CN102604695A - Method for improving stability of biological oil by adding ethyl acetate - Google Patents
Method for improving stability of biological oil by adding ethyl acetate Download PDFInfo
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- CN102604695A CN102604695A CN201110431336XA CN201110431336A CN102604695A CN 102604695 A CN102604695 A CN 102604695A CN 201110431336X A CN201110431336X A CN 201110431336XA CN 201110431336 A CN201110431336 A CN 201110431336A CN 102604695 A CN102604695 A CN 102604695A
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Abstract
The invention discloses a method for improving the stability of biological oil by adding ethyl acetate. The method is performed by adding the ethyl acetate in different concentrations into the biological oil. Preferably, the concentration in percentage by weight of the added ethyl acetate is 3%-15%. Tests of water content, pH value (25 DEG C) and kinematic viscosity (25 DEG C) of the biological oil without and with the addition of the ethyl acetate along with the changes in storage time find that the addition of the ethyl acetate can effectively inhibit the increase in the water content, improve the pH value to a certain extent and greatly reduce the viscosity of the biological oil. The method has the advantages of simple technology, low cost and no need of expensive equipment and strict conditions, and can effectively improve the stability of the biological oil and reduce the viscosity of the biological oil, and the obtained biological oil can be effectively stored for above 35 days at the temperature of 40 DEG C. The results of the invention have positive guiding significance for further expanding the range of application of the biological oil.
Description
Technical field
The present invention relates to a kind of method that improves bio oil stability, particularly a kind of through adding the method for ETHYLE ACETATE raising bio oil stability.
Background technology
The dual crisis of energy and environment is the significant challenge that face this century.Press present explored energy reserve in the world, oil will be exhausted in 40 years, and Sweet natural gas will exhaust in 60 years, and coal resources still can be exploited about 200 years.Simultaneously, a large amount of uses of fossil oil can cause acid rain, Greenhouse effect, thereby cause vegetation deterioration, and a series of ecological environment problems such as living species variety reduction have a strong impact on continuous development of society economy.
Biomass energy is the fourth-largest energy that is only second to oil, Sweet natural gas, coal, based on its green, cleaning, renewable, advantage such as raw material sources are abundant, the development research of biomass energy is become the emphasis of various countries' work.Propose in China's " medium-term and long-term development program of renewable energy source ": progressively improve the ratio of high-quality clean reproducible energy in energy structure; Strive making the renewable energy source consumption reach 15% of total energy consumption, make renewable energy technologies have the tangible market competitiveness to the year two thousand twenty.
The seventies in last century, the oil crisis of outburst made people begin to pay attention to the biomass liquefying Study on Technology.Biomass through pyrolysis is one of important way of biomass liquefying technology, enjoys people to pay close attention to owing to having wide industrial prospect.The biomass through pyrolysis technology is meant that biomass heat temperature raising under anaerobic or anoxia condition causes that the cracking of biomass polymer produces bio oil, combustible gas and charcoal.Compare with biomass; The bio oil of producing through biomass through pyrolysis; Its energy density is largely increased, and be more convenient for simultaneously transportation and storage not only can directly be used for the burning of equipment such as existing boiler; And can make its quality approach the quality of fossil oils such as diesel oil through further improvement processing, in addition can separation and Extraction go out the chemical of high added value.Based on this, can realize that the mass-producing of biomass resource and modernization utilize.But a series of polyreaction can slowly take place and cause its viscosity to increase in bio oil at normal temperatures, and the uniform bio oil of character will produce layering when being increased to a certain degree.In addition, bio oil also has high ignition temperature, HV; Severe corrosive is with fossil oil mixing not, general character such as high carbon residue content; This makes bio oil be difficult to directly apply to existing installation, must further improve its relevant nature, and wherein most critical is to improve its stability.
