EP0074983B1 - Sehr effektives verzuckerungsverfahren unter verwendung organischer lösungsmittel - Google Patents

Sehr effektives verzuckerungsverfahren unter verwendung organischer lösungsmittel Download PDF

Info

Publication number
EP0074983B1
EP0074983B1 EP19820900956 EP82900956A EP0074983B1 EP 0074983 B1 EP0074983 B1 EP 0074983B1 EP 19820900956 EP19820900956 EP 19820900956 EP 82900956 A EP82900956 A EP 82900956A EP 0074983 B1 EP0074983 B1 EP 0074983B1
Authority
EP
European Patent Office
Prior art keywords
acetone
sugars
hydrolysis
sugar
liquor
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP19820900956
Other languages
English (en)
French (fr)
Other versions
EP0074983A1 (de
Inventor
Laszlo Paszner
Pei-Ching Chang
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bau und Forschungsgesellschaft Thermoform AG
Original Assignee
Bau und Forschungsgesellschaft Thermoform AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US06/248,023 external-priority patent/US4409032A/en
Priority claimed from CA000395820A external-priority patent/CA1201115A/en
Application filed by Bau und Forschungsgesellschaft Thermoform AG filed Critical Bau und Forschungsgesellschaft Thermoform AG
Priority to AT82900956T priority Critical patent/ATE23364T1/de
Publication of EP0074983A1 publication Critical patent/EP0074983A1/de
Application granted granted Critical
Publication of EP0074983B1 publication Critical patent/EP0074983B1/de
Expired legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials

Definitions

  • the invention relates to a process for the production of sugars from particulate cellulose material by treating the material in a pressure vessel with a mixture of acetone and water containing a small amount of an acidic compound at elevated temperatures.
  • GB-A-416416 describes the recovery of cellulose by the extraction of lignin from a lignocellulose material with acetone or a mixture of acetone and water.
  • acetone in volume concentrations in water of greater than 70% with a catalytic amount of an acid greatly accelerates the hydrolysis rates of cellulosic materials at elevated temperatures by sugar-acetone-complex formation.
  • acetone complexes are found to hydrolyse roughly 500 times faster than the alkyl glucosides and polyglucan described in the prior art.
  • Further benefit of the acetone-sugar-complexes is their facile separation into individual sugar species based on such simple processes as volatilization, selective hydrolysis and liquid-liquid extraction. Complex formation of monomeric sugars in anhydrous acetone in the presence of mineral acids at room temperature is described in Methods in Carbohydrate Chemistry, Vol. II, pp. 318.
  • cellulosic material includes materials of vegetable and woody origin, i.e. cellulose and lignocellulose materials.
  • reaction vessels with inert linings are used to eliminate the sugar degradation catalyzing effects of transition metal ions such as Ni, Co, Cr, Fe and Cu which may be components of metallic vessel walls, tubing and other control elements with which the hot liquor comes into contact.
  • transition metal ions such as Ni, Co, Cr, Fe and Cu which may be components of metallic vessel walls, tubing and other control elements with which the hot liquor comes into contact.
  • the temperature of the reaction mixture be rapidly lowered to under 100°C to avoid unwanted degradation of the sugars. This is best accomplished by controlled flashing-off of the volatiles since sugar degradation was found to be insignificant below the boiling point of water even in the presence of dilute acids.
  • the cooling of the liquor can be continued to ambient temperatures or less (25°C) before fermentation or further processing.
  • the liquor-to-wood ratio can be kept constant at 10:1 as by necessity successive additions both wood and liquor will carry hydrolyzates of the residuals already within the reactor.
  • This also establishes sugar concentrations to' be in the order of 37 to 40% following flash evaporation of the volatiles.
  • Such high sugar solids concentrations were hitherto possible only with strong acid hydrolysis systems but not with dilute acid hydrolysis.
  • liquor to wood ratio is extremely important in organosolv and acid hydrolysis processes since it directly relates to energy inputs during the hydrolysis and solvent recovery as well as during alcohol recovery from the resulting aqueous solution following fermentation of the sugars to ethanol or other organic solvents.
  • liquor to wood ratio will have a profound effect on the economics of biomass conversion to liquid chemicals as well as the energy efficiency (energy gained over energy expanded in conversion) of the process.
  • Saccharification power and sugar survival were compared for three competitive systems namely: acidified water (aqueous weak acid), acidified aqueous ethanol and acidified aqueous acetone in the following example.
  • the combined filtrates were diluted to 100 ml with water and a half milliliter aliquot was placed in a test tube with 3 ml of 2.0 Normal sulfuric acid added and subjected to a secondary hydrolysis at 100°C by heating in a boiling water bath for 40 minutes.
  • the solution was neutralized on cooling and the sugars present in the solution were determined by their reducing power.
  • the results were thus uniform based essentially on the resultant monosaccharides liberated during the hydrolysis process.
  • Theoretical percentage of reducing sugars available after the hydrolysis of the substrate was determined by difference between the known chemical composition of the starting material and the weight loss incurred due to the hydrolysis.
  • Solid residues less than 50% in yield show high degree of crystallinity (87%) and are pure white, have a DP (degree of polymerization) of 130 to 350.
  • the invention allows facile segregation and nearly quantitative isolation of the five major wood sugars, if so desired.
  • the mixed nature of the sugar derivatives in aqueous hydrolyzates if such thorough and detailed separation is desired, it is always necessary to neutralize the recovered aqueous sugar wort after removal of the volatiles and concentrate the wort to a syrup.
  • the syrup is then redissolved in anhydrous acetone containing 3 percent acid, allowed to stand at least 6 hr until all sugars formed their respective di-acetone complexes before attempting the detailed separation as described below.
  • the separated sugar complexes are readily hydrolyzed in dilute acid on boiling at least 20 to 40 minutes.
  • the combined filtrate (127 ml) was neutralized and subjected to steam distillation in an all glass apparatus and approximately 35 ml distillate was collected. Both the distillate and residual solution were made up to 100 ml and 0.5 ml portions of each were acidified with sulfuric acid to 3 percent acid and boiled for 40 min on a water bath. The solutions were neutralized and the sugar reducing power determined by the Somogyi method. The yield of sugars was 1.89 g in the distillate and 1.96 g from the residual liquor.
  • Hydrolysate No. 3 contained only traces of lignin after evaporation of the acetone solvent too small to collect and determine gravimetrically. It was removed by centrifuging. The aqueous residue (97 ml) was acidified to 3 percent acid with sulfuric acid, boiled for 40 min and after neutralization filtered and made up to 100 ml. The reducing sugar content of the filtrate was determined by the Somogyi method to be 1.83 g. GC analysis of the alditol acetates determined on an aliquot sample indicated mainly glucose with traces of mannose and galactose.
  • Hydrolysate No. 4 and 5 were processed and analyzed in the same manner as No. 3. H-4 yielded 1.73 g reducing sugars and H-5 yielded 1.40 g sugars both being composed only of glucose as evidenced by GC analysis of an aliquot sample.
  • Example VI In a similar hydrolysis arrangement to Example VI 10 g OD Douglas-fir sawdust (to pass a 10 mesh screen), pre-extracted with dichloromethane and air dried to 8 percent moisture content in a controlled humidity room, was hydrolyzed with 80:20 acetone:water solvent containing 0.05 Normal Hydrochloric acid in five consecutive steps. Each reaction step consisted of three minutes at a reaction temperature of 200°C. The heating up time was 7 minutes. Again Hydrolysate No. 1 and 2 were combined whereas the subsequent fractions were analyzed separately.
  • the combined liquor of H-1 and H-2 yielded 2.39 g lignin on low temperature evaporation of the volatiles and 135 ml of aqueous liquor was collected on filtration of the powdered lignin.
  • the dried lignin had a weight average molecular weight of 3200.
  • the filtrate was neutralized to pH 8 and subjected to steam distillation in all glass apparatus.
  • the 28 ml distillate which was collected contained 0.62 g pentoses which after passing the filtrate through a cation exchange resin in the acid form and repeated steam distillation of the filtrate yielded 0.58 g xylose as determined by GC analysis.
  • the ethanol-petroleum ether solution was extracted with 5 ml portions of water and the collected aqueous layer combined with the syrup removed from the crystalline product above.
  • the solution was briefly heated to expel the alcohol, made up to 3 percent acid with hydrochloric acid, boiled for 40 min, neutralized with silver carbonate and alditol acetates were prepared for GC analysis.
  • the combined syrup and filtrate contained a total of 58 g sugars of which 0.29 g was galactose, 0.25 g was glucose and 0.04 g was mannose.
  • Hydrolysate No. 4 gave 1.66 g of pure glucose with only very small traces of lignin, whereas H-5 gave 1.85 g of glucose and no lignin. The undissolved residue was 0.18 g and was composed of 99 percent glucose.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • Organic Chemistry (AREA)
  • Saccharide Compounds (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (4)

