227
STUDIES ON THE、UTIL‡ZAT‡ON OF THE
BY−・PRODUCTS’0二F SOY■BEAN−PROTE耳N
昭ANl呼ACTU良E
VIⅠ.Summarizingr Discussion BySin,itir6KAWAMURA (LaboratoryofBiolo壷icalChehiistry) (ReceivedAug11St31,1954) lntrodll雨ion and Reviewや Theordinaryprocessesofmanufacturihg$Oybeanproteih(see・thestudies bytheauthorl−3)
ahdでeViewsbyCIRCLE4)andBuRNETT6))invoIvethefollowing two by・・PrOducts:(l)1iquid
WaSteSeparatedfromprecipitatedprotein,OrSO沖ean wi1ey,a$iti$Calledin recognition of
畠imilaritywithmilkwheyseparated from precipitatedca$ein,and(2)insol血1e mealresidue,
血ichisseparatedfromsoybeanextractOr di$Per*ion・
The utilization of these two by−prOducts has not yet bee血 Studied systematicalIy.The ぬthot6−11)p豆blishedtheresultsofhisinvestigation$Chieflycarriedoutundei・the guidance of thelatePr’Ofessor B11nSukeSuzuKIat the Laboratoryof BiologicalChemi血・yin the Faculty Of Agric111ture,Unjversityof Tokyo.
(靂a)Soybeanwheya血ditsnti且ization(seePaI・tI6り
The utilizationof soybean whey wasfir$t COnSidered.Asthe main constituent wasfound
tobe′$ugaI:Sinadilutesolution,utilizationasethylalcohoIwasconsideredchiefly・Acidhydrol−
ysisof wheycarbohydratesandalcoholicfermentationof whey sugaI二S Were Stlldied(Par仁Ⅰ乍)). AIcoholicfermentation of soybean carbohydrate was mentionedin some earlierliteratures12−・17’)
Soybean molasses studied byIwASA16)wa$ Sugar・rich residue containedin alcclholiclayer Separ’atedoncoolingthe miscella dbtainedin theextr・aCtion withhot ethanol18−24)(seethe note byIwASA95)originating from theinformation by the presentauthor).ヱWASAl′G)removed SaPOnin from thismOlasses by adding sulfuric acid and fermented the solution cont∂ining O・98%reducingSuga王Iand 6・60% total 8ugar(reducing sugar after hydrolysis)with wine
yeasts・Another $Oybean molasses, a by−prOduct of soybean extraction with azeotrIOpic miⅩture Of methanoland naphtha96N3O),WaS al$O Subjected to alcoholic fermentation31−I32)
NAKAMURAand K工N31)used jelly・1ike viscousliquid containing 41.7% s)01id matter,19.96% reducingsugarafter hydrolysis,aSthe raw】materialn The ratio of sugar consumed wasonly
12−32%withdilutedmolasses,72−80%withstrippedmola8SeS(removedfro竺reSidualmethanol),
90一92%withsulfuricacid−treatedmolasses(removedfromsaponin),201−28%withacid−hydrolyzed mOlasses,and70−91%with calciumhydroxide・treated mola$SeS弓3)。The GovernmentFermentation ResearchInstit血e32)obtained simi1ar result$ with crude soybean molasses containing 27%
methanol,40%water,20%fat,9%totalsugar,andl.7%crude protein,and notedthe adverse effectof$aPOninanditsdecompositionproducts.Thiseffectof saponin wasnotencounteredin theal血or’sexperiments.(Thesaponins34−36)werestudieddieflybyJapanesedlemistsinduding
Tech.Bull.Kagawa Agr.Coll. 228
MtJRAMATtT(1923)37)∂nd√StJM王Ⅲ(1929−1930)3S).)
MorerecentlyafewJapanesePaten吟牒押earedon.払erutiliz鱒OnOfpoybeanwhey・6TAN工39)
heated soybean whey with acid clay or active carbqn,and therlPaSSed electIic currentinto
wheytoremovefermentation−jnhibitings豆bBtanCeSpriortoalcoholic fermentation.SuEMURA40) added active clay to soybean whey to $eParate thiamine by adsorption。SuEMURA41)further utilizedacid−hydrolyzedresidueごtogether withLwhey’as童i血縫htsforyeast$.
Yos王DA!3)mentionedthesuitaiblityofsol豆ble9arbohydratesinsoybeanwheyfor gorwthof yeasts・He43)foundthat90%Qfp申ass享um甲d20%ofp串0叩horicacid were transferred from
COmmerCialnaphtha−defattedflakesiムtowhey,anddiscqssedtheutilization of soybeanwbeyas Culturemediumin manufaeturing penicilljn andfodder yeasts= As pointed o11t by BuRNETT5)
propagation of foodyeas七,7bY・ulq少jisておti.1is,(inves眈gated byXLATT etail舶)onpeanlユtprOtein W?Steliquor)享$Of血erestto m甲叩factuてerS
liquor represents卑Serious sewage・di$pOSalproblem.SヱBATA45)usedanaCtivateJd−SludgePrOQ牟$S tqlrdisp?SeOfwasteliquorf!OmSOybean−prOt酔fiber竿鱒ufacture・∴Thiswasteliq叩COntaiqed
OnlyOl24%residueonevapoIationandO・01,0・Oq芦%nitf,Og斡・Ten坤OuSandtonsof}thi革1iq鱒Or WOuldgive2”4tonsactivated sludge(drymat鱒∵),VVh坤VOtlldgivel,116cqbicmeters茸鱒eS
(5,113,qOO桓alり)bydigestion.
Inthemanufact甲‡e?ftohu(SOy申年anC呵)thefilt羊’atefromcoag血e
This wa声telまquoror wheyin tohumanufactu‡IeCO坤instilia如ne.TAKApA鱒d¢OWOrkers季G, 47)studied on the recovery of tbis thiamine.
Now,SOluble sugarSirlSOybean wheyaretoodill止etobe fermented without concentration・ Fuelneededin conc6ntrating alarge′arT)O11nt Of壷hbyformsan占 method ofutiliえingWhdy asthe source of ethylalcohol
Thus two methods were examined toJglVeLcongiderablyless di旭e:餌gar solu翫n:11the rei)eatedproteinextr・aCtionandtherebeatedacidleacmig(f}retreatrh6nt)′(Part)−:王Ⅰ7))。JThe■1衰ter was found superior:to the fbI血er.The$tudywas ektendedtoalcbhdic知・蕗砲ntatidnl6fthe sugar$Olutionobtainedbythelattermethod,}i.e.,repeatedacidpr・eirle去tment、(PartHI8))∴E宣伝n When acid pretreatmentisapplied,〆thereis formed wasteliquor,thati畠thefiltratefrom precipまtatedprotein.Thiswheyobtainedafter・addpretr占atment・WOuldcontain muchl由$SugarS thanthewheyobtained withoutpretreatment,−thoughtheauthorldid▲not analyze如Ch a whey・ Whensoluble9ugarSareutilizedon}repeatedacid11ea血ihg,thewhey=maサ’contaihverymin血e amount♪Of sbl11ble substances,Of which咄ilization would not deserve considerati6n.