In storage process; Between the unsaturated link(age) polymerization slowly or polycondensation can take place, esterification can take place in hydroxyl and carboxyl, and etherification reaction can take place for hydroxyl and carbonyl; These aging reactions cause the molecular-weight average of bio oil to increase, and macro manifestations is that viscosity increases.The cornstalk bio oil is measured in the kinematic viscosity under the differing temps, found when temperature is lower than 85 ℃, biological oil viscosity raises along with temperature and reduces, and meets the sticking warm universal correlation function of liquid; When temperature was higher than 85 ℃, biological oil viscosity raise along with temperature and rises.Result of study shows that there are reactions such as polymerization, esterification in bio oil inside, and small-molecule substance reaction generates macromolecular substance, causes the bio oil AV to increase, and high temperature helps reaction and carries out.Therefore, bio oil is left under the low temperature environment can inhibited reaction, increases stability.
The water that moisture that biomass material itself has and heat scission reaction process generate; Add that bio oil has very strong water absorbability, can absorb airborne water molecules, simultaneously; The inner a series of aging reactions that take place of bio oil also can produce a certain amount of water molecules, so the water ratio of bio oil is very high.Contain a certain amount of water in the bio oil and can reduce its viscosity; Change system pH; But along with the shelf-time prolongs, moisture content has surpassed certain limit (30%), and inner each the component compole gender gap of bio oil enlarges gradually; Originally the liquid of homogeneous just is difficult to keep evenly layering can occurring: one is highly viscous material mutually; Another is mutually for containing the liquid phase of water and soluble substance.
At present, a lot of scholars have done a large amount of research to how improving bio oil stability, as, through shortening, catalytic pyrolysis, gas phase catalysis, modes such as steam reforming and emulsification also can be mixed some organic solvents and improved its quality.The present invention improved on the bio oil Study on Stability basis through adding acetone in previous stage, improved bio oil stability through adding ETHYLE ACETATE.And the retrieval through to document is found, improves the bio oil Study on Stability through interpolation ETHYLE ACETATE and does not appear in the newspapers as yet.
Summary of the invention
The present invention is directed to the bio oil poor stability, viscosity changes problem greatly with waiting time, and a kind of method that ETHYLE ACETATE improves bio oil stability of adding is provided.The inner aging reaction of bio oil can produce water, and the water ratio increase can cause the bio oil physico-chemical property unstable, causes layering; Reduce the bio oil water ratio, can improve its stability.Whether stable the pH value be to estimate bio oil another index, and pH value descends, and helps aging reaction and carries out, so control the pH value and can improve bio oil stability.Viscosity is as estimating the important index whether bio oil inside aging reaction takes place, and its absolute value is more little, and relative growth rate is more little, explains that then the inner aging reaction of bio oil is inhibited, and stability is improved.Add and bio oil water ratio, kinematic viscosity (25 ℃) and the pH value (25 ℃) of adding ETHYLE ACETATE variation discovery through test with waiting time; Add the increase that ETHYLE ACETATE can effectively suppress water ratio; Improve its pH value to a certain extent, and can reduce biological oil viscosity dramatically.Therefore, the present invention has directive significance to the range of application of further expansion bio oil.
The objective of the invention is to realize: improve bio oil stability through in bio oil, adding ETHYLE ACETATE through following technical scheme.Being specially with the pine wood chip is raw material; Adopt the Shanghai Communications University's agricultural and the bubbling fluidized bed biomass fast pyrolysis device of biomass energy engineering center of biological institute independent development to produce bio oil; In the bio oil of newly producing, add a certain amount of ETHYLE ACETATE; Mix and be placed in the encloses container, put into thermostat container, under 40 ℃ of conditions, store.
The present invention comprises following steps:
The first step, biomass material are prepared: adopt the pine wood chip, after the screening of different meshes sieve, get the pine wood chip after the screening, dry 24h under 105 ℃ of temperature.
In second step, the producing of bio oil: adopting the bubbling fluidized bed biomass fast pyrolysis device, is that raw material is produced bio oil with dried pine wood chip, and its heat scission reaction temperature is 500 ℃, and fluidizing agent is a nitrogen, and fluidising air velocity is 60Lmin
-1
In the 3rd step, calculate the ETHYLE ACETATE addition: calculating is added mass percent concentration in a certain amount of bio oil be the quality of 3～15% required ETHYLE ACETATE.
In the 4th step, in bio oil, add ETHYLE ACETATE: take by weighing a certain amount of new system bio oil, add the ETHYLE ACETATE that calculates gained, process ETHYLE ACETATE after mixing and handle bio oil, place encloses container to store.
