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2009 Effective Phase Separation__ of Biomass Pyrolysis Oils by Adding Aqueous Salt Solutions

2009 Effective Phase Separation__ of Biomass Pyrolysis Oils by Adding Aqueous Salt Solutions
2009 Effective Phase Separation__ of Biomass Pyrolysis Oils by Adding Aqueous Salt Solutions

Effective Phase Separation of Biomass Pyrolysis Oils by Adding

Aqueous Salt Solutions

Qin-Hua Song,*Jun-Qi Nie,Ming-Guang Ren,and Qing-Xiang Guo Department of Chemistry,and Anhui Pro V ince Key Laboratory of Biomass Clean Energy,Uni V ersity of

Science and Technology of China,Hefei230026,China

Recei V ed February21,2009.Re V ised Manuscript Recei V ed April9,2009

Effective separation methods must be developed to generate fractions of similar polarity and to concentrate the undistillable compounds before bio-oils are to be a source of chemicals production.Phase separation is one effective pathway to realize initial separation of bio-oil.By adding a little salt(3wt%of bio-oil)or aqueous salt solution(10wt%of bio-oil)including LiCl,CaCl2,FeCl3,(NH4)SO4,K2CO3,and Fe(NO3)3,the pyrolysis bio-oil of rice husk would quickly form two phases(40-80wt%of the upper phase,20-60wt% of the bottom phase).On the basis of elemental analysis,13C NMR integrations and GC/MS analysis,it has been demonstrated that some major components in the bio-oil are concentrated in upper/bottom phases respectively.The upper layers exhibit high contents of water,acetic acid,and water-soluble compounds;low density,viscosity,and calori?c values;and high distillable substances(up to65%).The bottom layer consists of low water content,high lignin-pyrolysis compounds,and low distillable substances(<10%),with high viscosity and calori?c values.The physiochemical properties of two phases from the phase separation depend on the nature and dosage of salt added.

1.Introduction

Environmental problems and the need to develop value-added chemical products from biomass have in the past20years promoted the development of technologies to utilize biomass more ef?ciently.Many efforts have been made to convert biomass to liquid fuels and chemicals since the oil crises in the mid-1970s.1,2Fast-pyrolysis-derived bio-oils have potential as feed stocks for chemical production3-8and as a promising route to liquid fuels.1,8-11The composition and properties of the oils differ considerably from those of petroleum-based fuel oils. Because of some special properties of pyrolysis oils,many problems arise in their handing and utilization.1,12

Biomass-based pyrolysis oils have complex chemical com-position,including a large amount of water,carboxylic acids, carbolydrates,and lignin-derived substances.The oils are acidic, viscous,reactive,and thermally unstable.1The prevalence of dimeric to tetragmeric phenolic lignin decomposition products in bio-oil,together with water and a plethora of compounds of many classes,makes the fractional distillation of bio-oil impossible.Because of the huge range of polarities and the large fraction of oxygenated compounds,it is very dif?cult to separate the oils by column chromatography.Therefore,before bio-oils are to be a source of chemicals production,effective separation methods must be developed to generate fractions of similar polarity and to concentrate the undistillable compounds.1 The morphology and the chemical composition of bio-oils are strongly dependent on the pyrolysis process and the nature of the feedstock used.A microscopic analysis of bio-oils reveals the presence of a multiphase system that has been formed by solid particles,pasty structures,and droplets that constitute a complex colloidal system.13Bio-oils can be separated into water-soluble materials(high-polarity compounds)and water-insoluble materials(low-polarity components).The water-insoluble ma-terials are called lignin-derivative compounds,or pyrolytic lignin.7,14Depending on the dissolving strength of the continuous medium,which consists of water-soluble compounds,the lignin-derivative molecules can be found in a molecular state or in an associate form.It has been shown by previous researchers that in the presence of a large amount of water,the lignin derivative molecules spontaneously precipitate.15

Addition of water into pyrolysis oil in a suf?cient amount results in a phase separation.Upon adding water,a viscous oligomeric lignin-containing fraction settles at the bottom, whereas a water-soluble fraction rich in carbohydrate-derived compounds form an upper layer.Effective phase separation is bene?cial to separate and utilize the two phases.However,much

*To whom correspondence should be addressed.E-mail:qhsong@ https://www.doczj.com/doc/0e6438874.html,;phone:+86-551-3607524;fax:+86-551-3601592.

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Energy&Fuels2009,23,3307–33123307

10.1021/ef900143u CCC:$40.75 2009American Chemical Society

Published on Web04/29/2009

overlap of compound types exist in both fractions,and addition of large water quantities would result in further dif?culty of separation.

Osamaa et al.reported that fast pyrolysis of forestry residue produced an extractive-rich upper phase that varies from10to 25%of the total product and a bottom phase closely resembling the normal bark-free wood product.Phase separation occurs due to the higher extractive content of the residues which,due to their much lower oxygen content.Extractives are composed of hydrophobic components with a low polarity and density and phase separate,forming an upper phase that has a higher viscosity and heating value than the bottom phase.16-18

In this work,through adding inorganic salts in3wt%of

bio-oil or their solutions in10wt%of a bio-oil,the bio-oil can form two phases,upper/bottom layers,thus the bio-oil would be separated into two fractions.Some major components in bio-oil were concentrated in upper/bottom phase,respectively.This phase-separation process is similar with the sailing out of proteins.This separation method would have a potential as an initial separation of bio-oils.