(旦b).Aeid旦eaぬま訊gand豆t$n七星雲五za鮎n、。(seePaItSⅣr)md鱒))
Thoughtheauthor.decidedform壷rlytoomit地eprodess、Of purifying defattedflakeもprior toextr・aCtionofprotein学),hefoundthatacid pretreatment wa$rationalfrom the viewpoint of 血ilizingsolublecarbohydratetTheutilizabilityofcarbohydrateofacidleadling・aS the血aterial foralcohoiicfermentationwasestablishedbyexperimentsde$CribedinPartIぴ)”Ⅰトisnoteworthy
thatconcentrationprocessofsugarwithfueltould beexcludedbyrepeatingtheaddpretieatment;
treble,aCidleachingcontaining血out4%sugar CO111deasilybeob血nedand BuChleachin be fermented after hydroly8iswithout concentration・
The Azi−nO−mOtO Co”,the pioneerin・the manufacture of/mOnOSOdiilm琶1utamite ■
Vol・6,No.3(1955) 229 grantedsomepatentson utilizing acidleaching of soybeans for fermentation to bもtain ethyl alcoho14S),yeaStS49),Orbl血nolandacetone60).‘Soyb由n、、fiakestr・eatedwiぬdilute acidwi11give monosodiumglutamateinhigheryieldand better・Lqualitylthanflakesnot trebted.KAWA血ORl17’) Sttldiad onthe cultivation of yeast$tO utilize hydrochloric・aCidleaching小 His resul七・WaS
un$atisfaetory0wingtO}highsodium chloride content(6−9%)of the ne血ralized hydrolyzate.
Addleadhing’was repeated,three time$tO decreasethe concentration of sodium chloride、,in COmParisonwiththatofsugar,andthetIebleleaching,COdd′be11Sed more satisfactoriiy./Ina more recent patent SuEMURA51)recovered thamine fr・Om aCidleachingOf∵SOybぬnmeal.
RAWLING52)subjected defatted soybean mealto the actionofyeastto convert the contained
SugarSinto、alcohbland carbon dioxide,remOVed、thealcoholfrom the fermented residue,and thenwasheditwithanacidsolutionofpモ‡4.5−4.2.
(2)Inso頼bgeresidueandits11tiほz乱電ion(seePa工tSIV−Ⅴヱ∼)一−11))
The secondby・Prddu眈Of soybeanこPrOtein manufactilre,insoluble residue from匪btein eXtraCtioncontains,aS牒iveninPar・tⅣ9),1i%crude・かbtein(1eftinsoluble on extraction融ぬ
alkalinereagent),3%ash,27%cr・udefiber,and、69%nitrogenufree extra虎On mOisttlre・lfree
basis・Thecompositonandyieldofthe、residuemayvaryaccording′tothe degr・ee Of extracting
protein・Thustheinfluenceofthemethodofprotein manufacturewasstudiedontheyieldand
Car・bohydratecontent^oftheresidue9)・Theutilizationwasnatural1ycenteredon{that ofcarbohy・ drate・Thisinsolublecarbohydratewashydrolyzedwithacid(PartVIO)).The hydrolyzatewas fermentedwithdi$tille吏・yyeasts(PartVIll)).Theresultwasnotsatisfactory小 Theinsolubleby−PrOduttof:soybean−pr6teinmanufacturemay・be utilized(i)asitself,}Or (ii)aftermicrobiologicalorchemicalprocessing.Or(iii)theremaybe80memethodnottof6r・m thisby−prOduct,thatistheinsolめ1emattermay beincorporatedin thefinal如dduct(蝕ough thispr・OCed11reCannOtbesaidasノutilizationoftheby・prdductin protein manl鱈acture,a畠it・is notconcernedwiththemanufactureof proteinisolate).(i)些車重 Of protein−eXtraCtion re8idue asitself.The residue,When thorollghly extraCted andwaBhed,COn乞ainsonlya8mallamountofnitrogenousmatter(1l−15%c拍deproteinon{df・y basjs)・But,Whenprotein extraction or washingisin$ufficient,aS enCOuneredinindu鏡rial pr’OCeSSlng,a COn$iderablylarger amount of nitrogenous matterwi11beleftThe author had Often experience$ tO find such烏malyses onin$0111ble by−prOductin the affiliatedまactory. TAKAYAMA75)reportedthatpr・Otein・eXtraCtion residue after neutr:aliz慮on由Id drying contained 6・16%moisture,24・94%crude protein,9.57%fat,19.71%fiber,83小61%carbohydrate,6巾01% ash,i・55%potassiumoxide,and O.99%phosphoricacid。Thisresidueisconsiderablyrichinfat, and sothecrude protein contentof water−andfat・free residue maybeashighas29.6%.Such aresidue asthis′COntainingabout30%cr・udeproteinor4い7%nitrogenCanWellserveas organic
manureitself;mOreOVer this contains valuable elements such as phosphorus and pDtaSSium. HURUKAWAand ODA added saltsvaluable as fertilizer to prdein−eXtraCtion resid11e53),Or added
phosphoric,nitric,Sulfuric,Or hydrochlor・ic・aCid to proteinqe血・aCtion re8idue and then tteated
themiⅩturewithammOnia54)to produce fertilizer.
Whenimproved by somemeans,the pr・Ote圭n・・eXとraction residue may be11tilized as fodder. KANAI55)miⅩedtundra′andfishvisceratotheresidue toproducefodder、for domestic/animals
TecIl‖ Bull。Kagaw Agrn Coll. 230
and pou】血■y. く
KAZ汀UKA56〉reportedtheanimalfeedingtest with protein−eXtraCtion residue.Though・he Stated thatextractionof oiland proteinfromlOO parts of$Oybeans yield 40’;・60−partS reSidue, the present suthor9)dbtained theLyie旭of2P・37%for defatted mealor the yield of only17:・・31%
for{台OybearlS.KAZ汀UXA56)added8−10parts of O.2−0.5%sodium恥droxide}SOlutiontoipart Of defatted meal(withmethanol・血aphthaazeotropicmiⅩtureB6−80))and、dbtainedinsoldbleresidlue afterl′Or2tr・eatrnentS,Itisclear fromthe following analy8eSthat protein exttaCtion w∂S far
f【Om Sufficient:
? a畠h
()
No.1,reSidue fromlextn. 41.9 1.75 4.5 51.9%
No.2,re8idue from2extn$, 32.7 1“82 4.2 6l.3% The feedingeXperimentswithyoungalbinorats showed that the sampleLNo.1was higherin
nutIIitive value than the sample No.2,thatJthe芦amPleNo.トmaintainedthe bodylWeightof王atS for20daysbutitdid n9t Su$tain gr’OWth owing.tothelackof fat,vitamins A and Bgrqup, and thatthe寧amPle No.2decreased the body weightof.ratsleading㌧、tOdeath,0wingtO㌧軌e,1ack Of fatand vitamin$.The protein and s幻tsofprotein・eXtraCtion residue wa$COnSiderablynutritive
even h tbe$ample No‖ 2.
