US20130219776A1 - Process for the manufacture of butanol or acetone - Google Patents

Process for the manufacture of butanol or acetone Download PDF

Info

Publication number
US20130219776A1
US20130219776A1 US13/806,248 US201113806248A US2013219776A1 US 20130219776 A1 US20130219776 A1 US 20130219776A1 US 201113806248 A US201113806248 A US 201113806248A US 2013219776 A1 US2013219776 A1 US 2013219776A1
Authority
US
United States
Prior art keywords
substrate
draff
butanol
acetone
treating
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.)
Abandoned
Application number
US13/806,248
Other languages
English (en)
Inventor
Jane Samantha White
Kenneth Alexander Leiper
Martin Tangney
Sandra Messenger
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.)
CELTIC RENEWABLES Ltd
Edinburgh Napier University
Original Assignee
Individual
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
Application filed by Individual filed Critical Individual
Assigned to CELTIC RENEWABLES LIMITED reassignment CELTIC RENEWABLES LIMITED NUNC PRO TUNC ASSIGNMENT (SEE DOCUMENT FOR DETAILS). Assignors: THE COURT OF EDINBURGH NAPIER UNIVERSITY
Publication of US20130219776A1 publication Critical patent/US20130219776A1/en
Assigned to THE COURT OF EDINBURGH NAPIER UNIVERSITY reassignment THE COURT OF EDINBURGH NAPIER UNIVERSITY NUNC PRO TUNC ASSIGNMENT (SEE DOCUMENT FOR DETAILS). Assignors: WHITE, JANE SAMANTHA, MESSENGER, SANDRA, LEIPER, KENNETH ALEXANDER, TANGNEY, MARTIN
Abandoned legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/24—Preparation of oxygen-containing organic compounds containing a carbonyl group
    • C12P7/26—Ketones
    • C12P7/28—Acetone-containing products
    • C12P7/36—Acetone-containing products produced from substrate containing grain or cereal material
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/02—Monohydroxylic acyclic alcohols
    • C07C31/12—Monohydroxylic acyclic alcohols containing four carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C08B1/003—Preparation of cellulose solutions, i.e. dopes, with different possible solvents, e.g. ionic liquids
    • 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
    • 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
    • C10L1/023—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12F—RECOVERY OF BY-PRODUCTS OF FERMENTED SOLUTIONS; DENATURED ALCOHOL; PREPARATION THEREOF
    • C12F3/00—Recovery of by-products
    • C12F3/06—Recovery of by-products from beer and wine
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12F—RECOVERY OF BY-PRODUCTS OF FERMENTED SOLUTIONS; DENATURED ALCOHOL; PREPARATION THEREOF
    • C12F3/00—Recovery of by-products
    • C12F3/10—Recovery of by-products from distillery slops
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/16—Butanols
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/24—Preparation of oxygen-containing organic compounds containing a carbonyl group
    • C12P7/26—Ketones
    • C12P7/28—Acetone-containing products
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/24—Preparation of oxygen-containing organic compounds containing a carbonyl group
    • C12P7/26—Ketones
    • C12P7/28—Acetone-containing products
    • C12P7/34—Acetone-containing products produced from substrate containing protein as nitrogen source
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1011—Biomass
    • C10G2300/1014—Biomass of vegetal origin
    • 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
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/26—Composting, fermenting or anaerobic digestion fuel components or materials from which fuels are prepared
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a process for the manufacture of biofuels and renewable chemicals. More particularly, the invention relates to a process for the manufacture of butanol. The invention further relates to a process for the manufacture of acetone.
  • Biobutanol is produced by fermentation of biomass using bacteria, typically of the genus Clostridium. In addition to butanol, these organisms also produce acetone, which is an important solvent, and ethanol so the process is often referred to as “ABE process” (Acetone/Butanol/Ethanol process).
  • feedstocks or substrates include energy crops, such as sugar beets, sugar cane, corn grain and wheat, as well as agricultural by-products, such as straw and corn stalks.
  • biobutanol as a fuel has several advantages over the use of ethanol. However, as biobutanol production is currently more expensive than ethanol production it has not been commercialized on a large scale.
