CN106811228A - A kind of method of alcohols material and biomass copyrolysis - Google Patents
A kind of method of alcohols material and biomass copyrolysis Download PDFInfo
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- CN106811228A CN106811228A CN201510862577.8A CN201510862577A CN106811228A CN 106811228 A CN106811228 A CN 106811228A CN 201510862577 A CN201510862577 A CN 201510862577A CN 106811228 A CN106811228 A CN 106811228A
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- pyrolysis
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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
- C10G1/002—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
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/06—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation
- C10G1/065—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by destructive hydrogenation in the presence of a solvent
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
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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
- C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
- C10G1/086—Characterised by the catalyst used
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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
- 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
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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
- 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
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
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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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
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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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/54—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed
- C10G3/55—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds
- C10G3/57—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids characterised by the catalytic bed with moving solid particles, e.g. moving beds according to the fluidised bed technique
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- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
The invention discloses a kind of alcohols material and the method for biomass copyrolysis, it is primarily characterized in that, during biomass pyrolytic or thermal decomposition product catalytic cracking reaction, a certain amount of alcohols material is added as living radical and the donor of hydrogen, so that the living radical of alcohols cracking generation and pyrolysis combined with radical, so as to play a part of stabilization pyrolysis intermediate product, reduction pyrolysis carbon deposition quantity, reduce pyrolysis product viscosity；Meanwhile, used as hydrogen donor, alcohols material can provide hydrogen source in pyrolysis or catalytic pyrolysis process for reaction system, to play the effect such as thermal decomposition product hydrogenation, deoxidation.
Description
Technical field
The invention belongs to energy technology field, and in particular to a kind of conversion of biomass thermal produce fuel oil or
The method of other chemicals, relates more particularly to for by biomass pyrolytic or the derivative pyrolysis of its pyrolysis
The catalytic deoxidation of oil and the method that produces pyrolysis oil derived from hypoxic bio matter.
Background technology
Fast pyrogenation is that one kind uses pyrolysis reactor by organic carbonaceous biomass material, i.e. " biomass ",
300-900 DEG C is quickly heated up under anaerobic, it is produced solid product, product liquid and gaseous state
Thermal decomposition product.The condensable part (steam) of gaseous pyrolysis product is condensed into pyrolysis oil.Biomass pyrolysis oil
Can directly be burnt as fuel for some boilers and Industrial Stoves application, and be alternatively arranged as catalysis
Potential raw material in method is used to produce fuel in oil plant.However, biomass pyrolysis oil is complexity
Height oxygen close organic liquid, its property limits its use as bio-fuel at present.
For example, biomass pyrolysis oil has highly acidity and low energy densities, its major part is attributable in oil
Oxygenated hydrocarbons, it undergoes secondary reaction during storing.This kind of oxygenated hydrocarbons in biomass pyrolysis oil include
Carboxylic acid, phenol, cresols, alcohol, aldehyde etc..Pyrolysis oil derived from standard biologic matter includes more than 30wt%
The oxygen from these oxygenated hydrocarbons.Biomass pyrolysis oil changes into bio-fuel and chemicals needs biology
The deoxidation wholly or in part of pyrolysis oil derived from matter.This deoxidation can be via two main routes, i.e. water
Or CO2Elimination and carry out.But biomass pyrolysis oil deoxidation is easily caused into catalytic pyrolysis, catalysis
Pyrolysis or quick carbon distribution, blocking, the inactivation of catalytic hydrogenation treatment catalyst reactor.Obviously, just
It is the heat or acid catalyzed polymerisation due to each component of biomass pyrolysis oil, such as oily each component itself gathers
The second order reaction of conjunction.Accordingly, it is desirable to provide for producing hypoxic bio matter pyrolysis oil without blocking
Catalyst or the method for slowing down catalyst inactivation, thus improve run time and improve biomass pyrolysis oil
Processability.
The patent application of Application No. 201280060991.1 has been invented a kind of for by biomass derived
The method of pyrolysis oil deoxidation, using the pyrolysis oil for diluting containing phenol dilution agent biomass derived, and then with it is de-
VPO catalysts are contacted in hydrogen under hydroprocessing conditions.
