CN106010617A - Method for directionally preparing aromatic hydrocarbons by means of pyrolysis of biomass and plastic waste - Google Patents
Method for directionally preparing aromatic hydrocarbons by means of pyrolysis of biomass and plastic waste Download PDFInfo
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- CN106010617A CN106010617A CN201610425196.8A CN201610425196A CN106010617A CN 106010617 A CN106010617 A CN 106010617A CN 201610425196 A CN201610425196 A CN 201610425196A CN 106010617 A CN106010617 A CN 106010617A
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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 the field of biomass energy conversion and solid waste resource utilization, in particular to a method for directionally preparing aromatic hydrocarbons by means of pyrolysis of biomass and plastic waste. The method comprises the steps that the biomass and the plastic waste are subjected to pyrolysis separately; selective catalysis (primary catalysis) is conducted on pyrolysis products of the biomass and the plastic waste, macromolecular oxygenated compounds and long chain hydrocarbon substances which are relatively indolent and prone to coking in the products are selectively converted into micromolecular oxygenated compounds and short straight-chain olefins which are higher in activity; aromatic hydrocarbon products which are high in yield and selectivity are obtained by means of a shape selective catalytic reaction (secondary catalysis) of active micromolecular compounds on a molecular sieve catalyst, the coking deactivation rate of the catalyst is effectively decreased, and the catalyst life is prolonged. The method for directionally preparing the aromatic hydrocarbons by means of pyrolysis of the biomass and the plastic waste provides a novel approach for preparation of biomass-based aromatic hydrocarbon products.
Description
Technical field
The invention belongs to biomass energy conversion and solid waste resource recovery utilizes field, in particular it relates to one
Plant biomass and be pyrolyzed the beam system method for aromatic hydrocarbons with plastic refuse.
Background technology
Its reasonable development and utilization, as a kind of renewable and energy sources of neutral carbon, are contributed to alleviating by biomass
The problems such as china natural resources scarcity and environmental pollution, the sustainable development to China's economy and society is significant.
Biomass can be transformed into fuel and the chemical industry raw material of high added value by pyrolysis, and in thermal conversion processes
In the most do not produce NOx、SO2Deng pollutant, the most also realize CO2Zero-emission, therefore, biomass pyrolytic
It it is considered as a kind of effective way substituting fossil energy.
Aromatic hydrocarbons chemicals, as the basic material that a class chemical industry is important, prosperous because of downstream product demand in recent years
Containing, cause benzene, toluene etc. breach occur, the supply at China's dimethylbenzene (PX) is chronically at that supply falls short of demand especially
Situation.And aromatic hydrocarbons is mainly derived from coal tar and oil refining.Therefore, carry out with biomass for raw material preparation height
The research of quality Research on Aromatic Chemistry product is to alleviating energy shortage, ensureing that national energy security is significant.
