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Production of Furfural from Lignocellulosic Biomass Using Beta Zeolite and Biomass-Derived Solvent

Production of Furfural from Lignocellulosic Biomass Using Beta Zeolite and Biomass-Derived Solvent
Production of Furfural from Lignocellulosic Biomass Using Beta Zeolite and Biomass-Derived Solvent

ORIGINAL PAPER

Production of Furfural from Lignocellulosic Biomass Using Beta Zeolite and Biomass-Derived Solvent

Jean Marcel R.Gallo ?David M.Alonso ?

Max A.Mellmer ?Jher Hau Yeap ?Hui Chin Wong ?James A.Dumesic

Published online:29June 2013

óSpringer Science+Business Media New York 2013

Abstract The production of furfural from the C 5mono-saccharides xylose,arabinose and ribose,as well as from real biomass (corn ?ber),was studied using H-Beta zeolite as catalyst in a monophasic system with the biomass-derived solvent,gamma-valerolactone.Due to the combination of Br?nsted and Lewis acid sites on this catalyst (Br?n-sted:Lewis ratio =1.66),H-Beta acts as a bifunctional catalyst,being able to isomerize (Lewis acid)and dehydrate (Br?nsted acid)monosaccharides.The combination of Lewis and Br?nsted acid functionality of H-Beta was shown to be effective for the isomerization of xylose and arabinose,followed by dehydration.While no advantages were found in the conversion of xylose,higher furfural yields were achieved from arabinose,using H-Beta,73%,compared to sulfuric acid (44%)and Mordenite (49%).The furfural yields from corn ?ber for H-Beta,H-Mordenite and sulfuric acid were 62,44,and 55%,respectively,showing that H-Beta is particularly effective for conversion of this bio-mass feedstock composed of 45wt%hemicellulose,of which 66%is xylose and 33%arabinose.

Keywords Furfural áXylose áArabinose áCorn ?ber áBeta zeolite áBifunctional catalyst

1Introduction

Lignocellulosic biomass has shown to be an ef?cient source of carbon for the production of chemicals and fuels,and this

renewable resource is a promising alternative to petroleum.Furfural is the most commonly produced industrial chemical derived from lignocellulosic biomass,with an annual produc-tion [200,000ton [1].Due to its ?exibility in the production of chemicals and fuels,furfural has been considered to be one of the top value-added chemicals from biomass [2,3].For instance,furfural can be converted by hydrogenation into 2-methyltetrahydrofuran and 2-methylfuran,two additives for gasoline.Furthermore,aldol condensation of furfural and ace-tone followed by hydrogenation leads to high yields of liquid alkanes,which are appropriate for transportation fuels [4].Furfural is typically produced in one step by acid-cata-lyzed dehydration of C 5sugars,such as xylose.The eco-nomic viability and sustainability of the process plays a key role in the production of chemicals and fuels from biomass.Some of the problems in the commercial production of furfural from biomass arise from the low overall concen-tration of hemicellulose (*25%)[5]in most biomass sources,and the dependence of the process on mineral acid catalysts,which cannot be recovered and are typically neutralized,thereby adding to processing cost and com-plicating furfural puri?cation steps.Moreover,this process leads to moderate to low furfural yields (e.g.,\50%)[6]due to the presence of degradation reactions (resini?cation,condensation and fragmentation),requiring large amounts of lignocellulosic biomass to produce furfural.

Several methods have been proposed in the literature to increase furfural yields.For example,Dumesic and co-workers [7]proposed the use of a biphasic system consisting of an acidi?ed aqueous layer and 2-sec-butylphenol as organic extracting layer,achieving furfural yields of 78%while facilitating product separation and allowing the reuse of the catalytic layer [8].The substitution of homogeneous cat-alysts by solid acid catalysts would represent an important advance for economically viable conversion of the

J.M.R.Gallo áD.M.Alonso áM.A.Mellmer áJ.H.Yeap áH.C.Wong áJ.A.Dumesic (&)

Department of Chemical and Biological Engineering,University of Wisconsin-Madison,Madison,WI 53706,USA e-mail:dumesic@https://www.sodocs.net/doc/0116023334.html,

Top Catal (2013)56:1775–1781DOI 10.1007/s11244-013-0113-3

hemicellulosic fraction of biomass.Promising results using heterogeneous catalysts have been recently https://www.sodocs.net/doc/0116023334.html,ing MCM-22and its delaminated counterpart ITQ-2in a biphasic water–toluene system,xylose was dehydrated to furfural with 71%yield[9].Using a similar solvent system,H-Beta zeolite showed poor selectivity to furfural(54%),while a composite consisting of the same zeolite incorporated in the mesoporous scaffold of TUD-1enhanced the furfural yields to74%[10]. Mesoporous molecular sieves containing organosulfonic acid have also shown promising results,reaching furfural yields of 68%in a biphasic water–toluene solvent system[11]and 74%in DMSO[12];however,this class of materials is known to have low hydrothermal stability[13].

