CN101892079A - Method for refining pyrolysis lignin in biological oil - Google Patents
Method for refining pyrolysis lignin in biological oil Download PDFInfo
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Abstract
The invention provides a method for refining pyrolysis lignin in biological oil through cracking, which comprises the following steps of: a) washing the biological oil to obtain the pyrolysis lignin; b), adding alcohols into the pyrolysis lignin, and adding a catalyst with the hydrocracking function in an acidic environment; and c), performing hydrocracking at the reaction temperature of between 80 and 400 DEG C under the reactive pressure of between 0.1 and 30 MPa in the reducing atmosphere to obtain high-grade stable and volatile fuel. The method has the characteristics of high yield of cracking liquid, high cracking efficiency and difficult coking of the pyrolysis lignin.
Description
Technical field
The present invention relates to a kind of method for refining biological oil, especially relate to a kind of pyrolysis lignin in the bio oil is made with extra care and be the method for higher-grade liquid fuel.
Background technology
Human increasing to the demand of the energy, and current be the fossil oil worsening shortages of representative with oil, coal, and in use cause serious environmental to pollute, therefore need development cleaning, reproducible new forms of energy.Can be converted into gas, liquid and solid-fuelled renewable energy source--biomass as unique, have advantages such as the pollution of hanging down, distribution is wide, reserves are big.The exploitation of biomass renewable energy source has become the research focus of the world today.Wherein pyrolysis biomass technology can obtain the liquid fuel and the chemical of high added value, and fast pyrogenation can obtain the liquid product more than 70%, and promptly bio oil has the potentiality that replace petroleum products.
Yet there is following shortcoming in the bio oil of producing at present: viscosity is big, poor stability, corrodibility is strong, polarity is big, calorific value is low.Therefore must carry out catalytic refining to it, to improve its quality.
Bio oil purification techniques commonly used is divided into two classes: shortening and catalytic pyrolysis.Shortening be high pressure (10～20MPa) and hydrogen or hydrogen supply dissolvent existence condition under, by catalyzer bio oil is carried out hydrotreatment based on Ni-Mo, Co-Mo, the oxygen in the bio oil is with H
2O or CO
2Form remove.Catalytic pyrolysis process be catalyzer under normal pressure by thermochemical method with the oxygen in the bio oil with CO, CO
2, H
2The form of O is removed, and the oxygen level in the refining artifact oil obviously descends and obtains the less organic product of molecular weight.Although above two kinds of methods all can obtain the bio oil of higher quality, liquid yield is low, in the operation normal because coking reacts problems such as device obstruction and the serious inactivation of catalyzer, restricted the widespread use of above method.
Pyrolysis lignin is called the xylogen oligopolymer again, is one of biological main body of oil, accounts for the 20-30% of bio oil gross weight greatly.It is big that pyrolysis lignin has a molecular weight, the boiling point height, characteristics such as difficult volatilization and thermolability, at a lower temperature (80 ℃) promptly with bio oil in other compound or self react, generate bigger compound, cause bio oil aging and demixing phenomenon to occur.Bio oil is refining is carrying out more than 200 ℃ usually, and the charing coking very easily takes place pyrolysis lignin in this process, produces a large amount of coke and tar compounds, and is deposited on catalyst surface, and the covering catalyst avtive spot makes catalyst deactivation; These compounds also easily stop up reactor simultaneously, make the bio oil treating process be difficult to carry out.But simultaneously because pyrolysis lignin than other component calorific value height in the bio oil, if directly remove from bio oil, can cause the bio oil calorific value to decline to a great extent.Therefore, pyrolysis lignin is cracked into to have volatile, a stable organism refining most important for bio oil.In addition, pyrolysis lignin be with the phenolic compound be structural unit by the oligopolymer that certain way couples together, be the phenolic compound produced and the desirable feedstock of phenolic resin, be the beneficial direction that enlarges the application prospect of bio oil.
But present research to pyrolysis lignin mainly also rests on the affirmation of its structure and inquires into, the catalyzer that its catalytic pyrolysis uses mostly is small-bore zeolite molecular sieve class catalyzer such as CoMo/HZSM-5, yield of cracking liquid is lower, lysis efficiency is low, and the pyrolysis lignin coking is serious in cracking process, a large amount of inactivations of catalyzer.
