CN104046373A - Method for preparing bio-oil and synthesis gas from biomass - Google Patents
Method for preparing bio-oil and synthesis gas from biomass Download PDFInfo
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Abstract
The invention relates to a method for preparing bio-oil and synthesis gas from biomass. The method comprises the following steps: (1) in the presence of a heat carrier, biomass is subjected to a cracking reaction to obtain oil gas and solid products; (2) the oil gas undergoes oil-gas separation to separate pyrolysis gas from bio-oil; (e) the solid products undergo solid separation to separate coke from the heat carrier; and (4) the coke and a gasifying medium undergo a gasification reaction, and synthesis gas is separated from gasification reaction products. According to the method provided by the invention, bio-oil and synthesis gas can be simultaneously prepared by the use of biomass, and the prepared synthesis gas basically contains no tar.
Description
Technical field
The present invention relates to a kind of by biomass-making the method for bio-oil and synthetic gas.
Background technology
Biomass are a kind of reproducible green energy resources, comprise agricultural crop straw, forestry waste, feces of livestock and poultry, organic garbage of city, waterplant, energy-source plant etc.At present, global biomass consumption is only second to coal, oil, Sweet natural gas, occupies the 4th.According to biologist estimation, hundred million tons of the about 1400-1800 of biomass energy total amount of annual growth on the earth, are equivalent to 10 times of current world total energy consumption.China is large agricultural country, has every year a large amount of agricultural waste materials, and wherein stalk (straw, straw, cornstalk etc.) has 600,000,000 tons every year, approximately 3.89 hundred million tons of agricultural machining resistatess (rice husk, bagasse etc.).Biomass energy, as a kind of low-carbon (LC), low-sulfur, low nitrogen fuel, has the feature of carbon dioxide zero discharge, and it is conducive to alleviate day by day serious Greenhouse effect as a kind of clean energy.
The technology of utilizing of biomass is mainly divided into three kinds of modes: physical transformation, biotransformation and chemical transformation.Physical transformation refers to the compressed moulding of biomass, solves its transport and stores inconvenient problem.Biotransformation refers to that biomass obtain object product through microbiological treatment, and treatment capacity is subject to microorganism growth quantitative limitation.It is chemical transformation technology that biomass are applied maximum technology, comprises direct burning, gasification, thermo-cracking and pressurized liquefied four kinds of technology.Various technology adopt equipment and operating parameters separately, and produce product separately.The direct burning of biomass is prevailing biomass energy switch technologies, so-called directly burning is exactly the chemical reaction process that combustiblecomponents in fuel and oxygenant (being generally airborne oxygen) carry out chemical combination, in reaction process, strongly emit heat, and the temperature of products of combustion is raise.Its main purpose obtains heat exactly.Gasifying biomass utilizes airborne oxygen or oxygen carrier to make vaporized chemical exactly, the oxidation of coal in solid fuel is generated to the process of inflammable gas.Biomass through pyrolysis refers to that biomass are not having thermal destruction under oxygen or anoxia condition completely, and final product generates bio-oil and some by products.Bio-oil can replace oil for power through modification, or through further refining, can produce various Chemicals.Low-sulfur, low nitrogen, the low ash that simultaneously bio-oil the has characteristic of grading, become clean fuel, utilize efficient biomass switch technology, discarded biomass resource is converted to high-grade bio-oil fuel, not only can improve Agricultural Output, and can reduce pollution, and promote ecological benign cycle, make up the dependence to petroleum resources.Gasifying biomass is to utilize biomass and gasifying medium reaction to obtain synthetic gas, and this technology exists gaseous product to contain a small amount of tar, need to increase tar-removing device.Due to biomass, to contain oxide compound more, when pressurized liquefied, need to consume more hydrogen source, and its application has obtained restriction.
CN101544901A discloses a kind of biomass through pyrolysis and has produced the method for bio-oil, the method comprises: biomass enter fluidized-bed and mix generation scission reaction with thermal barrier, pyrolysis product and thermal barrier enter follow-up separator separates thermal barrier and pyrolysis product, thermal barrier enters thermal fluid heater, splitting gas and coke as pyrolysis product enter gas-solid separator below, coke and ash content enter thermal fluid heater, combustion of coke and not condensable splitting gas are with heat hot carrier, and the thermal barrier after intensification returns to fluidized-bed reactor.Thermal barrier in fluidized-bed reactor enters carrier separator together with pyrolysis product, has increased the oil gas residence time, has reduced the yield of bio-oil.
