CN104046373B - The method being prepared bio-oil and synthesis gas by biomass - Google Patents
The method being prepared bio-oil and synthesis gas by biomass Download PDFInfo
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Abstract
The present invention relates to a kind of method being prepared bio-oil and synthesis gas by biomass, the method comprises the following steps: biomass, in the presence of heat carrier, are carried out cracking reaction by (1), obtain oil gas and solid product；(2) described oil gas is carried out Oil-gas Separation, isolate cracking gas and bio-oil；(3) described solid product is carried out solid separation, isolate coke and heat carrier；(4) described coke and gasifying medium are carried out gasification reaction, and isolate synthesis gas from gasification reaction product.The described method provided according to the present invention can utilize biomass to prepare in bio-oil and synthesis gas, and the synthesis gas prepared simultaneously and be substantially free of tar.
Description
Technical field
The present invention relates to a kind of method being prepared bio-oil and synthesis gas by biomass.
Background technology
Biomass are a kind of reproducible green energy resources, including agricultural crop straw, forestry waste, poultry
Feces, organic garbage of city, water plant, energy-source plant etc..At present, whole world biomass consumption is only
Inferior to coal, oil, natural gas, occupy the 4th.Estimate according to biologist, the earth grows every year
Biomass energy total amount about 1400-1800 hundred million tons, be equivalent to 10 times of current world total energy consumption.China
For large agricultural country, there are substantial amounts of agricultural waste material, wherein straw (Caulis et Folium Oryzae, straw, corn stalk every year
Deng) there are 600,000,000 tons every year, agricultural machining residue (rice husk, bagasse etc.) about 3.89 hundred million tons.Biomass
Can have the feature of carbon dioxide zero discharge as a kind of low-carbon (LC), low-sulfur, low nitrogen fuel, it is as one
Plant clean energy resource to be conducive to alleviating the most serious greenhouse effect.
The technology that utilizes of biomass is broadly divided into three kinds of modes: physical transformation, biotransformation and chemical conversion.
Physical transformation refers to the compressed molding of biomass, solves its transport and stores inconvenient problem.Biotransformation
Referring to that biomass obtain purpose product through microbial treatments, treating capacity is by growth of microorganism quantitative limitation.
Biomass apply most technology to be chemical conversion technology, including directly burning, gasify, thermal cracking and adding
Four kinds of technology of hydraulic fluidization.Various technology use respective equipment and operating parameters, and produce respective product.
The directly burning of biomass is the most common biomass energy switch technology, and so-called directly burning is exactly in fuel
Combustible component and oxidant (the generally oxygen in air) carry out the chemical reaction process of chemical combination,
Course of reaction is released heat strongly, and makes the temperature of combustion product raise.Its main purpose obtains exactly
Heat.Gasification of biomass is exactly to utilize the oxygen in air or oxygen carrier to make gasifying agent, by solid fuel
In oxidation of coal generate fuel gas process.Biomass through pyrolysis refer to biomass entirely without oxygen or
Thermal degradation under anoxia condition, end product generates bio-oil and some by-products.Bio-oil is modified
Process can replace power oil, or through refining further, can produce various chemical products.Give birth to simultaneously
The low-sulfur that material oil has, low nitrogen, low ash grade characteristic so that it is become cleaning fuel, utilize efficient
Biomass switch technology, is converted to high-grade bio-oil fuel, not only by discarded biomass resource
Agricultural Output can be improved, and pollution can be reduced, promote ecological benign cycle, make up and oil is provided
The dependence in source.Gasification of biomass is to utilize biomass and gasifying medium reaction to obtain synthesis gas, this technology
There is gaseous product and contain a small amount of tar, need to increase tar-removing device.Owing to biomass contain oxidation
Thing is more, needs to consume more hydrogen source when pressurized liquefied, and its application is limited.
CN101544901A discloses a kind of method that biomass through pyrolysis produces bio-oil, the method
Including: biomass enter fluid bed and mix generation cracking reaction with heat carrier, and thermal decomposition product and heat carrier enter
Entering follow-up separator heat carrier and thermal decomposition product to be separated, heat carrier enters thermal fluid heater, as heat
The cracking gas of hydrolysis products and coke enter gas-solid separator below, coke and ash and enter carrier heating
Device, combustion of coke and the most condensable cracking gas are to heat heat carrier, and the heat carrier after intensification returns fluid bed
Reactor.Heat carrier in fluidized-bed reactor enters carrier separator together with thermal decomposition product, adds
The oil gas time of staying, reduce the yield of bio-oil.