Therefore, need provide a kind of effectively with pyrolysis lignin purified method in the bio oil.
Summary of the invention
The object of the present invention is to provide a kind of yield of cracking liquid height, lysis efficiency height, pyrolysis lignin are difficult for the method for pyrolysis lignin in the pyrogenic refining biological oil.
In order to realize above-mentioned at least one goal of the invention, pyrolysis lignin purified method in the bio oil provided by the present invention comprises the steps: a) bio oil to be obtained pyrolysis lignin through washing; B) in described pyrolysis lignin, add alcohols, and under sour environment, add catalyzer with hydrocracking function; And c) under reducing atmosphere, reaction pressure 0.1～30MPa, 80～400 ℃ of temperature of reaction are carried out hydrocracking, obtain stable, volatile higher-grade fuel.
Method provided by the present invention, wherein used bio oil can be to be raw material with various biomass, the hot cracked bio oil that forms of producing.With various biomass is raw material, and through the bio oil that fast pyrolysis is produced, washing obtains pyrolysis lignin.The alcohols that adds in the pyrolysis lignin is solvent and reactant, mix with bio oil or pyrolysis lignin, and have the tart catalyzer and add simultaneously, have under the condition of reducing atmosphere a certain amount of, in selected pressure and temperature scope, bio oil or pyrolysis lignin are carried out catalytic refining.The quality of refining back product liquid obviously improves: because hydrogenation, the calorific value of bio oil obviously improves; Wherein aldehyde ketone is converted into stable compounds such as alcohols by hydrogenating reduction, thereby has improved the stability of system; Organic acid is converted into stable ester compound by the esterification with alcohols, and system pH is obviously improved.Alcoholic solvent can be urged the into depolymerization of pyrolysis lignin, and prevents that it from assembling.Pyrolysis lignin generation scission of link under the effect of hydrocracking catalyst generates stable compound by hydrogenation, and an acidic catalyst also can promote the cracking of pyrolysis lignin simultaneously, finally makes it be cracked into volatile stable micromolecular compound.
Among the present invention, comprise as the alcohols of solvent and reactant: carbon 1 is to the monohydroxy-alcohol or the polyvalent alcohol of carbon 8.The mass ratio of alcohols and pyrolysis lignin is 0.05～100: 1.
Catalyzer of the present invention has shortening and catalytic pyrolysis characteristic simultaneously.Catalyzer of the present invention can comprise: any one or more in nickel, palladium, platinum, ruthenium, rhodium, iridium, cobalt, iron, the osmium.The existence of these metals makes catalyzer have the characteristic of hydrocracking.
According to an embodiment of the invention, catalyst system therefor of the present invention can also comprise one or more in any metal in IB family, IIB family, group vib, the VIIB family.These metals can add separately, also can make up interpolation, also these metals can be formed alloy and add.Mainly play the catalyst aid effect, thereby improve the active and stable of Primary Catalysts, and reduce its consumption.
According to an embodiment more of the present invention, catalyst system therefor of the present invention can also comprise one or more in group of the lanthanides, actinium series rare earth metal or the metal oxide.These master metal will play the effect of auxiliary agent, can prevent the inactivation of catalyzer, or play anti-carbon effect.
Provided by the present invention have the active catalyzer of hydrocracking can appendix at appendix on any or arbitrary group of micropore or mesoporous carrier.
One of according to the embodiment of the present invention, method provided by the present invention, its sour environment is by adding acidic substance or described catalyzer appendix being realized on acid carrier in reaction system.These acidic substance can wait and realize by adding various bronsted acid and Lewis acid, metal-salt and title complex, solid acid, heteropolyacid, molecular sieve.
Reducing atmosphere of the present invention is to realize by add in hydrogen, methane, sodium borohydride, formic acid, the sodium formiate any one or more in reaction system.
One of according to the embodiment of the present invention, the preferred reaction pressure of catalytic pyrolysis provided by the present invention is 1～15MPa, preferred temperature of reaction is 100～300 ℃.