Preferably, the pine wood chip after the said screening, requiring particle diameter is 30～80 orders.
Preferably, said bubbling fluidized bed biomass fast pyrolysis device is the bubbling fluidized bed biomass fast pyrolysis device of Shanghai Communications University's agricultural with biomass energy engineering center of biological institute independent development.
Preferably, said ETHYLE ACETATE is analytical pure ETHYLE ACETATE, pureness specifications >=99.5%.
Said storage, condition are steady temperature (40 ℃).
Preferably, the ETHYLE ACETATE best in quality per-cent that is added is 15%.
The present invention has following beneficial effect:
1, technology is simple, and this method only needs in bio oil, to add a certain amount of ETHYLE ACETATE, mixes the sealing storage, need not carry out complicated processing treatment to bio oil; Cost is low, does not need expensive equipment and strict condition.
2, in bio oil, adding mass percent concentration is that 3～15% ETHYLE ACETATE (>=99.5%) can effectively improve bio oil stability, reduces bio oil viscosity, can effectively store more than 35 days under 40 ℃.
Embodiment
Elaborate in the face of embodiments of the invention down: present embodiment provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment being to implement under the prerequisite with technical scheme of the present invention.
Embodiment 1
With the pine wood chip is raw material, adopts the Shanghai Communications University's agricultural and the bubbling fluidized bed biomass fast pyrolysis device of biomass energy engineering center of biological institute independent development to produce bio oil.Concrete steps are:
The first step, biomass material are prepared: adopt the pine wood chip, after the screening of different meshes sieve, get the pine wood chip after the screening, dry 24h under 105 ℃ of temperature; Pine wood chip after the said screening, particle diameter are 30 orders;
In second step, the producing of bio oil: adopting the bubbling fluidized bed biomass fast pyrolysis device, is that raw material is produced bio oil with dried pine wood chip, and its heat scission reaction temperature is 500 ℃, and fluidizing agent is a nitrogen, and fluidising air velocity is 60Lmin
-1
In the 3rd step, calculate the ETHYLE ACETATE addition: calculating is added mass percent concentration in a certain amount of bio oil be the quality of 3% required ETHYLE ACETATE; Said ETHYLE ACETATE is analytical pure ETHYLE ACETATE, pureness specifications >=99.5%;
In the 4th step, in bio oil, add ETHYLE ACETATE: take by weighing a certain amount of new system bio oil, add and calculate required ETHYLE ACETATE, process ETHYLE ACETATE after mixing and handle bio oil, place encloses container to store; The storage condition is 40 ℃ of steady temperatures.
It is 3% ETHYLE ACETATE group with adding mass percent concentration that made bio oil is divided into the blank group.Leave 2 groups of bio oil sealings under 40 ℃ of drying conditionss storage 35d, measure the Changing Pattern of bio oil characteristic (water ratio, pH value (25 ℃), kinematic viscosity (25 ℃)) with period of storage (35d).Add ETHYLE ACETATE to improving the stable effect of bio oil with the test data explanation of storing 0 day and storing 35 days below.
The water cut test result shows, the blank control group water ratio is increased to 16.32% from 15.65%, has increased by 4.28%; The bio oil water ratio that contains 3% ETHYLE ACETATE reduces to 14.74% from 15.18%, has reduced 2.90%.Compare with blank control group, the bio oil initial aqueous rate of adding 3% ETHYLE ACETATE descends, and its rate of increase is less than blank control group.
PH value test result shows, blank control group pH value (25 ℃) is reduced to 1.75 from 1.98, has reduced by 11.62%; The pH value (25 ℃) that contains the bio oil of 3% ETHYLE ACETATE is reduced to 1.76 from 1.99, has reduced by 11.56%.Compare with blank control group, the bio oil original ph of adding 3% ETHYLE ACETATE raises, and its rate of descent is less than blank control group.
The viscosity test result shows that blank control group viscosity (25 ℃) is from 90.3mm
2S
-1Be increased to 265.3mm
2S
-1, increased by 194%.The bio oil viscosity (25 ℃) that contains 3% ETHYLE ACETATE is from 59.173mm
2S
-1Be increased to 188.325mm
2S
-1, increased by 218%.Compare with blank control group, increase though add the bio oil viscosity rate of increase of 3% ETHYLE ACETATE, viscosity descends significantly.