At present single creature raw material prepares aromatic hydrocarbons technology still in laboratory development, and wherein, target product is received
Rate is low and catalyst easy in inactivation is still the bottleneck problem limiting the development of biomass aromatic hydrocarbons technology.Its basic reason is
Biomass material has lean hydrogen, oxygen-enriched feature.Research shows, available hydrogen carbon ratio H/C of raw materialeff And there is dependency, available hydrogen carbon ratio H/C between high valuable chemicals productivityeff≤ 1
Easily produce a large amount of carbon distribution during catalytic material pyrolysis thus cause rapid catalyst deactivation, it is difficult to be converted into high-quality
Hydrocarbon.And the H/C of standard biologic mattereffIt is only 0.1～0.3.Therefore, research is had to use " hydrogen-rich " and cheap
Plastic refuse as the biomass pyrolytic hydrogen supply that hydrogen source is " lean hydrogen ", catalyst can be alleviated to a certain extent because of long-pending
The deactivation prob that carbon causes, and improve biomass pyrolytic liquid product structure.And discard with plastics in biomass
There is synergism in thing catalytic conversion process altogether, new aromatic hydrocarbons can be formed by interacting between its thermal decomposition product and produce
Thing, improves aromatics yield and selectivity, such as further: furans and polyolefin heat in biomass pyrolysis product
Solve and between the small-numerator olefin compounds produced, occur diene synthesis reaction (Diels-Alder condensation reaction) to be formed
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 little molecular oxygen-containing compounds such as the aldehyde of biomass pyrolytic generation, ketone, alcohols are pyrolyzed alkene with plastic refuse
Hydrocarbon products can participate in the formation of aromatic hydrocarbons on molecular sieve catalyst surface by the reaction of hydrocarbon pond, is conducive to improving aromatics yield
With 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 and the plastic refuse copyrolysis commonly used raw material of aromatic hydrocarbons technology are with physical mixed side
Formula is reacted.This traditional method suffers from the drawback that the common catalytic thermal of (1) biomass and plastic refuse
Solution (including that the directly catalysis that raw material and catalyst are blended is pyrolyzed and the catalytic pyrolysis of copyrolysis generation pyrolysis oil) is concentrated
Directly converting on the molecular sieve catalyst that micropore is flourishing, owing to catalyst aperture is too small, biomass and polymer
In primary pyrolysis products, macromole oxygenatedchemicals and long chain hydrocarbon or macrocyclic compound are easier to be formed at catalyst surface
Coking, blocking or covering catalyst surface acid site and reduce catalyst activity, even result in catalyst and quickly lose
Live；(2) on the other hand, the macromolecular components in primary pyrolysis products is difficult to enter microporous molecular sieve catalyst vestibule
Inside is reacted, and brings difficulty to the transmission of raw material and product molecule, causes conversion ratio and reaction rate to reduce；(3)
Biomass differ greatly in terms of raw material mix, pyrolysis characteristics and product composition with plastic refuse, but conventional physical
The common catalysis pyrolysis of mixing raw material can only be carried out identical pyrolytic reaction (as biomass and plastics pyrolysis temperature,
The parameters such as the time of staying) and catalytic reaction (as biomass and plastic hot hydrolysis products carry out the catalysis of catalytic cracking reaction
The parameters such as agent kind and consumption) under the conditions of conversion, the adjustable degeneration of process reaction parameter is poor.
The patent of publication No. CN103484142A disclosed " a kind of be catalyzed pyrolysis prepare aromatic hydrocarbons composite catalyst and
Preparation method ", it is to use physical admixture to carry out common catalysis pyrolysis with catalyst biomass and polyolefinic raw materials,
Although more conventional physical mixed catalytic thermal transform mode is significantly increased on aromatic product selectivity and aromatic carbon yield,
Obtain the catalysis pyrolysis efficiency of higher biomass, but the method is except still having above-mentioned conventional method generally to exist
Outside drawback, further relate to the problem that catalyst separates with pyrolysis solid product difficulty.
Summary of the invention
It is an object of the invention to, exist such as with plastic refuse catalytic thermal solution preocess altogether for current biomass
The problems such as the easy coking of catalyst, target product productivity is relatively low, response parameter is adjustable degeneration difference, propose a kind of biomass
Being pyrolyzed the beam system method for aromatic hydrocarbons with plastic refuse, the method can obtain higher conversion and selective aromatic hydrocarbons
Product, it is achieved biomass convert to the orientation of high added value fuels and chemicals with plastic refuse.
To achieve these goals, the technical scheme is that
A kind of biomass that the present invention proposes and plastic refuse are pyrolyzed the beam system method for aromatic hydrocarbons, such as accompanying drawing 1 institute
Show.First biomass are pyrolyzed respectively with plastic refuse；Secondly by thermal decomposition product ground selective catalysis
(one stage catalyzing), by relative inertness, the macromole oxygenatedchemicals being easily formed coking and long catenanes in thermal decomposition product
Material is selectively converted to the higher little molecular oxygen-containing compound of activity and short linear alkene；Then by little point of activity
There is more high conversion and selective shape selective catalytic reaction (two grades of catalysis) over a molecular sieve catalyst in sub-compound,
Obtain more high yield and selective aromatic product, and effectively reduce the coking and deactivation speed of catalyst.