The invention discloses and a kind of bio oil and pyrolysis lignin are converted into the method for higher-grade fuel,, thereby obtain high-quality liquid fuel and chemical by hydrocracking catalytic refining bio oil and pyrolysis lignin.
This method technology is simple, easy to operate, and entire reaction course does not have carbon deposit substantially, and the liquid yield that obtains can reach more than 90%.Refining back products therefrom stability strengthens, and corrodibility reduces, and is easy to store and transportation, has good burning performance, and is expected to become the substitute of liquid fossil oil.Simultaneously, utilize this method, the most pyrolysis lignins in refining back all are degraded to stable volatile small molecules liquid organic compound, and the product liquid behind the pyrolysis lignin hydrocracking is mainly based on phenolic compound.Therefore this method is a kind of effective ways of cracking pyrolysis lignin, and the application of pyrolysis lignin is from now on had crucial influence.
Additional aspect of the present invention and advantage part in the following description provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Description of drawings
Above-mentioned and/or additional aspect of the present invention and advantage are from obviously and easily understanding becoming the description of embodiment below in conjunction with accompanying drawing, wherein:
Fig. 1 is the GC-MS figure before and after the pyrolysis lignin hydrocracking.
Embodiment
Describe embodiments of the invention below in detail.The embodiment that describes below is exemplary, only is used to explain the present invention, and can not be interpreted as limitation of the present invention.
Embodiment 1
Take by weighing 1 part of pyrolysis lignin and 11 parts of ethanol are put into it in 150mL autoclave, drop into 0.5 part of catalyzer (3%Ru/ZrO again
2/ SBA-15 is designated as RuZr).With the air in its still of hydrogen exchange three to four times, charge into the hydrogen of 2MPa again, so that reduce the content of air content, particularly oxygen in the still as far as possible, reduce atmosphere in the still to keep.Open whipping appts to 1000 right side of turning left, reheat to 150 ℃ was also kept 8 hours.Question response is cooled to room temperature after finishing, and collects liquid, gas and solid product.The liquids and gases product is analyzed its chemical constitution by GC-MS and GC.Its result is: liquid yield is 88.85%; The solid productive rate is 3.60%; Gas yield is 7.55%; Pyrolysis lignin is cracked into the productive rate of fluid organic material, i.e. productive rate (the Y of cracked oil
Oil) and calorific value be respectively 53.08% and 26.33MJ/Kg.
Embodiment 2
Take by weighing 1 part of pyrolysis lignin and 11 parts of ethanol are put into it in 150mL autoclave, drop into 0.5 part of catalyzer (3%Ru/ZrO again
2/ SBA-15 is designated as RuZr).With the air in its still of hydrogen exchange three to four times, charge into the hydrogen of 2MPa again, so that reduce the content of air content, particularly oxygen in the still as far as possible, reduce atmosphere in the still to keep.Open whipping appts to 1000 right side of turning left, reheat to 200 ℃ was also kept 8 hours.Question response is cooled to room temperature after finishing, and collects liquid, gas and solid product.The liquids and gases product is analyzed its chemical constitution by GC-MS and GC.Its result is: liquid yield is 85.29%; The solid productive rate is 3.25%; Gas yield is 11.46%; Pyrolysis lignin is cracked into the productive rate of fluid organic material, i.e. productive rate (the Y of cracked oil
Oil) and calorific value be respectively 56.77% and 26.84MJ/Kg.
Embodiment 3
Take by weighing 1 part of pyrolysis lignin and 11 parts of ethanol are put into it in 150mL autoclave, drop into 0.5 part of catalyzer (3%Ru/ZrO again
2/ SBA-15 is designated as RuZr).With the air in its still of hydrogen exchange three to four times, charge into the hydrogen of 2MPa again, so that reduce the content of air content, particularly oxygen in the still as far as possible, reduce atmosphere in the still to keep.Open whipping appts to 1000 right side of turning left, reheat to 260 ℃ was also kept 8 hours.Question response is cooled to room temperature after finishing, and collects liquid, gas and solid product.The liquids and gases product is analyzed its chemical constitution by GC-MS and GC.Its result is: liquid yield is 86.91%; The solid productive rate is 0.30%; Gas yield is 12.79%; Pyrolysis lignin is cracked into the productive rate of fluid organic material, i.e. productive rate (the Y of cracked oil
Oil) and calorific value be respectively 99.51% and 31.96MJ/Kg.