Embodiment 2
With the pine wood chip is raw material, adopts the Shanghai Communications University's agricultural and the bubbling fluidized bed biomass fast pyrolysis device of biomass energy engineering center of biological institute independent development to produce bio oil.Concrete steps are:
The first step, biomass material are prepared: adopt the pine wood chip, after the screening of different meshes sieve, get the pine wood chip after the screening, dry 24h under 105 ℃ of temperature; Pine wood chip after the said screening, particle diameter are 50 orders.
In second step, the producing of bio oil: adopting the bubbling fluidized bed biomass fast pyrolysis device, is that raw material is produced bio oil with dried pine wood chip, and its heat scission reaction temperature is 500 ℃, and fluidizing agent is a nitrogen, and fluidising air velocity is 60Lmin
-1
In the 3rd step, calculate the ETHYLE ACETATE addition: calculating is added mass percent concentration in a certain amount of bio oil be the quality of 6% required ETHYLE ACETATE; Said ETHYLE ACETATE is analytical pure ETHYLE ACETATE, pureness specifications >=99.5%;
In the 4th step, in bio oil, add ETHYLE ACETATE: take by weighing a certain amount of new system bio oil, add and calculate required ETHYLE ACETATE, process ETHYLE ACETATE after mixing and handle bio oil, place encloses container to store; The storage condition is 40 ℃ of steady temperatures.
It is 6% ETHYLE ACETATE group with adding mass percent concentration that made bio oil is divided into the blank group.Leave 2 groups of bio oil sealings under 40 ℃ of drying conditionss storage 35d, measure the Changing Pattern of bio oil characteristic (water ratio, pH value (25 ℃), kinematic viscosity (25 ℃)) with period of storage (35d).Add ETHYLE ACETATE to improving the stable effect of bio oil with the test data explanation of storing 0 day and storing 35 days below.
The water cut test result shows, the blank control group water ratio is increased to 16.32% from 15.65%, has increased by 4.28%, and the bio oil water ratio that contains 6% ETHYLE ACETATE reduces to 14.53% from 14.71%, has reduced 1.22%.Compare with blank control group, the bio oil initial aqueous rate of adding 6% ETHYLE ACETATE descends, and its rate of increase is less than blank control group.
PH value test result shows, blank control group pH value (25 ℃) is reduced to 1.75 from 1.98, has reduced by 11.62%; The pH value (25 ℃) that contains the bio oil of 6% ETHYLE ACETATE is reduced to 1.84 from 2.14, has reduced by 14.02%.Compare with blank control group, increase though add the bio oil pH value rate of descent of 6% ETHYLE ACETATE, the pH value increases.
The viscosity test result shows that blank control group viscosity (25 ℃) is from 90.3mm
2S
-1Be increased to 265.3mm
2S
-1, increased by 194%.The bio oil viscosity (25 ℃) that contains 6% ETHYLE ACETATE is from 44.492mm
2S
-1Be increased to 143.776mm
2S
-1, increased by 223%.Compare with blank control group, increase though add the bio oil viscosity rate of increase of 6% ETHYLE ACETATE, viscosity descends significantly.
Embodiment 3
With the pine wood chip is raw material, adopts the Shanghai Communications University's agricultural and the bubbling fluidized bed biomass fast pyrolysis device of biomass energy engineering center of biological institute independent development to produce bio oil.Concrete steps are:
The first step, biomass material are prepared: adopt the pine wood chip, after the screening of different meshes sieve, get the pine wood chip after the screening, dry 24h under 105 ℃ of temperature; Pine wood chip after the said screening, particle diameter are 60 orders.
