CN101812376B - Method for catalyzing, esterifying and upgrading bio-oil under microwave condition - Google Patents
Method for catalyzing, esterifying and upgrading bio-oil under microwave condition Download PDFInfo
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- CN101812376B CN101812376B CN2010101521154A CN201010152115A CN101812376B CN 101812376 B CN101812376 B CN 101812376B CN 2010101521154 A CN2010101521154 A CN 2010101521154A CN 201010152115 A CN201010152115 A CN 201010152115A CN 101812376 B CN101812376 B CN 101812376B
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Abstract
The invention discloses a method for catalyzing, esterifying and upgrading bio-oil under a microwave condition. In the method, acidic materials in the bio-oil are catalyzed, esterifyed and upgraded by adopting a ZnCl2-midified 732 type cation exchange resin as a catalyst and adding ethanol as a solvent and a reactant and under a microwave heating condition, and mixed solution of ethanol, acetic acid and furfural is adopted as imitation of a bio-oil complex system; esterification is performed under the condition of the catalyst of ZnCl2-midified 732 type cation exchange resin by adding a certain amount of hydrogen peroxide containing 30 percent of H2O2, and oxidizing furfural substances into the acidic materials, and a normal pressure microwave-assisted synthesis and extraction microwave reactor is adopted as a reaction device; the ZnCl2-midified 732 type cation exchange resin catalyst has better activity; and the conversion rate of the acetic acid which is obtained by catalyzing, esterifying and upgrading the bio-oil catalysis under the microwave condition reaches 70.37 percent; and the conversion rate of the furfural reaches 51.71 percent.
Description
Technical field
The present invention relates to the method for bio oil catalysis upgrading, particularly relating to the bio oil catalysis upgrading is catalyzing, esterifying and upgrading bio-oil under the microwave condition in the higher-grade liquid fuel.
Background technology
Biomass energy is the photosynthesis through green plants gets off the energy of solar radiation with a kind of biomass form fix the energy; Reserves are big, and are capable of circulation, and it is low to contain N, S amount; Highly clean; Lower atmospheric polluting material significantly, the clean quantity discharged of greenhouse gases carbonic acid gas is zero, helps to solve the environmental problem that fossil energy consumption brings.Problems such as International Crude Oil continuous rise, energy dilemma highlight make bio oil receive widely as a kind of environmentally friendly, renewable energy source and pay close attention to.Bio oil is by pyrolytic reaction and the quick refrigerative product through the short period of time such as straw, cauline leaf, has raw material abundance, advantage such as renewable, cheap.The COMPLEX MIXED objects system that bio oil is made up of hundreds of compounds such as organic acid, aldehyde, ether, ester, acetal, semi-acetal, keto-alcohol, alkene, aromatic hydrocarbons, polyatomic phenols.Especially acids and aldehyde material make strong, the poor stability of bio oil corrodibility, both have been unfavorable for that bio oil stored for a long time, have accelerated the loss of oil engine again, have limited the application of bio oil, therefore, must handle through upgrading.
Prior biological oil upgrading treatment process, referring to [1] Senol O I, Viljava T R, Krause A O I.Catal Today, 2005,100 (3): 331～335; [2] Nokkosmaki M I, Kuoppala E T, Leppamaki E A, et al.PyrolysisJournal of Analytical and Applied Pyrolysis, 2000,55 (1): 119～131; [3] Chiaramonti D, Bonini M, Fratini E, et al.Biomass Bioenergy, 3003,24 (3): 221～232; [4] Ikura M, Stanciulescu M, Hogan E.Biomass Bioenergy, 2004,227 (1): 101～108; [5] Takanabe K, Aika K I, Seshan K, et al.JCatal, 2004,227 (1): 101～108.Mainly bio oil is carried out upgrading through methods such as catalytic hydrodeoxygenation, steam catalytic pyrolysis, emulsification, steam reformings.These bio oil purified methods (shortening and catalytic pyrolysis) mainly are to reduce oxygen level, and oxygen is with CO
2And H
2The form of O removes, and it is relatively harsher that bio oil is carried out the upgrading reaction conditions, also high to the requirement of equipment itself; Usually all to be equipped with relevant high quality equipment, for example pass through the great variety of the bio oil temperature difference, fast liquefying gaseous state bio oil; Therefore equipment requirements will occupy very big ratio in bio oil is produced; Not only increased cost,, and increased operation easier like apparatus maintenance maintenance etc.
