matter and the long-chain hydrocarbons that effectively prevent easily formation coking contact with ZSM-5 catalyst, from
And reducing reduces catalyst coking rate；It is anti-to strengthen shape selective catalysis using the chemical reaction between active small molecular compound simultaneously
The synergy of process is answered, to generate the aromatic product of more high yield and selectivity.
(3) a kind of biomass provided by the invention is pyrolyzed beam system for the method for aromatic hydrocarbons with plastic refuse, breaches biography
The technology limitation of converting aromatic hydrocarbons processed altogether (is catalyzed), can complete that response parameter more comprehensively, scientifically optimize.Pass through
Classification pyrolysis-catalytic pyrolysis is carried out respectively to biomass and plastic refuse, realized to courses of reaction at different levels (including biomass
The catalytic pyrolysis process and shape selective catalytic reaction process of pyrolytic process, biomass and plastics thermal decomposition product with plastics) area
Do not regulate and control, such as different pyrolysis temperatures and catalytic temperature, the corresponding different pyrolysis temperatures of different material and catalyst.
Brief description of the drawings
Fig. 1 is that the biomass of the present invention and plastic refuse are pyrolyzed process schematic representation of the beam system for the method for aromatic hydrocarbons.
Embodiment
With reference to specific embodiment, the invention will be further described.
Embodiment 1
First, by biomass (stalk) under 700 DEG C, 10MPa in carrying out pyrolysis processing in pyrolysis reactor, produce with big
Biomass pyrolysis product based on molecular oxygen-containing compound；Simultaneously by plastic refuse (vinyon) under 400 DEG C, normal pressure
In carrying out pyrolysis processing in pyrolysis reactor, the plastics thermal decomposition product based on long-chain hydrocarbon compound is formed；Wherein, biomass
Charge-mass ratio with plastic refuse is biomass：Plastics=1:10.Secondly, biomass pyrolysis product is passed through into catalytic pyrolysis
ZrO in reactor2The superpower solid acid catalyst bed of base, 700 DEG C, 10Mpa, catalyst：Biomass=1:Enter under the conditions of 10
The one stage catalyzing cracking of row, forms the one stage catalyzing pyrolysis product of biomass based on small molecule oxygenatedchemicals；Simultaneously by plastics
Thermal decomposition product passes through SiO in catalytic cracking reaction device2·Al2O3Beds, 300 DEG C, normal pressure, catalyst：Plastics are discarded
Thing=10:One stage catalyzing cracking is carried out under the conditions of 1, forms the one stage catalyzing pyrolysis product of plastics based on short linear alkene.Most
Afterwards, by catalytic cracking reaction device after the one stage catalyzing pyrolysis product of biomass and the one stage catalyzing pyrolysis product of plastics being sufficiently mixed
Interior ZSM-5 microporous molecular sieve catalysts bed carries out two level shape selective catalysis conversion, and reaction temperature is at 300 DEG C, normal pressure, catalyst：
(biomass+plastic refuse)=10:1, form the target product based on light aromatics.
Embodiment 2
The present embodiment, using experimental method and step same as Example 1, difference is：
Biomass (rice husk) and the charge ratio of plastic refuse (polyvinyl chloride) are biomass：Plastics=10:1；
Biomass pyrolytic reaction condition is 350 DEG C, normal pressure；
Plastic refuse pyrolytic reaction condition is 900 DEG C, 10MPa；
The one stage catalyzing cracking reaction of biomass pyrolysis product uses Fe2O3The superpower solid acid catalyst of base, reaction condition are
300 DEG C, normal pressure, catalyst：Biomass=10:1；
The one stage catalyzing cracking reaction of plastic refuse thermal decomposition product uses γ-Al2O3Catalyst, reaction condition be 700 DEG C,
10Mpa, catalyst：Plastic refuse=1:10；
The two level shape selective catalysis of the one stage catalyzing pyrolysis product of biomass and the mixture of plastics one-level cracked pyrolysis product is anti-
It is 650 DEG C, 10MPa to answer reaction condition, catalyst：(biomass+plastic refuse)=10:1.
Embodiment 3
The present embodiment, using experimental method and step same as Example 1, difference is：
Biomass (wood chip) and the charge ratio of plastic refuse (polystyrene) are biomass：Plastics=1:1；
Biomass pyrolytic reaction condition is 550 DEG C, 5MPa；
Plastic refuse pyrolytic reaction condition is 550 DEG C, 5MPa；
The one stage catalyzing cracking reaction of biomass pyrolysis product uses SiO2·Al2O3Catalyst, reaction condition be 550 DEG C,
5MPa, catalyst：Biomass=1:1；
The one stage catalyzing cracking reaction of plastic refuse thermal decomposition product uses CaO catalyst, reaction condition is 550 DEG C, 5MPa,
Catalyst：Plastic refuse thermal decomposition product=1:1；
The two level shape selective catalysis of the one stage catalyzing pyrolysis product of biomass and the mixture of the one stage catalyzing pyrolysis product of plastics is anti-
It is 550 DEG C, 5MPa to answer reaction condition, catalyst：(biomass+plastic refuse)=1:1.
Embodiment 4
The present embodiment, using experimental method and step same as Example 1, difference is：
Biomass (stalk) and the charge ratio of plastic refuse (polyvinyl chloride) are biomass：Plastics=10:1；
Biomass pyrolytic reaction condition is 300 DEG C, 0.1MPa；
Plastic refuse pyrolytic reaction condition is 300 DEG C, 0.1MPa；
The one stage catalyzing cracking reaction of biomass pyrolysis product uses Fe2O3The superpower solid acid catalyst of base, reaction condition are
350 DEG C, 0MPa, catalyst：Biomass=10:1；
The one stage catalyzing cracking reaction of plastic refuse thermal decomposition product uses γ-Al2O3Catalyst, reaction condition be 350 DEG C,
0Mpa, catalyst：Plastic refuse=1:10；
The two level shape selective catalysis of the one stage catalyzing pyrolysis product of biomass and the mixture of plastics one-level cracked pyrolysis product is anti-
It is 350 DEG C, 0MPa to answer reaction condition, catalyst：(biomass+plastic refuse)=10:1.