In second step, the producing of bio oil: adopting the bubbling fluidized bed biomass fast pyrolysis device, is that raw material is produced bio oil with dried pine wood chip, and its heat scission reaction temperature is 500 ℃, and fluidizing agent is a nitrogen, and fluidising air velocity is 60Lmin
-1
In the 3rd step, calculate the ETHYLE ACETATE addition: calculating is added mass percent concentration in a certain amount of bio oil be the quality of 9% required ETHYLE ACETATE; Said ETHYLE ACETATE is analytical pure ETHYLE ACETATE, pureness specifications >=99.5%;
In the 4th step, in bio oil, add ETHYLE ACETATE: take by weighing a certain amount of new system bio oil, add and calculate required ETHYLE ACETATE, process ETHYLE ACETATE after mixing and handle bio oil, place encloses container to store; The storage condition is 40 ℃ of steady temperatures.
It is 9% ETHYLE ACETATE group with adding mass percent concentration that made bio oil is divided into the blank group.The sealing of 2 groups of bio oil left in store 35d 40 ℃ of drying conditionss under, mensuration bio oil characteristic (water ratio, pH value (25 ℃) kinematic viscosity (25 ℃)) is with the Changing Pattern of period of storage (35d).Add ETHYLE ACETATE to improving the stable effect of bio oil with the test data explanation of storing 0 day and storing 35 days below.
The water cut test result shows, the blank control group water ratio is increased to 16.32% from 15.65%, has increased by 4.28%, and the bio oil water ratio that contains 9% ETHYLE ACETATE reduces to 14.16% from 14.24%, has reduced 0.56%.Compare with blank control group, the bio oil initial aqueous rate of adding 9% ETHYLE ACETATE descends, and its rate of increase is less than blank control group.
PH value test result shows, blank control group pH value (25 ℃) is reduced to 1.75 from 1.98, has reduced by 11.62%; The pH value (25 ℃) that contains the bio oil of 9% ETHYLE ACETATE is reduced to 1.79 from 2.19, has reduced by 18.26%.Compare with blank control group, increase though add the bio oil pH value rate of descent of 9% ETHYLE ACETATE, the pH value increases.
The viscosity test result shows that blank control group viscosity (25 ℃) is from 90.3mm
2S
-1Be increased to 265.3mm
2S
-1, increased by 194%.The bio oil viscosity (25 ℃) that contains 9% ETHYLE ACETATE is from 36.554mm
2S
-1Be increased to 104.851mm
2S
-1, increased by 187%.Compare with blank control group, the bio oil initial viscosity that adds 9% ETHYLE ACETATE descends significantly, and its rate of increase is less than blank control group.
Embodiment 4
With the pine wood chip is raw material, adopts the Shanghai Communications University's agricultural and the bubbling fluidized bed biomass fast pyrolysis device of biomass energy engineering center of biological institute independent development to produce bio oil.Concrete steps are:
The first step, biomass material are prepared: adopt the pine wood chip, after the screening of different meshes sieve, get the pine wood chip after the screening, dry 24h under 105 ℃ of temperature; Pine wood chip after the said screening, particle diameter are 80 orders.
In second step, the producing of bio oil: adopting the bubbling fluidized bed biomass fast pyrolysis device, is that raw material is produced bio oil with dried pine wood chip, and its heat scission reaction temperature is 500 ℃, and fluidizing agent is a nitrogen, and fluidising air velocity is 60Lmin
-1
In the 3rd step, calculate the ETHYLE ACETATE addition: calculating is added mass percent concentration in a certain amount of bio oil be the quality of 12% required ETHYLE ACETATE; Said ETHYLE ACETATE is analytical pure ETHYLE ACETATE, pureness specifications >=99.5%;
In the 4th step, in bio oil, add ETHYLE ACETATE: take by weighing a certain amount of new system bio oil, add and calculate required ETHYLE ACETATE, process ETHYLE ACETATE after mixing and handle bio oil, place encloses container to store; The storage condition is 40 ℃ of steady temperatures.
It is 12% ETHYLE ACETATE group with adding mass percent concentration that made bio oil is divided into the blank group.Leave 2 groups of bio oil sealings under 40 ℃ of drying conditionss storage 35d, measure the Changing Pattern of bio oil characteristic (water ratio, pH value (25 ℃), kinematic viscosity (25 ℃)) with period of storage (35d).Add ETHYLE ACETATE to improving the stable effect of bio oil with the test data explanation of storing 0 day and storing 35 days below.