Corn?ber is a promising source of biomass for pro-duction of furfural,in view of its high hemicellulose con-tent.In particular,corn?ber is obtained from the processing of corn grain by wet-milling processes[14],and the hemicellulose content has been found to be between30 and57%[15].Typically,xylose accounts for more than 90%of the C5monosaccharides;however,in corn?ber, arabinose is responsible for around34%of the monosac-charide composition[15].While the literature for produc-tion of furfural from xylose is extensive,the conversion of arabinose has not been investigated in detail.

H-Beta zeolite contains high loadings of weak Lewis acid sites[16],in addition to Br?nsted acid sites,allowing it to act as both a Lewis and Br?nsted acid catalyst[17].It has been shown previously that Lewis acids are able to isomerize glucose and xylose to the more reactive isomers,fructose and xylulose,respectively.In the case of glucose,isomerization followed by dehydration has been shown to lead to5-hy-droxymethylfurfural in high yields.For xylose,the effect of isomerization has shown to improve furfural yield only when homogeneous catalysts are used[18].Isomerization of arab-inose followed by dehydration to produce furfural has not been studied and could be a promising route to obtain furfural with high selectivities.In this work,we investigate the per-formance of H-Beta in the conversion of xylose,arabinose and corn?ber.The results obtained with H-Beta are compared with sulfuric acid,the catalyst typically used for hemicellu-lose conversion,and H-Mordenite,which was recently shown to be an outstanding catalyst for xylose dehydration[19]. Finally,we hope that this work can be considered to be an example of the research approach championed by Professor Umit Ozkan:addressing important problems in heteroge-neous catalysis while generating fundamental principles and elucidating factors controlling catalyst performance.

2Experimental

Xylose(Sigma-Aldrich[99%),arabinose(Sigma-Aldrich [98%),ribose(Sigma-Aldrich[99%)and corn?ber (Grain Processing Corporation)were used directly without pretreatment.Sulfuric acid(Fluka0.5mol L-1standard solution)was used to prepare the solutions of homogeneous catalysts.Mordenite(Zeolyst SiO2/Al2O3=20)and Zeo-lite Beta(Zeolyst SiO2/Al2O3=25)were purchased in the ammonium form and converted to the proton form by calcination in air for5h at500°C(1°C min-1).

For reaction kinetics experiments using sugars,0.472g of a20wt%aqueous solution of monosaccharide,and 3.528g of gamma-valerolactone(GVL)were added in 10mL thick-walled glass reactors.For conversion of corn ?ber,the reactor was loaded with0.14g of corn?ber, 0.400g of water,and3.600g of GVL.To each reactor, 0.150g of H-Mordenite or H-Beta or the amount of sul-furic acid needed to make a0.05mol L-1solution was added.The reactors were placed in an oil bath at145or 160°C and stirred at700rpm.Reactors were removed from the oil bath at speci?c reaction times and cooled by ?owing compressed air.The liquid was analyzed to quan-tify reactants and products by HPLC[Waters2695system with a Bio-Rad Aminex HPX-87H column,RI410detector (monosaccharides)and a UV detector(furfural)].

The continuous experiments using H-Beta as catalyst and xylose as feedstock were performed in a?ow reactor operating in an up-?ow con?guration.The reactor(stain-less steel6.35mm OD)was loaded with H-Beta catalyst held between two end plugs of silica granules and quartz wool.The tubular reactor was?tted inside of an aluminum block and placed within an insulated furnace(Applied Test Systems).Bed temperature was monitored at the reactor wall using a Type K thermocouple(Omega)and controlled using a16A series programmable temperature controller (Love Controls).The tubular reactor was heated using a heating tape(OMEGA)and insulated with glass wool tape. The feed to the?ow reactor system was introduced into the reactor using an HPLC pump(Lab Alliance,Series I). Liquid samples were analyzed using an HPLC(Waters 2695system with a Bio-Rad Aminex HPX-87H column and a RI410detector).

3Results and Discussion

Recently,Dumesic and co-workers[19]have reported that the use of GVL as a solvent presents several advantages in the production of furfural from xylose using Br?nsted acid catalysts.In particular,xylose dehydration reactions occur faster in GVL than in water,which minimizes degradation products,and furfural is thus obtained at high yields ([70%)using monophasic systems.As shown in Fig.1, using a mixture of10wt%water in GVL as solvent,furfural can be produced from xylose in high yields([80%)with short reaction times(15min)using low concentrations of

sulfuric acid (0.05mol L -1);however,when other C 5sug-ars are used,such as arabinose and ribose,the furfural yields are signi?cantly lower (\55%).Table 1reveals that while arabinose and ribose showed similar reaction rate values,xylose undergoes up to 2times higher sugar conversion rate and 2.5times higher furfural production rate when using sulfuric acid.