The technological core of the present invention is through the catalytic pyrolysis to thermal decomposition product and promotes activated product (little molecular oxygen-containing
Compound and short linear alkene) formation, strengthening is beneficial to the synergism that aromatic hydrocarbons formed, and (Diels-Alder condensation is anti-
Should react with hydrocarbon pond), and then improve productivity and the selectivity of target product aromatic hydrocarbons；Meanwhile, plastic refuse heat is utilized
Solve the high hydrogen-carbon ratio thermal decomposition product produced to interact with oxygenatedchemicals in biomass pyrolysis product, effectively prevent
Oxygenatedchemicals occurs direct cracking reaction to form a large amount of carbon distribution at catalyst surface, reduces the inactivation of catalyst
Speed, extends catalyst service life.
A kind of biomass that the present invention proposes and plastic refuse are pyrolyzed the beam system method for aromatic hydrocarbons, including following step
Rapid:
(1) biomass are carried out at a certain temperature in pyrolysis reactor pyrolysis processing, formed and include that macromole contains
The biomass pyrolysis product of oxygen compound；
(2) plastic refuse is carried out at a certain temperature in pyrolysis reactor pyrolysis processing, formed with long chain hydrocarbon
Compounds is main plastic hot hydrolysis products；
(3) biomass pyrolysis product step (1) formed passes through catalytic cracking reaction device inner catalyst A bed
Carry out one stage catalyzing cracking, form the one stage catalyzing pyrolysis product of biomass based on little molecular oxygen-containing compound；
(4) plastic hot hydrolysis products step (2) formed is entered by catalytic cracking reaction device inner catalyst B bed
The one stage catalyzing cracking of row, forms the one stage catalyzing pyrolysis product of plastics based on short linear alkene；
(5) the plastics one-level that biomass one stage catalyzing hot tearing product step (3) formed and step (4) are formed
Catalytic pyrolysis product carries out two grades of shape selective catalysis by catalytic cracking reaction device inner catalyst C bed after being sufficiently mixed and turns
Change, form the target product based on light aromatics.
Long-chain hydrocarbon compound of the present invention includes the hydrocarbon compound of long linear and long-chain branch.Prepared by the present invention
In the middle of process obtains and end product is: macromole oxygenatedchemicals (such as saccharide and pyridines oxygenatedchemicals, with
And the aliphatic oxygenatedchemicals such as macromole acid, alcohol, ester), long linear and long-chain branch compounds be (such as more than C6
Long chain hydrocarbon and paraffin wax etc.), little molecular oxygen-containing compound (little point such as below C6 such as methanol, furfural, cyclopentenones
Sub-oxygenatedchemicals), short linear alkene (C6 and following short linear alkene thereof) and light aromatics (refer generally to benzene
The number of rings arene compounds less than or equal to 2, mononuclear aromatics and naphthalene, the indenes etc. two such as including benzene,toluene,xylene
PAH), above major name term is the compound that those skilled in the art is familiar with understanding.
According to method of the present invention, wherein, in step (1) biomass pyrolytic temperature at 300～700 DEG C；Excellent
Selection of land, biomass pyrolytic temperature is at 350～550 DEG C.
According to method of the present invention, wherein, in step (2) plastics pyrolysis temperature at 400～900 DEG C；Preferably
Ground, plastics pyrolysis temperature is at 450～650 DEG C.