The water cut test result shows, the blank control group water ratio is increased to 16.32% from 15.65%, has increased by 4.28%, and the bio oil water ratio that contains 12% ETHYLE ACETATE is increased to 13.85% from 13.77%, has increased by 0.58%.Compare with blank control group, the bio oil initial aqueous rate of adding 12% ETHYLE ACETATE descends, and its rate of increase is less than blank control group.
PH value test result shows, blank control group pH value (25 ℃) is reduced to 1.75 from 1.98, has reduced by 11.62%; The pH value (25 ℃) that contains the bio oil of 12% ETHYLE ACETATE is reduced to 1.79 from 2.22, has reduced by 19.37%.Compare with blank control group, increase though add the bio oil pH value rate of descent of 12% ETHYLE ACETATE, the pH value obviously improves.
The viscosity test result shows that blank control group viscosity (25 ℃) is from 90.3mm
2S
-1Be increased to 265.3mm
2S
-1, increased by 194%.The bio oil viscosity (25 ℃) that contains 12% ETHYLE ACETATE is from 29.289mm
2S
-1Be increased to 76.297mm
2S
-1, increased by 160%.Compare with blank control group, the bio oil initial viscosity that adds 12% ETHYLE ACETATE descends significantly, and its rate of increase is less than blank control group.
Embodiment 5
With the pine wood chip is raw material, adopts the Shanghai Communications University's agricultural and the bubbling fluidized bed biomass fast pyrolysis device of biomass energy engineering center of biological institute independent development to produce bio oil.Concrete steps are:
The first step, biomass material are prepared: adopt the pine wood chip, after the screening of different meshes sieve, get the pine wood chip after the screening, dry 24h under 105 ℃ of temperature; Pine wood chip after the said screening, particle diameter are 40 orders.
In second step, the producing of bio oil: adopting the bubbling fluidized bed biomass fast pyrolysis device, is that raw material is produced bio oil with dried pine wood chip, and its heat scission reaction temperature is 500 ℃, and fluidizing agent is a nitrogen, and fluidising air velocity is 60Lmin
-1
In the 3rd step, calculate the ETHYLE ACETATE addition: calculating is added mass percent concentration in a certain amount of bio oil be the quality of 15% required ETHYLE ACETATE; Said ETHYLE ACETATE is analytical pure ETHYLE ACETATE, pureness specifications >=99.5%;
In the 4th step, in bio oil, add ETHYLE ACETATE: take by weighing a certain amount of new system bio oil, add and calculate required ETHYLE ACETATE, process ETHYLE ACETATE after mixing and handle bio oil, place encloses container to store; The storage condition is 40 ℃ of steady temperatures.
It is 15% ETHYLE ACETATE group with adding mass percent concentration that made bio oil is divided into the blank group.Leave 2 groups of bio oil sealings under 40 ℃ of drying conditionss storage 35d, measure the Changing Pattern of bio oil characteristic (water ratio, pH value (25 ℃), kinematic viscosity (25 ℃)) with period of storage (35d).Add ETHYLE ACETATE to improving the stable effect of bio oil with the test data explanation of storing 0 day and storing 35 days below.
The water cut test result shows, the blank control group water ratio is increased to 16.32% from 15.65%, has increased by 4.28%, and the bio oil water ratio that contains 15% ETHYLE ACETATE is increased to 13.41% from 13.3%, has increased by 0.83%.The bio oil initial aqueous rate of adding 15% ETHYLE ACETATE descends, and its rate of increase is less than blank control group.
PH value test result shows, blank control group pH value (25 ℃) is reduced to 1.75 from 1.98, has reduced by 11.62%; The pH value (25 ℃) that contains the bio oil of 15% ETHYLE ACETATE is reduced to 1.82 from 2.26, has reduced by 19.47%.Compare with blank control group, increase though add the bio oil pH value rate of descent of 15% ETHYLE ACETATE, the pH value obviously improves.
The viscosity test result shows that blank control group viscosity (25 ℃) is from 90.3mm
2S
-1Be increased to 265.3mm
2S
-1, increased by 194%.The bio oil viscosity (25 ℃) that contains 15% ETHYLE ACETATE is from 22.265mm
2S
-1Be increased to 53.327mm
2S
-1, increased by 140%.Compare with blank control group, the bio oil initial viscosity that adds 15% ETHYLE ACETATE descends significantly, and its rate of increase is less than blank control group.
