WO1981003181A1 - Conversion thermochimique de biomasse en ethanol - Google Patents

Conversion thermochimique de biomasse en ethanol Download PDF

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Publication number
WO1981003181A1
WO1981003181A1 PCT/US1981/000529 US8100529W WO8103181A1 WO 1981003181 A1 WO1981003181 A1 WO 1981003181A1 US 8100529 W US8100529 W US 8100529W WO 8103181 A1 WO8103181 A1 WO 8103181A1
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WO
WIPO (PCT)
Prior art keywords
metal
ethanol
salt
metallic
carbonate
Prior art date
Application number
PCT/US1981/000529
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English (en)
Inventor
M Hillman
E Lipinsky
W Huffman
E Stambaugh
Original Assignee
Battelle Development Corp
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 US06/144,190 external-priority patent/US4523928A/en
Application filed by Battelle Development Corp filed Critical Battelle Development Corp
Priority to AU71718/81A priority Critical patent/AU7171881A/en
Priority to BR8108575A priority patent/BR8108575A/pt
Publication of WO1981003181A1 publication Critical patent/WO1981003181A1/fr
Priority to FI814145A priority patent/FI814145L/fi

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
    • C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
    • C12C11/00—Fermentation processes for beer
    • C12C11/02—Pitching yeast