1. Verfahren zur Gewinnung von Zuckern aus feinteiligem cellulosischem Material durch Behandeln des Materials in einem Druckbehälter mit einer Kochflüssigkeit, die aus Aceton und Wasser besteht und eine saure Verbindung in einer Konzentration von 0.001 bis 0.1 N enthält, bei einer Temperatur von 145 bis 230°C, wobei
a) das Gemisch von Aceton und Wasser eine Acetonkonzentration von über 70 Volum-% hat,
b) die Kochflüssigkeit und das feinteilige Cellulosematerial mit einer solchen Geschwindigkeit in den Druckbehälter eingebracht wird, daß die Zeit, die zwischen Beschickung und Austritt der Produkte verstreicht, die gemäß vorheriger Bestimmung für die Hydrolyse von 50% der Feststoffe erforderlich ist, nicht übersteigt,
c) die Produktlösung rasch auf unter 100°C gekühlt wird, um den Abbau der Zucker zu verhindern, so daß wenigstens 90% der gelösten Zucker gewonnen werden.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das cellulosische Material lignocellulosisches Material ist und die Produktlösung durch Entspannungsabdampfen des Acetons aus der Lösung von Zuckern und Lignin rasch auf 50°C gekühlt wird, um das Lignin auszufällen.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, daß das Gemisch von Wasser und Aceton ein Acetonkonzentration von 80 bis 90 Volum-% hat.
4. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß das Verhältnis Flüssigkeit zu cellulosischem oder lignocellulosischem Material 7:1 bis 10:1 beträgt.
EP19820900956 1981-03-26 1982-03-26 Sehr effektives verzuckerungsverfahren unter verwendung organischer lösungsmittel Expired EP0074983B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82900956T ATE23364T1 (de) 1981-03-26 1982-03-26 Sehr effektives verzuckerungsverfahren unter verwendung organischer loesungsmittel.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US06/248,023 US4409032A (en) 1977-08-31 1981-03-26 Organosolv delignification and saccharification process for lignocellulosic plant materials
CA000395820A CA1201115A (en) 1981-03-26 1982-02-09 High efficiency organosolv saccharification process
CA395820 1982-02-09
US248023 1994-05-24

Publications (2)

Publication Number Publication Date
EP0074983A1 EP0074983A1 (de) 1983-03-30
EP0074983B1 true EP0074983B1 (de) 1986-11-05

Family

ID=25669563

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19820900956 Expired EP0074983B1 (de) 1981-03-26 1982-03-26 Sehr effektives verzuckerungsverfahren unter verwendung organischer lösungsmittel

Country Status (6)

Country Link
EP (1) EP0074983B1 (de)
JP (1) JPH0785720B2 (de)
AR (1) AR227462A1 (de)
BR (1) BR8207243A (de)
DE (1) DE3274120D1 (de)
WO (1) WO1982003409A1 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
HU197774B (en) * 1983-02-16 1989-05-29 Laszlo Paszner Organic solvent process for the hydrolytic saccharification of vegetable materials of starch type
BR9600672A (pt) * 1996-03-08 1997-12-30 Dedini S A Administracao E Par Processo de hidrólise ácido de material lignocelulósico e reator de hidrólise
BRPI0505212A (pt) * 2005-11-01 2007-08-07 Dedini Sa Ind De Base aperfeiçoamentos em processo de hidrólise ácida rápida de material lignocelulósico e em reator de hidrólise
WO2008050740A1 (fr) * 2006-10-26 2008-05-02 Kawasaki Plant Systems Kabushiki Kaisha Procédé de saccharification/décomposition d'une biomasse à base de cellulose et dispositif de saccharification/décomposition
CN101711263B (zh) * 2007-05-31 2012-11-28 丽格诺新创有限公司 对木质纤维给料的连续逆流有机溶剂处理
JP2010081917A (ja) * 2008-10-02 2010-04-15 Toyota Motor Corp バイオマスの処理方法、及び有機酸又はアルコールの製造方法
WO2012097781A1 (de) * 2010-11-25 2012-07-26 Studiengesellschaft Kohle Mbh Verfahren zur säurekatalysierten depolymerisation von cellulose