Comparative example 1～4 finds that when the ETHYLE ACETATE mass percent concentration that adds was 15%, the initial aqueous rate of gained bio oil was minimum; Store after 35 days, the water ratio of bio oil is minimum, and the pH value is only than the bio oil group of adding 12% acetone low 0.02; Be higher than other each concentration group, viscosity is minimum, and the viscosity rate of increase is minimum; Therefore, take all factors into consideration, the ETHYLE ACETATE best in quality per-cent that is added is 15%.
Comparative Examples 1
With the pine wood chip is raw material, adopts the Shanghai Communications University's agricultural and the bubbling fluidized bed biomass fast pyrolysis device of biomass energy engineering center of biological institute independent development to produce bio oil.Concrete steps are:
The first step, biomass material are prepared: adopt the pine wood chip, after the screening of different meshes sieve, get the pine wood chip after the screening, dry 24h under 105 ℃ of temperature; Pine wood chip after the said screening, particle diameter are 40 orders.
In second step, the producing of bio oil: adopting the bubbling fluidized bed biomass fast pyrolysis device, is that raw material is produced bio oil with dried pine wood chip, and its heat scission reaction temperature is 500 ℃, and fluidizing agent is a nitrogen, and fluidising air velocity is 60Lmin
-1
In the 3rd step, calculate the acetone addition: calculating is added mass percent concentration in a certain amount of bio oil be the quality of 15% required acetone; Said acetone is analytical pure acetone, pureness specifications >=99.5%;
In the 4th step, in bio oil, add acetone: take by weighing a certain amount of new system bio oil, add and calculate required acetone, process the acetone treatment bio oil after mixing, place encloses container to store; The storage condition is 40 ℃ of steady temperatures.
It is 15% acetone group with adding mass percent concentration that made bio oil is divided into the blank group.Leave 2 groups of bio oil sealings under 40 ℃ of drying conditionss storage 35d, measure the Changing Pattern of bio oil characteristic (water ratio, pH value (25 ℃), kinematic viscosity (25 ℃)) with period of storage (35d).Add acetone to improving the stable effect of bio oil with the test data explanation of storing 0 day and storing 35 days below.
The water cut test result shows, the blank control group water ratio is increased to 16.32% from 15.65%, has increased by 4.28%, and the bio oil water ratio that contains 15% acetone is increased to 14.36% from 13.3%, has increased by 7.97%.
PH value test result shows, blank control group pH value (25 ℃) is reduced to 1.75 from 1.98, has reduced by 11.62%; The pH value (25 ℃) that contains the bio oil of 15% acetone is reduced to 1.89 from 2.29, has reduced by 17.47%.
The viscosity test result shows that blank control group viscosity (25 ℃) is from 90.3mm
2S
-1Be increased to 265.3mm
2S
-1, increased by 194%.The bio oil viscosity (25 ℃) that contains 15% acetone is from 18.6mm
2S
-1Be increased to 40.7mm
2S
-1, increased by 119%.
Comparative Examples 1 is compared discovery with embodiment 5, be at addition under the situation of mass percent concentration 15%, ETHYLE ACETATE and acetone are close to improving bio oil pH effect; The viscosity test result shows that the biological oil viscosity of acetone treatment is slightly less than ETHYLE ACETATE and handles bio oil; And the water cut test result finds, adds ETHYLE ACETATE the restraining effect that the bio oil water ratio increases is far superior to acetone.
For the effect of additive, can not should combine the variation of water ratio to carry out comprehensive evaluation singly from reducing the viscosity angle.The increase of water ratio is the result of reactions such as the inner esterification of bio oil, etherificate, and the water ratio increase must cause bio oil viscosity to reduce, mobile increasing, but high-moisture percentage is unfavorable for the stable storage of bio oil.Water ratio and viscosity test result show that under the prerequisite that water ratio reduces greatly, ETHYLE ACETATE is handled biological oil viscosity only slightly to be increased than the acetone treatment bio oil, and this more helps the stable storage of bio oil undoubtedly.