Definitions

  • the present invention relates to the synthesis of ethanol from biomass and, more particularly to such synthesis by a catalytic thermochemical process.
  • the present invention has solved the long standing problem of convertin biomass into ethanol by a process which does not involve fermentation. Als substantially all of the disadvantages inherent in conventional fermentation o biomass are obviated by the present invention.
  • the present invention is a method for therm ochemically converting a carbo hydrate material into ethanol.
  • Such method comprises establishing an aqueou reaction mixture of the carbohydrate and a metal salt in a reaction zone held a elevated temperature to form an intermediate metallic complex (eg. metalli sucrate) and/or a metallic laetate salt.
  • the metallic salt then is separated from th reaction mixture and pyrolyzed in a pyrolysis zone in the presence of water to for said ethanol.
  • Suitable carbohydrate materials are sacchariferous materials such a monosaccharides, polysaaccharides, and oligosaccharides.
  • Another aspect of th present invention involves the thermochemieal conversion of the carbohydrat material into ethanol " wherein the carbohydrate material, the metal salt, and wate are established in a reaction zone for the one-step conversion of the carbohydrat material into ethanol.
  • the metal of the metallic sal is restricted to a metal which when formed into the by-product metallic carbonate such carbonate will be decomposed in situ to generate a metallic oxide or hydroxide
  • a further aspect of the present invention is a method for making a liqui combustible fuel blend of combustible (fossil) fuel (eg.
  • gasoline-alcohol blend wherein the ethanol is made by the thermochemieal conversion of a carbohydrat material as described above and the product ethanol is blended with the combustibl fuel, eg. gasoline.
  • Advantages of the present invention include quick reaction times for convert ing carbohydrate feed into ethanol and specifically the ability to reduce the reactio time for making ethanol from 16-24 hours by conventional fermentation to a matte of minutes by the thermochemieal process of the present invention.
  • Anothe advantage of the present invention is the ability to efficiently and effectivel operate with impure carbohydrate feeds which cannot be tolerated by conventiona fermentation techniques.
  • a further advantage is the ability to convert man carbohydrate materials into ethanol which are unsuitable as feedstock for con ventional fermentation production of ethanol.
  • a still further advantage of th present invention is the probable volumetric reduction of by-products from th
  • thermochemically converting carbohydrate material feedstock into ethanol involves multiple chemical reaction steps which means flexibility in designing different operational modes for practicing the present invention. Though dominant chemical reactions can be attributed to the production of ethanol from carbohydrate feedstock, it should be recognized that competing reactions do occur during the process which often lead to by-products and lower yields of ethanol. In order to more fully appreciate the chemistry involved in the thermochemieal process of the present invention, the following postulated reactions for the process are given. It should be understood that such reactions are given for purposes of illustration only and are not to be interpreted as a limitation on the present invention. Such chemical reaction steps in the present process are as follows:
  • sucrose and calcium oxide feed materials is for purposes of illustrating the presen invention and is in no way a limitation on the present invention.
  • the calcium oxide catalyst is renewable product from the process which clearly provides certain economies t practice of the present invention.
  • the term "catalyst" to describe the metallic sal herein is used in the sense that there is no net consumption of the metallic salt i the process as the metallic salt is regenerable to its oxide or hydroxide form.
  • the present process possibly can be operated in step wise fashion (assuming the ability to isolate the various products of the individua reaction steps).
  • One of the clear advantages of the present invention is th discovery that by judicious selection of the reaction conditions prevailing in th process (for example, temperature, pressure, time, and the like), the present proces indeed can be operated in a distinct step-wise method following the chemica reactions outlined above.
  • the present process has the flexibility to b operated in various combinations of the reaction steps given above for additiona flexibility in operating the process efficiently and economically based upon availa bility of equipment, various carbohydrate feedstocks, various metal salts, and th like.
  • the present process can be optimized for various combinations o reactants and reaction conditions available to any operator of the process. Con ventional fermentation techniques for conversion of sugar to ethanol clearly do no have the choice of the various operational modes available to the present invention.
  • the individual chemical reaction steps involved in the process can be combine in several ways for the production of ethanol.
  • Various of these combinations provid distinct advantages over other combinations as will be readily apparent to thos skilled in this art.
  • the four chemical reaction steps can be operate individually, the first and second steps can be operated together, the first thre steps can be operated together and the like.
  • the fourth step will occur in situ under the reactio conditions prevailing in the process.
  • An advantage of isolating the metal carb hydrate complex from step (1) would be to reduce the volume of water typicall present in this step which would make ultimate separation of product ethanol fro
  • Suitable carbohydrate feedstock material for the present invention most often will be saecharides and often the term sugar will be used for their description.
  • Simple monosaeeharides for use in the present process include hexoses such as, for example, glucose, mannose, gallactose, gulose, formose, and fructose; pentoses such as, for example, arabinose, xylose, ribose, and rhamnose; tetroses such as, for example, erythrose and threose; and trioses such as, for example, glycerose.
  • saecharides such as, for example, gluconic acid, mono-, and di- phosphatates of fructose, etc.
  • conversion of pentose sugars by the preserft process will result in the production of one mole of a lactate salt and probably one mole of a glyeolate salt from reaction step (2).
  • the thermochemieal decomposition of such salts would yield one equivalent of ethanol and one equivalent of methanol which mixture would be suitable as a fuel ingredient.
  • the important consideration in the use of pentose sugars is that they will not poison the reaction which occurs with conventional fermentation processes because of the effect of by ⁇ product furfuraldehyde.
  • Additional carbohydrate feedstock include disaccharides such as, for example, sucrose, maltose, and the like.
  • suitable feedstock include polysaccharoses and oligosaccharides.
  • Such sugars can be derived from sugar crops such as sugar cane, sugar beets, or sweet sorghum; or by the partial or complete hydrolysis of starch or starch-like materials in grains such as corn, wheat, oats, and the like; or can be derived from other crops such as potatoes, yams, manioc, and the like.