2.Experimental Section

2.1.Bio-oil Production.The bio-oil studied herein has been obtained via fast pyrolysis of rice husk in an autothermal?uidized-bed pyrolyzer with a capacity of120kg/h oil at our laboratory (Anhui Province Key Laboratory for Biomass Clean Energy, University of Science and Technology of China).The pyrolysis device mainly consists of a hopper,two screw feeders,an electric heater,a?uidized-bed reactor,two cyclones,a condenser,and an oil pump,as well as some thermocouples and pressure meters.The hopper is used to contain feedstock such as rice husks,sawdust,or their mixture.The two screw feeders have the same con?guration and size;the?rst one is used to control the feeding rate and the second one operates at a relatively high speed to prevent jamming of the feeding system.The?uidized-bed reactor has a height of 2m and a diameter of0.7m,in which rice husks or sawdust are rapidly heated for pyrolysis.The electric heater can preheat the nitrogen to the temperature range of450-550°C before entering into the?uidized-bed reactor.The two cyclones are used to separate solid particles such as charcoal and ash from the hot gas.The condenser is equipped with some nozzles and a heat exchanger. The condenser can quickly cool the cleaned hot gas into a liquid. An oil pump is used to pump the condensed liquid from the bottom of the condenser to the nozzles on the top of the condenser.Pumping the cooled liquid back into the condenser assists in the scrubbing and condensation process.Thermocouples and pressure meters are used to monitor and control the pyrolysis system.More character-istics of the pyrolysis reactor have been described elsewhere.19 Physiochemical properties of the whole bio-oils used in this work are listed in Table1.

2.2.Phase Separation of Bio-oil.Phase separations of the bio-oil were performed through adding various inorganic salts into bio-oils.Samples of the bio-oil(10mL)were placeed into glass tubes (15mm in diameter,with a capacity of15mL)and0.3g salt or1 mL of30%salt aqueous solution were added with stirring and sonication in a water-cooled bath below15°C.Afterward,the tubes were sealed with para?lm and stored for10h at room temperature, forming two phases(upper/bottom layer).The upper layer was removed through pouring out from the tube for a large difference in viscosity of two phases,and the two phases were weighted and characterized,respectively.

2.3.Physicochemical Characterization.Physicochemical prop-erties,such as density,pH value,water content,gross calori?c value, and viscosity were determined using standard ASTM methods.The elemental composition(carbon,hydrogen,and nitrogen)was determined in an Elementar Vario El-III analyzer.The oxygen content was calculated by difference.

2.4.Nuclear Magnetic Resonance Analysis.13C NMR spectra of whole bio-oil and of the two phases were recorded in DMSO-d6 solutions at100.6MHz using a Bruker400MHz spectrometer according to the method in a literature.20Solutions of30wt% samples were employed.About104scans were accumulated for each sample13C spectrum using a90°pluse width together with broadband proton decoupling.Tubes of5mm diameter were used. Inverse gated decoupling was applied to void NOE effects in the 13C spectra.The integrated13C spectra were divided into?ve general chemical shift ranges for analysis:215-163ppm(carbonyl carbons),163-110ppm(total aromatic carbons),110-84ppm (carbohydrate-type carbons),84-54ppm(methoxy-or hydroxy-bound carbons),and54-1ppm(primary,secondary,tertiary,and most quaternary alkyl carbons).The aromatic region was further subdivided into125-112ppm(guaiacyl carbons)and112-110 ppm(syringyl carbons).20

2.5.Solvent Fractionation of the Upper Layer and the Bottom Layer and Gas Chromatography/Mass Spectrometry (GC/MS)Analysis.~10mL of the upper layer from phase separation was extracted three times(3×50mL)with diethylether. The ether-insoluble fraction was removed by?ltraction.The?ltrate was dried with anhydrous Na2SO4and?ltered.The ether-solubles and ether-insolubles were evaporated(<30°C),and the dried residues were weighed.Similarly,~2g of the bottom layer was extracted with dichloromethane(DCM)for three times(3×50 mL).The DCM-insoluble fraction was removed by?ltraction.The ?ltrate was dried with anhydrous Na2SO4and?ltered.The DCM-solubles and DCM-insolubles were evaporated(<40°C),and the dried residues were weighed.

The whole bio-oil and the fraction recovered of the upper layer and the bottom layer were dissolved in methanol,and dried with anhydrous Na2SO4and?ltered.The?ltrates were analyzed by GC/ MS(using an Varian24cb fused silica capillary column,30m×0.25mm i.d.,?lm thickness0.25μm),and the compounds of various fractions were identi?ed by GC/MS.Helium was used as the carrier gas,and the gas?ow was held constant at1mL/min. The injector temperature was280°C.The temperature program was2min at40°C,then at4°C/min to280°C,and5min at280°C.The interpretation of the spectra obtained by GC/MS spec-trometry was based on automatic library search and literature

(16)Oasmaa,A.;Kuoppala,E.;Gust,S.;Solantausta,Y.Energy Fuels 2003,17,1–12.