The patent application of Application No. 201380054271.9 has been invented a kind of catalytic cracking and has been derived from comprising life
The method of the pyrolysis oil of the material of material, its core is to mix the pyrolysis oil after small part deoxidation and pre-
Heat hydrocarbon charging to prepare incoming mixture, then by the mixture at a temperature of being not less than 400 DEG C
Contact to prepare cracked product with catalytic cracking catalyst in catalyst cracker.
It can be seen that, at present both at home and abroad mainly using catalytic hydrogenation and the method for catalytic pyrolysis deoxidation.Catalysis
In hydrogenation process, the oxygen in bio oil is removed after being reacted with hydrogen in the form of hydrone, catalytic pyrolysis
Deoxidation, is that oxygen is removed in the form of carbon monoxide, carbon dioxide etc. in the presence of catalyst, is lacked
While point is deoxidation, part carbon is also lost so that final products yield is not high.Therefore, such as
What overcomes catalytic deoxidation process catalyst to be easy to coking, reaction time problem long, and improves
The problems such as final products yield, is badly in need of solving.
Therefore, based on above technological difficulties, in the urgent need to a kind of efficient stable and relatively succinct life
Thing oil preparation method, while reducing bio oil oxygen content, improving its calorific value, it is ensured that the height of process
Effect stabilization, and maintenance process Technical Economy.
The content of the invention
It is simultaneously online excellent bio oil to be prepared the purpose of the present invention is to propose to a kind of biomass pyrolytic or catalytic pyrolysis
The method for changing its quality, thermal cracking is carried out using cheap living radical donor auxiliary biomass, excellent
The working process characteristic of metaplasia material, provides reactive hydrogen and other activity certainly during biomass cracking
By carriers such as bases, the biomass pyrolytic intermediate product degree of polymerization is greatly lowered, reduces its viscosity and acidity
Deng, and the oxygen content in bio oil is reduced, biological oily yield is improved, and improve the part of bio oil
Physicochemical property.
Biomass pyrolytic proposed by the present invention or catalytic pyrolysis prepare bio oil and on-line optimization its quality
Method, according to several exemplaries, by the method for biomass pyrolytic using alcohols material
Or its solution is total to catalytic pyrolysis with biomass copyrolysis or with biomass pyrolysis product.
The invention discloses a kind of alcohols material and the method for biomass copyrolysis, it is primarily characterized in that,
During biomass pyrolytic or thermal decomposition product catalytic cracking reaction, a certain amount of alcohols material conduct is added
The donor of living radical and hydrogen so that the living radical that alcohols cracking is produced and the free base junction of pyrolysis
Close, so as to play stabilization pyrolysis intermediate product, reduction pyrolysis carbon deposition quantity, reduce pyrolysis product viscosity
Effect；Meanwhile, used as hydrogen donor, alcohols material can be reaction system in pyrolysis or catalytic pyrolysis process
Hydrogen source is provided, to play the effect such as thermal decomposition product hydrogenation, deoxidation.
Biomass pyrolytic reaction of the present invention converts biomass thermal under being included in anaerobic or anoxia condition
For liquid or gaseous product process (specifically may include rotating cone flashing speed oven, fluid bed fast pyrolysis,
Fixed-bed pyrolysis, moving bed pyrolysis, microwave-heating)；The catalytic pyrolysis is in catalysis by thermal decomposition product
Carried out in the presence of agent quadric catalysis cracking process (specifically may include thermal decomposition product quadric catalysis cracking,
Pyrolysis gas-phase product on-line continuous catalytic pyrolysis).
Alcohols material of the present invention at least includes methyl alcohol, ethanol, propyl alcohol, butanol or their homology
One kind in the pure material or solution of thing.