  • Malt whisky refers to whisky which has been produced from no grain other than malted barley. Production of malt whisky begins with malting of barley by steeping the barley in water. Malting releases enzymes that break down starches in the grain and convert them into sugars. When the desired state of germination is reached, the malted barley is dried. The dried malted barley is mashed in a mash-tun. In mashing, the enzymes that were developed during the malting process are allowed to convert or hydrolyse the barley starch into sugar. The resulting liquid which contains the sugars is referred to as wort. This is transferred to a large vessel called a washback where it is cooled and allowed to ferment to form the “wash”. The residue remaining after extraction of the soluble sugars or wort is known as draff. This comprises spent barley solids or spent grains.
  • the wash is distilled in a copper distillation vessel or pot still known as a wash still to produce an alcohol-containing liquid distillate, known as low wines.
  • the distillation residue or liquor remaining in the pot still after the first distillation of spirit is known as pot ale or burnt ale.
  • the low wines are distilled for a second and sometimes a third time in spirit stills to produce raw spirit, which is matured in oak casks to produce malt whisky.
  • the remaining liquor in the second and subsequent distillations is called spent lees.
  • the by-products of the manufacture of malt whisky therefore comprise draff, pot ale and spent lees.
  • Draff contains the non-starch components of the original barley and generally represents about twenty five percent of the total malted barley added to the mash-tun. It is rich in digestible fibre and also contains concentrated protein and oil from the malted barley. It is palatable to all types of ruminant stock.
  • Pot ale has low total solids content and contains dead yeast cells, yeast residue, soluble protein, soluble nutrients, carbohydrates and other material from the fermentation and mashing steps. It can also contain a significant amount of copper from the stills themselves. Pot ale is rich in nutrients and may be used as a feed for most ruminant stock. However, due to its high copper content, it is not suitable for sheep. Draff and pot ale are currently categorised as being of low economic value.
  • the inventors of the present application have developed a process for the manufacture of butanol, acetone and/or other renewable chemicals which utilises low economic value by-products of the manufacture of malt whisky, such as draff, pot ale and/or spent lees.
  • a process for the manufacture of butanol and/or acetone comprising at least the steps of:
  • the invention extends to the use of diluents other than pot ale, such as water, spent lees and spent liquid from other fermentations.
  • the diluent is selected from the group consisting of pot ale, water, spent lees and spent liquid from other fermentations, or a combination thereof.
  • the diluent may be water.
  • biomass substrates include, but are not limited to, municipal waste, industrial biological waste, agricultural crops and crop residues, wood and forestry waste, marine biomass and bio-energy crops.
  • Specific examples include paper, sludge from paper manufacture, spent grains such as those derived from distillers and brewers, fruit and vegetable waste, waste from the baking industry, seaweed and seaweed extracts, wood chip and other forestry derivatives, food crops, such as grain and crop residues, chocolate, algae (macro and micro algae), non-edible crops (and residues) and energy crops, such as switchgrass.
  • a process for the manufacture of butanol and/or acetone comprising at least the steps of:
  • the substrate is paper, such as waste paper.
  • the diluent may be selected from the group consisting of pot ale, water, spent lees and spent liquid from other fermentations, or a combination thereof.
  • the diluent may be pot ale.
  • a process for the manufacture of butanol and/or acetone comprising at least the steps of:
  • the substrate is paper, such as waste paper.
  • a biofuel comprising butanol and/or acetone manufactured according to the process of any of the aspects of the present invention.
  • the one or more by-products of the production of malt whisky comprise draff, pot ale and/or spent lees.
  • Certain embodiments of the present invention utilise draff, pot ale, spent lees and/or other biomass substrates, such as waste paper.
  • the present inventors have surprisingly discovered that it is possible to carry out fermentation in the presence of pot ale. It was expected that the high copper content in the pot ale from the copper pot stills would inhibit butanol- and/or acetone-forming micro-organisms, such as bacteria of the genus Clostridium.