Embodiment 5
The present embodiment, using experimental method and step same as Example 1, difference is：
Biomass (rice husk) and the charge ratio of plastic refuse (polypropylene) are biomass：Plastics=1:1；
Biomass pyrolytic reaction condition is 550 DEG C, 10MPa；
Plastic refuse pyrolytic reaction condition is 650 DEG C, 10MPa；
The one stage catalyzing cracking reaction of biomass pyrolysis product uses SiO2·Al2O3Catalyst, reaction condition be 700 DEG C,
10MPa, catalyst：Biomass=1:1；
The one stage catalyzing cracking reaction of plastic refuse thermal decomposition product uses CaO catalyst, reaction condition is 800 DEG C,
10MPa, catalyst：Plastic refuse=1:1；
The two level shape selective catalysis of the one stage catalyzing pyrolysis product of biomass and the mixture of the one stage catalyzing pyrolysis product of plastics is anti-
It is 800 DEG C, 10MPa to answer reaction condition, catalyst：(biomass+plastic refuse)=1:1.
Non-elaborated part of the present invention belongs to techniques well known.
Certainly, the present invention can also have various embodiments, in the case of without departing substantially from spirit of the invention and its essence, be familiar with
Those skilled in the art can be made according to disclosure of the invention it is various it is corresponding change and deformation, but these it is corresponding change and
Deformation should all belong to the scope of the claims of the present invention.
Claims (17)
1. method of a kind of biomass with plastic refuse pyrolysis beam system for aromatic hydrocarbons, it is characterised in that comprise the following steps：
(1) biomass is formed into the biomass thermal for including macromolecular oxygenatedchemicals in carrying out pyrolysis processing in pyrolysis reactor
Solve product；
(2) plastic refuse is formed into the modeling for including long-chain hydrocarbon compound in carrying out pyrolysis processing in another pyrolysis reactor
Expect thermal decomposition product；
(3) biomass pyrolysis product that step (1) is formed is carried out into one-level by catalyst A beds in catalytic cracking reaction device to urge
Change cracking, form the one stage catalyzing pyrolysis product of biomass being mainly made up of small molecule oxygenatedchemicals；
(4) the plastics thermal decomposition product that step (2) is formed is subjected to one-level by catalyst B beds in another catalytic cracking reaction device
Catalytic pyrolysis, form the one stage catalyzing pyrolysis product of plastics being mainly made up of short linear alkene；
(5) the one stage catalyzing pyrolysis product of biomass that step (3) is formed and the one stage catalyzing cracking of plastics of step (4) formation are produced
Thing mixing after, by the 3rd catalytic cracking reaction device catalyst C beds carry out two level shape selective catalysis conversion, formed mainly by
The target product of light aromatics composition.
2. according to the method for claim 1, it is characterised in that step (1) the biomass pyrolytic temperature range be 300~
700℃。
3. according to the method for claim 2, it is characterised in that step (1) the biomass pyrolytic temperature is 350~550
℃。
4. according to the method for claim 1, it is characterised in that step (2) the plastic refuse pyrolysis temperature 300~
900℃。
5. according to the method for claim 4, it is characterised in that step (2) the plastics pyrolysis temperature is at 350~650 DEG C.
6. according to the method for claim 1, it is characterised in that step (3) described biomass pyrolysis product it is one stage catalyzing
Cracking reaction temperature range is at 300~700 DEG C.
7. according to the method for claim 1, it is characterised in that step (3) the one stage catalyzing cracking reaction temperature range
At 350~550 DEG C.
8. according to the method described in claim 1,6 or 7, it is characterised in that step (3) the catalyst A uses solid super strong
Acid catalyst or the cheap catalyst with middle macroporous structure.
9. according to the method for claim 8, it is characterised in that the catalyst A uses ZrO2、TiO2、Fe2O3And ZnO2Base
One or more in solid super acid catalyst, or using SiO2·Al2O3、γ-Al2O3Tri- kinds have middle macropore knot with CaO
One or more in the cheap catalyst of structure.
10. according to the method for claim 1, it is characterised in that step (4) the one stage catalyzing of plastics thermal decomposition product is split
Range of reaction temperature is solved at 300~800 DEG C.
11. according to the method for claim 10, it is characterised in that step (4) the plastics thermal decomposition product it is one stage catalyzing
Cracking reaction temperature range is at 350~650 DEG C.
12. according to the method described in claim 1,10 or 11, it is characterised in that step (4) the catalyst B is using in having
The cheap catalyst of macroporous structure.
13. according to the method for claim 12, it is characterised in that step (4) the catalyst B uses SiO2·Al2O3、
γ-Al2O3With the one or more in CaO.
14. according to the method for claim 1, it is characterised in that step (5) the two level shape selective catalytic reaction temperature exists
300~800 DEG C.
15. according to the method for claim 14, it is characterised in that step (5) the two level shape selective catalytic reaction temperature exists
350~650 DEG C.
16. according to the method described in claim 1,14 or 15, it is characterised in that step (5) the catalyst C uses ZSM-5
Micro porous molecular sieve.
17. according to the method for claim 1, it is characterised in that step (1) biomass and step (2) described plastics
The charge-mass ratio of discarded object is 1:10~10:1.
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