CN1272404C discloses a kind of biomass gasification method, and the method comprises: by two processes of the pyrolysis gasification of solid biomass pyrolysis and pyrolysis product separately, biomass are transformed into the inflammable gas that tar content is extremely low.First biomass are sent into pyrolysis reactor and carried out pyrolytic reaction, pyrolysis product comprises that pyrolysis gas and carbon residue enter in pyrolysis gasification device, with the oxygenant generation incomplete oxidation combustion reactions passing into, form the high-temperature zone of 900-1000 DEG C, now the heavy hydrocarbon of so-called tar is cracked into micro-molecular gas, after the red-hot charcoal layer generation reduction reaction in the gas after cracking and bottom, leaves gasifier.
But above-mentioned existing method can only utilize biomass to prepare separately bio-oil or synthetic gas, and does not utilize biomass to prepare the relevant report of bio-oil and synthetic gas simultaneously.
Summary of the invention
The object of the invention is to utilize technique can only prepare separately the defect of bio-oil or synthetic gas in order to overcome existing biomass, provide a kind of by biomass-making the method for bio-oil and synthetic gas.
The invention provides a kind of by biomass-making the method for bio-oil and synthetic gas, the method comprises: (1), under the existence of thermal barrier, carries out scission reaction by biomass, obtains oil gas and solid product; (2) described oil gas is carried out to gas-oil separation, isolate splitting gas and bio-oil; (3) described solid product is carried out to solid separation, isolate coke and thermal barrier; (4) described coke and gasifying medium are carried out to gasification reaction, and isolate synthetic gas from gasification reaction product.
Can utilize biomass to prepare bio-oil and synthetic gas according to described method provided by the invention simultaneously, and not basically contain tar in the synthetic gas of preparation, thereby without the tar of managing to remove in synthetic gas.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Brief description of the drawings
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 be provided by the invention described by biomass-making the process flow sheet for the method for bio-oil and synthetic gas.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
Described in provided by the invention, comprised for the method for bio-oil and synthetic gas by biomass-making:
(1) under the existence of thermal barrier, biomass are carried out to scission reaction, obtain oil gas and solid product;
(2) described oil gas is carried out to gas-oil separation, isolate splitting gas and bio-oil;
(3) described solid product is carried out to solid separation, isolate coke and thermal barrier;
(4) described coke and gasifying medium are carried out to gasification reaction, and isolate synthetic gas from gasification reaction product.
In step (1), there is no particular limitation for described crack reacting condition, can be the biomass through pyrolysis condition of this area routine.In the preferred case, in order to obtain higher bio-oil yield, described crack reacting condition comprises: temperature is 300-700 DEG C, more preferably 350-600 DEG C; Pressure is 0.1-20MPa, more preferably 0.1-10MPa; Time is 0.1-1000 second, is preferably 0.1-600 second.In the present invention, described pressure refers to absolute pressure.After service temperature in described scission reaction process refers to that biomass contact with thermal barrier, temperature when the two generation heat is transmitted and reaches balance.
Service temperature in described scission reaction process can be carried out flexible by the amount of the thermal barrier adding and temperature.There is no particular limitation for the temperature of described thermal barrier, can be the thermal barrier temperature of this area routine, for example, can be 600-1200 DEG C.Described thermal barrier can be the conventional thermal barrier using in this area, for example can be for being selected from least one in quartz sand, aluminum oxide, spent catalyst and Ceramic Balls.
There is no particular limitation for the particle size of described thermal barrier, can suitably select according to the particle size of conventional thermal barrier.Under preferable case, in order to make described thermal barrier show good heat-transfer effect, selecting particle size is the thermal barrier of 0.03-10 millimeter.In the present invention, particle size refers to the mesh size that obtains the screen cloth of this particle by screening.