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(19)Zheng,J.L.;Zhu,X.F.;Guo,Q.X.;Zhu,Q.S.Waste Management. 2006,26,1430–1435.

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D.;Mitchell,B.;Mohammad,J.;Cantrell,K.;Pittman,C.U.Jr.Energy Fuels2008,22,614–625.

(21)Faix,O.;Fortmann,I.;Meier,D.Holz.Roh.Werkst.1991,49,213–219.

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Table1.Physiochemical Properties of the Whole Oils in This

Work

property bio-oil A bio-oil B water content26.7wt%32.5wt% density 1.15kg/L 1.19kg/L

viscoisity at40°C25.6cSt12.1cSt

heating value,MJ/kg16.916.5

pH 3.2 2.8

element composition,wt%

C37.936.3

H7.397.35

N0.740.48

O(by difference)53.955.8

3308Energy&Fuels,Vol.23,2009Song et al.

data.21-24Peak area obtained from the ion chromatography is a qualitative content of a compound.

3.Results and Discussion

3.1.Salt-induced Phase Separation of Bio-oil.Addition of a little salt results in phase separation,and ratios of two phases are ca.50:50for LiCl and FeCl 3,38:62for (NH 4)2SO 4,and 61:39for Fe(NO 3)3.The water content of the upper lighter layer is 3-9times more than that of the bottom layer,and the heating value of the bottom heavy fraction is about twice the upper lighter layer (Table 2).

Several solutions of inorganic salts (30wt %)were added to bio-oil B,and phase separation occurred to form two phases after storage for 10h at room temperature.Because of a large difference in viscosities between upper and bottom phases (4.8cSt for upper phase,334.2cSt for bottom phase for LiCl solution-treating bio-oil),the upper phases can be poured out,and two phases were weighted respectively.The mass ratio of two phases and densities are listed in Table 3.

After addition of water in 10wt %of the bio-oil,the phase separation also occurs,and the boundary line of two phases is obscure,and the mass of the bottom layer is also less.Adding LiCl salt in 10%of bio-oil,the proportion of bottom layer is higher than that of its aqueous solution.Experiments further show that proportions of the bottom layers increase with mass and concentration of salt solution added.Adding 30wt %salt solution in 10wt %of bio-oil,the ratios of two phases are similar for all four salt solutions.If the percent concentration (30wt %)is changed as a molar concentration,the molar concentration of LiCl solution is about three times of other three solutions.For the product of ion number and charge in a solution,the latter three solutions are about three times that of

the LiCl solution.Thus,the phase separation depends on the number of ions and the charge of ions in a salt solution added.3.2.Physicochemical Properties of Two Phases.The water content of the upper lighter layer is usually two or more times higher than that of the bottom phase,and calori?c values of upper layers are two times lower than those of bottom phases.These data show that the upper layers include large amount of water and water-soluble compounds with high oxygen contents,such as carbonyl acids,“sugar”,and alcohol,etc.Among them,properties for LiCl salt-treating bio-oil are the most different between two phases.For example,the water content of the bottom layer is the lowest,and the largest difference in calori?c values of two phases,11.2MJ/kg for the upper layer and 28MJ/kg for the bottom layer.

Elemental Composition of the Two Phases.The elemental composition of two phases and the whole bio-oil were deter-mined and are listed in Tables 2and 4,respectively.The carbon contents of bottom layers are nearly twice those of upper layers.This is in agreement with the difference in their heating values.Hydrogen content of the upper layer is higher than that of the bottom phase.Both hydrogen content and nitrogen content in the upper layer of (NH 4)2SO 4sample are higher than the corresponding values of other samples.Carbon content in the upper layer of K 2CO 3sample is higher than those of other samples.These indicate that salt solutions added are mainly distributed in the upper phases.

NMR Analysis.13C NMR integrations for the whole bio-oil and treating bio-oils with two salt solutions were determined.The integrate region was divided into seven ranges,listed in Table 5.Data show that carbonyl,carbohydrate,and methoxy/hydroxy carbons are much higher for upper phases over bottom phases,and alkyl carbons in upper phases are less than those in bottom phases.The proportion of various aromatic carbons (total aromatic,guaiacyl,and syringyl carbons)in upper phases is much lower than that in bottom phases.These clearly show that upper phases include more carbonyl,methoxy/hydroxyl compounds,such as carbonyl acids,carbohydrate,aldehyde,

Table 2.Mass Percentages,Water Contents,Heating Values (HV),and Elemental Analysis for Two Phases from Phase

Separation of Bio-oil A a

elemental analysis (wt %)sample mass wt %H 2O

(wt %)HV (MJ/kg)C H N O b C/H bio-oil A 26.716.937.97.390.7454 5.1LiCl U c 5247.810.826.87.670.2765 3.5B c 48 5.822.050.37.13 1.23417.1FeCl 3U 4940.212.327.17.810.5265 3.5B 5110.519.846.77.07 1.2145 6.0(NH 4)2SO 4U 3848.511.230.58.42 2.1959 3.6B 6210.720.142.77.83 1.3248 6.0Fe(NO 3)3d

U 6135.713.233.17.06 1.4259 4.2B

39

13.2

19.1

48.8

7.34

1.81

42

6.7

a

Salts added in 3wt %of the bio-oil,unless otherwise indicated.b

Calculated by difference.c U:upper layer,B:bottom layer.d In 4wt %of the bio-oil.