  • Additional sugars suitable as feedstock for the present invention can be derived from lignoeellulosic materials such as agricultural and forestry residues or by-products such as, for example, corn stalks or corn cobs, sawdust and other forest residues, bagasse, cattle or other manure, leaves, newspaper from municipal waste, and the like.
  • Such agricultural and forestry residues preferably are hydrolyzed or at least partially hydrolylzed to sugars or oligosaccharides prior to their admission to the present process.
  • the present process also may utilize soluble polysaccharides
  • cr* such as, for example, soluble starch or polysaccharides that have been pretreated reduce the degree of crystallinity (e.g. amorphous cellulose).
  • Suitable catalysts for use in the present invention are those metal salts th can display a basic reaction in an acidic environment.
  • Preferable catalysts a oxides, hydroxides, and carbonates of alkali metals and alkaline earth metals.
  • alkali metals include lithium, sodium, potassium, rubidium, a cesium; and alkaline earth metals include beryllium, magnesium, calcium, strontiu and barium.
  • Additional catalysts useful in the present invention include salts amphoteric or transition metals such as salts of, for example, aluminum, zinc, lea barium, cadmium, magnesium, mercury, silver, cobalt, manganese, bismuth, galliu niobium, copper, iron, nickel, and the like, preferably provided as an oxid hydroxide, or carbonate.
  • Further suitable metallic salts include complex metall salts which contain one metal plus either a second metal or non-metal or oth anion.
  • Representative anions of such complex metallie salts can selected from the following: arsenate, chromate, ferricyanide, carbonate, silicat molybdate, (dibasic, tri-basic, pyro, meta, ortho) phosphate, plumbite, sulfat aluminate, bisulfite, (meta or tetra) borate, chlorate, chloraurate, chloroplatinat dithionate, manganate, nitrite, selenate (meta or ortho) silicate, stannate, sulfit tartrate, thiocyanate, thiosulfate, tungstate, vanadate, and the like.
  • metal oxides may be preferred for use in the process since metal oxides ca be generated from the process for recycle thereto.
  • selection of a metal whose carbonate decompos to metal oxide and carbon dioxide gas under the reaction conditions prevailing in th process may be desired for self-generating catalysts for the process.
  • met carbonates include, for example, magnesium carbonate, zinc carbonate, copp carbonate (possibly complexed with Cu(OH) mention), cadmium carbonate, mercuro carbonate, silver (I) carbonate, cobalt ( ⁇ ) carbonate, iron ( ⁇ ) carbonate, manganese carbonate, nickel carbonate, and lead carbonate, which can be decomposed at the pyrolysis temperatures of the process.
  • water is the preferred solvent of choice for use in the present process. It should be recognized, however, that excessive quantities of water in the reaction mixture may not be desirable because of later separation problems of product ethanol from water-ethanol mixtures. It, then, may be desirable to employ suitable organic solvents in the process to aid in subsequent purification efforts for recovery of the desired ethanol product. Such organic solvents preferably are water soluble though this is not necessary.
  • a particularly preferred organic solvent for use with water as a solvent system in the present invention is ethanol since ethanol is the product being made.
  • Reaction conditions for the present process include temperatures ranging from between about 150° to about 400°C. and above.
  • the actual temperatures employed in the process will depend necessarily upon which reaction steps are being run concurrently and upon the particular feedstock and metal salt employed in the process.
  • Preferred reaction temperatures for the overall process range from about 275 to 400 C. Since such elevated temperatures are required for the process, pressures preferably will be in the superatmospheric range especially when it is desired to retain the aqueous solvents in the process in the liquid phase. It should be recognized that atmospheric pressure and pressures slightly above atmospheric may find use in the present process. Preferable pressures range from about 500 to about 3,000 psig, though it may be convenient in running the process to maintain autogenous pressure. Again, the pressure used in the process will depend necessarily upon the other reaction conditions and reactants used in the process.
  • the process additionally may be conducted under an inert gas blanket or inert atmosphere especially when the process is conducted in several distinct stages.
  • inert gas atmosphere minimizes side reactions in the process.
  • Suitable inert or non-reactive gases in the process include, for example, nitrogen, carbon dioxide, propane, argon, and the like and even mixtures thereof.
  • the primary product of the present invention is ethanol though a variety other products and by-products normally will result from the process.
  • One su product is a metal carbonate which suitably is converted to additional metal oxi for use in the process.
  • Other products that may be produced by the process included for example, methanol and 2,4-dihydroxy-3-pentanone. It will be appreciated th the particular by-products resulting from the process will necessarily depend up particular reactants used in the process and especially the carbohydrate feedsto of choice, upon the particular reaction conditions maintained in the proces whether the process is run in distinct steps or as a one-step direct conversi ethanol process, and the like.
  • Such additional organic products produced by t process may be separated from the ethanol by fractionation techniques includi (molecular) distillation and crystallization, or can be left with the product ethan for use as a fuel additive or as a chemical feedstock for additional processing.
  • yields of t products resulting from the various reaction steps necessarily also depend upon t concentration of the reactants used as well as the other reaction conditions (e. tirtie, temperature, pressure, etc.).
  • the other reaction conditions e. tirtie, temperature, pressure, etc.
  • yields thereof depend upon the concentration of both t carbohydrate feedstock and the metal salt catalyst, as would be expected. Since t other reaction conditions established in the process (e.g. time, temperature, a pressure) appear to control the yields of products and by-products in the prese process to a greater extent than the particular ratio of reactants used, t proportion of reactants used in the process will be adjusted accordingly.
  • an ethanol product stream containing ethanol, carbon dioxide, water, and other volatile material can be vented from the freeboard space within the reactor continuously while the carbohydrate feedstock is fed to the reaction vessel continuously.
  • Metal carbonate product formed from the reaction can be removed as an underflow from the reaction vessel and sent to a combustion zone using coal, biomass, or other convenient fuel to regenerate metal oxide and carbon dioxide gas therefrom. The metal oxide then can be recycled to the reaction vessel on a continuous basis, if required.
  • the metal oxide will be regenerated in situ in the reactor so that at most only make-up metal salts should be required to be passed into the reaction zone. Separation of the ethanol from the ethanol product stream is practiced as described above.
  • a fixed bed of the catalyst metal salt can be maintained within a flow reaction vessel of suitable design (e.g., a tubular flow reactor) and an aqueous solution or dispersion of the carbohydrate material passed therethrough with the aqueous ethanol product stream withdrawn therefrom.