According to method of the present invention, wherein, in step (3), the one stage catalyzing cracking of biomass pyrolysis product is anti-
Answer temperature range at 300～700 DEG C, it is preferable that one stage catalyzing cracking reaction temperature range is at 350～550 DEG C；Catalysis
Agent A selects that macromole oxygenatedchemicals is had strengthening scission of link effect and anti-carbon solid super-strong acid of good performance is urged
Agent or there is the cheap catalyst of middle macroporous structure, it is preferable that use ZrO2、TiO2、Fe2O3And ZnO2Base
One or more in solid super-strong acid, or use SiO2·Al2O3、γ-Al2O3With CaO, there is middle macroporous structure
Cheap catalyst in one or more.Wherein, catalyst and biomass material are carried out instead by any mass ratio
Should, 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 of plastic hot hydrolysis products in step (4)
Temperature range 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 selects to have a long-chain hydrocarbons inexpensively urging of strengthening scission of link effect and anti-carbon middle macroporous structure of good performance
Agent, including SiO2·Al2O3、γ-Al2O3With one or more in the cheap catalyst of macroporous structure in CaO etc..
Wherein, catalyst is reacted by any mass ratio with plastic refuse raw material, it is preferable that catalyst: plastics
Waste materials=1:10～10:1 (mass ratio).
According to method of the present invention, wherein, in step (5), two grades of shape selective catalytic reaction temperature are at 300～800 DEG C,
Preferably, shape selective catalytic reaction temperature is at 350～650 DEG C；Catalyst C uses the ZSM-5 that selective activization is high micro-
Porous molecular sieve.Wherein, catalyst is reacted by any mass ratio with raw material (biomass+plastic refuse),
Preferably, catalyst: raw material (biomass+plastic refuse)=1:10～10:1 (mass ratio).
The present invention respectively walks the pressure condition in reaction and meets the conventional pressure of pyrolysis reactor or the use of catalytic cracking reaction device
Power scope, is not particularly limited.
According to method of the present invention, the most preferably, step (1) described biomass and step (2) are described
The charge ratio of plastic refuse raw material is biomass: plastic refuse=1:10～10:1 (mass ratio).
According to invention described in method, as supplement, described biomass are standard biologic raw material, as straw,
Rice husk, wood flour etc.；Described plastic refuse is available hydrogen carbon ratio H/CeffThe hydrogen-rich plastic material of >=1, such as poly-second
Alkene, polypropylene, polrvinyl chloride and polystyrene etc..
Pyrolysis reactor of the present invention can use conventional pyrolysis reactor, such as fixed bed, moving bed, fluid bed
Reactor or helical reactors etc..Described catalytic cracking reaction device can use Conventional catalytic cracking reactor, permissible
It is fixed bed, moving bed or fluidized-bed reactor or Cyclonic reactor etc..
The technical advantage that the present invention produces is specific as follows:
(1) present invention prepares high added value aromatic hydrocarbon product with biomass and plastic refuse for raw material, it is achieved that biological
The utilization in mass-energy source, and the minimizing of plastic solidification garbage, recycling, it is possible to produce good environment
Benefit and economic benefit.
(2) a kind of biomass that the present invention provides and plastic refuse are pyrolyzed the beam system method for aromatic hydrocarbons, more single
The catalysis pyrolysis of biomass or tradition are catalyzed pyrolysis way altogether can obtain more high yield and selective aromatic product, and
Effectively reduce catalyst coking rate, extend catalyst life.By selective catalysis cracking reaction by biomass pyrolytic
The long-chain hydrocarbons that in product, macromole oxygenatedchemicals and polyolefin pyrolysis produce is converted into little point that activity is higher
Sub-oxygenatedchemicals and short linear alkene, effectively prevent and be easily formed the high oxygen-bearing organic matter of coking and long catenanes
Material contacts with ZSM-5 catalyst, thus reduces reduction catalyst coking rate；Utilize active small molecular simultaneously
Chemical reaction between compound strengthens the synergism of shape selective catalytic reaction process, to generate more high yield and selectivity
Aromatic product.
(3) a kind of biomass that the present invention provides and plastic refuse pyrolysis beam system are for the method for aromatic hydrocarbons, breach
The technology of tradition altogether (catalysis) converting aromatic hydrocarbons processed is limited to, and can complete to carry out response parameter more comprehensively, science
Ground optimizes.By biomass and plastic refuse are carried out classification pyrolysis-catalytic pyrolysis respectively, it is achieved that at different levels instead
Answer process (include biomass and the pyrolytic process of plastics, biomass and plastic hot hydrolysis products catalytic pyrolysis process with
And shape selective catalytic reaction process) difference regulation and control, as corresponding not in different pyrolysis temperatures and catalytic temperature, different material
With pyrolysis temperature and catalyst etc..