Embodiment 4
Take by weighing 1 part of pyrolysis lignin and 11 parts of ethanol are put into it in 150mL autoclave, drop into 0.5 part of catalyzer (3%Ru/ZrO again
2/ SBA-15 is designated as RuZr).With the air in its still of hydrogen exchange three to four times, charge into the hydrogen of 2MPa again, so that reduce the content of air content, particularly oxygen in the still as far as possible, reduce atmosphere in the still to keep.Open whipping appts to 1000 right side of turning left, reheat to 280 ℃ was also kept 8 hours.Question response is cooled to room temperature after finishing, and collects liquid, gas and solid product.The liquids and gases product is analyzed its chemical constitution by GC-MS and GC.Its result is: liquid yield is 77.92%; The solid productive rate is 0.85%; Gas yield is 21.23%; Pyrolysis lignin is cracked into the productive rate of fluid organic material, i.e. productive rate (the Y of cracked oil
Oil) and calorific value be respectively 85.11% and 31.25MJ/Kg.
Embodiment 5
Take by weighing 1 part of pyrolysis lignin and 11 parts of ethanol are put into it in 150mL autoclave, drop into 0.5 part of catalyzer (3%Ru/ZrO again
2/ SBA-15 is designated as RuZr).With the air in its still of hydrogen exchange three to four times, so that reduce the content of air content, particularly oxygen in the still as far as possible, to keep inert atmosphere in the still.The HCOOH that adds 0.5 part is as hydrogen source.Open whipping appts to 1000 right side of turning left, reheat to 260 ℃ was also kept 8 hours.Question response is cooled to room temperature after finishing, and collects liquid, gas and solid product.The liquids and gases product is analyzed its chemical constitution by GC-MS and GC.Its result is: liquid yield is 84.31%; The solid productive rate is 1.34%; Gas yield is 14.35%; Pyrolysis lignin is cracked into the productive rate of fluid organic material, i.e. productive rate (the Y of cracked oil
Oil) and calorific value be respectively 83.88% and 26.19MJ/Kg.
The detailed results of embodiment 1-5 can see Table 1.
The cracking situation of table 1 pyrolysis lignin under the condition of differing temps and hydrogen donor
I:Y
Liquid, Y
SolidAnd Y
GasRepresent liquid, solid and gas yield respectively based on the amount calculating of ethanol (11 parts) and pyrolysis lignin (1 part) before the reaction.
Ii:y
OilThe expression pyrolysis lignin is cracked into the productive rate iii of fluid organic material: button removes the calorific value behind the second alcohol and water
As known from Table 1, temperature of reaction is the alcoholic acid supercritical temperature and directly is hydrogen donor and reduction during atmosphere with hydrogen that the lytic effect of pyrolysis lignin is better.
Fig. 1 is the GC-MS figure before and after the pyrolysis lignin hydrocracking, and PL ethanol solutions promptly represents the ethanolic soln of the preceding pyrolysis lignin of reaction among the figure, and wherein detectable volatile constituent is very limited.RuSZr-oil promptly represents the product liquid after utilizing RuSZr for catalyzer hydrocracking pyrolysis lignin.After handling through this system as can be seen from this figure, pyrolysis lignin is converted into effectively has volatile liquid organic product.
Embodiment 6
Take by weighing 1 part of pyrolysis lignin and 11 parts of ethanol are put into it in 150mL autoclave, drop into 0.5 part of catalyzer (3%Ru/HZSM is designated as RuHZSM) again.With the air in its still of hydrogen exchange three to four times, charge into the hydrogen of 2MPa again, so that reduce the content of air content, particularly oxygen in the still as far as possible, reduce atmosphere in the still to keep.Open whipping appts to 1000 right side of turning left, reheat to 260 ℃ was also kept 8 hours.Question response is cooled to room temperature after finishing, and collects liquid, gas and solid product.The liquids and gases product is analyzed its chemical constitution by GC-MS and GC.Its result is: liquid yield is 83.18%; The solid productive rate is 2.75%; Gas yield is 14.07%; Pyrolysis lignin is cracked into the productive rate of fluid organic material, i.e. productive rate (the Y of cracked oil
Oil) and calorific value be respectively 30.30% and 36.24MJ/Kg.