  • the present inventors have shown that when the substrate is diluted to lower the concentration of free copper ions to below 20 ⁇ M, there is no inhibitory effect.
  • pot ale in the manufacture of butanol, acetone and/or other renewable chemicals has several associated advantages. Pot ale is currently categorised as being of low economic value. The use of pot ale in the present invention allows the economic value of pot ale to be increased. Furthermore, the pot ale acts as a solvent to dissolve the substrate. Thus, the amount of water or other diluent required is reduced when pot ale is used. In addition, pot ale provides essential nutrients to the microorganisms improving the fermentation and overall conversion of substrate to products.
  • Draff in particular, is currently categorised as being of low economic value.
  • the draff, pot ale and/or spent lees are by-products of the manufacture of malt whisky.
  • the use of these by-products in the present invention thus allows low economic value by-products to be recycled and offers a unique solution to the disposal of these by-products of malt whisky production.
  • the present invention utilises biomass substrates, such as paper, and in particular waste paper.
  • biomass substrates such as paper, and in particular waste paper.
  • the present invention therefore further provides a solution to the disposal of waste paper, for example, old newspapers or used photocopier paper.
  • the substrate must be treated to hydrolyse it, thus breaking down the substrate into a form suitable for fermentation. Accordingly, in certain embodiments the substrate is subjected to one or more treatment steps to hydrolyse it, for example, mashing, heating, addition of acid or alkali, addition of enzymes or a combination thereof.
  • the treating of the substrate to hydrolyse it comprises the step of hydrolysing the substrate in the presence of water and hydrogen ions or water and hydroxide ions.
  • the treating of the substrate to hydrolyse it is carried out in the presence of any suitable acid which is capable of hydrolysing the substrate. Examples of suitable acids include sulphuric acid and nitric acid.
  • Sulphuric acid is a preferred example of an acid for use in the present invention.
  • the treating of the substrate to hydrolyse it comprises addition of one or more enzymes, such as cellulase and hemicellulase.
  • a combination of treatments may be utilised, for example, addition of both acid and enzymes, to provide a treated substrate in a form suitable for fermentation. The combination of treatments may be applied simultaneously or sequentially.
  • the treatment may comprise addition of enzymes.
  • the treatment may comprise addition of acid and enzymes.
  • Fermentation of the treated substrate is carried out at an initial pH in the range of 5.0 to 6.0, preferably in the range of 5.3 to 5.7 and more preferably at 5.5.
  • the use of this pH range has been shown to provide high yields of butanol and/or acetone. Furthermore, this pH range allows fermentation to be carried out without the need to remove solids therefrom, thus reducing costs and avoiding any technical problems caused by the requirement to remove solids. This pH range prevents any potential toxicity from the treated substrate while maximising butanol and/or acetone production.
  • Fermentation is carried out in the presence of a culture of butanol- and/or acetone-forming micro-organisms.
  • the butanol- and/or acetone-forming micro-organisms may be selected from any solvent producing micro-organisms which are capable of fermenting the substrate to form butanol and/or acetone.
  • Suitable micro-organisms include micro-organisms engineered to produce solvents. Examples of suitable micro-organisms include those currently used in ABE (Acetone/Butanol/Ethanol) manufacture, and, in particular, bacteria of the genus clostridium such as C. acetobutylicum, C. beijerinckii, C. saccharoperbutylacetonicum and C. saccharobutylicum.
  • the butanol- and/or acetone forming micro-organisms comprise C. acetobutylicum.
  • Fermentation is carried out at a concentration of free copper ions of less than 20 ⁇ M. This ensures that the presence of the copper ions have no/minimal negative effect.
  • water or another aqueous solution may be added to lower the concentration of free copper ions to below 20 ⁇ M free copper ions.
  • the concentration of free copper ions is less than 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 8, 7, 6 or 5 ⁇ M free copper ions during at least the fermentation step.
  • the concentration of free copper ions is less than 15 ⁇ M.
  • the concentration of free copper ions is less than 10 ⁇ M.
  • the treating and fermenting steps are carried out simultaneously. This reduces the amount of time required, the number of steps involved and the associated cost of manufacture.