When the alkaline proteinaceou$eXtr・aCtis obtained,bythe$Creenlng prOCe$S Of BELTER et al.67),、the.mealre8idue retain$a COn$iderable amountofprOteiIl,and りis valuable as a stdck feed,and has potentialiildustIialuse8,1becauseitislowin、Water−$01uble nonprotein meteぬ1畠, SuCh as$ugarS and salt$”as stated by Burnetヒ5)‘Thusitis usedin phenolic▲te$in,ht)t−preSS
plywood gllIeS58).‘t苅Iis mealre$idue co三池ins50−55%/pヱ・Oteinan(王 esseヱ1tially no′Water■・・SOltぬ1e
fraction,Wもichlatter has been removedin the′prOCeSSOf refiningthe protein. Formiila$ COntainingr・eSin andprotein materialsin∴匝e ratio of6:4are said tdgive rapidcuri王ig=′g1ue′1ilies
Which meet the established standar’ds for exterior gr’ade plywoodこwith a considerable$aVingSこin
giue cost.”5)Theinsoluble re8idue can also be′uSed for、the plastics.JUuAN and O.8ERG59) “have described moユdingpowders consistingofphenol−aldehyderesin$ Or urea−aldeh.yde′reSins
andthe reaction productof analdehyde with theins〇1uble meal、reSidue remaining fromL,the Ordinaryproteinisolation process”5)
An exa血ple of utiliえing proteiTi・・eXtraCtion residue by}phy由icalmeansis foundin a pat6nt
granted to‡‡6nenOilMillCo.6O)The residtle‘waspressedin afrarne togeぬerWith 3・20% SaWd11St Or bagas$ewithpressure(50・・500p、S.i.)at100・・150O forlO−60mintlteS tO form fiber
board.
(iia) Microbiologicallltil圭ztion of resid11e.AIcoholic fermentation′of residuehydrolyzat畠“as
investigated bythe a11thoris nota r−ationalmethod owingtOfu;furalformationand di舘tuityof SaCCharifまcationtoget reasonablycorlCentrated$ugdr solution・Combined utilization、of whey and
residue as the nutrient source for yeastswas original1y plannedbythe author.Thereis apatent
bySuEMURA41)い TAKADA61〉 cultivated 励′emOtheci’2tm aShbyiion thin$01uble residue from PrOtein extraction topro丘uce vitarnin B望COmplex.K6ji見n be p工■epar’ed from pro乞einrextraction
residue,by wa9hingwith water,netltralizingwith hydrochloricノaCid,∴WaShing■a痴iflwithⅥ唱ter., pressinglightiy,Steeping・in dilute aceticadd,preSSlngtOこmOisture contentof35−A=0%,heating
Vol.6,。No.8(1955) 281 by$uPerheated steamtovol如1ize?Ceticacid,、addingwhe鱒qrrice branorother carbohydrate S〇urCe and cultivating A頭ergillus oY:yZae62).UMEDA and coworkers63〉utiiizeiprotein・・eXtraCtion
residuecontaining3・2%nitr・OgenOr2げ%crudeprotei血astheraw material、for soy$血teand miso8ufficientlyg・OOdinfiavorandcolor..YoSIDA64)′foundthatthdhすdrolysisof‡eSiduewith hydrochior主cacidwasdifficult,butitwasfacilitated・璃血6npr畠1iminary’hydtolysiswithA卸drgi’llu.i
Or二y之ae 雨S made;he produced a血ino acid ct)ndi血t$′by thi$ micr・t)bioldgical and chemiぬ1
met壬10d
(iib))Chemicar・血iliz誠onof residue.Itwasthe author’saim′toextratt由muchpro七einLa$
possible fromdefatted soybean mealtoleave the residue chiefly consi$tingOf’carbohydr・ate.The 誠蛤ぬさtedutilizatibnofthisinsolubl色darbohすdtatea菖ethylalcoholprovedunsuitablefor{iIldu$trial
PurPOSe.The chief cause wasthe formation offurfural.The formationof、furfuralwas cci王鴎par・ed withotherindustrialrawmaterials,:餌Chaso癒しh豆11$,C6rncobs,and・CO蜘nseed、hulls,Whidl Contaid ab咄80%pentosan.Ther由id11efromJprOtdn一由柑Ctionofsoybeans contain a′Smallef amoilntl(i・7−へ19%)ofHpentbsan∴Th舶utiliz癒ionasthe r油materialof ftl血ralwotild
prof壬tabl金exceptinso血e畠pecial’cases.一Still也i岳utili左ation、血ay be co11ntedねs′c6nsiderable, 両血由トCOl叩1ed with further厄tili窟ation ofthe residue fr■0血steam distillatioh togetfurfural
A畠on毎Of畠uch dtim誠虐血追zation of、celldosic stlb岳tancebeleftafter鏡eam di頭11ati6n, pf毎pai威ion ofactive c鱒bぬWas su由esぬdbダthe′1畠te Dt.,BunsukeSuzuKt,butnoexperi血ental
gtudy豆畠s、ma漁、女oNDe.ぬd・王WAMAE65〉added’40・I50%beryliumiodide,gal1i血1Chioride, f)OtaSgiiitn’io血e,Chppe王∴thloride,OrboticLaCid<tOthe
bhdad:ivatedbす:hedtihg址700−8000for3ho11rStOpr畠par6advecarboll.AとcordingtoSエBATA45) drydistill洩ionbfprot6inLe女tr云ctionIこesiduegave306・・624cc…7b.6fvola七ilematter,COnSi畠tihg{6f 30%ca沌on dioxide三l’i%6Ⅹygeh,37%methane,11%hydrogen,and22%nitrogen and oth6r ga岳esdorI
withoiit fbt血inginsol豆ble ねdhesi17e and ot王1eI
(iii)堅些些 OfpreParlng/SOybean fnr
resid11eJFor adhesivepurPOS占notonlythe畠0沖e由IprOteinisolate,but扇sothedefa飴d soybean flo11rこi占us主d.‘】麗で畠soybeanwheyfractionisnotdesirablefor’adhesiveandplasticsVoLKOVet alこめpepti女edso沖岳ani)t・dtein而th菖odiumhydroxideandthehused excess hidrochloricacidtd precipitateit upon thei由01豆bleresid11e witho11t Separating thelatter to prepare plastics・
WAⅥLFORSS67)1e畠chedsoybe去n‘mealwithaweakacidat’theisoelectricpointbfsoybeぬglobdin, dissolvedtheJalkali−iolublepr{oteinih血epresenceoftheinsdluble residuecoぬpr・isingc占11血se, he血ite‡1豆1bse,and alkali−insolubleprotein,and separatedthe compositeofinsc・11ユble residue and precipitat畠dprot6in fromthe’soh址ion.INAGAX王etal・68〉didnotseparateihsoluble residue after steepin畠defatted soybeanmealihdiluteaddor alkali,but addedalkalior acid to precipitate
protein;Wheyfraction wasremovedandptdteinplusinsolubleresiduewasdriedandpulverized
DAV主bsoNG9〉三eCOVer占d・prOteinandh6mibelllユlosesim111taneouslyfi・OmSOybeanmeal;the soybean mealwasdigested withO..4%sodiumhydrdxide soll血on and the dispersion passed thro11gha 200−meSh screen to remove cellulose;the resultingliquid was acidified and the protein and
hemicellulose,Simlユ1taneouslyprecipitated,Were WaShedand dried・Theproduct wassuperiorto soybeanproteinisolateinadhe畠ivequalityandyield(50・60%ratherthan35%)・Thes寧methods
areinterestingfrom the viewpoint ofl止ilizing as much constituents as possible which由一e
了もcIl.Bull∴K喝aWa A酢.Cbllこ
Summari2;ed‡と、eSⅥ塁七s of Experim¢n七島 232
lり 甘地eom‡)OSま七ion of s¢y態¢amW如y?).