Sulfuric acid is the catalyst typically used for dehydra-tion of sugars,and it is ef?cient for conversion of glucose to levulinic acid [20],fructose to 5-hydroxymethylfurfural [21]and xylose to furfural [19].However,as shown in Fig.1and Table 1,sulfuric acid is not an ef?cient catalyst for dehydration of arabinose and ribose,which can be detrimental to the production of furfural from biomass sources with high arabinose content such as corn ?bers.Therefore,the use of a simple Br?nsted acid is not suf?-cient to convert arabinose and ribose to furfural in high yields.

Previous reports have shown that combination of a Lewis acid and a Br?nsted acid can be bene?cial for sugar conversion reactions.For example,glucose is converted to 5-hydroxymethylfurfural in low yields in the presence of mineral acids;however,when a Lewis acid,such as AlCl 3,is added to the reaction,the yields increase signi?cantly [8].Recently,Lobo and co-workers [22]have proposed that by using a combination of Lewis acid and Br?nsted

acid catalysts,xylose is ?rst isomerized to xylulose and lyxose,which are subsequently dehydrated to furfural.Accordingly,the rate of xylulose dehydration is higher compared to xylose,allowing for a decrease in the reaction temperature [22];however,the furfural yields in this sys-tem were lower than 15%.A recent report has investigated the role of Lewis and Br?nsted acid sites in furfural pro-duction using zirconium phosphate,SiO 2–Al 2O 3,WO X /ZrO 2,gamma-alumina,and HY zeolite as catalysts.Fur-fural selectivity was shown to increase with an increase in the Br?nsted to Lewis acid site ratio of the catalyst [23].In contrast,Abu-Omar and co-workers [18]have shown that in a biphasic system using AlCl 3as Lewis acid and HCl as Br?nsted acid,xylose or lignocellulosic biomass can be converted to furfural with yields around 60%.The prob-lem with this biphasic system is that the organic layers extract part of the homogeneous catalysts,making the product separation complicated [8].

To our knowledge,no studies have been carried out on the conversion of arabinose in the presence of a combi-nation of Lewis and Br?nsted acids.This approach could be an alternative option to achieve high furfural yields from these sugars.Therefore,we investigated a heterogeneous catalyst containing both Lewis and Br?nsted acid func-tionality,with the hope that this system could achieve performance similar to the homogeneous AlCl 3/HCl cata-lyst system.As mentioned previously,H-Beta zeolite can act as both a Lewis and Br?nsted acid catalyst,and this material was thus a candidate for this study.In order to study the ef?ciency of H-Beta for the production of furfural from C 5sugars,this catalyst was used in the conversion of xylose,arabinose and ribose,as shown in Fig.2.

As seen in Fig.2and Table 2,when H-Beta is used as the catalyst,the yields for furfural are similar using any of the C 5monosaccharides as https://www.sodocs.net/doc/0116023334.html,paring the results in Figs.1and 2,it can be seen that using xylose as feed,furfural can be produced with 87%yield using sulfuric acid as the catalyst,while 71%yield is obtained using H-Beta.However,H-Beta appears to be signi?cantly more selective for production of furfural using arabinose or ribose as feed,reaching furfural yields around 73and 72%,respectively,compared to *44and 54%furfural yields using sulfuric acid (Table 1).The reason for the improved behavior of H-Beta could be due to the Lewis acid sites being able to isomerize arabinose and ribose into ribulose which could increase the selectivity to

furfural.

Fig.1Furfural yields obtained using 2wt%monosaccharide in GVL containing 10wt%water as solvent and 0.05M sulfuric acid as catalyst at 170°C

Table 1C 5sugar conversion rate and furfural production rate using 2wt%monosaccharide in GVL containing 10wt%water as solvent and 0.05M sulfuric acid at 170°C

Catalyst Feed C 5sugar conversion rate (mmol mL -1h -1)Maximum furfural yield (%)Furfural production rate (mmol mL -1h -1)H 2SO 4

Xylose 1.1870.77Arabinose 0.5440.29Ribose

0.6

54

0.26

In order to better understand the effect of H-Beta in the production of furfural,a reaction kinetic study was carried out using the two most abundant C 5isomers present in biomass,i.e.,xylose and arabinose.Figure 3a–d shows the conversion of xylose and arabinose at 145and 160°C using H-Beta as catalyst and GVL with 10wt%water as solvent.