  • a flow reaction vessel of suitable design e.g., a tubular flow reactor
  • the carbohydrate feedstock and metallic salt can be fed to a reaction vessel such as described for the one-step process.
  • the reaction mixture can be conventionally cooled for precipitation of the salt therefrom.
  • Other methods for separation of the solid salt from the reaction mixture include evaporation or distillation of the aqueous phase therefrom.
  • Other conventional separation tech- niques additionally may be employed.
  • SUBSTITUTE ⁇ separation and recovery from water.
  • a metal lactate salt by t two-step process, such recovered salt can be pyrolyzed to product ethanol described above.
  • a metallic sucrate salt With separation and recovery of a metallic sucrate salt, such sa can be converted to product ethanol in a one-step process or can be converted to t metallic lactate salt which can be recovered and the recovered lactate sa pyrolyzed to product ethanol.
  • Possible optimization of yields of the vario intermediates may be realized by such distinct step-wise practice of the process well as a reduction of the proportion of water carried forward in the process.
  • the recovery of the intermediate metallic carbohydrate complex (eg. metalli sucrate salt) and metallic lactate salt separately may be termed a multi-ste process for production of ethanol according to the present invention.
  • the metalli lactate salt whether produced directly from the carbohydrate feedstock or pr Jerusalemd from the recovered metallic sucrate salt intermediate, can be pyrolyzed t ethanol utilizing a variety of equipment.
  • a fluidized bed of th concentrated metallic lactate salt, optionally containing inert solids or oth reactant solids (eg. metal salt catalyst) can be established utilizing a supporting g of carbon dioxide or the like preferably containing steam for providing the wate necessary or the pyrolysis reaction to occur as desired.
  • the ethanol product strea would be • vented from the reactor and sent to purification operations.
  • Soli withdrawn from the fluidized bed can include the metal carbonate product or met oxide, depending upon the particular metal utilized in the process and the particul pyrolysis conditions established in the fluidized bed reactor.
  • falling-bed type reactor also could be employed as well as could any oth convenient gas-solids reactor.
  • An aqueous sugar (sucrose) solution i fed to a tubular flow reactor maintained at about 250°C.
  • the residence time o the reactants in the tubular flow reactor is about 2 minutes.
  • the aqueous reactio mixture withdrawn from the tubular flow reactor is sent to a flash evaporator an preeipitator wherein water is flash-evaporated from the reaction mixture and th calcium lactate is precipitated therefrom.
  • the water may be recycled directly t the tubular flow reactor or can be used to form additional aqueous sugar feedstoc for the process.
  • the concentrated calcium lactate is sent to a fluidized pyrolysi
  • bagasse or other convenient fuel can be combusted in the kiln for converting the limestone into lime (calcium oxide) and carbon dioxide gas which is used to fluidize the solids in the fluidized pyrolysis bed.
  • the regenerated lime then can be sent back to the tubular flow reactor as indicated above.
  • a one gallon, stainless steel, Autoclave Engineers' magna drive autoclave was set up with both vapor phase and liquid phase sampling tubes.
  • the liquid phase dip tube was arranged so the line could be back-flushed with nitrogen.
  • sucrose table sugar
  • 118.6 grams of calcium hydroxide 118.6 grams
  • 580 ml of deionized water was placed between the liner and the autoclave.
  • the autoclave was purged twice with nitrogen and the pressure was returned to atmospheric.
  • the autoclave was heated, with stirring, for two hours to 300°C.
  • An 18.0 gram sample of tan liquid was then removed. This is referred to as the zero time sample.
  • the reac temperature was maintained at 300° 3°. Additional samples were taken at t following times (after zero time sample): 30 mins (13.7 gm), 1 hr (15.1 gm), 2 (15.1 g ), 3.5 hrs (17.8 g), 5 hrs (17.6 gm). A vapor sample (12.9 gm of condens liquid) was also removed at 5 hours. The heater and stirrer were shut off and t autoclave was allowed to cool down overnight. The residual slurry in the glass lin was 516 grams and an additional 157 grams of material was recovered from betwe the autoclave and glass liner. Also 15 grams of material was recovered by flushi the lines. The total material recovered was 798 grams compared to 935.6 gra charged.
  • Example 1 was charged 111 gms of sucrose (table sugar), 73 gms of calcium oxid and 405 ml of deionized water. The autoclave was pressure tested with nitrogen
  • Example 2 To the one liter autoclave described in Example 2 was charged 74 gms of sucrose, 70 gms of sodium hydroxide pellets, and 500 ml of deionized water. Oxygen then was introduced into the head space in the autoclave to a pressure of 400 psig. The reactor was heated to 267°C over a three hour time period. At this temperature the autoclave pressure was determined to be 1,000 psig. The autoclave was maintained at 267° + 5°C with stirring for an additional 95 minutes during which time the pressure in the autoclave dropped to about 725 psig. A total of 626 gms of liquid slurry was recovered from the reaction mixture which represents over 97% of the 644 gms of material initially charged to the reactor.
  • the slurry was filtered and the filtrate analyzed for ethanol by the gas chromatography technique described in connection with Example 1.
  • the filtrate was determined to contain 7.0 gms of ethanol.
  • ethanol represented 94.7% by weight of the volatile organic materials in the reaction product. Again, the chemistry of the reaction is demonstrated in this example.
  • Example 2 To the one liter autoclave described in Example 2 was charged 111 gms of sucrose, 106 gms of zinc oxide, and 405 ml of deionized water. The autoclave was sealed and pressure checked at 2,000 psig with nitrogen gas. After releasing the pressure to atmospheric, the reactor was heated to 300°C over a 70 minute time period, and then maintained at 300° + 2°C for 6 hours. After the autoclave had cooled to room temperature overnight, there was a residual pressure in the
  • OMPI autoclave 400 psig. This pressure is due to carbon dioxide gas being released the decomposition of zinc carbonate under the reaction conditions. Note that Examples 1 and 2 the pressure in the reactor upon its cooling was not abo atmospheric pressure which is consistent with the formation of calcium carbonate the reaction which is not decomposable under the reaction conditions. Also, ther was no increase in the autoclave pressure in Example 3 following termination of t reaction which again is consistent with the formation of by-product sodiu carbonate which is not decomposable under the reaction conditions.
  • the one liter autoclave described above was charged with 115 gms of solubl starch, 93 gms of cuprous, oxide, and 405 ml of water.
  • the autoclave was pressur tested and then heated to the reaction temperature used in Example 4. After th autoclave was cooled to room temperature overnight, there was a residual pressur of 275 psig therein due to carbon dioxide gas in the autoclave. This carbon dioxid gas is produced by the decomposition of cuprous carbonate which is formed in th reaction to regenerate the cuprous oxide catalyst.
  • the liquid slurry was recovere from the autoclave and determined to weigh 568 gms.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