Soybean wheyiS、aVやrydil嘘e solutionand even th或fromthe first protein extractcontains Only2・3%solid matter.This$Oiid matterd阜SSDIvedi草1Wheycon!is享SOf23・6−24・7%crudepro・ 胞in,24.・8%
38−39%of totalsolid m細er,in comparisonwith the value(50.5%)of nitrogen−free extf■aCtl・
Ro11ghlysayi王Ig,SOybean wheycontains2−3%splidmatter consistingr of carbohydr.ate,prOtein, and ashin the ratio2:1:1.
About30%(29.5・・35.0,arithmeticaverage32・1%)of、Crudeprpteip.in wheyis QQagd殖1e
by heaヒP‡・in tbe董0工’‡n Of albumin・
When sodium$ulfiteis use季冬s proteinTdiるpe王.・Slng agent,Whey<wi11contain sulfur dioxide
Or$ulfite.Somedeterm.inaもions made for sulfur dioxideCOntentOf、whe、y Showedthatitis ve王y low.Besides,S豆1furouS aCid caq be easily、rer鱒OVed,byev寧pqration duringconcentrationof・Whey・ Whenitis used as the rawr materialfor alcoholicL ferme叫ation,,it fnu$t be concentr’atedlby hea血g.Thus sulfur dioxide was fo11ndun卿pqrtant・$inc寧the sample contains org?nlP substances,iodine紳・殖On C鱒nOtbe usedin determlnlng 叩1furo】uS aCid.、Sulfurous acid was di融illed,0Ⅹ主dized tosuifuricacid,,Which wa亭dete工■mine¢as barium sulfatelSulfiteisdistilied after acidifyingthe sample,}and free sulfurousacidi$qistilledin‘Carbon dioxide stream・from non・l!re準dsa準ple・So錘ean wheyi$itself寧Cidic・Thus幸tfollowstha七al1sulfuraioxideisin freeform.Thefresh wheyitself,COntained 9<・031rO・056 g・川1・Sulfur dio二gide・Thi$qOnte叫 decrea苧edonlyplightly(toO・026g”/dlい)whenpre・Cipita鱒W坤Calciutn c寧rbpnate was removed byfiltr・ation.、Calcium sulまiteisinsolublein water,butdis$01ves/in 串queOuS SOlution of sdfur dioxidetoformcalcitlm bi$ulfite”Sulfur dioxide?OntentOf whey,dec;reaS寧dtolβSS than O・006 g.,./dl.(probablymuchlessthanthis),Whe享IWheyⅥⅥSeVqPOr鱒dtoone−fourthvolume・
Soybean芦COntainnoneoronlytra9eOfreducingsugars7Q),bl止aspointedoutbyTAKAYAMA75?,
soybean wheycontainedreducing sl哨arS・馳reported that a′Sample of wheycontained O・162 g・/dll‥reduci甲gSug甲S and O・989g・/dl・七Otalsugars巾TheauthorcouldconfiI:m nOt Oniy the
presenceofreducin革Sugarinwhey,butalsotheincrea甲OfreduCingsugarinag■1PgOf whey・ The reducingrsugarsof wheyarepresumedtob鐸glucose,fructoue,andgalactosederived fro鱒 hydrolysisof sucrose,raffinose,andstachypsepresentinsoybe?nS,争SWaS COnfirmedlater70)・ Th9叩alyticalre凱舶showedthatthewhey containing O・823g・/dl・tOtalsugar containedth? followingram・OuntSOfreducing$ugarWhenkeptat70:thedayofp草・eparatio王ユ0・2728,3daysafter prepar・atiQnO=3998,5daysafterpreparationOl4537,and12daysafterpreparation O・6108g・/dl・
(asglucose).Sincealsoinboiledwheysamp19theincreaseof reducingsugar wasevident,this hydroly$ismaybenonenzymaticreactionl(Laterexperiments detected sucrose,raffinose,and 8taChyoseinsoybeanWhey70〉aswellasi!ldefattedsoyb寧anS73)・)
2.Aeid血yむ0!ysis(♪fwh¢y earbohydyaぬ6)
Experimentsonthe determination oftotalcarbDhydrate ofdefattedflakesbyacidhydrolysi871)
showed that boiling withi15,3,and 6% hydro血loric acid gavelO.2,13′7,and19。6% r・edudng・Sugar after hydrolysis on air・dry ba$is,reSpeCtively,and、that′the time of heatinghad
Ypl・6,堅0 ) 23声 ?e撫OSe(a無tJ声%q’ude弊9r)響qL叫er p91y早野?harid?9,・While$Pybe甲Whey cQptains} 幸uck王!igherpolysaccharid乳a$坤eyare軸軸bleinweakalkalin9I:eage如知extra$t軸proteiD. Thusthe亨・eSultsa$COrdi阻ゆacidc9nCentrationm早ydi蜘′between}Whole defatted flakes甲d wi1eylr Theco誓9e坤ationsofhydrochloricノaCido貰‥
牢桓、hydr91ys吏苧望SCO草野areqてWithbc坤準acids,3%画dgaVehighe9tredtlCingI
i誓?0甲p率$On画bO小5,′i・5,叩d6%・T申e§qnCe呼atiqnofb油血lo‡・ic早堪andtOtal苧ugaチ (a苧g叫?甲り、阜軍.g■・彿w鮮学,三甲鱒吋y,ノウ・学年,0‥716;1…7年 P・叩;軍・・季7,0・β23;
0・750・T王10S9払ご■sul餌ic卑CidⅥ杷工■e,′草・eSpe坤Vely,P・52,0・590;王・57,0.636;3.i5,仇687;and
e conditionsof acidhydrolysis of soybean whey with sulfuric acid J
in苧ufficient,du‡ati9nO董王IydrI91ysis need i*ons ofrbydrQlysisarebo主軸withl・5% S叫furicacid for2.hour寧.