Embodiment 7
Take by weighing 1 part of pyrolysis lignin and 11 parts of ethanol are put into it in 150mL autoclave, drop into 0.5 part of catalyzer (3%Ru/HY is designated as RuHY) again.With the air in its still of hydrogen exchange three to four times, charge into the hydrogen of 2MPa again, so that reduce the content of air content, particularly oxygen in the still as far as possible, reduce atmosphere in the still to keep.Open whipping appts to 1000 right side of turning left, reheat to 260 ℃ was also kept 8 hours.Question response is cooled to room temperature after finishing, and collects liquid, gas and solid product.The liquids and gases product is analyzed its chemical constitution by GC-MS and GC.Its result is: liquid yield is 79.87%; The solid productive rate is 5.52%; Gas yield is 14.61%; Pyrolysis lignin is cracked into the productive rate of fluid organic material, i.e. productive rate (the Y of cracked oil
Oil) and calorific value be respectively 33.07% and 38.65MJ/Kg.
Embodiment 8
Take by weighing 1 part of pyrolysis lignin and 11 parts of ethanol are put into it in 150mL autoclave, drop into 0.5 part of catalyzer (3%Pd/ZrO again
2/ SBA-15).With the air in its still of hydrogen exchange three to four times, charge into the hydrogen of 2MPa again, so that reduce the content of air content, particularly oxygen in the still as far as possible, reduce atmosphere in the still to keep.Open whipping appts to 1000 right side of turning left, reheat to 260 ℃ was also kept 8 hours.Question response is cooled to room temperature after finishing, and collects liquid, gas and solid product.The liquids and gases product is analyzed its chemical constitution by GC-MS and GC.Its result is: liquid yield is 82.27%; The solid productive rate is 1.61%; Gas yield is 16.12%; Pyrolysis lignin is cracked into the productive rate of fluid organic material, i.e. productive rate (the Y of cracked oil
Oil) and calorific value be respectively 81.26% and 27.67MJ/Kg.
The detailed results of embodiment 6-8 can see Table 2.
The cracking situation of table 2 pyrolysis lignin under the condition of different catalyzer
I:Y
Liquid, Y
SolidAnd Y
GasRepresent liquid, solid and gas yield respectively based on the re-computation of ethanol (11 parts) and pyrolysis lignin (1 part) before the reaction.
Ii:Y
OilThe expression pyrolysis lignin is cracked into the productive rate iii of fluid organic material: button removes the calorific value behind the second alcohol and water
As known from Table 2, when catalyzer was the mesoporous material class catalyzer of load Ru, the lytic effect of pyrolysis lignin was better.
Embodiment 9
Take by weighing 1 part of pyrolysis lignin and 11 parts of ethanol are put into it in 150mL autoclave, drop into 0.5 part of catalyzer (3%Ru/SO again
4 2-/ ZrO
2/ SBA-15 is designated as RuSZr).With the air in its still of hydrogen exchange three to four times, charge into the hydrogen of 2MPa again, so that reduce the content of air content, particularly oxygen in the still as far as possible, reduce atmosphere in the still to keep.Open whipping appts to 1000 right side of turning left, reheat to 260 ℃ was also kept 8 hours.Question response is cooled to room temperature after finishing, and collects liquid, gas and solid product.The liquids and gases product is analyzed its chemical constitution by GC-MS and GC.Its result is: liquid yield is 88.98%; The solid productive rate is 0.93%; Gas yield is 10.09%; Pyrolysis lignin is cracked into the productive rate of fluid organic material, i.e. productive rate (the Y of cracked oil
Oil) and calorific value be respectively 96.10% and 34.94MJ/Kg
Take by weighing 1 part of pyrolysis lignin and 11 parts of ethanol are put into it in 150mL autoclave, drop into 0.5 part of catalyzer (SO again
4 2-/ ZrO
2/ SBA-15 is designated as SZr).With the air in its still of hydrogen exchange three to four times, charge into the hydrogen of 2MPa again, so that reduce the content of air content, particularly oxygen in the still as far as possible, reduce atmosphere in the still to keep.Open whipping appts to 1000 right side of turning left, reheat to 260 ℃ was also kept 8 hours.Question response is cooled to room temperature after finishing, and collects liquid, gas and solid product.The liquids and gases product is analyzed its chemical constitution by GC-MS and GC.Its result is: liquid yield is 86.17%; The solid productive rate is 5.12%; Gas yield is 8.71%; Pyrolysis lignin is cracked into the productive rate of fluid organic material, i.e. productive rate (the Y of cracked oil
Oil) and calorific value be respectively 36.73% and 26.04MJ/Kg.