Accompanying drawing explanation
Fig. 1 is that the biomass of the present invention are pyrolyzed the beam system process schematic representation for the method for aromatic hydrocarbons with plastic refuse.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
First, by biomass (straw) 700 DEG C, in pyrolysis reactor, carry out pyrolysis processing under 10MPa, produce
Life is based on the biomass pyrolysis product of macromole oxygenatedchemicals；Simultaneously by plastic refuse (vinyon)
400 DEG C, in pyrolysis reactor, carry out pyrolysis processing under normal pressure, form the plastics based on long-chain hydrocarbon compound
Thermal decomposition product；Wherein, biomass are biomass with the charge-mass ratio of plastic refuse: plastics=1:10.Secondly,
By biomass pyrolysis product by ZrO in catalytic cracking reaction device2Base superpower solid acid catalyst bed, 700 DEG C,
10Mpa, catalyst: carry out one stage catalyzing cracking under the conditions of biomass=1:10, formed with little molecular oxygen-containing compound
It it is the main one stage catalyzing pyrolysis product of biomass；Simultaneously by plastic hot hydrolysis products by catalytic cracking reaction device
SiO2·Al2O3Beds, 300 DEG C, normal pressure, catalyst: carry out one under the conditions of plastic refuse=10:1
Level catalytic pyrolysis, forms the one stage catalyzing pyrolysis product of plastics based on short linear alkene.Finally, by biomass one
Level catalytic pyrolysis product passes through ZSM-5 in catalytic cracking reaction device after being sufficiently mixed with the one stage catalyzing pyrolysis product of plastics
Microporous molecular sieve catalyst bed carries out two grades of shape selective catalysis and converts, reaction temperature at 300 DEG C, normal pressure, catalyst:
(biomass+plastic refuse)=10:1, forms the target product based on light aromatics.
Embodiment 2
The present embodiment, uses experimental technique same as in Example 1 and step, and difference is:
Biomass (rice husk) are biomass with the charge ratio of plastic refuse (polrvinyl chloride): 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 is
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 is 700 DEG C,
10Mpa, catalyst: plastic refuse=1:10；
The one stage catalyzing pyrolysis product of biomass is anti-with two grades of shape selective catalysis of the mixture of plastics one-level cracked pyrolysis product
Answering reaction condition is 650 DEG C, 10MPa, catalyst: (biomass+plastic refuse)=10:1.
Embodiment 3
The present embodiment, uses experimental technique same as in Example 1 and step, and difference is:
Biomass (wood flour) are biomass with the charge ratio of plastic refuse (polystyrene): 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 is 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；
Two grades of shape selective catalysis of the mixture of the one stage catalyzing pyrolysis product of biomass pyrolysis product one stage catalyzing with plastics are anti-
Answering reaction condition is 550 DEG C, 5MPa, catalyst: (biomass+plastic refuse)=1:1.
Embodiment 4
The present embodiment, uses experimental technique same as in Example 1 and step, and difference is:
Biomass (straw) are biomass with the charge ratio of plastic refuse (polrvinyl chloride): 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 is
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 is 350 DEG C,
0Mpa, catalyst: plastic refuse=1:10；
The one stage catalyzing pyrolysis product of biomass is anti-with two grades of shape selective catalysis of the mixture of plastics one-level cracked pyrolysis product
Answering reaction condition is 350 DEG C, 0MPa, catalyst: (biomass+plastic refuse)=10:1.
Embodiment 5
The present embodiment, uses experimental technique same as in Example 1 and step, and difference is:
Biomass (rice husk) are biomass with the charge ratio of plastic refuse (polypropylene): 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 is 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；
Two grades of shape selective catalysis of the mixture of the one stage catalyzing pyrolysis product of biomass pyrolysis product one stage catalyzing with plastics are anti-
Answering reaction condition is 800 DEG C, 10MPa, 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 present invention spirit and essence thereof,
Those of ordinary skill in the art can make various corresponding change and deformation according to disclosure of the invention, but these phases
The change answered and deformation all should belong to the scope of the claims of the present invention.