き・A眉e◇血¢点ie f¢rmenta七ねm、¢君、$dybean w血eyや)
No畠1coholi占fermentationocc11r・fed☆ithsbybbanwheyitself.Eveilthe acid七ydroliTZate>Of Whey、Showed noferhentatio由.With toncentiat崩励eすth色yeaSt No.2d亘d notf金rmentit,the yeas七っNo∴1andノNo.3showed知血ent撼ぬ由vi相場ef誠dofsu卸cons血p鮎姑左9a組63彩ら
respe輌ely/Thehydrol吏Zatelb董■Cbn6e壷・ated’wh針tontainhg2.457g./dl.sugar・waSf壷1y
ferme雨ed;、theratio′Of sugar cdnsumption was、withthe yeast Nd.1,62;Nbn2,64;1去hdNo。3, 83%.The◎e畠retheleSults of払efirsttrial、fermentationwithdistillery ye∂StS Offered by′the hborato叩OfLFermentation,Facl血yof Agriculture,Univer9ityof Tokyo・
The results,Of>the second trialfehnentation are as血1lows巾 Cbntentrated・両もeywashydrbト
yzedwithsulfuricacidandthehydrolサZate>WaS neutrralizedwith calcium carbonaie top王ま46. The sample containingCalCium 8ulfatepreCipitate::董眈meiduring tLea七 Steriliz畠tion and th癒 sepa畑edfromsuchprecipitatewerefe血entedw紙hthr畠占gtrbins∴戚ノdistiliery yeast畠(血eas hthefirsttrialfeImentation)・The′ratio:6f sugai:tonsumed was similarly high(82q90%) irre$PeCtive offiltration fr・Om Calcium$ulfate.Dir6Ct determi這dtioh of ethylaltohol(by the specificgravity血曲od)showedlhigherreshlt(yeastNo.王,i’2±Nd、2,69;andNo.3,85%) f6rfiltereds’ample’払anforunfilteredones(yeastNo。l,64;No.2,53;andNo.3,81%).
Wheyhas兢rogenousas
in、concen七rated whey coilSistsofめoutequalamountsdfproteo畠e and nbnproteinic s止bstanc由u
Thefermentdbilityofwheysugars was壷ellestablished,butitisnotpracticaltoconcentrate whey−withfuel。This consideration、′ledtothe studiesthat follow・
4.甘血¢甲e坤odo君eonc甲血a電通g彗典型eゐ坤0血ydra七es7)・
Thecarboわ・ydl弛COntainedin$OybegT}Whey?rfiltrate from precipitated proteinis cal1ed
soluble carbo享1ydrate,While that coqtainedin theinsoluble residue separated from protein disp甲やni苧Cal1edinsolublecarbohy4ratebytheauthor・
The wheyitself contain声Only2・3%solid m牟tter,COnSisぬg、Ofsugars(01igOSaCCharides), 誓・udeprotein,andashinthe埠pIOXimateratioof2‥11:1・Fermentation wassuccessfuiwith 中野.PO鱒entrated toabp坤One・・fourthvolume,OrthatCOntaining2・5−4い5%sug声r
Tech.Bul1.Kagawa Agr.Coll. 234 (A)totreatanotherbatchofdefdttedflakeswithalkaiine中Ofprot占ihtopi車掌 dodbly(drfurthertrIebly)concehtratedprotmidisper$i?n,from obtainedbyacidifi占ation(repeated withdiluteacid(priortoproteindispersionwithalkaiihesolution)todissoIveas血ユChsu車Ⅰニラ andaslittleproteinaspossible
itwasfbundthatrepeateddispersion(A)gavetoovit?定s di*ersion to beやヰipul豪占よ technical1yeasily巾Incomparis6n壷ththis,aCidleachi鴎oradd‥extr・ad:COn6ehtr・atedby,repeakd add−tr由癒ment(B)did not become visdous add pres占rfted ho diffi占血yih ha這dli地.:th壷去
concentrating of sc11uble carbohydrate can be attained by repeating acid−treatment Of defatt6d
fl白kes,
(A)Inrep?ating・PiIOteindisbersingr9Cedure&i申alkaliムesolutiontwoqrthee methodofextracぬgneWmealwiththefir・Stpfot6in白血dct may glVe Whey
g./dl.suga‡・,butpr・Oteinextractbecomestooviscoustobemanipulatedeasily.An6th占rm6th読 practicdblein the factorly prOduced whey containing・Onlyl.5宮。/dliS喝ar When、the、血eal払 s叫Ition、ratioisl:100r O王11y,1g.!dl.、S叫gar Whe享l七hemealtos)1ution.ratioisl:15.These whey早年re nOtlikelytpfermentwithol止CC>nCentrating・Thus repeateddispersion^wi11giyegr’
difficultyOf th寧 p;■Oper prOCeSS Of preparing∴prOtein,、OrWillgive only dil咄e whey、1The COnClu$ionisthattherepeateddjspersioncannotbe.appliedin concentrating s〇1uble carbphy毎・
(B)The experiment$ Carried out to k‡IOW the effect ofacid−treatment pribr、tO PrOtein extractionrevealedthatcarbc・hydrate dis$C>1ved wasabout55・70%of totalcarbohydrateで16.′0%)
Of the mealregardless of the strength of acid,・・・・・・thereノCOuld be・found no clearrelation:betwee血
the anountof dissoIved carbohydrateand theノamOuntOf acid usedq,andthatnitr・OgenOuS matter dissolvedbeloweredto10,15%oftotalnitr’OgenOuS}matter(nitrogen7・77%)of、the’meal∴ノi鱒 CertainconceIltrationsof acid・Herenotthe concentrationof acidbutthe amount of acid(morβ PreCiselytheamountof dissociated hydrogenions)isofimportanceb thatis the hydrogen=ion COnCentration plays the role.Itis evidentthat nitrogenous matter dissoIved by acid−treatment bepomesminimalatitsisoelectricpc>int.Stronger orLWeaker?Cid than this point}wiildis草QIve 叩Orenitrog■enOuSmatter・Thusacid・・treatment8hould be perfo羊med under qp申malconditions for
protein(mipimumdissolution)andnotunderoptimalconditionsforsugars(maximumqiss)1qtioIl). Theisoelectric point of soybe鱒 prOteinis pH 4.2−4.4 according’tO the pre8e叫a叫hor3・’76)
SMITHand C工RCLE77)8howedpI王4・1−4・2tobe、isoelectricpointa‡ld pH4.0・・4.7asisoel阜¢煎 range.When pH4.2is aimed at,for example,addition of O.07−0.08N sulfuric acidin the mealto acid ratioofl:5made the acidleaching atisoelectricpoint.TheamOunt and c.)nCen,・ tration of acid tobe11Seユvaries natural1yaccording tothe meal.
tt wasfo11ndthatpHof themixtureof acidleadling at p壬‡4巾2 and new d占fattっd meム1
becamenear5.0小Thisfactwasnotthoro11ghlyinvestigated,biltitmightbeattribilteitobuffer adionof soybeanmeal・Nowfromthepr.acticalviewpointitisnecessar・ytOmake thepHofthe miⅩture4・2rapidlybysupplementingdil嘘eacid・Iftoodiluteacid(eng・0.1Nsulf血・i6atid) is11Sed,thetotaivolllmeincreases and the concentration oIsllgar・decreases。Thi$is to be avoided,aSthedliefdbjettisnowtoconcentrate8〇iublecarbohydrate.WhenlNsulf11rCicadd WaS uSedthetr’ebleleadlingcontainedasmucha$4・3女・/dl・tOtalsugar.Itis nっteworthyth畠t
Vol.d,No、.3(1955) 235 Ⅰ■edudng朗唱即.
5.′A富e定虫0鮎飴γぬeれ也七五on、Of禽ぷid 属地e血まmgS).
Acidleachi痩Obtainedbysingletre癒rhentwascoiicentrated and ferm占hted with di5tillery yeaBtS,butthe
Thefei血中融onof、trebleatidl占a6hin壷や岳e吏telienE”Thesamplさcontainbd9小畠8白 t(血1soiid,3.846主・educing・siigar,豪d
血erねtioof紬gar.consiimedwasrmirethdh’
6.甘血e yi¢はand eompos五色五¢n¢君主ns(〉g阻も屋e rcs五鮎¢9〉.