In a preferred embodiment, for making biomass cracking fully, described biomass were preferably heated to 100-300 DEG C before carrying out scission reaction.
In a preferred embodiment, for making biomass cracking fully, the particle size of biomass described in scission reaction process is 0.05-5 millimeter.In order to obtain the biomass of above-mentioned particle size, large-sized biomass can be pulverized and realized.
In the present invention, described biomass can be the biomass material of various routines, for example can be for being selected from least one in agricultural crop straw, agricultural waste material, forestry waste, organic waste, waterplant and energy-source plant.
Described scission reaction can be carried out in the cracking reactor of various routines, as long as can realize biomass cracking reaction.Described cracking reactor can be selected from one or more the array configuration in fluidized-bed reactor, riser reactor, down-flow reactor and moving-burden bed reactor.
In step (2), the process of described gas-oil separation can adopt conventional method to implement.For example, can be according to the difference of the condensing temperature of each different components in oil gas, adopt separation column or adopt the mode of temperature control condensation to separate.
In step (3), the process that described solid separates can be implemented in conventional solid separator, as long as this solid separator can be by particle separation of different nature.Described solid separator can be for example fluidized-bed reactor.
In the present invention, the working order of step (2) and (3) does not limit, and step (2) and (3) can at random successively operate, and also can the two implement simultaneously.
In the present invention, describedly can also be comprised for the method for bio-oil and synthetic gas by biomass-making: by burning combustiblematerials, isolated thermal barrier in step (3) is heated, and thermal barrier circulation after heating is as the thermal barrier in step (1).In the preferred case, with isolated splitting gas in step (2) as at least part of described combustiblematerials, also by isolated splitting gas in combustion step (2), isolated thermal barrier in step (3) is heated, and the thermal barrier circulation after heating is used as to the thermal barrier at least part of step (1).Under this preferable case, utilize the splitting gas being produced by biomass to carry out heat supply, realize the comprehensive utilization of resource, reduce energy consumption.Most preferably, the thermal barrier in step (1) is all from by isolated splitting gas in combustion step (2), isolated thermal barrier in step (3) being heated to the thermal barrier of the heating obtaining.
In the present invention, burning combustiblematerials can carry out the process that in step (3), isolated thermal barrier heats in conventional well heater.
In step (4), there is no particular limitation for described gasification condition, can be the vapourware of this area routine.In the preferred case, described gasification condition comprises: temperature is 700-1500 DEG C, more preferably 800-1000 DEG C; Pressure is 0.1-20MPa, more preferably 0.1-10MPa; Time is 0.1-60 minute, is preferably 0.1-30 minute.
In gasification reaction process, there is no particular limitation for the usage ratio of described coke and described gasifying medium, feeds intake according to the charging capacity of conventional coke gasification process.Under preferable case, the weight ratio of described coke and described gasifying medium is 1:0.1-2, is preferably 1:0.5-1.5.
In the present invention, described gasifying medium can be the conventional gasifying medium using in this area, for example, can be at least one in air, oxygen, water vapour and oxygen rich gas.Under preferable case, in order to obtain good gasification result, described gasifying medium is selected the mixed gas of water vapour and oxygen.Further preferably, in the mixed gas of water vapour and oxygen, the mol ratio of water vapour and oxygen is 1-20:1, more preferably 5-15:1.The temperature of described gasifying medium can be 150-800 DEG C, is preferably 200-600 DEG C.When described gasifying medium is water vapour or while containing water vapour, the temperature of water vapour can be 150-800 DEG C, is preferably 200-600 DEG C.In the time that described gasifying medium is oxygen or oxygen-containing gas, the temperature of oxygen or oxygen-containing gas can be room temperature to 800 DEG C, is preferably room temperature to 500 DEG C.
Described gasification reaction can carry out in the gasifying reactor of various routines, as long as can realize the gasification reaction of coke.Described gasifying reactor for example can be selected from one or more the array configuration in dense fluidized bed bioreactor, riser reactor, down-flow reactor and moving-burden bed reactor.
