CN101812376A - 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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- 239000012075 bio-oil Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 19
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract description 57
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000005886 esterification reaction Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 16
- 230000032050 esterification Effects 0.000 claims abstract description 15
- 239000000376 reactant Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 17
- 229920005989 resin Polymers 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 238000012986 modification Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000011701 zinc Substances 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000000969 carrier Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 238000004088 simulation Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- 238000005342 ion exchange Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 4
- 238000007144 microwave assisted synthesis reaction Methods 0.000 abstract 1
- 238000000874 microwave-assisted extraction Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 230000009466 transformation Effects 0.000 description 15
- 239000002028 Biomass Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 238000007233 catalytic pyrolysis Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241001464837 Viridiplantae Species 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 150000002373 hemiacetals Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- JSPLKZUTYZBBKA-UHFFFAOYSA-N trioxidane Chemical compound OOO JSPLKZUTYZBBKA-UHFFFAOYSA-N 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Fats And Perfumes (AREA)
- Catalysts (AREA)
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 by green plants is fixed up the energy of solar radiation with a kind of biomass form the energy, reserves are big, capable of circulation, 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 be subjected to paying close attention to widely as a kind of environmentally friendly, renewable energy source.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, hemiacetal, 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 by 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, it is relatively harsher that bio oil is carried out the upgrading reaction conditions, requirement to equipment itself is also high, 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 as maintenance of equipment 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% hydrogen peroxide, 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 instrument as reaction unit, concrete operations are: add ethanol, acetate, furfural, hydrogen peroxide and catalyzer in Kjeldahl flask by a certain percentage, and put into magneton, and Kjeldahl flask is put into the microwave reaction instrument, 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 of the present invention: acetate: the mass ratio of furfural, hydrogen peroxide is: 3.80: 1.57: 1.12: 1.
The mass ratio of catalyzer of the present invention and reaction solution is 1: 20～155, and optimum proportion is 1: 20.6.
Active ingredient Zn in the catalyzer of the present invention
2+The mass percent of content is 0.15%.
Stirring velocity 400rpm of the present invention ± 2rpm, microwave power 100～400W is adjustable, best microwave heating power 400W.
Reaction times of the present 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% represents the massfraction of reactive metal in catalyzer, Zn
2+Represent that 732 type resins submit the metal ion of changing.
The used Na of the present invention
+Type 732 type resins are that Shanghai is converged magnificent resin chemical industry company limited and produced, outward appearance be pale brown look to the brown spherical particle, the form of dispatching from the factory is the sodium type, its main performance index: mm 〉=95 granularity %:(0.315-1.25); 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 storng-acid cation 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 storng-acid cation exchange resin carrier, under the room temperature with massfraction be 0.15% liquor zinci chloridi dipping carry out ion-exchange, 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 gas-chromatography.
Transformation efficiency is defined as follows:
The present invention finds with 732
#Storng-acid cation exchange resin is a carrier, by 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 is strong more to be beneficial to whole esterification 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 microwave heating more can promote the carrying out of esterification upgrading process effectively than traditional heating in 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 High Temperature High Pressure, 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 unstable in the bio oil and 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 the hydrogen peroxide oxidation furfural can be obtained, be 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 again with the 4%NaOH immersion after being washed till the outflow clear water with deionized water, 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 storng-acid cation exchange resin carriers carry out ion-exchange 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% hydrogen peroxide, 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 instrument as reaction unit, concrete operations are to add ethanol, acetate, furfural, hydrogen peroxide and catalyzer in Kjeldahl flask by a certain percentage, and put into magneton, and Kjeldahl flask is put into the microwave reaction instrument, 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 results are shown in 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 | Hydrogen peroxide quality/g | Acetate transformation efficiency/% | Furfural transformation efficiency/% |
| 732 resins | ??15.8 | ??6.3 | ??4.64 | ??4.16 | ??63.33 | ??45.96 |
| Catalyzer | Ethanol quality/g | Quality of acetic acid/g | Furfural quality/g | Hydrogen peroxide quality/g | Acetate transformation efficiency/% | Furfural transformation efficiency/% |
| ??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, hydrogen peroxide 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 results are shown in 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, 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 under catalyst levels 0.2g, 0.5g, 0.75g, 1.0g, 1.5g condition, other activity rating condition is identical with embodiment 1 except that the catalyst levels condition.The results are shown in 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, do five group reactions respectively under reaction times 10min, 20min, 30min, 40min, 50min, 60min condition, other activity rating condition is identical with embodiment 1 except that the reaction times condition.The results are shown in 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, do six group reactions respectively under heating in water bath and microwave heating condition, and other activity rating condition is identical with embodiment 1 except that the type of heating condition.The results are shown in Table 5.