Table 3.Average Values for Mass Ratio,Water Contents,Calori?c Values for Two Phases from Phase Separation of

Bio-oil B a density H 2O (wt %)HV (MJ/kg)reagents added M b mass ratio U:B c U B U B U B H 2O 95:5 1.15 1.2239.718.612.823.0LiCl d 2.3664:36 1.18 1.2541.816.311.228.0LiCl 0.6474:26 1.14 1.2142.616.512.623.4CaCl 2

0.2474:26 1.13 1.2342.017.812.423.8(NH 4)2SO 40.2178:22 1.16 1.2340.119.012.523.3K 2CO 3

0.20

74:26

1.14

1.27

42.4

17.3

13.7

24.5

a

30%aqueous solution in 10wt %of the bio-oil,unless otherwise indicated.b Molar concentrations of salt in bio-oil.c U:upper layer,B:bottom layer.d Neat LiCl in 10wt %of the bio-oil.

Table 4.Elemental Composition of the Whole Bio-oil B and

Corresponding Phase-separating Bio-oils a

elemental analysis (wt %)

sample solutions added C H N O b C/H bio-oil 36.37.350.4856 4.9upper layer

LiCl 29.27.920.2963 3.7CaCl 2

28.97.940.2863 3.6(NH 4)2SO 428.68.040.8663 3.6K 2CO 330.87.880.3361 3.9bottom layer

LiCl 51.4 6.800.64417.6CaCl 2

51.6 6.810.79417.6(NH 4)2SO 451.3 6.820.90417.5K 2CO 3

52.0

6.82

0.65

41

7.6

a

30%aqueous solution in 10wt %of the bio-oil.b

Calculated by

difference.

Table 5.

13

C NMR Integrations (%)for Whole Bio-oil B and Corresponding Separating Bio-oils

LiCl K 2CO 3type of carbon δ(ppm)bio-oil B (%)U a B a U B carbonyl

215-16317.918.312.017.69.3total aromatic

163-11019.112.842.416.048.7aromatic (guaiacyl)125-11210.7 6.718.0 6.918.8aromatic (syringyl)112-1100.20.2 1.00.2 1.8carbohydrate 110-848.811.6 3.211.3 1.9mthoxy/hydroxy 84-5430.536.817.233.814.4alkyl carbons

54-1

23.3

20.6

25.1

21.3

25.6

a

U:upper layer,B:bottom layer.

Phase Separation of Biomass Pyrolysis Oils

Energy &Fuels,Vol.23,20093309

ketone,and alcohols,and bottom phases are lignin-pyrolysis products with phenyl rings.

Sol V ent Fractionation of the Upper Layer and the Bottom Layer.The upper-layer bio-oils from phase separation induced by LiCl and K 2CO 3solutions were dissolved in diethylether.The ether-insoluble fraction was removed by ?ltration.The ether solubles and insolubles were evaporated (<30°C)and weighted,the percentage corresponding to each fraction and their elemental compositions are presented in Table 6.The ether solubles have only about 28%,and up to 58%for the ether insolubles in upper phases.In addition,a part of the volatile compounds was lost in evaporation,and these compounds should be low-boiling-point.

In the same way,the bottom-layer bio-oils from phase separation induced by LiCl and K 2CO 3solutions were dissolved in dichloromethane (DCM).The DCM-insoluble fraction was removed by ?ltration.The DCM solubles and insolubles were evaporated (<40°C)and weighted,and the percentage corre-sponding to each fraction and their elemental compositions are presented in Table 6.The DCM solubles have similar percent-ages to the DCM insolubles,40-50%.The percentages of the DCM solubles for LiCl sample are higher than those of K 2CO 3,and the DCM insolubles of K 2CO 3sample higher over LiCl sample.In evaporation,a part of volatile compounds for bottom layers were also lost,and much less than upper https://www.doczj.com/doc/0e6438874.html,paring percentages of solubles in two phases,those in the bottom layers (ca.52%)are nearly twice more than those in the upper layers (ca.28%).

The chemical compositions of the upper layer are different from the compositions of the bottom layer and of the whole bio-oil.Bottom layers have higher non-or low-polarity solvent-soluble fractions than upper layers and the whole bio-oil.Contrary to this,bottom layers exhibit the lowest content of high-polarity methanol-soluble fraction,and upper layers have the highest methanol-soluble fraction (near to 100%).These differences are due to high polarity of upper layers,related to low polarity of bottom layers.The fractions recovered were further analyzed by GC/MS,shown in Figure 1.