As seen in Fig.3a–d,in the presence of H-Beta,xylose is isomerized to xylulose and lyxose,while arabinose is isomerized to ribulose and ribose.These results are in accordance with previous literature studying the isomeri-zation of monosaccharides in the presence of solid Lewis acid catalysts [24].Our analytical technique did not allow for component separation of xylulose from lyxose and ribulose from ribose;therefore,they were quanti?ed as mixtures.

In the conversion of xylose at 145°C,it can be seen (Fig.3a)that in the ?rst minutes of reaction,xylose isom-erization is the predominant reaction and the dehydration reaction becomes more evident when the concentration of the xylulose ?lyxose is higher.At 160°C (Fig.3b),95%of xylose and its isomers were converted within 60min of reaction time with a furfural selectivity of 75%.In the conversion of arabinose at 145°C (Fig.3c),furfural and a mixture of ribulose and ribose were formed concomitantly,

presenting similar concentrations at 10min of reaction.At 160°C (Fig.3d),99%of the monosaccharides were con-verted within 60min with 74%selectivity to furfural.For both xylose and arabinose,after complete conversion of the monosaccharides at 160°C (Fig.3b,d),the reaction was prolonged for additional 60min with no signi?cant reduc-tion of furfural concentration,indicating that furfural is stable under these reaction conditions.

The combination of Lewis acid and Br?nsted acid sites in H-Beta seems to make an effective bifunctional catalyst for isomerization followed by dehydration.Previous stud-ies using a combination of solid Lewis and Br?nsted acids,such as Sn-Beta/Amberlyst-70and Sn-Beta/HCl,led to low furfural yields [22,25].Apparently,the synergistic effect of Lewis and Br?nsted acid sites in the H-Beta pores allows for more selective conversion of C 5sugars.Furthermore,it has been previously shown that strong solid Lewis acids can lead to the formation of degradation products from xylose and furfural [19,23].The presence of weak Lewis sites in H-Beta can be an advantage,since they are suf?-ciently strong for sugar isomerization,but apparently are not as active to produce degradation products.Moreover,since the solvent contains 10%water,it appears that these sites are also water-resistant,a characteristic present in few Lewis acid materials.

In a recent work,zeolites and solid catalysts containing organosulfonic acid were shown to be highly selective for the production of furfural from xylose [19].Zeolites are promising catalysts because carbon deposits typically formed in conversion of sugars can be removed by calci-nation.Therefore,the performance of two zeolites (H-Beta and H-Mordenite)was compared to sulfuric acid,the cat-alyst typically employed for furfural production,Fig.4a–b.The Br?nsted to Lewis acid ratio for the commercial cat-alysts used in this work is 1.66for H-Beta and 4.66for H-Mordenite [26].

As shown in Fig.4a,furfural is produced more rapidly from xylose using both sulfuric acid and H-Beta,compared to slower production using H-Mordenite.However,in all cases,high yields of furfural ([70%)are obtained.Table 3shows the turnover frequencies (TOF)for sugar dehydration and furfural production.H-Beta is more active than H-Mordenite (2times)and sulfuric acid (5.5times)when normalizing the rate by the total number of acid sites,and the TOF over H-Beta is 2.8and 8.8times

higher

Fig.2Furfural yields obtained using 2wt%monosaccharide in GVL containing 10wt%water as solvent and 3.75wt%H-Beta at 160°C

Table 2C 5sugar conversion rate and furfural production rate using 2wt%monosaccharide GVL containing 10wt%water as solvent and 3.75wt%H-Beta at 160°C

Catalyst Feed C 5sugar conversion rate (mmol mL -1h -1)Maximum furfural yield (%)Furfural production rate (mmol mL -1h -1)H-Beta

Xylose 0.46710.27Arabinose 0.50730.34Ribose

0.38

72

0.26

compared to H-Mordenite and sulfuric acid,respectively,if only the Br?nsted acid sites are considered.These data are in agreement with previous results that show the dehy-dration of xylulose is faster compared to xylose [22].For the conversion of arabinose,a high furfural yield (73%)was obtained using H-Beta zeolite as the catalyst,while furfural yields below 50%were obtained using sulfuric acid or H-Mordenite.In this case,the

differences

Fig.3Conversion of xylose at a 145°C and b 160°C,and conversion of arabinose at c 145°C and d 160°C using 3.75wt%H-Beta as catalyst,2wt%monosaccharide and GVL containing 10wt%water as

solvent

Fig.4Dehydration of a xylose and b arabinose at 160°C using 0.05M sulfuric acid,3.75wt%H-Mordenite and 3.75wt%H-Beta as catalysts,2wt%monosaccharide and GVL containing 10wt%water as solvent

in TOF are even higher,and the rate of furfural production per acid site is one order of magnitude faster using H-Beta compared with H-Mordenite and sulfuric acid.Therefore, while the use of a bifunctional Lewis and Br?nsted acid catalyst does not improve the furfural yield from xylose,it seems to be required for the rapid conversion of arabinose. Further studies must be carried out to understand this behavior;however,the higher rate achieved by the com-bination of Lewis and Br?nsted acidity might be related to the formation of xylulose,which is known to have a lower dehydration activation energy compared to xylose.