Experiments‘were made.to.8ee the.、influence.of′the method of extr・aCting pro短in on the yield and car・bohy融ate COntent、‥0阜ノins頑鳴1e resi由纏.r.When protein extractionis reasonably
thorough,100 parts mealwi1トgive 20 paTtSinsoluble residue containing30% carbohydiIate (tot幻sugarafterhydrolysis),
Theinsoluble resid11e COntained:3%ash,{、1i−i5%;Crude protein,23−27% crude・fiber,59; 61%、nitt・Oten・free/eXtraCt,and37−40%reducing凱唱ar.’after二hydrolysison moisture−free basi臥
The fu血ralyield of this、r’eSidueLWaSノ8・・iO%・.ThisICOrre革pOndsto15・・19%araban,bl址‘埠 contains血Onic acid cons鮎11e卯;^:One餌ample、Of>,1ater,an?1ysis/gaVe√7..87%furfuralyiβ1dand 8125%1止onicacid,Or7’.50%\tlTOnOIBCtO軍Ie andll.76%arab叩1O,ア3):
Theinsoluble re革idue contailned norm?nQT O工∴9hg¢S翠CCharides,∴Most of the nitrog・en:frle9 extractwas.consideredわ’申∋in,t桓・fo叩Of苧?「Cal1erihernicellulose・The a甲Ount Ofisolated hemicellulo昏eWaSSmal1(9nly垂Out’i7%・鱒紅塵画Cellt1lo甲).Theh画Cel!ulose of声?ybe墾IS
has been furtherin\▼eStigatedT一二▼てい
7.Ae互d最Iy血0五y・Sis(〉f¢arb¢毎むat¢im色蝕e¥・eSid弘¢蝕ompro七¢五n¢Ⅹ七raetiomlO)∴ Acid‘軒d史01纏softbei・由iぬeinぬ畠咄OClave wムs uムsui由馳0Ⅵrin宮tO tbe知血左tion of
fiirfuralfrompentoselinitsTheyieldlofi・ed.ucingitlgarWaSlow.UilderIatmOSpherIic pr:e去s鹿; the}be誌tcondiiions壷r占to甲Se19paチ・tS3%畠血ri占acid畠ndtoheatat980for・2・5ho
鼠A靂eく殖¢鮎ferm金ntat亘¢m Ofac五d毎む0望yz離¢く〉f resid旺efromprO七ein extr鱒¢七ionll).
Thealcoholicfermentation wasdifficuitwherltheacidhydrOlyzateofin$01uble9arbohydr準 of soybea播is the sta‡ting material”AIcoholic fermentation of acid hydrolyzate obtainedby al止OClaving the residue was11nSuCCeSSful・:Ri扇ng}Of sugar concentration would notleadtoa
bette葦r甲ult,Sincesteamdistillation(caIriedoutto repove fuでfural)would decompose once− formed9ugar小 Anyhow alcoholicfermentati9牟 Of hydrolyzateobtained byal血Cla扇ngis not a rationalmethod of utilizinginsol一ユble二neSiduefrom protein extraction・
Acid hydrolyzate obtained und.er’atmOSPheircpressure gave no satisfactoryresult of fermen二 tation,aSthe concentration of8ugar WaS uneXpeCtedlylowThe reducing sugar
amount of46−49%is not recommended tobe utilizeまas ethylalcohol,Since the fermentability was nothigh.It wascalculateithathydrolyzate of theinsoluble darbc)hydrate cod$isted of53い7% 如云ose,19.5%galactose,and2白・8%arabinosein themolarratioor56・2%如cose,20.4%
g81actose,and23.4%arabinoseinthe&eightratioonthebよsisofselectiiefemぬtationbyth6 two strains ofdistilleI・yyea$tS uSed・
Tedh・Bull∵鱒喝aWa皐gr・Coll・
236
PracticaE Consideratioll
Thenature ofby・rprOducts variesaccor・dingtOthe processes董or manl血cturing the main
PrOduct・、Yetitisvalidthatsoybeanoilindustryproducedtheby−PrOduct,?Oybe甲Cake,′.rich inpr・Otein,andthen$Pybeanpr9teinindustry produced the by,prOducts,COnSisting・Chiefly of Carbohydrate”T始infereTICe車SOneOftheguidingideasoftheau払orhlOughoutthe?e頭udies T桓efor?,utilizati乳Ofcarbohydratewas血diedandtheconclusionsarethatlSOltible?arbo寧y‥
drateisea車1y,f$rmented′byPi?tilleryyea恥andinsolublecarbohydratei$nOtS0年串寧ily卸町ent:
ed.Thusliquidwasteismoreeasilyutilizablethanthesolid wastefrom the chemicalnature
Of carbohydrate contained.
From●anOtherこ☆iewpoint,{however,SOlid wasteiseasilymanipulatedanddispo$edof,While
th畠、:disposal/of}1iquid waste form$aprOblem.Thoughsoll血1e car・bohydratehrasprovedt6 easilyfermentable,、PrOfitable utilization needs manymoteintensive8tudies.
MOHLMAN78)cal1ed a比ention to the financialprobleminvoIvediilthe disposal’,Ofliquid
industri盆1waste$;ahdnthen pointed thatthetedlnicalproblem was twofold:“first,tO/retOVer
salva畠eable mateiせ晦:po姦siblyataprofit,■and$eCOndly,tOadqptmethodsofsewage漑eatX舵nt primaryaf土dsecohd&ry,tOthetreatfnentOfresiduaiindustrialwastes・,,
‡trmaすbe、more、Orlessしpi・evailing’fact}that“considerable\prOgre$Sha$been made}inわrofitT able utilization of the soiid wa畠tes and the more concentratedliquid e■ffluents,’bu七’the 血ote
dihite effhi6nts stil16ffe王IpOlluモiらn’problems,”aspointed ot止for thewastes ofノC追uS>fruits
industr・y”).恥e血inぬewell−eStbblishedinddstryofpulp andpapermanufacmie,$ulfite・1iquor cbhtaidihgatrre血ehdbus′▼Wealthofnatutlalresourcescontinuesto be wasteliquor8P)・AIsb‖in
GreatBritainverylittleprogresshasbeenmadeinthe treatment ofindusもrial☆asぬWaぬrbダ
fermentation〃81).