GC/MS Analysis of the Fractions Obtained.The whole bio-oil and DCM-soluble fractions of the two phases of LiCl-solution treating bio-oil were dissolved in methanol,dried with anhydrous Na 2SO 4,and ?ltered.The ?ltrates were analyzed by GC/MS.The chromatograms are shown in Figure 1,and the main compounds identi?ed are listed in Table 7.

Acetic acid in the upper layer has very high proportion,and less for the bottom layer.Some high-polarity compounds have higher proportions in the upper layer over bottom layer,such as ketone (No.4),alcohols (21,22),bisphenol (35),https://www.doczj.com/doc/0e6438874.html,pounds with high proportions in the bottom layer are most lignin-pyrolysis compounds,such as 18,23,24,26,33,34,36,37,41-45,47,48,50-52,54-56,58,and 59.Total percentages

of lignin-pyrolysis products (or compounds with phenyl groups)are 26.0,28.6,and 50.4%for whole bio-oil,the upper layer,and the bottom layer,respectively.The extractive contents of two phases show near to twice in the bottom layers over the upper layers’.Thus,the content of pyrolytic lignin in the bottom layers should be 3-4times more than those in the upper layers.There is one compound with high proportions in the whole bio-oil,levoglucosan (53),but it is very less in the soluble fractions of two phases.This may be that this compound with high polarity cannot be extracted by a low-polarity solvent,dichlo-romethane.Although it was not detected in the soluble fractions of two phases,it should be distributed in the upper layers with high polarity.

Bio-oils represent a complex colloidal multidispersed system containing char particles,waxy materials (e.g.,fatty acids,fatty alconols,sterols,and aliphatic hydrocarbons),and aqueous droplets and micelles formed from lignin derivatives in a matrix of hollocellulose-derivatived compounds and water.25,26The

Table 6.Elemental Composition of Solvent Fraction of Two

Phases from Phase Separation of Bio-oil B

elemental analysis (wt %)sample

yield (wt %)C H N O a

C/H

upper ether-so1uble

LiCl 28.449.7 6.950.3143.17.2K 2CO 3

27.450.7 6.840.3142.17.4ether-insoluble LiCl

57.923.38.090.3268.3 2.9K 2CO 3

56.526.78.090.4964.7 3.3bottom DCM-soluble LiCl

52.258.6 6.090.3635.09.6K 2CO 3

45.858.1 5.980.3635.69.7DCM-insoluble LiCl

41.056.5 5.82 1.2136.49.7K 2CO 3

45.0

56.1

5.62

1.10

37.210.0

a

Calculated by difference.

Figure 1.Total ion chromatography for the whole bio-oil B and DCM-soluble fraction of two phases from LiCl solution-induced phase separation.

3310Energy &Fuels,Vol.23,2009Song et al.

lignin derivatives are assumed to be solvated in the system by the water-soluble molecules,where they agglomerate and form micelles.On this account,the lignin-derived water-insoluble fraction would be suspended in micellar or microemulsion phases by the continuous aqueous phase,which acts as a bridging agent between the high-molecular-mass lignin and the continuous aqueous phase.Addition of a salt aqueous solution into the bio-oil causes precipitation of the lignin fraction by destroying hydrogen bonds and dispersing the bridging com-ponents,which causes agglomerization and separation of the lignin micelles.Meanwhile,water-insoluble compounds with low polarity separate from aqueous phase and agglomerate with the lignin derivatives.In addition,the complex may be formed between pyrolytic lignin and metal ion such as ferrum ion,

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D.;Roy,C.Energy Fuels2006,20,364–375.

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D.;Roy,C.Energy Fuels2006,20,786–795.

Table7.Chemical Composition of the Upper Layer,the Bottom Layer,and Whole Bio-oil B

peak areas(%) peak No.main and indenti?ed compounds RT a(min)mol mass bio-oil B U b B b 1acetic acid 2.316020.128.3 3.82 2hydroxyacetaladehyde 2.61600.48<0.010.34 3propanoic acid 3.57147<0.01 1.18<0.01 4acetol 3.96747.897.72 2.93 5glycerin 4.6643/45/61 2.73 1.31 1.75 61-hdroxy-2-butanone 6.38880.72 1.050.47 7ethylene glycol monoacetate7.2743/73/86<0.010.450.58 82,3-dihydroxypropanal7.3890 1.260.70.63 9butanedial8.8043/57/580.5<0.010.61 103-furfural9.4196 2.59 2.63 3.34 112-cyclopenten-1-one9.81820.91 1.081 121-acetyloxy-2-propanone10.89116 1.02 1.41 1.05 132-methyl-2-cyclopenten-1-one11.77960.60.730.76 141-(2-furanyl)-ethanone12.031100.330.370.51 15unknown12.13142<0.010.730.44 162-hydroxy-2-cyclopenten-1-one12.79980.430.460.45 173-furan methanol13.40980.710.870.66 18phenol13.9394 1.54 1.99 2.76 195-methyl-2-furfural14.381100.70.60.84 203-methyl-2-cyclopenten-1-one14.8096 1.24 1.76 1.62 212(5H)-furanone15.0684 2.57 3.67 2.88 222-hydroxy-3-methyl-2-cyclopenten-1-one16.52112 2.5 3.73 3.56 23o-cresol16.681080.96 1.22 1.66 24m-cresol17.49108 1.92 2.59 2.96 25unknown17.9043/57/73 1.1510.63 26guaiacol18.63124 3.58 4.967.9 27methyl2-furoate19.321260.270.420.39 283-ethyl-2-hydroxy-2-cyclopenten-1-one19.531260.510.710.98 295-hydroxymethyldihydrofuran-2-one19.75116 1.480.630.92 304-methyl-5H-furan-2-one19.95980.720.70.83 312,3-xylenol20.051220.27<0.010.56 32maltol20.601260.690.620.63 33p-ethylphenol20.82122 1.37 1.31 3.18 344-methylguaiacol22.01138 2.4 2.72 5.82 35catechol22.78110 2.36 4.04 3.8 36coumaran23.44120 1.62 1.15 1.82 374-ethylguaiacol24.711520.990.97 2.14