In step (4), gasification reaction product generally includes synthetic gas and lime-ash.The method of isolating synthetic gas from gasification reaction product can adopt conventional gasification purifying method to implement, and particularly, sepn process can comprise the purifying step such as dedusting, depickling.Described synthetic gas refers to the synthetic gas of this area routine, wherein mainly contains hydrogen, carbon monoxide, methane and carbon dioxide.
Described in of the present invention, had the following advantages for the method tool of bio-oil and synthetic gas by biomass-making:
The present invention is by combining the process of the thermo-cracking of biomass and coke gasification, both utilized biomass to produce bio-oil, the coke that utilizes again biomass cracking to produce gasifies with producing synthesis gas, and while having avoided biomass direct gasification, synthetic gas contains tar.And, in the process of recycle thermal barrier, can heat thermal barrier with the energy of biomass self, realize the comprehensive utilization of resource, reduce energy consumption.
The invention will be further described by the following examples.
Embodiment 1
The present embodiment for illustrate of the present invention described by biomass-making the method for bio-oil and synthetic gas.
As shown in Figure 1, by sawdust, (particle size is 0.07-3 millimeter, shown in table 1 composed as follows) be heated to 150 DEG C as biomass, then add in fluidized bed cracking reactor, and with high-temperature heat carrier from well heater (quartz sand, particle size is 0.04-1 millimeter, temperature is 850 DEG C) contact, controlling reactor batch temperature is 500 DEG C, reacts 10 minutes under 0.1MPa.After fluidized bed cracking reactor for treatment, obtain oil gas and solid product, oil gas is introduced follow-up oil and gas separating system, separates and obtains splitting gas and bio-oil, in splitting gas injection heating device, burns and heats with the thermal barrier to reuse.Solid product is introduced in solid separator (fluidized-bed reactor) and is carried out solid separation, and isolated thermal barrier enters in well heater and heats; Isolated coke is introduced in gasifying reactor, and to gasification to the water vapor of 50 weight parts and the mixed gas of oxygen (600 DEG C) that pass into the coke based on 100 weight parts in reactor, wherein, water vapor and oxygen mole be 6:1, under 900 DEG C, 0.1MPa, carry out gasification reaction 30 minutes.The gasification product generating injects follow-up gas treating system and separates, and isolated lime-ash discharger from gasification product is collected synthetic gas.Split product except thermal barrier is as shown in table 2, and the composition of synthetic gas is as shown in table 3.
Table 1
Embodiment 2
The present embodiment for illustrate of the present invention described by biomass-making the method for bio-oil and synthetic gas.
By sawdust, (particle size is 0.07-2 millimeter, composition is as shown in Table 1) be heated to 200 DEG C as biomass, then add in fluidized bed cracking reactor, and with high-temperature heat carrier (quartz sand from well heater, particle size is 0.04-1 millimeter, temperature is 800 DEG C) contact, controlling reactor batch temperature is 400 DEG C, reacts 15 minutes under 0.1MPa.After fluidized bed cracking reactor for treatment, obtain oil gas and solid product, oil gas is introduced follow-up oil and gas separating system, separates and obtains splitting gas and bio-oil, in splitting gas injection heating device, burns and heats with the thermal barrier to reuse.Solid product is introduced in solid separator (fluidized-bed reactor) and is carried out solid separation, and isolated thermal barrier enters in well heater and heats; Isolated coke is introduced in gasifying reactor, and to gasification to the water vapor of 50 weight parts and the mixed gas of oxygen (200 DEG C) that pass into the coke based on 100 weight parts in reactor, wherein, water vapor and oxygen mole be 9:1, under 800 DEG C, 0.1MPa, carry out gasification reaction 30 minutes.The gasification product generating injects follow-up gas treating system and separates, and isolated lime-ash discharger from gasification product is collected synthetic gas.The composition of the split product except thermal barrier is as shown in table 2, and the composition of synthetic gas is as shown in table 3.
Embodiment 3
The present embodiment for illustrate of the present invention described by biomass-making the method for bio-oil and synthetic gas.