Procede de conversion thermochimique d'un materiau d'hydrate de carbone en ethanol dans lequel le materiau d'hydrate de carbone et un sel reagissent ensemble a une temperature elevee pour former un sel complexe intermediaire d'hydrate de carbone et/ou un sel metallique de lactate qui est ensuite pyrolise en presence d'eau dans l'ethanol. Des materiaux preferes d'hydrate de carbone pour ce procede sont des types differents de sucres et le sel metallique est de preference un oxyde, un hydroxyde ou un carbonate metallique. Le complexe intermediaire et/ou le sel de lactate peut etre separe de son melange de reaction aqueuse avant sa pyrolyse afin de reduire la separation definitive de l'ethanol de l'eau. Alternativement, le metal du sel metallique peut etre du type qui est decompose par son carbonate en oxyde metallique et acide carbonique pendant l'etape de pyrolyse du procede de maniere a produire ce sel metallique in situ.
PCT/US1981/000529 1980-04-28 1981-04-23 Conversion thermochimique de biomasse en ethanol WO1981003181A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU71718/81A AU7171881A (en) 1980-04-28 1981-04-23 Thermochemical conversion of biomass to ethanol
BR8108575A BR8108575A (pt) 1980-04-28 1981-04-23 Conversao termoquimica de biomassa para etanol
FI814145A FI814145L (fi) 1980-04-28 1981-12-23 Termokemisk omvandling av biomass till etanol

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US14419480A 1980-04-28 1980-04-28
US14418980A 1980-04-28 1980-04-28
US144194 1980-04-28
US06/144,190 US4523928A (en) 1980-04-28 1980-04-28 Gasohol production from thermochemical conversion of biomass to ethanol

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WO1981003181A1 true WO1981003181A1 (fr) 1981-11-12

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EP (1) EP0050653A4 (fr)
JP (1) JPS57500610A (fr)
BR (1) BR8108575A (fr)
IL (1) IL62733A0 (fr)
WO (1) WO1981003181A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2742018A1 (fr) * 2011-08-12 2014-06-18 University College Cardiff Consultants Limited Procédé de fabrication d'alcools
RU2691660C1 (ru) * 2018-11-26 2019-06-17 федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский горный университет" Способ извлечения концентратов металлов из нефти

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1527504A (en) * 1918-06-25 1925-02-24 Us Ind Alcohol Co Aeroplane motor fuel
US1578201A (en) * 1920-02-28 1926-03-23 Gen Motors Corp Fuel
US2024565A (en) * 1931-10-29 1935-12-17 Standard Brands Inc Process for the production of lactic acid
US2177557A (en) * 1937-02-24 1939-10-24 Method of treating wood or lignine
US2382889A (en) * 1941-07-22 1945-08-14 Lock Ritchie Hart Manufacture of lactic acid and salts thereof
US2989569A (en) * 1955-02-04 1961-06-20 Udic Sa Conversion of wood sugars to polyols

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1527504A (en) * 1918-06-25 1925-02-24 Us Ind Alcohol Co Aeroplane motor fuel
US1578201A (en) * 1920-02-28 1926-03-23 Gen Motors Corp Fuel
US2024565A (en) * 1931-10-29 1935-12-17 Standard Brands Inc Process for the production of lactic acid
US2177557A (en) * 1937-02-24 1939-10-24 Method of treating wood or lignine
US2382889A (en) * 1941-07-22 1945-08-14 Lock Ritchie Hart Manufacture of lactic acid and salts thereof
US2989569A (en) * 1955-02-04 1961-06-20 Udic Sa Conversion of wood sugars to polyols

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Nouv. Ser. T. XLV, Societe Chimique, pp. 79-81, (1886), HANRIOT, "Sur la Decomposition Pyrogenee des Acides de la Serie Grasse". *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2742018A1 (fr) * 2011-08-12 2014-06-18 University College Cardiff Consultants Limited Procédé de fabrication d'alcools
US9108896B2 (en) 2011-08-12 2015-08-18 University College Cardiff Consultants Limited Method of making alcohols
RU2691660C1 (ru) * 2018-11-26 2019-06-17 федеральное государственное бюджетное образовательное учреждение высшего образования "Санкт-Петербургский горный университет" Способ извлечения концентратов металлов из нефти

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EP0050653A4 (fr) 1982-08-11
BR8108575A (pt) 1982-04-06
JPS57500610A (fr) 1982-04-08
EP0050653A1 (fr) 1982-05-05
IL62733A0 (en) 1981-06-29

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