CN1272404C discloses a kind of biomass gasification method, and the method includes: by solid biomass
Biomass separately, is become tar content extremely low by cracking two processes of gasification of pyrolysis and thermal decomposition product
Fuel gas.First biomass being sent into pyrolysis reactor and carries out pyrolytic reaction, thermal decomposition product includes pyrolysis
Gas and carbon residue enter in cracking gasifier, with the oxidant generation incomplete oxidation combustion reaction being passed through, shape
Becoming the high-temperature region of 900-1000 DEG C, now the heavy hydrocarbon of so-called tar is cracked into micro-molecular gas,
Gasifier is left after the layer of charcoal generation reduction reaction that gas after cracking is red-hot with bottom.
But, above-mentioned existing method is manufactured separately bio-oil or synthesis gas only with biomass, and
Do not utilize biomass to prepare the relevant report of bio-oil and synthesis gas simultaneously.
Summary of the invention
The invention aims to overcome existing biomass economy technique that biomass can only be manufactured separately
Oil or the defect of synthesis gas, it is provided that a kind of method being prepared bio-oil and synthesis gas by biomass.
The invention provides a kind of method being prepared bio-oil and synthesis gas by biomass, the method bag
Include: biomass, in the presence of heat carrier, are carried out cracking reaction by (1), obtain oil gas and solid product；
(2) described oil gas is carried out Oil-gas Separation, isolate cracking gas and bio-oil；(3) by described solid
Body product carries out solid separation, isolates coke and heat carrier；(4) described coke and gasifying medium are entered
Row gasification reaction, and isolate synthesis gas from gasification reaction product.
Biomass can be utilized to prepare bio-oil and synthesis according to the described method that the present invention provides simultaneously
Gas, and the synthesis gas prepared are substantially free of tar, thus without managing to remove Jiao in synthesis gas
Oil.
Other features and advantages of the present invention will be described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with
Detailed description below is used for explaining the present invention together, but is not intended that limitation of the present invention.?
In accompanying drawing:
Fig. 1 is the technique being prepared the method for bio-oil and synthesis gas described in present invention offer by biomass
Flow chart.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that this place is retouched
The detailed description of the invention stated is merely to illustrate and explains the present invention, is not limited to the present invention.
What the present invention provided described prepared the method for bio-oil and synthesis gas by biomass and includes:
(1) in the presence of heat carrier, biomass are carried out cracking reaction, obtain oil gas and solid produces
Thing；
(2) described oil gas is carried out Oil-gas Separation, isolate cracking gas and bio-oil；
(3) described solid product is carried out solid separation, isolate coke and heat carrier；
(4) described coke and gasifying medium are carried out gasification reaction, and separate from gasification reaction product
Go out synthesis gas.
In step (1), there is no particular limitation for described crack reacting condition, can be that this area is normal
The biomass through pyrolysis condition of rule.In the preferred case, in order to obtain higher bio-oil yield, institute
State crack reacting condition to include: temperature is 300-700 DEG C, more preferably 350-600 DEG C；Pressure is
0.1-20MPa, more preferably 0.1-10MPa；Time is the 0.1-1000 second, the preferably 0.1-600 second.
In the present invention, described pressure refers to absolute pressure.Operation temperature during described cracking reaction refers to
Temperature after biomass contact with heat carrier, when the two occurs heat transfer and reaches balance.
Operation temperature during described cracking reaction can be carried out by the amount of the heat carrier added and temperature
Flexible.There is no particular limitation for the temperature of described heat carrier, can be the heat carrier of this area routine
Temperature, such as, can be 600-1200 DEG C.Described heat carrier can be heat carrier commonly used in the art,
Can be such as at least one in quartz sand, aluminium oxide, dead catalyst and Ceramic Balls.
There is no particular limitation for the particle size of described heat carrier, can be according to the granule of conventional heat carrier
Select appropriately sizedly.Under preferable case, in order to make described heat carrier show preferable heat-transfer effect,
The heat carrier selecting particle size to be 0.03-10 millimeter.In the present invention, particle size refers to by sieve
Get the mesh size of the screen cloth of this granule.
In a preferred embodiment, for enabling biomass to crack fully, described biomass are being carried out
100-300 DEG C it is preferably heated to before cracking reaction.
In a preferred embodiment, for enabling biomass to crack fully, institute during cracking reaction
The particle size stating biomass is 0.05-5 millimeter.In order to obtain the biomass of above-mentioned particle size, permissible
Large-sized biomass are pulverized and realizes.