Summary of the invention
The present invention be directed to during existing normal condition bio oil upgrading handles, problem such as reaction conditions is very harsh, and equipment quality requires high, and operation easier is big, proposition under unconventional condition microwave heating, a kind of catalysis upgrading method of esterification bio oil.
The method of catalyzing, esterifying and upgrading bio-oil under the microwave condition provided by the present invention adopts with ZnCl
2732 type Zeo-karbs of modification are catalyzer; Under microwave heating condition; Add ethanol as solvent and reactant, the acidic substance in the bio oil are carried out the catalytic esterification upgrading, adopt of the simulation of the mixing solutions of ethanol, acetate, furfural as the bio oil complex system; Add and contain H
2O
2Be 30% ydrogen peroxide 50, oxidation furfural class material is an acid, at ZnCl
2Esterification under the 732 type cation exchange resin catalyst conditions of modification; Employing normal pressure microwave-assisted is synthetic and extract the microwave reaction appearance as reaction unit, and concrete operations are: in Kjeldahl flask, add ethanol, acetate, furfural, ydrogen peroxide 50 and catalyzer by a certain percentage, and put into magneton; Kjeldahl flask is put into the microwave reaction appearance, open water of condensation, set certain temperature; In the reaction times, rotating speed reacts under microwave heating condition; After reaction finished, inclining reaction solution.
Ethanol according to the invention: acetate: the mass ratio of furfural, ydrogen peroxide 50 is: 3.80: 1.57: 1.12: 1.
The mass ratio of catalyzer according to the invention and reaction solution is 1: 20～155, and optimum proportion is 1: 20.6.
Active ingredient Zn in the catalyzer according to the invention
2+The mass percent of content is 0.15%.
Stirring velocity 400rpm according to the invention ± 2rpm, microwave power 100～400W is adjustable, best microwave heating power 400W.
Reaction times according to the invention is 10～60min, and optimum reacting time is 60min, 45～85 ℃ of temperature of reaction, and optimal reaction temperature is 75 ℃.
The present invention adopts the simulation of the mixing solutions of ethanol, acetate, furfural as the bio oil complex system.
The ZnCl that the present invention is used
2Modification 732 type cation exchange resin catalyst method for expressing: 0.15%Zn
2+/ 732 resin catalysts, wherein 0.15% representes the massfraction of reactive metal in catalyzer, Zn
2+Represent that 732 type resins submit the metals ion of changing.
The used Na of the present invention
+Type 732 type resins are that Shanghai is converged magnificent resin chemical industry ltd and produced, and outward appearance is pale brown look to a brown spherical particle, and the form of dispatching from the factory is the sodium type, its main performance index: granularity %: (0.315-1.25) mm>=95; Moisture content %:46-52; Mill back rate of small round spheres %:>=95; The rate of expansion that makes the transition %:Na-H, 8-10; PH use range: 1-14; Exchanging equivalent mmol/g:>=4.5; Wet volume density g/ml:0.77-0.87; Wet true density g/ml:1.24-1.28.
ZnCl of the present invention
2The preparation method of modification 732 type cation exchange resin catalysts is with the Na of market purchase
+Type 732 types are counted fat and are washed with deionized water, soak 4～8 hours with 4%NaOH then, are washed till neutrality with deionized water; Soaked 4～8 hours with 4%HCl again, be washed till pH=6 with deionized water; Cryodrying is H
+Type 732 type strongly acidic cationic exchange resin carriers; Getting a certain amount of zinc chloride and deionized water, to be made into mass concentration be 0.15% liquor zinci chloridi, adds 732
#The strongly acidic cationic exchange resin carrier, use under the room temperature massfraction be 0.15% the liquor zinci chloridi dipping carry out IX, be washed till no Cl with deionized water at last
-Till, be dried to constant weight in the vacuum drying oven, obtain 0.15%Zn
2+/ 732 resin catalysts.
Analyze among the present invention and carry out qualitatively with gas chromatography mass spectrometry, carry out quantitatively with gc.
Transformation efficiency defines as follows:
The present invention finds with 732
#Strongly acidic cationic exchange resin is a carrier, through load Zn
2+Increase the acidity of resin catalyst, can improve its catalytic activity.Experiment is found: with ZnCl
2Modification 732 type Zeo-karbs are that catalyzer has activity preferably aspect catalyzing, esterifying and upgrading bio-oil; There is synergistic effect between metal position and the acidic site on the modified catalyst; The rising of temperature of reaction, the prolongation in reaction times, the increase of catalyst levels and the acidity of solid acid are beneficial to whole esterification more by force more.