Embodiment 11
Take by weighing 1 part of pyrolysis lignin and 11 parts of ethanol with in its input 150mL autoclave, drop into 0.5 part of catalyzer (ZrO again
2/ SBA-15 is designated as Zr).With the air in its still of hydrogen exchange three to four times, charge into the hydrogen of 2MPa again, so that reduce the content of air content, particularly oxygen in the still as far as possible, reduce atmosphere in the still to keep.Open whipping appts to 1000 right side of turning left, reheat to 260 ℃ was also kept 8 hours.Question response is cooled to room temperature after finishing, and collects liquid, gas and solid product.The liquids and gases product is analyzed its chemical constitution by GC-MS and GC.Its result is: liquid yield is 88.17%; The solid productive rate is 4.59%; Gas yield is 7.24%; Pyrolysis lignin is cracked into the productive rate of fluid organic material, i.e. productive rate (the Y of cracked oil
Oil) and calorific value be respectively 46.18% and 25.48MJ/Kg.
Embodiment 12
Take by weighing 1 part of pyrolysis lignin and 11 parts of ethanol are put into it in 150mL autoclave.With the air in its still of hydrogen exchange three to four times, charge into the hydrogen of 2MPa again, so that reduce the content of air content, particularly oxygen in the still as far as possible, reduce atmosphere in the still to keep.Open whipping appts to 1000 right side of turning left, reheat to 260 ℃ was also kept 8 hours.Question response is cooled to room temperature after finishing, and collects liquid, gas and solid product.The liquids and gases product is analyzed its chemical constitution by GC-MS and GC.Its result is: liquid yield is 88.98%; The solid productive rate is 4.27%; Gas yield is 6.77%; Pyrolysis lignin is cracked into the productive rate of fluid organic material, i.e. productive rate (the Y of cracked oil
Oil) and calorific value be respectively 51.28% and 27.87MJ/Kg.
The detailed results of embodiment 9-12 can see Table 3.
The cracking situation of table 3 pyrolysis lignin under the condition of different zirconium catalyst series
I:Y
Liquid, Y
SolidAnd Y
GasRepresent liquid, solid and gas yield respectively based on the amount calculating of ethanol (11 parts) and pyrolysis lignin (1 part) before the reaction.
Ii:Y
OilThe expression pyrolysis lignin is cracked into the tight rate iii of fluid organic material: button removes the calorific value behind the second alcohol and water
As known from Table 3, pyrolysis lignin is cracked into micromolecular compound effectively under Supercritical Ethanol, hydrogen and homemade catalyzer RuSZr or RuZr condition.
In sum, load Ru's has a tart mesoporous catalyst hydrocracking pyrolysis lignin and generate and to have volatile, stable liquid organic product effectively.