In view of the results in Fig.4,it can be concluded that for a biomass feedstock in which the hemicellulose fraction is composed primarily of xylose,both H-Mordenite and H-Beta would be promising catalysts for production of furfural;however,if arabinose is also present,then H-Beta would be the most appropriate catalyst.In order to test this hypothesis,corn?ber was used as feedstock.Corn?ber (hulls or bran)is obtained from the processing of corn grain by wet-milling processes[14],and analysis revealed a loading of45wt%of C5sugars,comprised of66%xylose and33%arabinose.A problem with using solid catalysts is that they are limited to the conversion of soluble feedstock, representing a drawback compared to the commercial pro-cess that used mineral acids and lignocellulosic feeds. Dumesic and co-workers[20]have recently reported that GVL is capable of solubilizing biomass(cellulose),allowing for the conversion of this feedstock to levulinic acid cata-lyzed by solid acids.Therefore,the use of GVL as solvent opens new opportunities for the conversion of soluble and insoluble biomass feedstocks,taking the process to another level towards cost-effectiveness and sustainability.

Figure5shows the production of furfural from corn ?ber using sulfuric acid,H-Mordenite,and H-Beta as cat-alysts and using GVL containing10wt%water as solvent. As seen in Fig.5,production of furfural using sulfuric acid is slightly faster compared to https://www.sodocs.net/doc/0116023334.html,ing sulfuric acid, the maximum furfural yield is obtained at30min(55%).Using H-Beta,62%furfural yield is obtained at120min, and the furfural yield is stable for https://www.sodocs.net/doc/0116023334.html,ing H-Mordenite,the maximum yield(44%)is reached at 180min.In the case of corn?ber,the furfural production is slower using solid catalysts,as the corn?ber needs to be dissolved in the GVL[27,28].Importantly,H-Beta led to the highest furfural yields,showing the importance of the combination of Lewis acid and Br?nsted acid for the conversion of an arabinose-rich feedstock.

Finally,we have conducted experiments to study the stability of H-Beta in a?ow reactor.Figure6shows that high yields of furfural([70%)can be achieved the?rst 20h time-on-stream(100%xylose conversion);however, the catalyst deactivates slowly and yields around50%are achieved after120h(75%xylose conversion).The activity could not be restored upon calcination in air,and further experiments concerning the stability and regenera-bility of the catalyst need to be done,mostly in presence of real feeds.

Table3Turnover frequencies for C5monosaccharide conversion and furfural production over sulfuric acid,H-Mordenite and H-Beta at160°C using GVL containing10wt%water as solvent

Catalyst Br?nsted sites

(mmol g-1)[26]Lewis sites

(mmol g-1)[26]

Xylose as feed Arabinose as feed

C5sugar TOF10-4

(s-1)

Furfural TOF10-4

(s-1)

C5sugar TOF10-4

(s-1)

Furfural TOF10-4

(s-1)

Total

sites

Bronsted

sites

Total

sites

Bronsted

sites

Total

sites

Bronsted

sites

Total

sites

Bronsted

sites

H-Beta0.2690.16258.092.941.566.575.0120.250.581.0 H-

Mordenite

0.3310.07127.633.618.822.825.731.2 6.17.4

Sulfuric acid 20.4–10.510.58.48.4 6.2 6.2 4.1

4.1

Fig.5Conversion of corn?ber at160°C using0.05M sulfuric acid,

3.75wt%H-Mordenite and3.75wt%H-Beta as catalysts and GVL

containing10wt%water as solvent.3.75wt%corn?ber

4Conclusions

We have achieved high furfural yields from xylose,arab-inose,and ribose of 71,73,and 72%,respectively,using H-Beta zeolite as a catalyst in a monophasic system with the biomass-derived solvent,GVL.H-Beta has shown to be a better catalyst than sulfuric acid in the conversion of arabinose and ribose to furfural,while sulfuric acid is better for the dehydration of xylose.Due to the combina-tion of Lewis and Br?nsted acid sites in H-Beta,the con-version of sugars catalyzed by this zeolite follows a mechanism different from that observed for predominantly Br?nsted acid catalysts,such as sulfuric acid and H-Mordenite.In the presence of H-Beta,xylose is isom-erized to xylulose and lyxose and arabinose to ribulose and ribose,followed by dehydration to furfural.Corn ?ber,composed of 45wt%C 5sugars,of which 66%is xylose and 33%arabinose,was also used as feedstock,and fur-fural yields for H-Beta,H-Mordenite and sulfuric acid were equal to 62,55and 44%,respectively.Accordingly,H-Beta appears to be an appropriate catalyst for biomass feedstocks high in arabinose content;however,if the hemicellulose fraction is composed primarily of xylose,both H-Mordenite and H-Beta appear to be promising catalysts.