38 1.4:3.6-dianhydro-D-glucopyranose25.5769/98/990.93 1.14<0.01

39unknown26.1343/60/970.920.750.93 405-hydroxymethyl-2-furaldehyde26.24126 1.11 1.48 1.58 414-vinylguaiacol26.691500.510.48 1.29 42R-ethyl-p-methoxybenzyl alcohol27.35166<0.01<0.010.78 43eugenol27.581640.710.61 1.87 44syringol29.41154 1.06 1.39 2.12 455-propenylguaiacol29.561640.330.330.93 46unknown30.70240 1.03<0.01<0.01 47isoeugenol31.011640.650.55 1.88 48vanillin31.49152 1.320.86 1.66 492-hydroxy-3-isopropyl-6-methyl-2-cyclohexen-1-one31.91168<0.010.280.55 504-propanylguaiacol33.14166<0.010.360.46 514-acetylguaiacol33.961660.640.75 1.47 52guaiacylacetone35.181800.80.76 1.39 53levoglucosan36.0260/73/9810.29<0.01<0.01 54coniferyl alcohol36.621800.320.30.78 554-allylsyringol39.42194<0.01<0.010.45 564-hydroxy-2-methoxycinnamaldehyde41.60178 1.480.94 3.5 574-acetylsyringol41.641960.370.37<0.01 584-hydroxy-3-methoxy-cinnamic acid methyl ester43.66208<0.01<0.010.34 592,3-dimethoxy-10,11-dihydro-dibenzo[b,f]oxepin-10-ol62.67272<0.01<0.01 1.75

a Retention time.

b U:upper layer,B:bottom layer.

Phase Separation of Biomass Pyrolysis Oils Energy&Fuels,Vol.23,20093311

leading it to settle at the bottom.Therefore,addition of salt aqueous solution breaks the weak equilibrium of the bio-oil system and causes phase separation.This phase-separation is similar to the salting out of proteins to some extent.

4.Conclusion

The major conclusion of this study is that addition of a little salt(3wt%of bio-oil)or a solution(10wt%of bio-oil)into bio-oil can quickly result in phase separation(40-80wt%of top phase,20-60wt%of bottom phase),and the ratio of the two phases depends on salt added and its dosage.Some compounds with similar polarity are concentrated in different phases,such as acetic acid,alcohols,and other water-soluble compounds in upper layers,and lignin-pyrolysis compounds in bottom layers.Phase separation forming two phases have large differences in physcochemical properties.The upper layers exhibit high contents of water,acetic acid,and water-soluble compounds,low density and viscosity,low calori?c values,and high distillable substances(up to65%);and the bottom layers have right contrary properties,low contents of water,high lignin-pyrolysis compounds,high viscosity and calori?c values,and low distillable substances(<10%).The nature of salt and its dosage would in?uence the physicochemical properties and components of the two phases from the phase separation. However,addition of neat water in10wt%of bio-oil results in a very low proportion of the bottom,5%,and the two phases do not have large differences in their physcochemical properties. Addition of salt aqueous solution would destroy hydrogen bonds and enhance polarity of aqueous phase,and cause agglomer-ization and separation of the lignin micells.This phase separation is promising as a method for initial separation of bio-oils. Further research will be focused on optimizing the phase separation conditions for various salts or salt solutions,and effective utilization of two phases,such as distillization to upper layers and fraction with solvents of bottom layers. Acknowledgment.This project was supported by National Basic Research Program of China(973Program No.2007CB210205). We thank Professor Xifeng Zhu for his valuable suggestions.

EF900143U

3312Energy&Fuels,Vol.23,2009Song et al.