Theseqitationsweremadenottoshowtbattheexperimentalstudiesdescribedinthisseries
ar・enO!.useful,帥topointo血theserious寧eSSOftheproblemof utilizingby・PrOducts・Whep soybeanprotein享芦manufacturedon someindustrialscale,there are produced vaste products notwithstandingtheestablishmentofthe methodsofthedisposalof the waste products・P Thus thesestudies壬ierepresぬted、☆illbeofvalueindetermlnlngthedirectibnoffactorymanufactur’ein relation to the disposalof solid ahdliquid wastes
Con(:靂usion
Mylaboratory?Ⅹp9rirnents?Ouldestdblishthemethod ofutilizi喝SO旭1ecarbohydiat壷s, whiletheyfailedtofinda8uitablemethodofutilizinginsohble carbohydratら・HoⅥ即eモ,froin thepr?Cticalviewpointtheipsolubleresidueismoreeasilydisposedofthan theliquid☆astes・
Thusitis concludedthatsolliblecarbohydrate shodd be concentrated and11tilized before the
alkaiineextr云cti9nOfpro!einbythemethodOfrep甲tedacidtres這らstancesstlCh鱒thiamjnemayalsQberecovered・)Themotheriiquorfromp‡eCipit∂tedproteih shouldcontainaslittleorganicsubstances.aspossibletofacilitatethesewageprOblemL・Thefinal wasteliqv9rbec9甲eSVerydiluteafteracid pretreatment followed by alkaline extractionいThe insolublemealresiduemaybeutilizedassuchorafter・prOCeSSing,Ormay beincorporatedLiTl
237
Vdl.6,rNo.3(1955)
Åekn¢☆!edgme雨
The authorwishes to expr−eSS his sincere・thankfulness to the′1ateI)r.Bunsl血e SuzuK王 andtoIDr.Mas11miKANAI,under whose如idance thess s七udies wer・e made.He’alsowishes to thankProf。Kin,ichir6SA.KAGUC王‡Iand Prof.Toshinobu ASAIof the University of Tdkyo, Wb6werekindenoughtoムffervaluableStrai虫SOfdistillery\y由st斎、The加血壷is gratef111t6 I)r・TaijiKuROKÅM‡,伽dir・e占ぬ吏Idf払i畠C油壷,Wh6gav占′血e甲hveni6ncedf
Publishing−the studies.
\\、鮎sぬ産品(血班sわあya血払)
Porpr・ePariproteinon e18Ojfabo.毒SengraSigita.ioniordina di毎払alkalion por solvi pr・Ot寧inonell争、叩如erialo,kaiノ如ealdoTla鱒/aCid9nal1a aikalia.soIvaうO POr・preCipitiproteinon Tieloniakiras du kromprodukto桓:(l)iikvakromprodukto apar七igata de precipitita proteino kaj(2)nesoIveblares瑚0}apaItig細ade proteinsolvaうOu
Gisnunmi6−11)s如dislar咄iliga翫鉦deambau kromprodukto.i.r6arla eefa komponajo de ambauestaskarbohidrato3mistudispor utiligiilihpetferhentadopor、akiri′etanolon.Lalikv畠 kromprod血0(1)entenasbonefer・m苧nteblan占tkeron(畠議会上やrafin6zo,kajstakiozo,
hidrolizatoj)70,73),tamenlanesoIvebla去olid云re$ta16(幻ehtenaspblis払rido両(h6mideldozd読 73・74)kaiceldozon,preCipe)nefacilehidrolizeblム3nnekferment6bla3p・
GitiupaperOpri血・iba$miajnstudoinresumekajdivei■Sajnprqppnojp pQr頑1igi1akro produktojncitanteentllte81kon99r;鱒ajnliteraturoindej?Panaj kaj eksterladaj autoroj・
Lako頭111do}eStaSke oni11nueekstraktusqlveblan sl*eI−On per aCido eeizoel鍵tra p11nkto de sojfabo・prOteino,utiugu畠inper fermentado,kaiposte ekstraktu proteinon・Tiamanier’e Oni
povo$akirietanolon(kaj ankauvitaminon、Bl)kajlalikva・foriga30如i含OStre dilua,‘killne prezentosmalfacilonpordisうeti・ノNesolvel班=■eStaうOpovasestiutilightakieltia au post mikro・
biologiaaukemiatraktado∴
‡ノi七era竜眼貰・e C長七¢d
l)SKAWAMURA:Studiesonthei血ufactur占′0董s擁eanp主0ぬnhI・Generalintroductionahd pr61iminary
expeIimen七S‖β祝JJlCo〝4㌢・ト摘如昭乙履むZ,1】16(1951)・
2)岬:DohII:Ext工attion云fsdybeaムoilDe加ed占oybeanふeala;therawmaterialformanufac・
turing soybean pIOteinIbid17−36
3)−‥Do・ⅠⅠⅠ・ExtractionandpIeCipitationofprotein”Small・−SCale血anufactureofsoybeanproもeiム
TβCゐ‖助JJい凡噂α紺αAgγ・CoJJ4,206一一25(1953)
4)ShJCIRCLE,inK”SlMARKLEY(edl):Soybeans and SdiTbean PIOducts,l,288N−318(1950)hInteト science Publishers,New YoIk
5)R小 S.BuRNE汀査∂壱d2,1003−1053(1951)
6)S.RAWAMURA:Sttldies ontheu七ilizationo董by−prOducts bf soybean・−prOtein manuiacture・Ⅰ”AIcoholまd
fementation of the wastel享quor of protein manufacture小J“Agy・.Chem.Sdc..傾an23,129−34(1949)・
7)−:Do・II.Concentrationo董solublecarbohydi’ateS”Ibid”23,310−15(1950)・ 8)M叫‥DoIII”AIcoholicfermenta七iono董acidextrbct”Ibidl2i・383−5(1951) 9)−‥Do・ⅠⅤ・Componentsofthe工eS3duefrompIOteinextraction”Ibidu385ニ8
10)脚‥LDo・VtAcidhydrolysisofthecaIbohydIateOftheieSiAne fIbm pioteinextractionlJSoc βγβ紺摘g,.わ♪α陀仏E,65−7(1951)”
Tecb・Bull・鱒a甲甲声勘Collこ
238
11)納−・−−−−:Do.ⅤⅠ.AIcoholic fermentation oiacid hydrolyzate of theIeSidue from p=Otein extIaCtion