Angle from long-term storage; Add the moisture increase that ETHYLE ACETATE can effectively reduce bio oil, and reduce bio oil viscosity to a great extent, this explanation ETHYLE ACETATE is as a kind of suppressor factor; Suppressed the inner many reactions of bio oil, this effect is continuable; Add acetone and reduce bio oil viscosity to a great extent; But increase the bio oil water ratio simultaneously; This explanation acetone is as a kind of reactant, replaces in the bio oil in some macromole that contain carbonyl and the bio oil activeconstituents reaction generation ether material and stops the reaction that causes generating high polymer to be carried out, and can predict; Along with reaction consumes, the effect of acetone is unsustainable.
To sum up can reach a conclusion, ETHYLE ACETATE is superior to acetone for the effect that improves bio oil stability.
Claims (7)
1. the method through additive raising bio oil stability is characterized in that, in bio oil, adds ETHYLE ACETATE.
2. improve the stable method of bio oil according to claim 1 is said through additive, it is characterized in that, comprise following steps:
The first step, biomass material are prepared: adopt the pine wood chip, after the screening of different meshes sieve, get the pine wood chip after the screening, dry 24h under 105 ℃ of temperature;
In second step, the producing of bio oil: adopting the bubbling fluidized bed biomass fast pyrolysis device, is that raw material is produced bio oil with dried pine wood chip, and its heat scission reaction temperature is 500 ℃, and fluidizing agent is a nitrogen, and fluidising air velocity is 60Lmin
-1
In the 3rd step, calculate the ETHYLE ACETATE addition: calculating is added mass percent concentration in a certain amount of bio oil be the quality of 3～15% required ETHYLE ACETATE;
In the 4th step, in bio oil, add ETHYLE ACETATE: take by weighing a certain amount of new system bio oil, add and calculate required ETHYLE ACETATE, process ETHYLE ACETATE after mixing and handle bio oil, place encloses container to store.
3. according to claim 1 or 2 said methods, it is characterized in that through additive raising bio oil stability, the pine wood chip after the said screening, requiring particle diameter is 30～80 orders.
4. according to claim 1 or the 2 said methods that improve bio oil stability through additive; It is characterized in that; Said bubbling fluidized bed biomass fast pyrolysis device is the bubbling fluidized bed biomass fast pyrolysis device of Shanghai Communications University's agricultural with biomass energy engineering center of biological institute independent development.
5. according to claim 1 or 2 said methods, it is characterized in that said ETHYLE ACETATE is analytical pure, pureness specifications >=99.5% through additive raising bio oil stability.
6. according to claim 1 or 2 said methods, it is characterized in that through additive raising bio oil stability, said storage, condition is 40 ℃ of steady temperatures.
7. according to claim 1 or 2 said methods, it is characterized in that the ETHYLE ACETATE best in quality per-cent that is added is 15% through additive raising bio oil stability.
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| CN103242916A (en) * | 2013-05-08 | 2013-08-14 | 上海交通大学 | Method for improving stability of bio-oil |
| CN105733478A (en) * | 2014-12-08 | 2016-07-06 | 仲恺农业工程学院 | Method for reducing viscosity of SEBS-g-MAH solution |
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| JAMES P. DIEBOLD等: "Additives To Lower and Stabilize the Viscosity of Pyrolysis Oils during Storage", 《ENERGY & FUELS》 * |
| M.E. BOUCHERA等: "Bio-oils obtained by vacuum pyrolysis of softwood bark as a liquid fuel for gas turbines. Part I: Properties of bio-oil and its blends with methanol and a pyrolytic aqueous phase", 《BIOMASS AND BIOENERGY》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103242916A (en) * | 2013-05-08 | 2013-08-14 | 上海交通大学 | Method for improving stability of bio-oil |
| CN105733478A (en) * | 2014-12-08 | 2016-07-06 | 仲恺农业工程学院 | Method for reducing viscosity of SEBS-g-MAH solution |
| CN105733478B (en) * | 2014-12-08 | 2017-11-28 | 仲恺农业工程学院 | A kind of method of reduction SEBS g MAH solution viscosities |
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