列车时刻表计算

第一题 某同学买了一张列车时刻表.他注意到在北京和上海间往返的D31和D32次动车的运行时刻表如下: 他了解了D31次列车由北京开往上海,D32次列车由上海开往北京.这两次列车每天各发一趟.自北京到上海铁路长1463km.根据列车时刻表回答下列问题: (1)你从列车时刻表所列各项内容可以获得哪些信息(写出两条) (2)计算说明D31、D32次列车运行时间差为多少? (3)计算D39次列车由北京开往上海的平均速度是多少km/h? 第二题 在火车站,通常可见到列车运行时刻表,其中T114次列车时刻表可知,列车从上海至蚌埠 第三题 下表是T721次空调特快列车的运行时刻表。求:列车全程的运行时间和全程的平均速度分别是多少?在哪两个城市间行驶最快?当天16:00列车的瞬时速度多大? 第四题 根据如表所示的列车时刻表,计算该次列车从北京南站到上海虹桥站运行的平均速度,以及从曲阜东站到常州北站运行的平均速度. 某次列车的时刻表

火车由南京驶往上海,(1)实际运动的时间是多少?全程的平均速度是多少?(2)火车运行所花时间最多的路段是哪一段?此路段火车的平行速度最小吗?(3)火车运行路程最长的路程是哪一段?此路段火车的平行速度最大吗? 第六题 第七题 下表是某次列车的运行时刻表,列车准点运行时,由曲靖到安顺这段路程的平均速度为

第八题 根据右边列车时刻表计算出火车-直达特快Z51从北京到南通所需要的时间,如果从北京到南通火车行驶的距离是1325km,请计算出这列火车行驶的平均速度是多少km/h(结果保留整数) 第九题 根据图中的列车时刻表,计算D5次列车从葫芦岛北到沈阳的平均速度.(时间和路程的单位分别用h和km) 第十题 下表是从北京到杭州和从杭州到北京的T31、T32列车时刻表,请你根据表中信息求解下列问题:

2009年度个人工作总结,年终总结

2009年度个人工作总结,年终总结 2009年度个人工作总结 时光如白驹过隙,历史的车轮飞驰而逝,2009年的日历正一页一页悄然翻过,伴随着时代前进的步伐,回首自己一年来经历的风雨路程,我作出如下个人工作总结: 一、工作回顾 2009年是不平凡的一年,祖国六十华诞的盛大庆典带给每个中国人无比的鼓舞和震撼,在欣喜于祖国强大、人民安康的自豪中总结个人的工作,我更加感受到做好本职工作是每个工作人员的崇高使命。 1) 加入洪盛行这个团队已近半载,让我倍受到这个大家庭的温暖与和谐,在此我感谢各位同事的关照与工作的积极配合,近入公司时我对瓷砖的了解只是了了而知,通过在国安居的学习让我很快融入陶瓷这个具有强烈竟争的行业,对我们公司品牌(格莱斯)进行了深入的了解. 2) 通过这半年的学习我个人觉得我们公司抛光砖在市场上具有一定的优势(货美价廉),但是现在的设计师对仿古砖的倾向度是兼知的,我们公司的仿古砖(骆驼)在市场是具备一定的特色,也深受设计师的欢迎,但是货源与质量让我们感觉很头痛. 3) 对于做家装的设计公司我们公司的价格很难让设计师操作. 二工作计划 “用心工作、踏实做人”,一直是我的座右铭。尽管我们在工作中兢兢业业,但完美离我们总有一步之遥,经过半年来的努力,工作没大的起色,也没大的失误,平庸的业绩使我更清醒地看到了自身存在的问题 1) 加强对客源资源的整核与巩固,形成自已的一个客户圈. 2) 对于强势的竟争对手与关系复杂的客户作出一定有效的对策 3) 设计师方面我个人一直未有一个明确思路与操作方案希望在今年得以突破.

4) 自我解压,调整心态,创新求变。心态决定工作的好坏,所以在工作中要不断自我调适,把控积极乐观情绪的方向,时刻以饱满的热情迎接每天的工作和挑战。创新是一个民族的灵魂,只有不断在思维上求创新,工作才能出亮点。 三找好航标,定位人生 “路漫漫其修远兮,吾将上下而求索。”我们的人生之路都将历经坎坷不断前行,所以走好每一步都至关重要,每个人都应找好人生的航标,找到一条适合自己的路来走,才能在风雨兼程的路上实现自己的价值,见到风雨之后的彩虹。 我踏入建材销售行业是一直做“工程”的, “工程”在这个行当里看起来是高度尖端的, 但是从这些年的工作实践中我悟出了很多,其实做什么工作不重要,重要的是要肯学肯干,给自己定好位,每一项工作都可以发掘自己的潜力,因为人的潜力是无尽的。刚刚踏入这个行当拜访客户时让自己感觉到胆怯与自卑, 甚至认为自己真的不适合做这份工作,但是自己一直是比较坚持.固执与不认输的,上天不辜有心人,慢慢的发现自己可以克服这个障碍,工地复杂的人际关系没那么可怕,也不再担心客人不理我,久久不与我签单反到而来的大忽悠了, 逐渐找到了自己的方向。也许我们不知道明天会发生什么,但是我清楚自己今天应该做什么。 岁月无声,步履永恒。我们迈过一道道坎走向明天,做好本职工作,争当自己的主人,明天定将更美好!