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB416549A (en) * 1933-03-07 1934-09-07 Henry Dreyfus Improvements in the manufacture of cellulose and lignocellulosic materials
CH202534A (de) * 1937-05-27 1939-01-31 F Reemtsma Philipp Verfahren zur Herstellung eines nicht zur Ernährung von Meschen oder Tieren bestimmten zuckerhaltigen Produktes durch Aufschliessen cellulosehaltiger Massen mittels Halogenwasserstoff in Gegenwart eines flüssigen organischen Lösungsmittels für letzteren.
DE2737118A1 (de) * 1977-08-17 1979-03-01 Projektierung Chem Verfahrenst Verfahren zur gewinnung von zuckern, gegebenenfalls cellulose und gegebenenfalls lignin aus lignocellulosischen pflanzlichen rohstoffen
JPS5526279A (en) * 1978-08-11 1980-02-25 Paszner Laszlo Treatment of lignocellulose containing substance
CA1150012A (en) * 1980-07-25 1983-07-19 Pei-Ching Chang Aqueous catalysed solvent pulping of lignocellulose

Also Published As

Publication number Publication date
AR227462A1 (es) 1982-10-29
JPH0785720B2 (ja) 1995-09-20
JPS58500431A (ja) 1983-03-24
BR8207243A (pt) 1983-03-01
WO1982003409A1 (en) 1982-10-14
DE3274120D1 (en) 1986-12-11
EP0074983A1 (de) 1983-03-30

Similar Documents

Publication Publication Date Title
US4470851A (en) High efficiency organosolv saccharification process
AU579094B2 (en) Improved organosolv process for hydrolytic decomposition of lignocellulosic and starch materials
US5395455A (en) Process for the production of anhydrosugars from lignin and cellulose containing biomass by pyrolysis
US5730837A (en) Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars
US3212933A (en) Hydrolysis of lignocellulose materials with solvent extraction of the hydrolysate
SU1194282A3 (ru) Способ разложени лигноцеллюлозного материала
Dominguez et al. Dilute acid hemicellulose hydrolysates from corn cobs for xylitol production by yeast
EP0824616B1 (de) Verfahren zur schnellen säurehydrolyse eines lignocellulosischen materials und hydrolysereaktor
US4160695A (en) Process for the production of glucose from cellulose-containing vegetable raw materials
US5125977A (en) Two-stage dilute acid prehydrolysis of biomass
SE440086B (sv) Forfarande for utvinning av sockerarter, lignin och ev cellulosa ur lignocellulosahaltigt vegetabiliskt material
US2959500A (en) Process for the saccharification of cellulose and cellulosic materials
CA1105457A (en) Process for the winning of xylose by hydrolysis of residues of annuals
JP2010531215A (ja) バイオマス成分の分離プロセス
NO312070B1 (no) Fremgangsmåte ved en prosess for fremstilling av gj¶rbart sukker fra celluloseholdige råstoffer
US3479248A (en) Process for solubilizing the hemicellulose of vegetable materials and for recovering the sugars from the solubilized hemicellulose
GB1582479A (en) Process for the production of xylan
US3065263A (en) Process for the manufacture of levulinic acid
WO1982003409A1 (en) High efficiency organosolv saccharification process
SU1701115A3 (ru) Способ получени сахаров из целлюлозосодержащего материала
BR102022005698A2 (pt) Processo para tratamento de biomassa lignocelulósica
CA1201115A (en) High efficiency organosolv saccharification process
US4916242A (en) Combined process for thermally and chemically treating lignocellulose-containing biomass and for producing furfural
EP0096497B1 (de) Auflösen und Hydrolysieren von Cellulosehaltigen Materialien
EP3822407B1 (de) Verfahren zur herstellung von bioprodukten aus lignocellulosischem material

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Designated state(s): AT BE CH DE FR GB LI NL SE

17P Request for examination filed

Effective date: 19830317

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR GB LI NL SE

REF Corresponds to:

Ref document number: 23364

Country of ref document: AT

Date of ref document: 19861115

Kind code of ref document: T

REF Corresponds to:

Ref document number: 3274120

Country of ref document: DE

Date of ref document: 19861211

ET Fr: translation filed
PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
EAL Se: european patent in force in sweden

Ref document number: 82900956.2

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19950925

Year of fee payment: 14

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19951130

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19960326

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19960326

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19961203

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19980925

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19980928

Year of fee payment: 17

Ref country code: CH

Payment date: 19980928

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19980930

Year of fee payment: 17

Ref country code: AT

Payment date: 19980930

Year of fee payment: 17

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990326

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990327

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990331

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990331

BERE Be: lapsed

Owner name: BAU- UND FORSCHUNGSG- THERMOFORM A.G.

Effective date: 19990331

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19991011

Year of fee payment: 19

EUG Se: european patent has lapsed

Ref document number: 82900956.2

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19991130

EUG Se: european patent has lapsed

Ref document number: 82900956.2

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011001

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20011001