  • the treating and fermenting steps are carried out sequentially.
  • draff may be pre-treated in two steps, first with acid and then enzyme, prior to fermentation.
  • the fermented product further comprises one or more of the compounds selected from the group comprising ethanol, carbon dioxide, hydrogen, acetate and butyrate. Butanol and/or acetone may be separated out of the fermented product using conventional separation techniques. Alternatively, the fermented product may be used as a fuel or otherwise without further purification.
  • the spent grain consists of 100% malted barley.
  • the malt whisky is a Scotch malt whisky.
  • biomass refers to butanol made from biomass.
  • wort refers to the composition of spent barley solids and spent grain which remains in a mash-tun after the liquor (wort) has been drawn off in the manufacture of malt whisky.
  • pot ale refers to the liquor remaining in the wash (copper pot) still after the first distillation in the manufacture of malt whisky. It is the residue of the wash after extraction by distillation of the low wines.
  • solid lees refers to the liquor remaining in the distillation vessel after second and subsequent distillations in the manufacture of malt whisky. It is the residue of the low wines after extraction by distillation of raw spirit.
  • malted barley is understood herein to refer to substrates which contain no, or only very minimal, types of grain other than malted barley. It therefore encompasses by-products of the manufacture of malt whisky. It is intended to encompass malted barley grains containing minor impurities other than other types of grain.
  • concentration of free copper ions refers to the concentration of copper ions which is not bound to solids, that is, the concentration of copper ions in the supernatant.
  • concentration of copper ions refers to the concentration of copper ions which is not bound to solids, that is, the concentration of copper ions in the supernatant.
  • the total concentration of copper in the pot ale will be higher than the concentration of free copper ions as some copper remains bound to solids, such as dead yeast cells.
  • the term “Scotch whisky” as used herein refers to whisky made in Scotland.
  • the malt whisky is a malt whisky manufactured in other countries, such as Ireland or India, where the process for manufacture of malt whisky in that country is similar or identical to the process used in Scotland for the manufacture of Scotch malt whisky.
  • FIG. 1 shows the influence of initial pH on fermentation of acid and enzyme pre-treated draff in pot ale by C. acetobutylicum ATCC 824.
  • Draff was pre-treated with 0.08 M H 2 SO 4 and the pH adjusted to between pH 5.0-6.0 prior to enzyme addition. After enzyme hydrolysis, the pH was adjusted to 4.5, 4.8, 5.0, 5.5, 6.0 or 6.5 for fermentation.
  • FIG. 1( a ) shows sugars resulting from acid and enzyme treatment
  • FIG. 1( b ) shows residual sugars after fermentation
  • FIG. 1( c ) shows the ABE products from fermentation
  • FIG. 1( d ) shows yield of butanol and ABE from draff;
  • FIG. 2 compares ABE production by C. acetobutylicum ATCC 824 from acid-pre-treated draff in either water or pot ale. After acid treatment, the pH was adjusted to pH 5.5 and enzymes and microorganisms added;
  • FIG. 3 shows ABE production by C. acetobutylicum ATCC 824 and C. beijerinckii NCIMB 8052 from draff at 1 L scale;
  • FIG. 4 shows ABE production by C. saccharoperbutylacetonicum NCIMB 12606 from (a) white office paper and (b) newspaper dissolved in either water or 50% pot ale.
  • Clostridia were maintained as spore suspensions at 4° C. Spores were heat shocked at 80° C. for 10 minutes and inoculated into reinforced clostridia media (RCM, Oxoid Ltd, Cambridge, UK). Cultures were incubated for 24 hours and then subcultured into tryptone-yeast extract-ammonium acetate media (TYA) media containing glucose before being used as a starting culture (at 5% v/v) for all experiments.
  • TYA tryptone-yeast extract-ammonium acetate media
  • TYA consisted of (g/l) tryptone, 6; yeast extract, 2; ammonium acetate, 3; KH 2 PO 4 , 0.5; MgSO 4 .7H 2 O, 0.3; FeSO 4 .7H 2 O, 0.01 supplemented with 5% glucose. All clostridia cultures were incubated in an anaerobic workstation under an N 2 —H 2 —CO 2 (80:10:10) atmosphere at 33° C. For 1 L scale, fermentations were conducted in fermenters (Biostat A Plus, Sartorius Stedim Ltd, Surrey, UK). Oxygen-free conditions were achieved by sparging the media in the fermenters with oxygen-free N 2 for 1 hour prior to inoculation with clostridia. For all 1 L fermentations, agitation was set at 200 rpm and temperature at 33° C.