Embodiment 13
Get 1 part of bio oil and 2 parts of ethanol that contain 30% pyrolysis lignin it is put in the 150mL autoclave, drop into 0.1 part of catalyzer (SO again
4 2-/ ZrO
2/ SBA-15 is designated as SZr).With the air in its still of hydrogen exchange three to four times, charge into the hydrogen of 2MPa again, so that reduce the content of air content, particularly oxygen in the still as far as possible, reduce atmosphere in the still to keep.Open whipping appts to 1000 right side of turning left, reheat to 280 ℃ was also kept 3 hours.Question response is cooled to room temperature after finishing, and collects treated oil.For ease of describing, this treated oil is designated as SZr-oil, treated oil is analyzed its chemical constitution by GC-MS and GC.Its result is: viscosity is 1.5mm
2/ s; Density is 0.84g/ml; The pH value is 5.3; It is 14.7MJ/Kg that button removes the calorific value of the treated oil behind the ethanol; The content of the moisture in the treated oil, ethanol and oil is respectively 17.3%, 70.7% and 12.0%.
Embodiment 14
Take by weighing 1 part of bio oil and 2 parts of ethanol that contain 30% pyrolysis lignin it is put in the 150mL autoclave, drop into 0.1 part of catalyzer (3%Pd/SO again
4 2-/ ZrO
2/ SBA-15 is designated as PdSZr).With the air in its still of hydrogen exchange three to four times, charge into the hydrogen of 2MPa again, so that reduce the content of air content, particularly oxygen in the still as far as possible, reduce atmosphere in the still to keep.Open whipping appts to 1000 right side of turning left, reheat to 280 ℃ was also kept 3 hours.Question response is cooled to room temperature after finishing, and collects treated oil, for ease of describing, this treated oil is designated as PdSZr-oil.Treated oil is analyzed its chemical constitution by GC-MS and GC.Its result is: viscosity is 1.6mm
2/ s; Density is 0.84g/ml; The pH value is 4.7; It is 20.1MJ/Kg that button removes the calorific value of the treated oil behind the ethanol; The content of the moisture in the treated oil, ethanol and oil is respectively 16.2%, 65.8% and 18.0%.
Comparing embodiment 1
Getting 1 part of bio oil and 2 parts of ethanol that contain 30% pyrolysis lignin puts into it in 150mL autoclave.With the air in its still of hydrogen exchange three to four times, so that reduce the content of air content, particularly oxygen in the still as far as possible, to keep inert atmosphere in the still.Open whipping appts to 1000 right side of turning left, reheat to 280 ℃ was also kept 3 hours.Question response is cooled to room temperature after finishing, and collects treated oil.For ease of describing, this treated oil is designated as NoCat-oil, treated oil is analyzed its chemical constitution by GC-MS and GC.Its result is: viscosity is 1.6mm
2/ s; Density is 0.89g/ml; The pH value is 5.5; It is 6.2MJ/Kg that button removes the calorific value of the treated oil behind the ethanol; The content of the moisture in the treated oil, ethanol and oil is respectively 29.9%, 63.5% and 6.6%.
Relatively seeing the following form of NoCat-oil and embodiment 1 and 2 gained bio oil:
Table 1 differential responses condition is to the influence of treated oil quality
A: the massfraction of treated oil behind the massfraction of second alcohol and water is removed in this expression
B: calorific value herein is the calorific value after button removes the alcoholic acid calorific value
C: stock oil is by 1 part of bio oil and 2 parts of systems that dehydrated alcohol is formed
More than as seen Bi Jiao detailed results under Supercritical Ethanol and hydrogen condition, utilizes Pd/SO
4 2-/ ZrO
2The refining bio oil that contains pyrolysis lignin of/SBA-15, the quality of refining artifact oil obviously improves: viscosity and density obviously descend, and pH value and calorific value then obviously improve.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claims and equivalent thereof.
Claims (10)
1. pyrolysis lignin purified method in the bio oil comprises the steps:
A) bio oil is obtained pyrolysis lignin through washing;
B) in described pyrolysis lignin, add alcohols, and under sour environment, add catalyzer with hydrocracking function; And
C) under reducing atmosphere, reaction pressure 0.1～30MPa, 80～400 ℃ of temperature of reaction are carried out hydrocracking, obtain stable, volatile higher-grade fuel.
2. method according to claim 1, wherein said alcohols comprise monohydroxy-alcohol or the polyvalent alcohol of carbon 1 to carbon 8.
3. method according to claim 1, the mass ratio of wherein said alcohols and described pyrolysis lignin are 0.05～100: 1.