乃摘.78−一80. 12)A.′L肌ALLOIS:C¢〝奴′錘d・98,1923(1880);93,281(18飢)(thIOugbC・ⅥEHMER,1929)・ ヰ3)Sad?k5tiSAT6:T Soq・Chem・hd・.Japan23,1”24,109−34,219−36,321−42(1920);7bch・Re?is・ 70加点洋肋壱び 2・1−124(1921)・ 14)苓enziMA叩MOT?andK・M幣VA‥み轡牒中野り鱒擁(Rept・Inst・B工e中喝)No・107,1 15)B望m6RoRUSyOandS KAWAI:点呼ヂ α励′αJエαみ・,50〝才力肋紹Cカ〟㌢オq馳?紺α.γC〃18,仁22(1934) 止 16)Yosabu工0IwASA:JAgγ C烏β沼.SクC−胸α〝13,233−5(1937) 17)TosiI6KAWAMORl:ZγOZqgakuZass多(JIJnd巾Fe工mentation)15,55lp4(1937) 18)Masano工iSAT6andTIT6:Repi.CentralLab・,SouihMbnwia 19)H SAKAIandM SAT6:1bid”14,1−9(1929) 20)MSAでるa這dM YoRO晶ぷ繍10⊥15. 21)S諺bitiSBRA姦ndlM SAT6(bMinamiMansyuTetudaK・Ki・e・ ?atent79,6β5,†anこ 7,1928 22)n4.SAr6andYlIs【DA(tothesameCo・):Japan Patent80,567,Feb・18,]928 23)−−andTpへIT6(tqthesameCo・):Japan”Patent82,719,July,301928・ 2年)一丁r (七OthesameトCo・):lIapan・Patent88,043,Aug・28,1930・ 25)Y∴王WASA:ムAg7・C鮎澗・割払ルゆ鱒15,473−7(1939)・ 26)MlnOru MASINO:Jて5〃C・Cゐβ研・趣♂・.J如α花32,866−71(1929)・ 27)−・−andS・NISIMURA:乃掃・34,1036−40(1931) 28)−鵬 and+‥乃≠dlO40−4・ 29)−一仙:乃よd 36,807−11(1933)・ 30)SyuitiI60TIandM MASINO:Japan・Patent79,135,Nov 27,1928 9け血羞u6’NふKふMbkAJandK6dも女ふ:Kqgdku;KbgyoSitm(Mふterまalsfoi・Chem・ 32)l■(蛾ih旭岳、ムiGo繭hm6nt、Ferふe血a七ionRe血・ChInst・)‥iyusei(WineSp油 33)M・′M・ASINoand、M・NA癒AMURA‥}Japan∴PatentAppll3061,June15,■1940; 34)・Y6bei.HASIMOTO:励離毎期雄加徹(.丁一・.Tapan・′Cbem・)5,・593一丁5(1951)i 35)A。.MEY耶,0・.TEGER,andLRuzICXA‥月め・C彪研いノkね33,672−・87,687−99(195p)・ 36)B”Fl・DAUBERr,inK S”MARkLEY(ed…)‥SoybeansandSoyceanProducts,1,374N7(1950)・Ci”4) 37)SyunsukeMuRAMALIU:f ChemSoc”.7*an44,1035−49(1923) 3恥Y望早坤eS?MIKI‥。/・′AダいC点呼…Soc・ノ如α〝5,7亭7−52(1929);6・783−90(1930)・ 39)YosioOLIANI:一TapanPatent163,898,May9,1944 40)鱒e押keSuガM叩A(toNihonY車KL K”):JapanいPatent163,14?,MaI申23?1944 41)−M山∼・叫‥JapanPatent163,841,Aprま115,1944 4亭)叫nazるYosIDA;杓γ¢忍α脚〃5γ〝如5,100−−−2(1950)・ 43)一・・・−−・一−−:撒d3,19−20(19亜) 44)T.丁・KLu‡,F pP■互1もK8R,ノA・FPoM鱒S,andNl・PoRGES:OjJ&5頑22,319−20(1945) 45)SabuI6SIBムーA:/・SocCカβ椚助成ルゆ紛ぃ郎,130−4,136−8(1941) 46)Ry6heiTAKADAandTosiomiNAGATA:ZγOZOgakuZassi(JlIndl、Fermentation)2l,803−10(1943) 47)‘、MasanobuMAT叩AMAandR・TAKA?‥丸‥花立−d小22・11∵T17(1944) 48)∴Zyuns阜n<YAMAYA(toAzま−nO−mOtOKIK)‥JapanlPatentlll・160,June17,1935 49仁一ーー一山山川欄一‥Tapan」P如ent。111,037,.ト出e7,1935 50)J−− 川−、:・Tapa王1Patent122,091,Oct・7・1937 51)KSucMUR.1(toNibonYusiK・K):一Tapan・Patent170,587,Oct20,1945 52)F” 4188鼻(1940)・
Volハ 隼,No・3(1955) 239
53)SeisiHtJRUXAWAandKen’itiODA(to NipponZinz6Hiry6Ⅸ.K.):Japan 7,302,Sept.15,1932.
54)『−:.Tap竿恥′率tぬ七叩4;7卑7,Jぬ25,土93≠こ 55)MasumiKANAI(toNihonY11SiK.K.):Japan..Pat占nt145,446,Sept,10,1941. 56)Su$umuKAZITURA,:物α烏%侮γ∂5如∂(Ma勧’ials矩工qh由n・Ind)・12,191−4(1939)・ 57)PlAlBELTE:R,AClBECKEL,andAKlSMITZI:bld.Eng.Chem.36,799−803(1944) 58)G・ElBABCOCKandA・K・SMITH:、即id.39,85十8(1947) 59)PLJuuANandElB・OziE℡G(toThe GliddenCo.):U,S.Patent2,281,584(1942) 60)′年毎ma?a耳鱒WそRA,SlSAXU苧ADA, J坤5, 61)軸ぬeiTAkふDA(toNagaokeh蜘zyo):Japチn∴pa七ent166,804,Au女こ25,\1944・ 62)Silmi品asaTAREDA(t6Sy痛よSangy6Kl.rK・):Jabad.PatentノAppl.5i50∴octl:26,i942 凝)Isad血石DA,/s−.iAMAGln門, 6勾M∴YosI占A:∨笹γ0点αγ占お写γ〟ゐ¢3,87−−90(1946)∵ 65)KinsukeKoND6and HirosiIwAMAE:Japねn.Pat色n七<124,203;、March22,∴19β8∴ 66)E」N.VoLKOV,P.q∴GRIGO準V,and′Ⅴ小GvLYAEV.:0タg.Chem,,hld.(U.$S小RJ)6;517−18(1939); C.A34,24909(1940). 67)E・WAH工・FORS亨(!oLTheGliddenCo・):U”S”P苧tent2,284,1700,June,.2,I942;〈C・4:36,LL67041(1942) 68)K・<匝AGA賢‡ァK・ⅩATAOXA,andT・ア阜平ADA(やMitu坤まⅩaseり野郎や革翠町)■‥Tapan・Pa平戸tユ68,274, 恥Ⅴ 69)q・D今ゃⅠ0長‥U∫S.Pat如2,464,075,MaIC8,194?;C.A…43,3663∂(1949). 70)S’:KA☆A㌫mi:StudiesnSOybedncarbohydi・ateS,IlSugar CoJJ4,65−71く1952)
71)∴:Do,ⅠⅠ,.The carbohydrate content of defatted soybeans.Zbid.5,1−14(1953)
72)一一:Db.血∴Seb如a吏i6h、ofhemicellulos占s.Ibid:てi90⊥8
73)÷−」L一:Dd.ⅠⅤ∴D3terhidationof・Oligo由cchaiid6sL:J,Agr・.Chem;Soc.7JtWan29;851r3(1954)
74) ト ,T小Kol)ayaS姑 孤4L.裾ma,a涙=肱.Mino:Do.Ⅴ.Isolationand some pIOpeIt亘e琴Of−botTWa吟r・一 甲Inbl寧bemicellplos?・助〃4許・Cカ禦・坤….拗α搾19,99(1弊5) 75)YositaI■6T冬草チ 76)KenziTsII,HhIwAMOrO,andSl一正AWAMURA:Theisoelectric′pOinf Of sQyb甲n・pモOtein?n 4㌢偉才.5cよ\JⅥ加朋と放払1,47−−53(1953) 77)AX.SMrTHand S.JCユRCLE:hd.物.Cあ♂m.38,1414−18(1938〉. 78)F小 Wけ MoI王1MAN:乃柑購,467(1952). 79)HⅥ「von LoESECKB:乃孟一正476−82小 80)H.R‖ MIJRDOCR:乃さd.507−13 81)BA.Sou川GATE:J∂左d524∬30
240 Tech.Bull.Xagawa Agr.Coll.