The present invention adopts two kinds of different type of heating of microwave and water-bath under the constant situation of other conditions, the result shows that the carrying out that more can promote esterification upgrading process effectively heated in microwave heating than traditional water bath.Catalytic esterification improving quality of bio oil is under the situation of not deoxidation, the oxygenatedchemicals in the bio oil to be carried out upgrading under the microwave condition; Generate stable and inflammable oxygen-bearing organic matter; Bio oil just might be at normal pressure like this, carries out upgrading under the mild reaction conditions of non high temperature (about 100 ℃).And microwave heating has that heat-up rate is fast, homogeneous heating and do not have characteristics such as lag-effect; Obviously the generation of productive rate and minimizing by product is carried out, is improved in accelerated reaction; System has good emulsifying effect; The system of being heated can produce partial HTHP, can promote the carrying out that react, thereby greatly reduce the reaction times.
The present invention is owing to adopt ZnCl
2Modification 732 type Zeo-karbs are catalyzer; The esterification upgrading is carried out in acid to the bio oil system; Help with in the bio oil unstable with have the nonflammable acid of corrodibility and be converted into more easily and stablize inflammable ester class, and the corresponding acidic substance catalytic esterification that can the hydrogen peroxide oxidation furfural be obtained is converted into corresponding ester class; Improve the stability of bio oil, reduced acid content.Under the microwave condition under the optimal conditions of catalyzing, esterifying and upgrading bio-oil the transformation efficiency of acetate reach 70.37%, the furfural transformation efficiency reaches 51.71%.
Embodiment
Embodiment 1
Preparation of catalysts: with the Na of market purchase
+Type 732 type Zeo-karbs were washed till neutrality with deionized water in 4-8 hour with the 4%NaOH immersion after being washed till the outflow clear water with deionized water again, soaked 4-8 hour with 4%HCl again, were washed till pH=6 with deionized water, and cryodrying promptly obtains H
+Type 732 type strong-acid ion exchange resins.Getting a certain amount of zinc chloride and deionized water, to be made into mass concentration be 0.15% ZnCl
2Solution adds H
+Type 732 type strongly acidic cationic exchange resin carriers carry out IX with the modified solution dipping under the room temperature, are washed till no Cl with deionized water at last
-Till (with 1%AgNO
3Be indicator), be dried to constant weight in the vacuum drying oven, promptly obtain testing used ZnCl
2Modification 732 type cation exchange resin catalysts are expressed as 0.15%Zn
2+/ 732 resin catalysts.
0.15%Zn
2+/ 732 resin catalysts are used for the method for catalyzing, esterifying and upgrading bio-oil, adopt the simulation of the mixing solutions of ethanol, acetate, furfural as the bio oil complex system; Add a certain amount of H that contains
2O
2Be 30% ydrogen peroxide 50, oxidation furfural class material is an acid, at ZnCl
2Esterification under the 732 type cation exchange resin catalyst conditions of modification; The catalyst activity evaluation response adopts the normal pressure microwave-assisted to synthesize and extracts the microwave reaction appearance as reaction unit, and concrete operations are in Kjeldahl flask, to add ethanol, acetate, furfural, ydrogen peroxide 50 and catalyzer by a certain percentage, and put into magneton; Kjeldahl flask is put into the microwave reaction appearance, open water of condensation, set certain temperature; In the reaction times, conditions such as rotating speed are reacted under microwave heating condition; All products all in Kjeldahl flask, are not done the turnout reason in the reaction process.After reaction finished, cold slightly, inclining reaction solution.
Microwave power 100～400W is adjustable, and present embodiment is set microwave power 400w, stirring velocity 400rpm ± 2rpm, and reaction times 60min, 75 ℃ of temperature, the mass ratio of catalyzer and reaction solution is 1: 20.6.The acetate transformation efficiency of esterification under this optimal conditions reaches 70.37%, and selectivity reaches 100%; Furfural transformation efficiency 51.71%, the result sees table 1.