(完整word)路程速度时间应用题(三年级)

路程速度时间应用题 解决路程、速度、时间这类问题,我们必须要理清这三者之间的数量关系: 路程=速度×时间;时间=路程÷速度;速度=路程÷时间。 例1. 一辆大巴车从张村出发,如果每小时行驶60千米,4小时就可以到达李庄。结果只用了3个小时就到达了。这辆汽车实际平均每小时行驶多少千 米? 试一试: 一列火车,提速前平均每小时行驶71千米,从秦皇岛到邯郸用12小时,提速后平均每小时行驶95千米,提速后从秦皇岛开往邯郸大约需要几小时? 例2. 石家庄到承德的公路长是546千米。红红一家从石家庄开车到承德游览避暑山庄,如果平均每小时行驶78千米,上午8时出发,那么几时可以到 达? 试一试: 一辆从北京到青岛的长途客车,中途经过天津和济南。北京到天津137km;天津到济南360km;济南到青岛393km。早晨6:30从北京发车,平均每小时行驶85千米,大约何时可以到达青岛?

例3.从小明家到济南共360千米,爸爸开车上午10时从家出发,平均每小时行驶110千米,他下午1时能到达济南吗? 试一试: 小楠家到学校的路程长302米,他下午1时56分从家出发,2时1分到达学校。小楠平均每分钟大约走多少米? 课外作业 1.从甲地到乙地936千米,一辆车3小时走216千米,照这样的速度, 从甲地出发经过几小时后可以到达乙地? 2.汽车以72千米/时的速度从甲地到乙地,到达后立即以48千米/时的 速度返回甲地,求该车的平均速度 3. 一辆大巴车从深圳出发开往广西,原计划每小时行驶60千米,8小时 就可以到达目的地。结果只用了6个小时就到达了。这辆汽车实际平 均每小时行驶多少千米?

2013陕西高考数学文科试题

2013年普通高等学校招生全国统一考试 数学(文史类) 第一部分(共50分) 一、选择题:在每小题给出的四个选项中,只有一项符合题目要求(本大题共10小题,每小题5分,共50分) 1. 设全集为R , 函数()1f x x =-的定义域为M , 则C M R 为 (A) (-∞,1) (B) (1, + ∞) (C) (,1]-∞ (D) [1,)+∞ 2. 已知向量 (1,),(,2)a m b m ==, 若a //b , 则实数m 等于 (A) 2- (B) 2 (C) 2-或2 (D) 0 3. 设a , b , c 均为不等于1的正实数, 则下列等式中恒成立的是 (A) · log log log a c c b a b = (B) · log lo log g a a a b a b = (C) ()log g o lo g a a a b c bc = (D) ()log g og o l l a a a b b c c +=+ 4. 根据下列算法语句, 当输入x 为60时, 输出y 的值为 (A) 25 (B) 30 (C) 31 (D) 61 5. 对一批产品的长度(单位: mm )进行抽样检测, 下图喂检测结果的频率分布直方图. 根据标准, 产品长度在区间[20,25)上的为一等品, 在区间[15,20)和区间[25,30)上的为二等品, 在区间[10,15)和[30,35)上的为三等品. 用频率估计概率, 现从该批产品中随机抽取一件, 则其为二等品的概率为 (A) 0.09 (B) 0.20 (C) 0.25 (D) 0.45 6. 设z 是复数, 则下列命题中的假命题是 (A) 若20z ≥, 则z 是实数 (B) 若20z <, 则z 是虚数 (C) 若z 是虚数, 则20z ≥ (D) 若z 是纯虚数, 则20z < 7. 若点(x ,y )位于曲线y = |x |与y = 2所围成的封闭区域, 则2x -y 的最小值为 (A) -6 (B) -2 (C) 0 (D) 2 8. 已知点M (a ,b )在圆221:O x y +=外, 则直线ax + by = 1与圆O 的位置关系是 输入x If x ≤50 Then y = 0.5 * x Else y = 25 + 0.6*(x -50) End If 输出y

2009年终工作总结

2009年终工作总结

立足本职转观念 创新方法求进步 ——2009年工作总结 2009年分管师德建设、德育教育、卫生防疫、党务宣传、职称评定、继续教育、语言文字等工作。 一年中,坚持践行“三个代表”重要思想,以科学发展观为指导,积极投身农村教育向城区教育的变革,主动加压增干劲,积极探索变观念,多方学习强自身,创新方法提实效,圆满地完成了上级领导赋予的各项工作,现总结如下: 一、师德建设贴近实际凝心聚力共谱新篇 前几年的师德建设,教师的路线政策水平,思想道德境界,业务素质能力,教育教学能力得到很大的提高,为贤台乡教育事业的进步,提升在满城县的名望,提供了强大的精神力量。锻造出了爱岗敬业、敢于吃苦、锐意进取、默默奉献的师资队伍。面对区划调整的变化,虽有一时的惶然,但冷静思考,我们坚持认为“不论是农村教育,还是城区教育,要完成既定的教育目标,还得需要这支队伍,还得在磨砺教师队伍上做文章。因此,2009年的师德建设我们依然没有放松,而是继续抓实抓细。 1、广泛宣传,在我国经济发展大背景下,高新区凭借自身优势,更是高歌猛进,经济高速发展,教育必然也要大发展,我们不只是要从中得到实惠,享受发展成果,更应该主动参与其中,为高新区教育的起步腾飞贡献自己的力量。每个教师的人生观、价值观、工作能力、

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