Acknowledgments This work was supported in part by the U.S.Department of Energy Of?ce of Basic Energy Sciences,and by the DOE

Great Lakes Bioenergy Research Center (https://www.sodocs.net/doc/0116023334.html, ),which is supported by the U.S.Department of Energy,Of?ce of Science,Of?ce of Biological and Environmental Research,through Cooperative Agreement DE-FC02-07ER64494between The Board of Regents of the University of Wisconsin System and the U.S.Department of Energy.

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Fig.6Furfural yield in a continuous ?ow reactor.2wt%xylose in GVL with 10wt%water as solvent.160°C,13atm,WHSV =0.24h -1

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2、放空阀全开:放空阀指示为0% 3、润滑油压正常 4、润滑油温正常 5、动力油压正常 6、逆止阀全关 7、存储器复位:按下存储器复位按钮,即可复位,若复位不成 需查看停机画面。 8、试验开关复位:按下试验开关按钮即可,试验开关按钮在风 机启动后,将自动消失,同时试验开关也自动复位。 当以上条件达到时,按下“允许机组启动”按钮,这时机组允许启动指示变为红色,PLC机柜里的“1KA”继电器将导通。机组允许启动信号传到高压柜,等待电机启动。开始进行高压合闸操作,主电机运转,主电机运转稳定后,屏幕上主电机运行指示变红。这时静叶释放按钮变红,按下静叶释放按钮后,静叶从14度开到22度,静叶释放成功指示变红。 应继续观察风机已平稳运行后,按下自动操作按钮,启机过程结束。 B、停机画面: 停机是指极有可能对风机产生巨大危害的下列条件成立时,PLC 会让电机停止运转: 1、风机轴位移过大

“the way+从句”结构的意义及用法

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不对。 Theway(that ,in which)you’re doingit is comple tely crazy.你这么个干法,简直发疯。 Weadmired him for theway inwhich he facesdifficulties. Wallace and Darwingreed on the way inwhi ch different forms of life had begun.华莱士和达尔文对不同类型的生物是如何起源的持相同的观点。 This is the way(that) hedid it. I likedthe way(that) sheorganized the meeting. 3.theway(that)有时可以与how(作“如何”解)通用。例如: That’s the way(that) shespoke. = That’s how shespoke.

用友T+软件系统操作手册范本

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目录 一、系统登录 (3) 1.1、下载T+浏览器 (3) 1.2、软件登陆 (3) 二、基础档案设置 (5) 2.1、部门、人员档案设置 (5) 2.2、往来单位设置 (6) 2.3、会计科目及结算方式设置 (6) 三、软件操作 (9) 3.1、凭证处理 (9) 3.1.1、凭证填制 (9) 3.1.2、凭证修改 (10) 3.1.3、凭证审核 (11) 3.1.4、凭证记账 (12) 3.2、月末结转 (13) 四、日常帐表查询与统计 (14) 4.1、余额表 (14) 4.2、明细账 (15) 4.3、辅助账 (16) 五、月末结账、出报表处理 (17) 5.1、总账结账 (17) 5.2、财务报表 (20)

一、系统登录 1.1、下载T+浏览器 首次登陆需要用浏览器打开软件地址,即:127.0.0.1:8000(一般服务器默认设置,具体登陆地址请参考实际配置),第一次登陆会提示下载T+浏览器,按照提示下载安装T+浏览器,然后打开T+浏览器,输入软件登陆地址。 ,T+浏览器, 1.2、软件登陆 按键盘上的“回车键(enter)”打开软件登陆页面,如下: 选择选择“普通用户”,输入软件工程师分配的用户名和密码,选择对应的账套,以下以demo 为例,如下图:

点击登陆,进入软件,

二、基础档案设置 2.1、部门、人员档案设置 新增的部门或者人员在系统中可按照如下方法进行维护,

2.2、往来单位设置 供应商客户档案的添加方法如下: 添加往来单位分类: 2.3、会计科目及结算方式设置会计科目:

威利普LEDESC控制系统操作说明书

LED-ECS编辑控制系统V5.2 用 户 手 册 目录 第一章概述 (3) 1.1LED-ECS编辑控制系统介绍 (3) 1.2运行环境 (3) 第二章安装卸载 (3) 2.1安装 (3) 2.2卸载 (5) 第三章软件介绍 (5) 3.1界面介绍 (5) 3.2操作流程介绍 (13) 3.3基本概念介绍 (21) 第四章其他功能 (25) 4.1区域对齐工具栏 (25) 4.2节目对象复制、粘贴 (26) 4.3亮度调整 (26) 第五章发送 (27) 5.1发送数据 (27) 第六章常见问题解决 (28) 6.1计算机和控制卡通讯不上 (28) 6.2显示屏区域反色或亮度不够 (29)

6.3显示屏出现拖尾现象,显示屏的后面出现闪烁不稳定 (29) 6.4注意事项 (31) 6.5显示屏花屏 (31) 6.6错列现象 (32) 6.7杂点现象 (32) 第一章概述 1.1LED-ECS编辑控制系统介绍 LED-ECS编辑控制系统,是一款专门用于LED图文控制卡的配套软件。其具有功能齐全,界面直观,操作简单、方便等优点。自发布以来,受到了广大用户的一致好评。 1.2运行环境 ?操作系统 中英文Windows/2000/NT/XP ?硬件配置 CPU:奔腾600MHz以上 内存:128M 第二章安装卸载 2.1LED-ECS编辑控制系统》软件安装很简单,操作如下:双击“LED-ECS编辑控制系统”安装程序,即可弹出安装界面,如图2-1开始安装。如图所示 图2-1 单击“下一步”进入选择安装路径界面,如图2-2,如果对此不了解使用默认安装路径即可 图2-2 图2-3 单击“完成”,完成安装过程。 2.2软件卸载如图2-2 《LED-ECS编辑控制系统V5.2》提供了自动卸载功能,使您可以方便的删除《LED-ECS编辑控制系统V5.2》的所有文件、程序组件和快捷方式。用户可以在“LED-ECS编辑控制系统V5.2”组中选择“卸载LED-ECS编辑控制系统V5.2”卸载程序。也可以在“控制面板”中选择“添加/删除程序”快速卸载。卸载程序界面如图2-4,此时选择自动选项即可卸载所有文件、程序组和快捷方式。 图2-4 第三章、软件介绍

way 用法

表示“方式”、“方法”,注意以下用法: 1.表示用某种方法或按某种方式,通常用介词in(此介词有时可省略)。如: Do it (in) your own way. 按你自己的方法做吧。 Please do not talk (in) that way. 请不要那样说。 2.表示做某事的方式或方法,其后可接不定式或of doing sth。 如: It’s the best way of studying [to study] English. 这是学习英语的最好方法。 There are different ways to do [of doing] it. 做这事有不同的办法。 3.其后通常可直接跟一个定语从句(不用任何引导词),也可跟由that 或in which 引导的定语从句,但是其后的从句不能由how 来引导。如: 我不喜欢他说话的态度。 正:I don’t like the way he spoke. 正:I don’t like the way that he spoke. 正:I don’t like the way in which he spoke. 误:I don’t like the way how he spoke. 4.注意以下各句the way 的用法: That’s the way (=how) he spoke. 那就是他说话的方式。 Nobody else loves you the way(=as) I do. 没有人像我这样爱你。 The way (=According as) you are studying now, you won’tmake much progress. 根据你现在学习情况来看,你不会有多大的进步。 2007年陕西省高考英语中有这样一道单项填空题: ——I think he is taking an active part insocial work. ——I agree with you_____. A、in a way B、on the way C、by the way D、in the way 此题答案选A。要想弄清为什么选A,而不选其他几项,则要弄清选项中含way的四个短语的不同意义和用法,下面我们就对此作一归纳和小结。 一、in a way的用法 表示:在一定程度上,从某方面说。如: In a way he was right.在某种程度上他是对的。注:in a way也可说成in one way。 二、on the way的用法 1、表示:即将来(去),就要来(去)。如: Spring is on the way.春天快到了。 I'd better be on my way soon.我最好还是快点儿走。 Radio forecasts said a sixth-grade wind was on the way.无线电预报说将有六级大风。 2、表示:在路上,在行进中。如: He stopped for breakfast on the way.他中途停下吃早点。 We had some good laughs on the way.我们在路上好好笑了一阵子。 3、表示:(婴儿)尚未出生。如: She has two children with another one on the way.她有两个孩子,现在还怀着一个。 She's got five children,and another one is on the way.她已经有5个孩子了,另一个又快生了。 三、by the way的用法