Alcohols material of the present invention participates in pyrolytic reaction mode at least includes in the following manner one of which：
Enter pyrolysis reactor 4 after being mixed with biomass material to participate in pyrolytic reaction, enter heat with pyrolysis carrier gas
Solve reactor 4, independently enter pyrolysis reactor 4；The alcohols material participates in catalytic cracking reaction mode
At least include in the following manner one of which：Enter catalytic reforming reaction section 5 with carrier gas or catalytic reforming is anti-
Device 9, independence is answered to be mixed into pyrolysis reaction section 5 or catalytic reforming reactor 9 and heat solution liquid product
Even laggard common entrance catalytic cracking reaction device.
According to an exemplary, the present invention is provided and for biomass pyrolytic or catalytic pyrolysis to prepare life
The method of oily simultaneously its quality of on-line optimization of thing, methods described includes making raw material and containing alcohol comprising biomass
Class material is mixed with predetermined ratio, and the raw material input containing alcohols material and biomass then is contained into deoxidation
In the pyrolysis reactor 4 of catalyst or thermoset carrier, pyrolytic reaction is rapidly completed, the pyrolysis for being generated
Product is primary pyrolysis oil.
According to another exemplary embodiment, the present invention is provided and prepares biomass pyrolytic or catalytic pyrolysis
The method of bio oil and on-line optimization its quality, methods described includes making the raw material comprising biomass continuous
In the pyrolysis reactor 4 being input into for the purpose of obtaining liquid product, fast pyrogenation is carried out, while in original
The pyrolysis zone of material is continuous to be input into alcohols material, predetermined alcohols material additional proportion according to preset ratio
Determined by the mass velocity of the sterling or the mass velocity of solution containing alcohols material and biomass material.
According to another exemplary embodiment, the present invention is provided and prepares biomass pyrolytic or catalytic pyrolysis
The method of bio oil and on-line optimization its quality, methods described includes making the raw material comprising biomass continuous
In the pyrolysis reactor being input into for the purpose of obtaining liquid product, fast pyrogenation is carried out, gas phase will be pyrolyzed
Product introduces another catalytic reforming reactor 9 after isolating ash content through cyclone separator 6, deposited in catalyst
Catalytic pyrolysis is carried out under, for the purpose of realizing deoxidation.In catalytic reforming reactor 9, continuously press
Alcohols material is input into according to preset ratio, predetermined alcohols material additional proportion is by the sterling containing alcohols material
Or the mass velocity of solution determines with the mass velocity of biomass pyrolytic gas phase product and catalyst.
The method of alcohols material of the present invention and biomass copyrolysis, it is characterised in that：The alcohols
Material consumption (or mass flowrate) is the 1%-200% of material quality (or mass flowrate).
Carrier gas used is for inert gas in pyrolytic process of the present invention or can provide hydrogen source in pyrolytic process
Or the gas of change reaction system saturated vapor pressure, at least including vapor, N2、CO、CH4、H2、
One kind in ethanol (gas), methyl alcohol (gas).
Added in pyrolysis or catalytic cracking reaction and promote alcohols material to decompose urging for generation living radical
Agent (such as Cu/ZrO2,CuO/ZrO2Deng).
Pyrolytic process of the present invention uses heat carrier, including quartz sand, microspherical catalyst etc..
Catalysis pyrolytic process of the present invention uses filler loaded catalyst, and filler used is that inertia is hard
Matter framework material, at least including the one kind in porous ceramics, ceramic honey comb, magnet ring；The catalyst
One kind in including each molecular sieve analog, modified molecular screen, load type metal catalyst etc. or they answer
Close.
Depth can be used for using the liquid phase pyrolysis product or catalytic pyrolysis product obtained by the method for the invention
Degree hydrogenation produces high hydrocarbon fuel, is directly used as fuel oil or for synthesizing or directly extracting other chemistry
Product.
Brief description of the drawings
Fig. 1 is a kind of fluid bed fast pyrolysis structure of reactor schematic diagram of embodiment.
Fig. 2 is the fluid bed fast pyrolysis structure of reactor schematic diagram of another embodiment.