4. method according to claim 1, wherein said catalyzer comprises: any one or more in nickel, palladium, platinum, ruthenium, rhodium, iridium, cobalt, iron, the osmium.
5. method according to claim 5, wherein said catalyzer comprise one or more in any metal in IB family, IIB family, group vib, the VIIB family.
6. according to claim 4 or 5 described methods, wherein said catalyzer comprises one or more in group of the lanthanides, actinium series rare earth metal or the metal oxide.
7. method according to claim 1, wherein said catalyzer appendix is on any one or one group of micropore or mesoporous carrier.
8. method according to claim 1, wherein said sour environment is by adding acidic substance or described catalyzer appendix being realized on acid carrier in reaction system.
9. method according to claim 1, wherein said reducing atmosphere are to realize by add in hydrogen, methane, sodium borohydride, formic acid, the sodium formiate any one or more in reaction system.
10. method according to claim 1, wherein the reaction pressure among the step c is preferably 1～15MPa, and temperature of reaction is preferably 100～300 ℃.
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| CN102875752A (en) * | 2011-12-05 | 2013-01-16 | 山东圣泉化工股份有限公司 | Lignin modified thermoplastic phenolic resin and preparation method thereof |
| CN102876350A (en) * | 2012-09-26 | 2013-01-16 | 中国科学技术大学 | Method for preparing alkane fuel with high cetane number by catalyzing plant oil or long-chain fatty acid by Ru catalyst and application thereof |
| CN103173243A (en) * | 2011-12-23 | 2013-06-26 | 中国林业科学研究院木材工业研究所 | Method for hydrofining biomass alcoholysis heavy oil |
| CN103170345A (en) * | 2011-12-23 | 2013-06-26 | 中国林业科学研究院木材工业研究所 | Supported catalyst, and preparation method and application thereof |
| CN103459562A (en) * | 2010-11-04 | 2013-12-18 | 雅宝欧洲有限责任公司 | Hydrodeoxygenation of pyrolysis oil in presence of admixed alcohol |
| CN103484158A (en) * | 2013-09-05 | 2014-01-01 | 北京林业大学 | Method for preparing chemicals containing phenols and aromatic hydrocarbons from bio-oil pyrolysis lignin through catalysis |
| CN103820141A (en) * | 2012-11-16 | 2014-05-28 | 中国科学院大连化学物理研究所 | Method of utilizing biological pyrolysis oil to prepare liquid fuel |
| US20140250774A1 (en) * | 2013-03-08 | 2014-09-11 | Upm-Kymmene Corporation | Process for modifying bio-oil |
| CN108499598A (en) * | 2018-02-26 | 2018-09-07 | 中山大学惠州研究院 | It is a kind of multistage porous molecular sieve N-Meso-ZSM-5 catalyst and its catalysis pyrolysis lignin prepare bio oil method |
| CN111057568A (en) * | 2019-12-25 | 2020-04-24 | 华南理工大学 | Method for improving yield of lignin pyrolysis oil and application thereof |
| CN115672379A (en) * | 2022-09-29 | 2023-02-03 | 中国农业大学 | Preparation method and application of Ru-ZnOSBA-15 catalyst |
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| CN103820141B (en) * | 2012-11-16 | 2015-09-30 | 中国科学院大连化学物理研究所 | A kind of biological cracked oil prepares the method for liquid fuel |
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| CN103484158A (en) * | 2013-09-05 | 2014-01-01 | 北京林业大学 | Method for preparing chemicals containing phenols and aromatic hydrocarbons from bio-oil pyrolysis lignin through catalysis |
| CN108499598A (en) * | 2018-02-26 | 2018-09-07 | 中山大学惠州研究院 | It is a kind of multistage porous molecular sieve N-Meso-ZSM-5 catalyst and its catalysis pyrolysis lignin prepare bio oil method |
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| CN111057568B (en) * | 2019-12-25 | 2020-12-22 | 华南理工大学 | Method for improving yield of lignin pyrolysis oil and application thereof |
| CN115672379A (en) * | 2022-09-29 | 2023-02-03 | 中国农业大学 | Preparation method and application of Ru-ZnOSBA-15 catalyst |
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