The reaction result and the blank assay result of ethanol, acetate and the esterification of furfural microwave under the table 1 different catalysts condition
| Catalyzer | Ethanol quality/g | Quality of acetic acid/g | Furfural quality/g | Ydrogen peroxide 50 quality/g | Acetate transformation efficiency/% | Furfural transformation efficiency/% |
| 732 resins | 15.8 | 6.3 | 4.64 | 4.16 | 63.33 | 45.96 |
| Zn 2+/ 732 resins | 15.8 | 6.3 | 4.64 | 4.16 | 70.37 | 51.71 |
| SO 4 2-/ZrO 2 | 15.8 | 6.3 | 4.64 | 4.16 | 33.70 | 27.61 |
| HZSM-5 | 15.8 | 6.3 | 4.64 | 4.16 | 20.98 | 21.4 |
| Pt/HZSM-5 | 15.8 | 6.3 | 4.64 | - | 25.36 | 9.31 |
| - | 15.8 | 6.3 | 4.64 | 4.16 | 8.89 | 35.07 |
| - | 15.8 | 6.3 | 4.64 | 6.34 | 0 |
Reaction conditions: microwave power 400w, catalyst levels 1.5, ydrogen peroxide 50 4.16g, 75 ℃ of temperature of reaction, reaction times 60min, stirring velocity 400rpm.
Embodiment 2
Reactant and consumption thereof are identical with embodiment 1, and catalyzer is 1.5gZn
2+/ 732 resins are done five group reactions respectively under 45 ℃ of temperature of reaction, 55 ℃, 65 ℃, 75 ℃, 85 ℃ conditions, other activity rating condition is identical with embodiment 1 except that the temperature of reaction condition.The result sees table 2.
Ethanol, acetate and furfural microwave esterification result under table 2 differing temps
| Temperature/℃ | 45 | 55 | 65 | 75 | 85 |
| Acetate transformation efficiency/% | 46.85 | 54.38 | 63.46 | 70.37 | 68.46 |
| Furfural transformation efficiency/% | 31.52 | 38.34 | 46.62 | 51.71 | 50.24 |
Embodiment 3
Reactant and consumption thereof are identical with embodiment 1; Under catalyst levels 0.2g, 0.5g, 0.75g, 1.0g, 1.5g condition, do the five group reactions mass ratio of corresponding catalyzer and reactant (be respectively 1: 154.5,1: 71.8,1: 41.2,1: 30.9,1: 20.6) respectively, other activity rating condition is identical with embodiment 1 except that the catalyst levels condition.The result sees table 3.
Ethanol, acetate and furfural microwave esterification result under the table 3 different catalysts consumption
| Catalyst levels/g | 0.2 | 0.5 | 0.75 | 1.0 | 1.5 |
| Acetate transformation efficiency/% | 40.59 | 59.18 | 61.15 | 66.65 | 70.37 |
| Furfural transformation efficiency/% | 43.61 | 40.11 | 40.50 | 45.72 | 51.71 |
Embodiment 4
Reactant and consumption thereof are identical with embodiment 1; Catalyzer is a modified resin; Under reaction times 10min, 20min, 30min, 40min, 50min, 60min condition, do five group reactions respectively, other activity rating condition is identical with embodiment 1 except that the reaction times condition.The result sees table 4.
Ethanol, acetate and furfural microwave esterification result under the table 4 differential responses time conditions
| Reaction times/min | 10 | 20 | 30 | 40 | 50 | 60 |
| Acetate transformation efficiency/% | 28.19 | 47.52 | 57.35 | 61.90 | 66.28 | 70.37 |
| Furfural transformation efficiency/% | 24.97 | 31.34 | 38.12 | 43.56 | 51.36 | 51.71 |
Embodiment 5
Reactant and consumption thereof are identical with embodiment 1, and catalyzer is a modified resin, under heating in water bath and microwave heating condition, do six group reactions respectively, and other activity rating condition is identical with embodiment 1 except that the type of heating condition.The result sees table 5.