In the present invention, described biomass can be the biomass material of various routine, such as, can be choosing
Plant from agricultural crop straw, agricultural waste material, forestry waste, organic waste, water plant and the energy
At least one in thing.
Described cracking reaction can be carried out in the cracking reactor of various routines, as long as being capable of biology
Matter cracking reaction.Described cracking reactor can be selected from fluidized-bed reactor, riser reactor,
One or more combining form in down-flow reactor and moving-burden bed reactor.
In step (2), the process of described Oil-gas Separation can use the method for routine to implement.Such as,
Fractionating column can be used according to the difference of the condensation temperature of each different component in oil gas or uses temperature control cold
Solidifying mode separates.
In step (3), the process that described solid separates can be implemented in conventional solid separator,
As long as granule of different nature can be separated by this solid separator.Described solid separator such as may be used
Think fluidized-bed reactor.
In the present invention, the operation order of step (2) and (3) does not limit, step (2) and (3)
Can the most successively operate, it is also possible to the two implements simultaneously.
In the present invention, described prepared the method for bio-oil and synthesis gas by biomass and can also include:
By burn combustible thing, isolated heat carrier in step (3) is heated, and the heat load after heating
Body is recycled as the heat carrier in step (1).In the preferred case, with isolated in step (2)
Cracking gas is as at least part of described combustible, namely passes through isolated cracking in combustion step (2)
Isolated heat carrier in step (3) is heated by gas, and is recycled as by the heat carrier after heating
At least partly heat carrier in step (1).Under this preferable case, utilize by splitting that biomass produce
Vent one's spleen heat supply, it is achieved that the comprehensive utilization of resource, reduce energy consumption.Most preferably, step (1)
In heat carrier all be from by isolated cracking gas in combustion step (2) in step (3) point
The heat carrier of the heating that the heat carrier separated out carries out heating and obtains.
In the present invention, the mistake that isolated heat carrier in step (3) is heated by burn combustible thing
Journey can be carried out in conventional heater.
In step (4), there is no particular limitation for described gasification condition, can be that this area is conventional
Vapourware.In the preferred case, described gasification condition includes: temperature is 700-1500 DEG C, more preferably
800-1000℃；Pressure is 0.1-20MPa, more preferably 0.1-10MPa；Time is 0.1-60 minute,
It is preferably 0.1-30 minute.
During gasification reaction, the usage ratio of described coke and described gasifying medium the most particularly limits
Fixed, carry out feeding intake according to the inventory of conventional coke gasification process.Under preferable case, described Jiao
The weight ratio of charcoal and described gasifying medium is 1:0.1-2, preferably 1:0.5-1.5.
In the present invention, described gasifying medium can be gasifying medium commonly used in the art, such as may be used
Think at least one in air, oxygen, steam and oxygen rich gas.Under preferable case, in order to obtain
Preferably gasification result, described gasifying medium selects steam and the mixed gas of oxygen.Further preferably
Ground, in the mixed gas of steam and oxygen, the mol ratio of steam and oxygen is 1-20:1, more
It is preferably 5-15:1.The temperature of described gasifying medium can be 150-800 DEG C, preferably 200-600 DEG C.
When described gasifying medium be steam or containing steam time, the temperature of steam can be 150-800
DEG C, preferably 200-600 DEG C.When described gasifying medium is oxygen or oxygen-containing gas, oxygen or oxygen-containing
The temperature of gas can be room temperature to 800 DEG C, be preferably room temperature to 500 DEG C.
Described gasification reaction can be carried out in the gasification reactor of various routines, as long as being capable of coke
Gasification reaction.Described gasification reactor such as can be selected from dense-phase fluidized bed reactor, riser
One or more combining form in reactor, down-flow reactor and moving-burden bed reactor.
In step (4), gasification reaction product generally includes synthesis gas and lime-ash.Produce from gasification reaction
The method isolating synthesis gas in thing can use the coal gasification purification method of routine to implement, specifically, point
The purifying step such as dedusting, deacidification can be included from process.Described synthesis gas refers to the synthesis that this area is conventional
Gas, wherein mainly contains hydrogen, carbon monoxide, methane and carbon dioxide.