财政票据 网络版 电子化系统开票端操作手册

财政票据(网络版)电子化系统 开票端 操 作 说 明 福建博思软件股份有限公司

目录 1.概述 业务流程 流程说明:

1.单位到财政部门申请电子票据,由财政把单位的基本信息设置好并审核完后,财政部门给用票单位发放票据,单位进行领票确认并入库。 2.在规定时间内,单位要把开据的发票带到财政核销,然后由财政进行审核。 系统登录 登入系统界面如图: 登录日期:自动读取主服务器的日期。 所属区划:选择单位所属区划编码。【00安徽省非税收入征收管理局】 所属单位:输入单位编码。 用户编码:登录单位的用户编码【002】 用户密码:默认单位密码为【123456】 验证码:当输入错误时,会自动换一张验证码图片; 记录用户编码:勾选系统自动把用户编码保存在本地,第二次登录不需要重新输入。 填写完正确信息,点【确定】即可登入系统。 进入系统 进入系统界面如图: 当单位端票据出现变动的时候,如财政或上级直管下发票据时,才会出现此界面:

出现此界面后点击最下方的确认按钮,入库完成。 当单位端票据无变动时,直接进入界面: 2.基本编码人员管理 功能说明:对单位开票人员维护,修改开票人名称。 密码管理 修改开票人员密码,重置等操作。 收发信息 查看财政部门相关通知等。

3.日常业务 电脑开票 功能说明:是用于开票据类型为电子化的票据。 在电脑开票操作界面,点击工具栏中的【增加】按钮,系统会弹出核对票号提示框,如图: 注意:必须核对放入打印机中的票据类型、号码是否和电脑中显示的一致,如果不一致打印出来的票据为无效票据,核对完后,输入缴款人或缴款单位和收费项目等信息,全部输入完后,点【增加】按钮进行保存当前票据信息或点【打印】按钮进行保存当前票据信息并把当前的票据信息打印出来;点电脑开票操作界面工具栏中的【退出】则不保存。 在票据类型下拉单框中选择所要开票的票据类型,再点【增加】进行开票。

用友T软件系统操作手册

用友T软件系统操作手 册 Pleasure Group Office【T985AB-B866SYT-B182C-BS682T-STT18】

用 友 T+ 软 件 系 统 操 作 手 册 版本号:目录

一、系统登录 、下载T+浏览器 首次登陆需要用浏览器打开软件地址,即:(一般服务器默认设置,具体登陆地址请参考实际配置),第一次登陆会提示下载T+浏览器,按照提示下载安装T+浏览器,然后打开T+浏览器,输入软件登陆地址。 ,T+浏览器, 、软件登陆 按键盘上的“回车键(enter)”打开软件登陆页面,如下: 选择选择“普通用户”,输入软件工程师分配的用户名和密码,选择对应的账套,以下以demo为例,如下图: 点击登陆,进入软件, 二、基础档案设置 、部门、人员档案设置 新增的部门或者人员在系统中可按照如下方法进行维护, 、往来单位设置 供应商客户档案的添加方法如下: 添加往来单位分类: 、会计科目及结算方式设置 会计科目: 系统预置170个《2013小企业会计准则》科目,如下:

结算方式,如下: 三、软件操作 、凭证处理 填制 进入总账填制凭证菜单,增加凭证,填制摘要和科目,注意有辅助核算的会计科目, 以下为点开总账的处理流程图: 如若现金流量系统指定错误,可按照以下步骤修改: 凭证在没有审核时,可以直接在当前凭证上修改,然后点击“保存”完成修改; 凭证审核 进入总审核凭证菜单下,如下图: 选择审核凭证的会计期间: 、凭证记账 进入凭证菜单下的记账菜单, 、月末结转 期间损益结转 四、日常帐表查询与统计 、余额表 用于查询统计各级科目的本期发生额、累计发生额和余额等。传统的总账,是以总账科目分页设账,而余额表则可输出某月或某几个月的所有总账科目或明细科目的期初余额、本期发生额、累计发生额、期末余额,在实行计算机记账后,我们建议用户用余额表代替总账。

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创维液晶拼接控制系统 软件操作指南 【LCD-CONTROLLER12】 请在使用本产品前仔细阅读该用户指导书

温馨提示:: 温馨提示 ◆为了您和设备的安全,请您在使用设备前务必仔细阅读产品说明书。 ◆如果在使用过程中遇到疑问,请首先阅读本说明书。 正文中有设备操作的详细描述,请按书中介绍规范操作。 如仍有疑问,请联系我们,我们尽快给您满意的答复。 ◆本说明书如有版本变动,恕不另行通知,敬请见谅!

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图4 4.选择键,进入下一界面如图5 图5 5.选中项,再选择键,进入下一界面如图6

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