Ethanol, acetate and furfural microwave esterification result under the table 5 different heating mode
Claims (6)
1. the method for the catalysis upgrading of esterification simulation bio oil system under the microwave condition is characterized in that adopting with ZnCl
2732 type Zeo-karbs of modification are catalyzer, under microwave heating condition, add ethanol as solvent and reactant, and the acidic substance in the bio oil are carried out the catalytic esterification upgrading; Adopt of the simulation of the mixing solutions of ethanol, acetate, furfural as the bio oil complex system; Add and contain H
2O
2Be 30% ydrogen peroxide 50, oxidation furfural class material is an acid, adds ethanol, at ZnCl
2Esterification under the 732 type cation exchange resin catalyst conditions of modification; Employing normal pressure microwave-assisted is synthetic and extract the microwave reaction appearance as reaction unit; Concrete operations are: in Kjeldahl flask, add ethanol, acetate, furfural, ydrogen peroxide 50 and catalyzer by a certain percentage, and put into magneton, Kjeldahl flask is put into the microwave reaction appearance; Open water of condensation, set 45～85 ℃ of temperature of reaction, reaction times 10～60min; Stirring velocity 400rpm ± 2, microwave power 100～400W reacts under the setting microwave heating condition; After reaction finished, inclining reaction solution; Said ZnCl
2The catalyzer of 732 type Zeo-karbs of modification is expressed as 0.15%Zn
2+/ 732 resins, wherein 0.15% representes the massfraction of reactive metal in catalyzer, Zn
2+Expression 732
#The cocommutative metals ion of resin; Said ethanol: acetate: furfural: the mass ratio of ydrogen peroxide 50 is 3.80: 1.57: 1.12: 1; The mass ratio of said catalyzer and reaction solution is 1: 20～155.
2. method according to claim 1 is characterized in that 75 ℃ of temperature of reaction.
3. method according to claim 1 is characterized in that reaction times 60min.
4. method according to claim 1 is characterized in that microwave heating power 400W.
5. method according to claim 1, the mass ratio that it is characterized in that catalyzer and reaction solution is 1: 20.6.
6. method according to claim 1 is characterized in that said ZnCl
2The preparation process of 732 type cation exchange resin catalysts of modification is: with the Na of market purchase
+Type 732 type Zeo-karbs are washed with deionized water, soak 4～8 hours with 4%Na0H then, are washed till neutrality with deionized water; Soaked 4～8 hours with 4%HCl again, be washed till pH=6 with deionized water; Cryodrying obtains H
+Type 732 type strongly acidic cationic exchange resin carriers; Getting zinc chloride and deionized water, to be made into mass concentration be 0.15% liquor zinci chloridi, adds H
+Type 732 type strongly acidic cationic exchange resin carriers, use under the room temperature massfraction be 0.15% the liquor zinci chloridi dipping carry out IX, be washed till no Cl with deionized water at last
-Till, be dried to constant weight in the vacuum drying oven, obtain 0.15%Zn
2+/ 732 resin catalysts, wherein 0.15% representes the massfraction of reactive metal in catalyzer, Zn
2+Represent that 732 type resins submit the metals ion of changing.
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| CN102796573B (en) * | 2012-07-24 | 2014-09-17 | 北京金骄生物质化工有限公司 | Low-freezing biodiesel combined fuel and preparation method thereof |
| CN102851072A (en) * | 2012-07-30 | 2013-01-02 | 东南大学 | Method for refining waste paperboard pyrolytic oil |
| CN102925293A (en) * | 2012-10-10 | 2013-02-13 | 上海交通大学 | Method for preparing high-quality esterification bio-oil by catalytic esterification reaction |
| CN105777582B (en) * | 2016-05-05 | 2017-08-04 | 青岛市市立医院 | A kind of method for preparing cancer therapy drug Vorinostat |
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| GB9426066D0 (en) * | 1994-12-22 | 1995-02-22 | Radlein Desmond S G | Method of upgrading biomass pyrolysis liquids for use as fuels and as a source of chemicals by reaction with alcohols |
| DE10243700A1 (en) * | 2002-09-20 | 2004-04-01 | Oelmühle Leer Connemann Gmbh & Co. | Method and device for producing biodiesel |
| CN100494317C (en) * | 2006-03-03 | 2009-06-03 | 张展洪 | Production of biological diesel oil |
| CN101144025B (en) * | 2007-09-05 | 2011-05-11 | 中国林业科学研究院林产化学工业研究所 | Method for separating and modifying biomass cracking oil to modified biological oil |
| CN101148598A (en) * | 2007-09-06 | 2008-03-26 | 浙江大学 | Catalytic quality improving method for biomass thermal cracking oil by one-step hydrogenating and esterifying aldehyde and acid |
| CN101358138B (en) * | 2008-09-23 | 2011-08-24 | 浙江大学 | Method for improving quality of biomass oil |
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