  • draff as received from the distilleries, had a moisture content between 75-80%. Where stated, draff was dried at 80° C. to a moisture content of approximately 4% and milled prior to further processing.
  • Solvents (ethanol, acetone and butanol) were analysed using a Chrompack 9001 gas chromatograph equipped with a flame ionisation detector and a CP SIL 5CB column of length 10 m and diameter 0.32 mm (all Chrompack, Middelburg, Netherlands). All samples were filtered through 0.2 ⁇ m cellulose acetate syringe filters before analysis and concentrations were determined by reference to ethanol, acetone and butanol standards.
  • the monosaccharide composition of the draff was analysed according to the Laboratory Analytical Procedure developed by the National Renewable Energy Lab for the analysis of structural carbohydrates (Sluiter et al., 2008. NREL. Laboratory analytical procedure for the determination of structural carbohydrates and lignin in biomass. NREL/TP-510-42618).
  • the results of the analysis are provided in Table 1.
  • Glucose, xylose and arabinose were the predominant sugars, with very low levels of galactose (less than 2%) and no mannose detected.
  • Pot ale was collected from a Scottish malt distillery and analysed for copper content.
  • the pot ale had 71.8 ⁇ M total Cu of which 21.1 ⁇ M was determined to be available as “free” Cu in the supernatant with the rest bound to the solids.
  • fermentation of 5% glucose in 100 ml TYA media supplemented with different concentrations of Cu was compared (Table 3).
  • Cu had no effect on ABE production at 5 and 10 ⁇ M with ABE concentrations of approximately 12 g/l being similar to that of the control without Cu.
  • ABE concentration was reduced to 8.6 g/l, indicating that at this concentration Cu was inhibitory to clostridia.
  • the pot ale had a “free” Cu content of 21.1 ⁇ M, it was decided to test clostridia fermentation in half strength pot ale in order to reduce the Cu concentration below inhibitory levels.
  • Half-strength pot ale supplemented with glucose provided enough nutrients for growth of 824 with ABE production similar to the TYA control (Table 3).
  • the initial sugar concentration was monitored before fermentation and the residual sugar, ABE concentration and ABE yield were calculated after fermentation ( FIG. 1 ).
  • the initial concentration of sugars was similar for all samples, with approximately 9.6, 11.2, and 9.9 g/l glucose, xylose and arabinose. No growth or gas production was apparent at pH 5.0 or lower and no sugars were utilised.
  • ABE production was greatest at pH 5.5 (14.2 g/l) with a yield of 13.2 g/100 g draff. This was reduced at pH 6.0, with 9.3 g ABE/100 g draff. At pH 6.5, approximately half the sugar was utilised but there was poor conversion to ABE with a final concentration of 2.3 g/l.
  • draff Dried, milled draff (10.5% w/v) was pre-treated with 0.08 M H 2 SO 4 in either water or pot ale in 250 ml duran bottles by sterilisation at 121° C. for 15 minutes. After cooling the pH was adjusted to 5.5 by the addition of 10 M NaOH. Cellulase and hemicellulase enzymes and C. acetobutylicum ATCC 824 inoculum were added and bottles incubated at 33° C. The ABE concentration was determined after fermentation ( FIG. 2 ). For draff in water, ABE yield was 14.0 g ABE/100 g draff whereas in pot ale, a yield of 14.9 g ABE/100 g draff resulted.
  • Draff (10.5% w/v) was pre-treated with 0.08 M H 2 SO 4 in 50% pot ale in 1 L fermenters by sterilisation at 121° C. for 15 minutes.
  • draff was used wet, as received from the distillery, without any further processing.
  • the pH was adjusted to pH 5.5 by the addition of 10 M NaOH and the fermenters were sparged with N 2 .
  • enzymes and either 824 or 8052 were added and solvents were analysed at the end of the fermentation. Fermentation by C. acetobutylicum ATCC 824 and C. beijerinckii NCIMB 8052 resulted in ABE levels of 11.3 and 12.8 g/l, respectively ( FIG. 3 ). This corresponded to conversion rates of 10.6 and 12.1 g ABE per 100 g draff, respectively.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Genetics & Genomics (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Microbiology (AREA)
  • Biotechnology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Liquid Carbonaceous Fuels (AREA)
  • Micro-Organisms Or Cultivation Processes Thereof (AREA)
US13/806,248 2010-07-01 2011-06-30 Process for the manufacture of butanol or acetone Abandoned US20130219776A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB10110799 2010-07-01
GBGB1011079.9A GB201011079D0 (en) 2010-07-01 2010-07-01 Process for the manufacture of biofuels
PCT/GB2011/051237 WO2012001416A1 (en) 2010-07-01 2011-06-30 Process for the manufacture of butanol or acetone