The present invention described is prepared the method for bio-oil and synthesis gas by biomass and has the advantage that
The present invention, by the thermal cracking of biomass and the process of coke gasification being combined, has both utilized life
Material produces bio-oil, and the coke utilizing again biomass cracking to produce carries out gasifying with producing synthesis gas,
When avoiding biomass direct gasification, synthesis gas contains tar.And, recycling the process of heat carrier
In, with the energy of biomass self, heat carrier can be heated, it is achieved that the comprehensive utilization of resource,
Reduce energy consumption.
The invention will be further described by the following examples.
Embodiment 1
The present embodiment is for illustrating the described side being prepared bio-oil and synthesis gas by biomass of the present invention
Method.
As it is shown in figure 1, sawdust (particle size is 0.07-3 millimeter, forms as shown in table 1 below) is made
Be heated to 150 DEG C for biomass, be subsequently adding in fluidized bed cracking reactor, and with from heater
High-temperature heat carrier (quartz sand, particle size is 0.04-1 millimeter, and temperature is 850 DEG C) contacts, and controls
Reactor batch temperature is 500 DEG C, reacts 10 minutes under 0.1MPa.React through fluidized bed cracking
Device obtains oil gas and solid product after processing, oil gas introduces follow-up oil and gas separating system, and isolated cracks
Gas and bio-oil, the heat carrier with to reuse that carries out in cracking gas injection heating device burning heats.
Solid product introduces and carries out solid separation in solid separator (fluidized-bed reactor), and isolated heat carries
Body enters in heater and heats；Isolated coke introduces in gasification reactor, and to gasification to instead
Answer water vapour and the mixed gas of oxygen of 50 weight portions being passed through coke based on 100 weight portions in device
(600 DEG C), wherein, water vapour and oxygen mole are 6:1,900 DEG C, carry out under 0.1MPa
Gasification reaction 30 minutes.The gasification product generated injects subsequent gases cleaning system and separates, from gas
Change isolated lime-ash discharger in product, collect synthesis gas.Pyrolysis product beyond heat extraction carrier is such as
Shown in table 2, the composition of synthesis gas is as shown in table 3.
Table 1
Embodiment 2
The present embodiment is for illustrating the described side being prepared bio-oil and synthesis gas by biomass of the present invention
Method.
Sawdust (particle size is 0.07-2 millimeter, and composition is as shown in Table 1) is heated as biomass
To 200 DEG C, be subsequently adding in fluidized bed cracking reactor, and with the high-temperature heat carrier (stone from heater
Sand, particle size is 0.04-1 millimeter, and temperature is 800 DEG C) contact, control reactor batch temperature
It is 400 DEG C, reacts 15 minutes under 0.1MPa.Oil is obtained after fluidized bed cracking reactor for treatment
Gas and solid product, the oil gas follow-up oil and gas separating system of introducing, isolated cracking gas and bio-oil,
The heat carrier with to reuse that carries out in cracking gas injection heating device burning heats.Solid product introduces solid
Carrying out solid separation in body separator (fluidized-bed reactor), isolated heat carrier enters in heater
Heat；Isolated coke introduces in gasification reactor, and to gasification be passed through in reactor based on
The water vapour of 50 weight portions of the coke of 100 weight portions and the mixed gas (200 DEG C) of oxygen, wherein,
Water vapour and oxygen mole are 9:1,800 DEG C, carry out gasification reaction 30 minutes under 0.1MPa.
The gasification product generated injects subsequent gases cleaning system and separates, isolated ash from gasification product
Slag discharger, collects synthesis gas.The composition of the pyrolysis product beyond heat extraction carrier is as shown in table 2, closes
The composition becoming gas is as shown in table 3.
Embodiment 3
The present embodiment is for illustrating the described side being prepared bio-oil and synthesis gas by biomass of the present invention
Method.
Sawdust (particle size is 0.07-3 millimeter, and composition is as shown in Table 1) is heated as biomass
To 150 DEG C, be subsequently adding in fluidized bed cracking reactor, and with the high-temperature heat carrier (stone from heater
Sand, particle size is 1-2 millimeter, and temperature is 850 DEG C) contact, controlling reactor batch temperature is
600 DEG C, react 5 minutes under 0.1MPa.Obtain after fluidized bed cracking reactor for treatment oil gas and
Solid product, oil gas introduces follow-up oil and gas separating system, isolated cracking gas and bio-oil, cracking
The heat carrier with to reuse that carries out in gas injection heating device burning heats.Solid product introduces solid and divides
Carrying out solid separation in device (fluidized-bed reactor), isolated heat carrier enters in heater and carries out
Heating；Isolated coke introduces in gasification reactor, and is passed through in reactor based on 100 to gasification
The water vapour of 50 weight portions of the coke of weight portion and the mixed gas (500 DEG C) of oxygen, wherein, water
Steam and oxygen mole are 9:1,900 DEG C, carry out gasification reaction 15 minutes under 0.1MPa.Raw
The gasification product become injects subsequent gases cleaning system and separates, isolated lime-ash from gasification product
Discharger, collects synthesis gas.The composition of the pyrolysis product beyond heat extraction carrier is as shown in table 2, synthesis
The composition of gas is as shown in table 3.