Claims (10)
1. biomass are pyrolyzed the beam system method for aromatic hydrocarbons with plastic refuse, it is characterised in that include following
Step:
(1) biomass are carried out in pyrolysis reactor pyrolysis processing, form the life including macromole oxygenatedchemicals
Material pyrolysis product；
(2) plastic refuse is carried out in another pyrolysis reactor pyrolysis processing, formed and include long-chain hydrocarbon
The plastic hot hydrolysis products of thing；
(3) biomass pyrolysis product step (1) formed passes through catalytic cracking reaction device inner catalyst A bed
Carry out one stage catalyzing cracking, form the one stage catalyzing pyrolysis product of biomass being mainly made up of little molecular oxygen-containing compound；
(4) plastic hot hydrolysis products step (2) formed passes through another catalytic cracking reaction device inner catalyst B bed
Layer carries out one stage catalyzing cracking, forms the one stage catalyzing pyrolysis product of plastics being mainly made up of short linear alkene；
(5) the plastics one-level that the one stage catalyzing pyrolysis product of biomass step (3) formed and step (4) are formed
After the mixing of catalytic pyrolysis product, carry out two grades by the 3rd catalytic cracking reaction device inner catalyst C bed and shape-selective urge
Change and convert, form the target product being mainly made up of light aromatics.
Method the most according to claim 1, it is characterised in that step (1) described biomass pyrolytic temperature
Scope is 300～700 DEG C；Preferably, biomass pyrolytic temperature is at 350～550 DEG C.
Method the most according to claim 1, it is characterised in that step (2) described plastic refuse is pyrolyzed
Temperature is at 300～900 DEG C；Preferably, plastics pyrolysis temperature is at 350～650 DEG C.
Method the most according to claim 1, it is characterised in that step (3) described biomass pyrolysis product
One stage catalyzing cracking reaction temperature range at 300～700 DEG C, it is preferable that one stage catalyzing cracking reaction temperature range exists
350～550 DEG C.
5. according to the method described in claim 1 or 4, it is characterised in that step (3) described catalyst A adopts
By solid super acid catalyst or the cheap catalyst with middle macroporous structure, it is preferable that use ZrO2、TiO2、
Fe2O3And ZnO2One or more in base solid super acid catalyst, or use SiO2·Al2O3、γ-Al2O3With
CaO tri-kinds has one or more in the cheap catalyst of middle macroporous structure.
Method the most according to claim 1, it is characterised in that step (4) described plastic hot hydrolysis products
One stage catalyzing cracking reaction temperature range is at 300～800 DEG C；Preferably, one stage catalyzing cracking reaction temperature range exists
350～650 DEG C.
7. according to the method described in claim 1 or 6, it is characterised in that step (4) described catalyst B adopts
By the cheap catalyst with middle macroporous structure, it is preferable that use SiO2·Al2O3、γ-Al2O3With in CaO
Plant or several.
Method the most according to claim 1, it is characterised in that the described two grades of shape selective catalysis of step (5) are anti-
Answer temperature at 300～800 DEG C；Preferably, two grades of shape selective catalytic reaction temperature are at 350～650 DEG C.
9. according to the method described in claim 1 or 8, it is characterised in that step (5) described catalyst C adopts
Use ZSM-5 micro porous molecular sieve.
Method the most according to claim 1, it is characterised in that step (1) described biomass and step (2)
The charge-mass ratio of described plastic refuse is 1:10～10:1.
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| CN114433054B (en) * | 2021-12-22 | 2023-07-25 | 山东科盟新能源开发集团有限公司 | Method for preparing monocyclic aromatic hydrocarbon by catalyzing pyrolysis of solid waste through boron-doped activated carbon |
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