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2011/051237 A-371-Of-International WO2012001416A1 (en) 2010-07-01 2011-06-30 Process for the manufacture of butanol or acetone

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/407,715 Continuation US20170137849A1 (en) 2010-07-01 2017-01-17 Process for the manufacture of butanol or acetone

Publications (1)

Publication Number Publication Date
US20130219776A1 true US20130219776A1 (en) 2013-08-29

Family

ID=42669031

Family Applications (10)

Application Number Title Priority Date Filing Date
US13/806,302 Abandoned US20130298453A1 (en) 2010-07-01 2011-06-30 Process for the manufacture of butanol or acetone
US13/806,248 Abandoned US20130219776A1 (en) 2010-07-01 2011-06-30 Process for the manufacture of butanol or acetone
US15/297,813 Abandoned US20170159079A1 (en) 2010-07-01 2016-10-19 Process for the manufacture of butanol or acetone
US15/407,715 Abandoned US20170137849A1 (en) 2010-07-01 2017-01-17 Process for the manufacture of butanol or acetone
US15/852,364 Abandoned US20180119177A1 (en) 2010-07-01 2017-12-22 Process for the manufacture of butanol or acetone
US15/852,556 Abandoned US20180119178A1 (en) 2010-07-01 2017-12-22 Process for the manufacture of butanol or acetone
US16/156,335 Abandoned US20190040419A1 (en) 2010-07-01 2018-10-10 Process for the manufacture of butanol or acetone
US16/156,618 Abandoned US20190040420A1 (en) 2010-07-01 2018-10-10 Process for the manufacture of butanol or acetone
US16/453,294 Active US11046977B2 (en) 2010-07-01 2019-06-26 Process for the manufacture of butanol or acetone
US16/792,470 Active US11198889B2 (en) 2010-07-01 2020-02-17 Process for the manufacture of butanol or acetone

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US13/806,302 Abandoned US20130298453A1 (en) 2010-07-01 2011-06-30 Process for the manufacture of butanol or acetone

Family Applications After (8)

Application Number Title Priority Date Filing Date
US15/297,813 Abandoned US20170159079A1 (en) 2010-07-01 2016-10-19 Process for the manufacture of butanol or acetone
US15/407,715 Abandoned US20170137849A1 (en) 2010-07-01 2017-01-17 Process for the manufacture of butanol or acetone
US15/852,364 Abandoned US20180119177A1 (en) 2010-07-01 2017-12-22 Process for the manufacture of butanol or acetone
US15/852,556 Abandoned US20180119178A1 (en) 2010-07-01 2017-12-22 Process for the manufacture of butanol or acetone
US16/156,335 Abandoned US20190040419A1 (en) 2010-07-01 2018-10-10 Process for the manufacture of butanol or acetone
US16/156,618 Abandoned US20190040420A1 (en) 2010-07-01 2018-10-10 Process for the manufacture of butanol or acetone
US16/453,294 Active US11046977B2 (en) 2010-07-01 2019-06-26 Process for the manufacture of butanol or acetone
US16/792,470 Active US11198889B2 (en) 2010-07-01 2020-02-17 Process for the manufacture of butanol or acetone

Country Status (11)