Ethanol, acetate and furfural microwave esterification result under the table 5 different heating mode
Claims (6)
1. the method for catalyzing, esterifying and upgrading bio-oil 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% hydrogen peroxide, 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 instrument as reaction unit; Concrete operations are: add ethanol, acetate, furfural, hydrogen peroxide and catalyzer in Kjeldahl flask by a certain percentage, and put into magneton, Kjeldahl flask is put into the microwave reaction instrument, 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; Described ZnCl
2The catalyzer of 732 type Zeo-karbs of modification is expressed as 0.15%Zn
2+/ 732 resins, wherein 0.15% represents the massfraction of reactive metal in catalyzer, Zn
2+Expression 732
#The cocommutative metal ion of resin; Described ethanol: acetate: the mass ratio of furfural is 3.80: 1.57: 1.12: 1; The mass ratio of described catalyzer and reaction solution is 1: 20～155.
2. according to the method for catalyzing, esterifying and upgrading bio-oil under the described microwave condition of claim 1, it is characterized in that 75 ℃ of temperature of reaction.
3. according to the method for catalyzing, esterifying and upgrading bio-oil under the described microwave condition of claim 1, it is characterized in that reaction times 60min.
4. according to the method for catalyzing, esterifying and upgrading bio-oil under the described microwave condition of claim 1, it is characterized in that microwave heating power 400W.
5. according to the method for catalyzing, esterifying and upgrading bio-oil under the described microwave condition of claim 1, the mass ratio that it is characterized in that catalyzer and reaction solution is 1: 20.6.
6. according to the method for catalyzing, esterifying and upgrading bio-oil under the described microwave condition of claim 1, it is characterized in that described 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%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 obtains H
+Type 732 type storng-acid cation 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 storng-acid cation exchange resin carriers, under the room temperature with massfraction be 0.15% liquor zinci chloridi dipping carry out ion-exchange, 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% represents the massfraction of reactive metal in catalyzer, Zn
2+Represent that 732 type resins submit the metal ion of changing.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796573A (en) * | 2012-07-24 | 2012-11-28 | 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 |
| CN105777582A (en) * | 2016-05-05 | 2016-07-20 | 青岛辰达生物科技有限公司 | Method for preparing anticarcinogen vorinostat |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0718392A1 (en) * | 1994-12-22 | 1996-06-26 | Radlein, Desmond St. A.G. | Method of upgrading biomass pyrolysis liquids for use as fuels and as a source of chemicals by reaction with alcohols |
| US20050204612A1 (en) * | 2002-09-20 | 2005-09-22 | Joosten Connemann | Method and device for producing biodiesel |
| CN1818027A (en) * | 2006-03-03 | 2006-08-16 | 张展洪 | Production of biological diesel oil by catalyst consisting of phase-transferring agent mixture |
| CN101144025A (en) * | 2007-09-05 | 2008-03-19 | 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 |
| CN101358138A (en) * | 2008-09-23 | 2009-02-04 | 浙江大学 | Method for improving quality of biomass oil |
| CN101531922A (en) * | 2009-04-10 | 2009-09-16 | 中国林业科学研究院林产化学工业研究所 | Method for raising quality of biomass pyrolysis oil by reactive extraction |
-
2010
- 2010-04-20 CN CN2010101521154A patent/CN101812376B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0718392A1 (en) * | 1994-12-22 | 1996-06-26 | Radlein, Desmond St. A.G. | Method of upgrading biomass pyrolysis liquids for use as fuels and as a source of chemicals by reaction with alcohols |
| US20050204612A1 (en) * | 2002-09-20 | 2005-09-22 | Joosten Connemann | Method and device for producing biodiesel |
| CN1818027A (en) * | 2006-03-03 | 2006-08-16 | 张展洪 | Production of biological diesel oil by catalyst consisting of phase-transferring agent mixture |
| CN101144025A (en) * | 2007-09-05 | 2008-03-19 | 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 |
| CN101358138A (en) * | 2008-09-23 | 2009-02-04 | 浙江大学 | Method for improving quality of biomass oil |
| CN101531922A (en) * | 2009-04-10 | 2009-09-16 | 中国林业科学研究院林产化学工业研究所 | Method for raising quality of biomass pyrolysis oil by reactive extraction |
Non-Patent Citations (2)
| Title |
|---|
| 《催化学报》 20090831 郑小明等 生物质热解油品位催化提升的思考和初步进展 765-769 1-6 第30卷, 第8期 2 * |
| 《石油化工》 20100131 陈宏桦等 微波条件下阳离子江湖胺树脂催化提质生物油 13-16 1-6 第39卷, 第1期 2 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102796573A (en) * | 2012-07-24 | 2012-11-28 | 北京金骄生物质化工有限公司 | Low-freezing biodiesel combined fuel and preparation method thereof |
| 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 |
| CN105777582A (en) * | 2016-05-05 | 2016-07-20 | 青岛辰达生物科技有限公司 | Method for preparing anticarcinogen vorinostat |
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