By sawdust, (particle size is 0.07-3 millimeter, composition is as shown in Table 1) be heated to 150 DEG C as biomass, then add in fluidized bed cracking reactor, and with high-temperature heat carrier (quartz sand from well heater, particle size is 1-2 millimeter, temperature is 850 DEG C) contact, controlling reactor batch temperature is 600 DEG C, reacts 5 minutes under 0.1MPa.After fluidized bed cracking reactor for treatment, obtain oil gas and solid product, oil gas is introduced follow-up oil and gas separating system, separates and obtains splitting gas and bio-oil, in splitting gas injection heating device, burns and heats with the thermal barrier to reuse.Solid product is introduced in solid separator (fluidized-bed reactor) and is carried out solid separation, and isolated thermal barrier enters in well heater and heats; Isolated coke is introduced in gasifying reactor, and to gasification to the water vapor of 50 weight parts and the mixed gas of oxygen (500 DEG C) that pass into the coke based on 100 weight parts in reactor, wherein, water vapor and oxygen mole be 9:1, under 900 DEG C, 0.1MPa, carry out gasification reaction 15 minutes.The gasification product generating injects follow-up gas treating system and separates, and isolated lime-ash discharger from gasification product is collected synthetic gas.The composition of the split product except thermal barrier is as shown in table 2, and the composition of synthetic gas is as shown in table 3.
Comparative example 1
Directly carry out gasification reaction using injecting gasifying reactor as the sawdust of biomass, and operational condition in gasification reaction process is identical with embodiment 1.Shown in the table 3 composed as follows of the synthetic gas obtaining as a result.
Comparative example 2
Directly carry out heat scission reaction using injecting fluidized bed cracking reactor as the sawdust of biomass, and operational condition in heat scission reaction process is identical with embodiment 1.The composition of the split product obtaining as a result, is as shown in table 2.
Table 2
Table 3
Data by above-mentioned table 2 and 3 can be found out, can utilize biomass to prepare bio-oil and synthetic gas according to described method provided by the invention simultaneously, and do not basically contain tar in the synthetic gas of preparation.
Claims (12)
1. the method for bio-oil and synthetic gas by biomass-making, the method comprises the following steps:
(1) under the existence of thermal barrier, biomass are carried out to scission reaction, obtain oil gas and solid product;
(2) described oil gas is carried out to gas-oil separation, isolate splitting gas and bio-oil;
(3) described solid product is carried out to solid separation, isolate coke and thermal barrier;
(4) described coke and gasifying medium are carried out to gasification reaction, and isolate synthetic gas from gasification reaction product.
2. method according to claim 1, wherein, in step (1), the condition of described scission reaction comprises: temperature is 300-700 DEG C, and pressure is 0.1-20MPa, and the time is 0.1-1000 second.
3. method according to claim 2, wherein, the condition of described scission reaction comprises: temperature is 350-600 DEG C, and pressure is 0.1-10MPa, and the time is 0.1-600 second.
4. method according to claim 1, wherein, in step (4), the condition of described gasification reaction comprises: temperature is 700-1500 DEG C, and pressure is 0.1-20MPa, and the time is 1-60 minute.
5. method according to claim 4, wherein, the condition of described gasification reaction comprises: temperature is 800-1000 DEG C, and pressure is 0.1-10MPa, and the time is 1-30 minute.
6. method according to claim 1, wherein, in step (4), the weight ratio of described coke and described gasifying medium is 1:0.1-2.
7. according to the method described in claim 1 or 6, wherein, described gasifying medium is the mixed gas of water vapour and oxygen, and the mol ratio of water vapour 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 DEG C.
9. method according to claim 1, wherein, described method also comprises: by isolated splitting gas in combustion step (2), isolated thermal barrier in step (3) is heated, and the thermal barrier circulation after heating is used as to the thermal barrier at least part of step (1).
10. according to the method described in claim 1 or 9, wherein, in step (1), the temperature of described thermal barrier is 600-1200 DEG C, described thermal barrier is at least one being selected from quartz sand, aluminum oxide, spent catalyst and Ceramic Balls, and the particle size of described thermal barrier is 0.03-10 millimeter.
11. methods according to claim 1, wherein, the particle size of described biomass is 0.05-5 millimeter.
12. according to the method described in claim 1 or 11, and wherein, described biomass are at least one being selected from agricultural crop straw, agricultural waste material, forestry waste, organic waste, waterplant and energy-source plant.
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