Country Link
US (10) US20130298453A1 (zh)
EP (2) EP2588621B1 (zh)
JP (2) JP5836370B2 (zh)
CN (2) CN103154260B (zh)
AU (2) AU2011273151B2 (zh)
CA (2) CA2803107A1 (zh)
DK (2) DK2588620T3 (zh)
ES (2) ES2607799T3 (zh)
GB (1) GB201011079D0 (zh)
PL (2) PL2588621T3 (zh)
WO (2) WO2012001417A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11046977B2 (en) 2010-07-01 2021-06-29 Celtic Renewables Limited Process for the manufacture of butanol or acetone
US20220386643A1 (en) * 2019-10-29 2022-12-08 Fuji Oil Holdings Inc. Cocoa substitute

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103917512A (zh) 2011-05-27 2014-07-09 加利福尼亚大学董事会 将发酵混合物转化为燃料的方法
GB201220604D0 (en) 2012-11-16 2013-01-02 William Grant & Sons Holdings Ltd Spent solids processing
CN105026321B (zh) 2012-11-16 2018-11-16 布雷高有限公司 谷物加工
CN105308015A (zh) 2013-04-26 2016-02-03 加利福尼亚大学董事会 燃料制造方法
BR102013022434B8 (pt) * 2013-09-02 2022-06-21 Advel Tecnologia E Comercio Eireli Processo para fermentação microbiana de substratos açucarados
BR112016021993A2 (pt) 2014-03-24 2017-10-24 Bp Corp North America Inc métodos para produção de cetonas cíclicas e acíclicas
CN107108428A (zh) 2014-10-29 2017-08-29 加利福尼亚大学董事会 使用胺催化剂制备燃料、汽油添加剂和润滑剂的方法
CN107107047B (zh) 2014-10-29 2020-05-22 加利福尼亚大学董事会 用胺催化剂制备燃料、汽油添加剂和润滑剂的方法
CN108690666A (zh) * 2017-04-06 2018-10-23 阿尔卑斯技术株式会社 一种燃料添加剂的制备方法、燃料添加剂及其用途
GB202004205D0 (en) 2020-03-23 2020-05-06 Mialgae Ltd Use of by-products from the alcoholic beverage manufacturing industry

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB190601962A (en) * 1906-01-25 1907-01-17 Saville S 1902 Ltd New or Improved Treatment of Brewers Grains or Draff for the Production therefrom of Material suitable for use as a Yeast-food and for other purposes.
GB190702591A (en) * 1907-02-01 1908-01-16 Georges Reynaud Treatment of Pot-ale whereby, Fermentation and other Products are Obtained.
GB191401962A (en) 1913-01-24 1914-08-27 Raymond Ware Improvements in Valve Mechanism for Internal Combustion Engines.
GB191302591A (en) 1913-01-31 1913-10-16 John Henry Holmes Device for Controlling the Speed of Motor Cars and the like Driven by Internal Combustion Engines.
GB464127A (en) * 1934-07-12 1937-04-12 Commercial Solvents Corp Butyl alcohol fermentation process
FR2488272B2 (fr) * 1980-06-09 1990-09-07 Inst Francais Du Petrole Nouvaux carburants a base d'alcool butylique et d'acetone
GB8418506D0 (en) 1984-07-20 1984-08-22 Brewing Res Found Utilization of spent grains
CN1183401A (zh) * 1996-11-14 1998-06-03 方宁 用酒糟生产复合甘油
JP2005328801A (ja) * 2004-05-21 2005-12-02 Yanmar Co Ltd ブタノールの生産方法
BRPI0706760A2 (pt) 2006-01-27 2011-04-05 Univ Massachusetts sistemas e métodos para produção de biocombustìveis e materiais relacionados
FR2908423B1 (fr) * 2006-11-14 2011-01-07 Air Liquide Procede de fabrication de biere.
WO2009045527A1 (en) * 2007-10-03 2009-04-09 Michigan State University Improved process for producing sugars and ethanol using corn stillage
WO2010083652A1 (en) * 2009-01-23 2010-07-29 Breeze Global, Inc. Production of organic solvent by different combination of wastes
CN101709308A (zh) * 2009-10-22 2010-05-19 河南健古生物工程有限公司 一种小麦酒精废糟液生产真菌菌粉及真菌多糖的方法
GB201011079D0 (en) 2010-07-01 2010-08-18 Court Of Edinburgh Napier Univ Process for the manufacture of biofuels