Comparative example 1
Directly will carry out gasification reaction, and gasification reaction in the sawdust injection gasification reactor of biomass
During operating condition same as in Example 1.As a result, the composition of the synthesis gas obtained such as table 3 below institute
Show.
Comparative example 2
Directly will carry out heat scission reaction in the sawdust injection fluidized bed cracking reactor of biomass, and
Operating condition during heat scission reaction is same as in Example 1.As a result, the group of the pyrolysis product obtained
Become as shown in table 2.
Table 2
Table 3
By the data of above-mentioned table 2 and 3 it can be seen that can utilize according to the described method of present invention offer
Biomass are prepared in bio-oil and synthesis gas, and the synthesis gas prepared simultaneously and are substantially free of tar.
Claims (11)
1. the method being prepared bio-oil and synthesis gas by biomass, the method comprises the following steps:
(1) in the presence of heat carrier, biomass are carried out cracking reaction, obtain oil gas and solid produces
Thing；
(2) described oil gas is carried out Oil-gas Separation, isolate cracking gas and bio-oil；
(3) described solid product is carried out solid separation, isolate coke and heat carrier；
(4) described coke and gasifying medium are carried out gasification reaction, and separate from gasification reaction product
Go out synthesis gas；
Wherein, by isolated cracking gas in combustion step (2) to isolated heat in step (3)
Carrier heats, and the heat load being recycled as at least part of step (1) by the heat carrier after heating
Body；
In step (1), the temperature of described heat carrier is 600-1200 DEG C, and described heat carrier is for being selected from
At least one in quartz sand, aluminium oxide, dead catalyst and Ceramic Balls, the particle size of described heat carrier
For 0.03-10 millimeter.
Method the most according to claim 1, wherein, in step (1), described cracking reaction
Condition include: temperature is 300-700 DEG C, and pressure is 0.1-20MPa, and the time is the 0.1-1000 second.
Method the most according to claim 2, wherein, the condition of described cracking reaction includes: temperature
Degree is for 350-600 DEG C, and pressure is 0.1-10MPa, and the time is the 0.1-600 second.
Method the most according to claim 1, wherein, in step (4), described gasification reaction
Condition include: temperature is 700-1500 DEG C, and pressure is 0.1-20MPa, and the time is 1-60 minute.
Method the most according to claim 4, wherein, the condition of described gasification reaction includes: temperature
Degree is for 800-1000 DEG C, and pressure is 0.1-10MPa, and the time is 1-30 minute.
Method the most according to claim 1, wherein, in step (4), described coke and institute
The weight ratio stating gasifying medium is 1:0.1-2.
7. according to the method described in claim 1 or 6, wherein, described gasifying medium be steam and
The mixed gas of oxygen, and the mol ratio of steam and oxygen is 1-20:1.
8. according to the method described in claim 1 or 6, wherein, the temperature of described gasifying medium is
150-800℃。
Method the most according to claim 1, wherein, the particle size of described biomass is 0.05-5
Millimeter.
10. according to the method described in claim 1 or 9, wherein, described biomass are selected from crops
At least one in garbage, forestry waste, organic waste, water plant and energy-source plant.
11. according to the method described in claim 1 or 9, and wherein, described biomass are selected from crops straw
At least one in stalk, forestry waste, organic waste, water plant and energy-source plant.
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| CN108251135A (en) * | 2016-12-28 | 2018-07-06 | 赵钧永 | The method of pyrolysis and special pyrolysis system |
| CN108251134A (en) * | 2016-12-28 | 2018-07-06 | 赵钧永 | A kind of method of pyrolysis and special pyrolysis system |
| CN108251142A (en) * | 2016-12-28 | 2018-07-06 | 赵钧永 | The method of coal pyrolysis and special pyrolysis system |
| CA3152668A1 (en) * | 2022-03-18 | 2023-09-18 | Groupe Onym | Method for pyrolysis of woody biomass |
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