Wherein：1st, carrier gas enters pipeline, 2, screw input feeder, 3, alcohols material enter pipeline, 4,
Pyrolysis reactor, 5, catalytic reforming reaction section, 6, cyclone separator, 7, condenser, 8, product
Discharge line, 9, catalytic reforming reactor, 10, alcohols material inlet port, 11, pyrolytic reaction expands
Section.
Specific embodiment
It is described below exemplary only in nature, and do not limit it is of the invention or it is of the invention application and
Use.
Embodiment 1：
Maize cob meal powder stock (particle diameter 0.5-1mm) is continuous by screw input feeder 2 after 100g is dried
Feeding fluid bed fast pyrolysis reactor 4, as shown in figure 1, conveying speed is 7-8g/min, fluid bed
Bed is quartz sand.The top of pyrolysis reactor 4 is the ZSM-5 catalyst of ceramic load, for being catalyzed
Gaseous product produced by cracking pyrolytic reaction.Pyrolysis carrier gas is 20% ethanol solution steam, by being pyrolyzed
The bottom of reactor 4 enters, and mass flow is 10g/min.Pyrolysis and catalytic pyrolysis in fluidized-bed reactor
Temperature is 500 DEG C.Gained pyrolysis liquid phase product form is as shown in table 1.
The biomass of table 1 and ethanol solution copyrolysis organic liquid phase product result
| Carrier gas condition | Organic acid | Ketone | Furans | Phenol | Hydrocarbon | Benzofuran | Other |
| 20wt% ethanol | 3.0% | 16.2% | 3.2% | 33.1% | 33.0% | 6.9% | 4.6% |
| 5wt% ethanol | 4.2% | 24.5% | 4.6% | 52.0% | 4.5% | 10.2% | 0.0% |
Obviously, with the increase of amount of alcohol under pyrolysis atmosphere, hydrocarbon component is significantly increased in pyrolysis product,
And it causes the component of the furans, ketone and organic acid of pyrolysis oil product stability difference to be greatly decreased.
Embodiment 2：
Maize cob meal powder stock (particle diameter 0.5-1mm) is continuous by screw input feeder 2 after 100g is dried
Feeding fluid bed fast pyrolysis reactor 4, as shown in Fig. 2 conveying speed is 7-8g/min, fluid bed
Bed is quartz sand.The upper catalyst reforming reaction of pyrolysis reactor 4 section 5 is the ZSM-5 of ceramic load
Catalyst, for the gaseous product produced by catalytic pyrolysis pyrolytic reaction.Pyrolysis carrier gas is nitrogen, by
The bottom of pyrolysis reactor 4 enters, and volume flow is 30L/min, and absolute ethyl alcohol is by pyrolytic reaction expanding reach
11 bottom enters, and mass flowrate is 2g/min.Pyrolysis and catalytic pyrolysis temperature in fluidized-bed reactor
It is 500 DEG C.Gained pyrolysis liquid phase product form is as shown in table 2.
The biomass of table 2 and the common catalytic pyrolysis organic liquid phase product result of ethanol solution
| Carrier gas condition | Organic acid | Ketone | Furans | Phenol | Hydrocarbon | Benzofuran | Other |
| Absolute ethyl alcohol | 1.2% | 36.07% | 12.7% | 1.7% | 46.9% | 0 | 0.6% |
Embodiment 3：
By powder stock after 100g maize straw dilute acid hydrolysis, (hydrolytic process removes hemicellulose, particle diameter
0.5-1mm, content of cellulose 53%, content of lignin 40%, other impurities 7%) by spiral conveying
Device 2 is continuously introduced into fluid bed fast pyrolysis reactor 4, as shown in figure 1, conveying speed is 7-8g/min,
Fluidized bed material is quartz sand.The upper catalyst reforming reaction of pyrolysis reactor 4 section 5 is ceramic load
ZSM-5 catalyst, Si/Al=25, for the gaseous product produced by catalytic pyrolysis pyrolytic reaction.Pyrolysis
Carrier gas is the superheated steam produced by the heating of 10% ethanol water, is entered by the bottom of pyrolysis reactor 4,
Volume flow is 33L/min.Pyrolysis and catalytic pyrolysis temperature are 550 DEG C in fluidized-bed reactor.Gained
Pyrolysis liquid phase product form is as shown in table 3.
The biomass of table 3 and the common catalytic pyrolysis organic liquid phase product result of ethanol solution
| Carrier gas condition | Organic acid | Ketone | Furans | Phenol | Hydrocarbon | Benzofuran | Other |
| Absolute ethyl alcohol | 0 | 13.5% | 8.7% | 21.7% | 40.1% | 7.4% | 8.6% |
The above embodiments merely illustrate the technical concept and features of the present invention, and this is familiar with its object is to allow
The personage of technology will appreciate that present disclosure and implements according to this, can not limit the present invention with this
Protection domain.Any equivalent change or modification in accordance with the spirit of the invention, should all cover
Within protection scope of the present invention.
Claims (11)
1. a kind of method of alcohols material and biomass copyrolysis, it is characterised in that in biomass pyrolytic
Or during catalytic cracking reaction, add alcohols material, make it with biomass material copyrolysis or with heat
The common catalytic pyrolysis of solution product.
2. according to alcohols material described in claim 1 and the method for biomass copyrolysis, it is characterised in that：
Biomass thermal is converted into liquid or gas by the biomass pyrolytic reaction under being included in anaerobic or anoxia condition
The process of body product；The catalytic pyrolysis is that thermal decomposition product is carried out into quadric catalysis in the presence of a catalyst
The process of cracking.
3. according to alcohols material described in claim 1 and the method for biomass copyrolysis, it is characterised in that：
The alcohols material at least pure material including methyl alcohol, ethanol, propyl alcohol, butanol or their homologue
Or the one kind in solution.
4. according to alcohols material described in claim 1 and the method for biomass copyrolysis, it is characterised in that：
The alcohols material participates in pyrolytic reaction mode at least includes in the following manner one of which：With biology
Enter pyrolysis reactor participation pyrolytic reaction after the mixing of matter raw material, pyrolysis reactor is entered with pyrolysis carrier gas,
Independently enter pyrolysis reactor；
The alcohols material participates in catalytic cracking reaction mode at least includes in the following manner one of which：With
Carrier gas enters catalytic cracking reaction device, independently enters pyrolysis reactor and the mixing of heat solution liquid product
Laggard common entrance catalytic cracking reaction device.
5. according to alcohols material described in claim 1 and the method for biomass copyrolysis, it is characterised in that：
The alcohols material consumption is the 1%-200% of material quality.
6. according to alcohols material described in claim 1 and the method for biomass copyrolysis, it is characterised in that：
Carrier gas used is for inert gas in pyrolytic process or can provide hydrogen source or change reaction system in pyrolytic process
The gas of saturated vapor pressure, at least including vapor, N2、CO、CH4、H2, ethanol solution steam,
One kind in methanol solution steam.
7. according to alcohols material described in claim 1 and the method for biomass copyrolysis, it is characterised in that：
Added in pyrolysis or catalytic cracking reaction and promote alcohols material to decompose the catalysis for producing living radical
Agent.
8. according to alcohols material described in claim 1 and the method for biomass copyrolysis, it is characterised in that：
The pyrolytic process uses heat carrier；The catalysis pyrolytic process uses filler loaded catalyst.
9. according to alcohols material described in claim 8 and the method for biomass copyrolysis, it is characterised in that：
The heat carrier is quartz sand, microspherical catalyst；The catalysis pyrolytic process is urged using filler support type
Agent, filler used is inertia hard skeleton material, and the catalyst includes each molecular sieve analog, is modified
One kind in molecular sieve, load type metal catalyst or theirs is compound.
10., according to alcohols material described in claim 9 and the method for biomass copyrolysis, its feature exists
In：The framework material at least includes the one kind in porous ceramics, ceramic honey comb, magnet ring.
A kind of 11. applications of claim 1 methods described, it is characterised in that：Using methods described institute
Obtained liquid phase pyrolysis product or catalytic pyrolysis product produce high hydrocarbon fuel, directly for deep hydrogenation
As fuel oil or for synthesizing or directly extracting other chemicals.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109762582A (en) * | 2019-01-22 | 2019-05-17 | 广西壮族自治区林业科学研究院 | A kind of intermittent multifunctional biomass pyrolysis plant of environmental protection |
| CN111234857A (en) * | 2020-02-11 | 2020-06-05 | 西安石油大学 | Method for regulating and controlling composition of biomass pyrolysis product by using methane catalytic activation process |
| CN111320518A (en) * | 2018-12-14 | 2020-06-23 | 中国科学院大连化学物理研究所 | Method for preparing olefin and aromatic hydrocarbon by hydrogen-assisted methane activation |
| CN112852457A (en) * | 2020-12-30 | 2021-05-28 | 东南大学 | Method for rapidly evaluating quality of lignin pyrolysis bio-oil based on free radical detection and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1432626A (en) * | 2002-11-08 | 2003-07-30 | 华东理工大学 | Catalytic cracking process of refining biological oil |
| CN101680167A (en) * | 2007-03-02 | 2010-03-24 | Eth苏黎世公司 | Method for the breakdown of lignin |
| CN102531816A (en) * | 2010-12-28 | 2012-07-04 | 中国科学院大连化学物理研究所 | Method for preparing low carbon olefin by catalytic pyrolysis of microalgae |
| CN103508858A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Method for preparing aromatic compounds employing catalytic cracking of industrial lignins |
| US20140130402A1 (en) * | 2012-11-15 | 2014-05-15 | University Of Georgia Research Foundation, Inc. | Torrefaction reduction of coke formation on catalysts used in esterification and cracking of biofuels from pyrolysed lignocellulosic feedstocks |
-
2015
- 2015-12-01 CN CN201510862577.8A patent/CN106811228A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1432626A (en) * | 2002-11-08 | 2003-07-30 | 华东理工大学 | Catalytic cracking process of refining biological oil |
| CN101680167A (en) * | 2007-03-02 | 2010-03-24 | Eth苏黎世公司 | Method for the breakdown of lignin |
| CN102531816A (en) * | 2010-12-28 | 2012-07-04 | 中国科学院大连化学物理研究所 | Method for preparing low carbon olefin by catalytic pyrolysis of microalgae |
| CN103508858A (en) * | 2012-06-29 | 2014-01-15 | 中国科学院大连化学物理研究所 | Method for preparing aromatic compounds employing catalytic cracking of industrial lignins |
| US20140130402A1 (en) * | 2012-11-15 | 2014-05-15 | University Of Georgia Research Foundation, Inc. | Torrefaction reduction of coke formation on catalysts used in esterification and cracking of biofuels from pyrolysed lignocellulosic feedstocks |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111320518A (en) * | 2018-12-14 | 2020-06-23 | 中国科学院大连化学物理研究所 | Method for preparing olefin and aromatic hydrocarbon by hydrogen-assisted methane activation |
| CN111320518B (en) * | 2018-12-14 | 2021-08-31 | 中国科学院大连化学物理研究所 | Method for preparing olefin and aromatic hydrocarbon by hydrogen-assisted methane activation |
| CN109762582A (en) * | 2019-01-22 | 2019-05-17 | 广西壮族自治区林业科学研究院 | A kind of intermittent multifunctional biomass pyrolysis plant of environmental protection |
| CN111234857A (en) * | 2020-02-11 | 2020-06-05 | 西安石油大学 | Method for regulating and controlling composition of biomass pyrolysis product by using methane catalytic activation process |
| CN112852457A (en) * | 2020-12-30 | 2021-05-28 | 东南大学 | Method for rapidly evaluating quality of lignin pyrolysis bio-oil based on free radical detection and application |
| CN112852457B (en) * | 2020-12-30 | 2021-11-23 | 东南大学 | Method for rapidly evaluating quality of lignin pyrolysis bio-oil based on free radical detection and application |
| US11703469B2 (en) | 2020-12-30 | 2023-07-18 | Southeast University | Rapid evaluation method for quality of lignin-pyrolyzed bio-oil based on radical detection and application thereof |
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