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11046977B2 (en) 2010-07-01 2021-06-29 Celtic Renewables Limited Process for the manufacture of butanol or acetone
US11198889B2 (en) 2010-07-01 2021-12-14 Celtic Renewables Limited Process for the manufacture of butanol or acetone
US20220386643A1 (en) * 2019-10-29 2022-12-08 Fuji Oil Holdings Inc. Cocoa substitute

Also Published As

Publication number Publication date
AU2011273152A1 (en) 2013-01-10
ES2607799T3 (es) 2017-04-04
US11198889B2 (en) 2021-12-14
WO2012001417A1 (en) 2012-01-05
HK1182739A1 (zh) 2013-12-06
DK2588621T3 (en) 2018-04-09
US20180119178A1 (en) 2018-05-03
JP2013529473A (ja) 2013-07-22
JP5836370B2 (ja) 2015-12-24
US20190040420A1 (en) 2019-02-07
AU2011273151B2 (en) 2015-07-02
WO2012001416A1 (en) 2012-01-05
EP2588620B1 (en) 2016-09-21
CN103154260B (zh) 2015-04-22
US20200181655A1 (en) 2020-06-11
PL2588621T3 (pl) 2018-07-31
ES2663719T3 (es) 2018-04-16
AU2011273152B2 (en) 2015-09-10
US20170137849A1 (en) 2017-05-18
AU2011273151A1 (en) 2013-01-10
US20200149074A1 (en) 2020-05-14
US20130298453A1 (en) 2013-11-14
US11046977B2 (en) 2021-06-29
CA2803127A1 (en) 2012-01-05
DK2588620T3 (da) 2016-12-19
CA2803107A1 (en) 2012-01-05
EP2588620A1 (en) 2013-05-08
US20180119177A1 (en) 2018-05-03
US20190040419A1 (en) 2019-02-07
GB201011079D0 (en) 2010-08-18
EP2588621B1 (en) 2018-01-10
JP5818887B2 (ja) 2015-11-18
CA2803127C (en) 2020-09-29
PL2588620T3 (pl) 2017-03-31
CN103154260A (zh) 2013-06-12
JP2013534422A (ja) 2013-09-05
CN103119171A (zh) 2013-05-22
US20170159079A1 (en) 2017-06-08
CN103119171B (zh) 2016-01-20
EP2588621A1 (en) 2013-05-08

Similar Documents

Publication Publication Date Title
US11198889B2 (en) Process for the manufacture of butanol or acetone
Qureshi et al. Production of butanol (a biofuel) from agricultural residues: Part I–Use of barley straw hydrolysate
EP2955231B1 (en) Processes using antibiotic alternatives in bioethanol production
Taherzadeh et al. Bioethanol production processes
DK3177728T3 (en) IMPROVED FERMENTATION PROCEDURES USING XYLANASE AND PECTINASE
Subashini et al. Ethanol production from sago waste using Saccharomyces cerevisiae Vits-M1
KR20110097432A (ko) 바이오에탄올 폐발효액을 이용한 부탄올의 제조방법
US9611492B2 (en) Use of vinasse in the process of saccharification of lignocellulosic biomass
HK1182739B (zh) 製造丁醇或丙酮的工藝
HK1182740A (zh) 製造丁醇或丙酮的工藝
HK1182740B (zh) 製造丁醇或丙酮的工藝
Yohannan et al. Distiller’s spent grains: a substrate for bioethanol?

Legal Events

Date Code Title Description
AS Assignment

Owner name: CELTIC RENEWABLES LIMITED, UNITED KINGDOM

Free format text: NUNC PRO TUNC ASSIGNMENT;ASSIGNOR:THE COURT OF EDINBURGH NAPIER UNIVERSITY;REEL/FRAME:030795/0763

Effective date: 20130626

AS Assignment

Owner name: THE COURT OF EDINBURGH NAPIER UNIVERSITY, UNITED K

Free format text: NUNC PRO TUNC ASSIGNMENT;ASSIGNORS:WHITE, JANE SAMANTHA;LEIPER, KENNETH ALEXANDER;TANGNEY, MARTIN;AND OTHERS;SIGNING DATES FROM 20140310 TO 20140414;REEL/FRAME:032884/0195

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION