WO1995017517A1 - Commercial ethanol production process - Google Patents
Commercial ethanol production process Download PDFInfo
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- WO1995017517A1 WO1995017517A1 PCT/US1994/014566 US9414566W WO9517517A1 WO 1995017517 A1 WO1995017517 A1 WO 1995017517A1 US 9414566 W US9414566 W US 9414566W WO 9517517 A1 WO9517517 A1 WO 9517517A1
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- 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
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
- C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23K—FODDER
- A23K10/00—Animal feeding-stuffs
- A23K10/30—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms
- A23K10/37—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms from waste material
- A23K10/38—Animal feeding-stuffs from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms from waste material from distillers' or brewers' waste
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- 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
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- 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
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
- Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
- Y02P60/87—Re-use of by-products of food processing for fodder production
Definitions
- the present invention relates to processes and facilities for automated treatment of municipal solid waste materials, waste sludge and scrap tires to remove and reclaim any usable materials and for producing commercial ethanol.
- the present invention further relates to a method for removing the heavy metals associated with the cellulosic component of municipal solid waste.
- solid waste materials and waste sludge are disposed of by land fill and/or incineration.
- Environmental restrictions on both land fills and incinerators demand that an alternative solid waste solution be implemented.
- the public outcry concerning pollution caused by incinerators has halted construction of many new incinerator projects.
- the government, as a reaction to the problems associated with land fills, has mandated that recycling be employed to conserve natural resources and arrest the flow of solid waste materials into land fills.
- a number of technologies have been developed to recover recyclable materials from solid waste, to produce fuel, and to produce commercially useful alcohols and gas. For example:
- U.S. 5,198,074 discloses a process to produce ethanol from bamboo which involves chipping, shredding and washing of the bamboo, pressing to remove the water. The fiber is then prehydrolyzed with steam to give dissolved sugars and fermented to give ethanol.
- U.S. 5,184,780 discloses a system for treating solid waste having one or mo i re treatment lines for processing the solid waste to recover recyclable materials such as corrugated paper, ferrous metals, plastic products, paper and glass.
- U.S. 5,135,861 discloses ethanol production from biomass which is hydrolyzed using the carbon dioxide produced from the fermentation reaction or the naturally occurring organic acids from citrus wastes as a catalyst.
- U.S. 5,104,419 discloses a method of producing methanol from solid waste, for example, municipal solid waste, by partially oxidizing and combusting solid waste material, conducting the combustion gases, oxygen and carbon dioxide through the solid waste material, separating the less volatile components of the gas from the more volatile components, and reacting the more volatile components with carbon dioxide to form methanol.
- U.S. 5,060,871 discloses methods of separating metal alloy particles by utilizing the difference in particle size, density and/or electric conductivity.
- U.S. 5,036,005 discloses a method for the continuous fermentation production of fuel grade ethanol from a sugar, where the ethanol is removed in a solvent extraction column containing a solvent which is non-toxic to the fermentation microorganisms.
- U.S. 5,009,672 discloses a process for the recycling and recovery of urban solid waste components by high pressure compression and screening as well as magnetic separation steps.
- the recovered putrescible organic component is then subjected to a process of anaerobic fermentation to give a biogas which can be used directly for the production of electric power.
- U.S. 4,974,781 discloses a paper and plastic separation process which subjects the materials to moisture and heat to repulp the paper. The repulped materials are then separated from the non-pulpable materials and are then recycled, combusted or used as a feedstock in a chemical process.
- U.S. 4,952,503 discloses a process for the continuous production of ethanol using a centrifugal separation step to remove the yeast.
- U.S. 4,874,134 discloses a process for treating solid waste to recover recyclable materials such as corrugated paper, ferrous metals, non-ferrous metals, plastic products, paper and glass containers, as well as biodegradable waste materials which may be processed to give a compost.
- recyclable materials such as corrugated paper, ferrous metals, non-ferrous metals, plastic products, paper and glass containers, as well as biodegradable waste materials which may be processed to give a compost.
- the bulky valuables, non-processable materials and redeemable materials are first recovered, a first ferrous metal fraction is then separated magnetically, the waste material is then shredded, a second ferrous metal fraction is then separated magnetically, and the paper fraction is then separated pneumatically to give a biodegradable fraction which can then be composted.
- U.S. 4,692,167 discloses an apparatus for processing solid wastes for the production of a granule solid fuel by grinding, magnetically separating ferrous metals, screening, drying, gravity separation, cyclone separation, screening and press granulating.
- U.S. 4,650,689 discloses a process for the preparation of ethanol from cellulosic materials by subjecting the cellulosic materials to a highly concentrated mineral acid gas such as HC1 under pressure, and treatment with hot water to give a wort containing sugars which can be fermented.
- a highly concentrated mineral acid gas such as HC1 under pressure
- U.S. 4,612,286 discloses a method for the acid hydrolysis of biomass having fermentable materials in a countercurrent diffusion treatment structure.
- the acid is about 2 to 10% by volume sulfuric acid.
- U.S. 4,553,977 discloses a method for separating solid waste components with a first trommel screen which removes aluminum cans to give an organics-rich fraction from which recyclable fiber products may be separated. Steel cans are removed by magnetic separation. The organics are isolated for use as a fuel, with or without pulping to recover paper pulp.
- U.S. 4,541,530 discloses a method for separating metallic particles from non-metallic particles of processed solid waste by homogenizing and magnetically treating components of the waste to give a metallic concentrate, for example, an aluminum concentrate.
- U.S. 4,384,897 discloses a method for treating biomass material by a two stage hydrolysis treatment, wherein in the first stage, the more easily hydrolyzed polysaccharides are depolymerized and in the second stage, the more difficultly depolymerizable polysaccharides are depolymerized.
- the biomass material may be subjected to a sensitization step between the first and the second hydrolysis stages by contact with molecular oxygen.
- the acids are neutralized with a base such as calcium carbonate or hydroxide to give a solution which is suitable for fermentation to give ethanol.
- U.S. 4,341,353 discloses a method of recovering fuel and recyclables from refuse using disk screens and air classifiers.
- U.S. 4,288,550 discloses a method of digesting garbage by anaerobic fermentation in the presence of ethanol producing yeast to directly convert starch to ethanol without a hydrolysis pretreatment and thereafter subjecting the product to methane producing anaerobic fermentation to give methane.
- U.S. 4,069,145 discloses a method for separating particles of greater electrical conductivity from particles of lesser electrical conductivity in an electromagnetic eddy current separator apparatus.
- U.S. 4,063,903 discloses an apparatus for the disposal of solid wastes by recovering the inorganic components and converting the organic component to a fuel or a fuel supplement.
- the shredded material is treated with an acid which is heated and dried and ground to give a finely divided fuel product.
- the process for the continuous, automated treatment of municipal solid waste material to remove and reclaim any usable materials and for producing commercial ethanol comprises the following steps:
- step (c) shredding the cellulosic component obtained in step (b);
- step (e) removing the soluble component obtained in step (d) from the insoluble component; (f) drying the insoluble component obtained in step (e);
- step (g) treating the dried insoluble component obtained in step (f) with about 1: 1 concentrated sulfuric acid (about 70%) to insoluble component, by weight, to give a partially hydrolyzed mixture; (h) diluting the partially hydrolyzed mixture obtained in step (g) with water at a temperature of about 80°C to about 100°C to give a solution containing, e.g. about 4 to 6 parts water to about 1 parts partially hydrolyzed material, by weight; (i) agitating the diluted mixture obtained in step (h) for about 1 to
- step (n) fermenting with yeast the solution obtained in step (m) at about
- the invention also relates to a method of removing trace heavy metals and chlorides from the cellulosic component of municipal solid waste, comprising the following steps:
- the invention further relates to a method of producing ethanol and removing essentially all of the heavy metals and chlorides from the cellulosic component of municipal solid waste (MSW), comprising
- step (a) shredding the cellulosic component of municipal solid waste; (b) treating the shredded component obtained in step (a) with about
- step (c) diluting the partially hydrolyzed mixture obtained in step (b) with water having a temperature of about 80 to 100° C to give a suspension with a liquid: solid ratio of about 5:1 and a sulfuric acid concentration of about 12%;
- step (d) agitating the diluted mixture obtained in step (c), e.g. for about 1 to 4 hours at about 80 to 100°C to give a digested material
- FIG. 1 is a flow chart detailing the complete process for the treatment of municipal solid waste material: Reference Equipment Description
- the solid waste material may be obtained directly from a municipality or may be municipal solid waste that was previously land-filled and subsequently recovered.
- the solid waste material is admitted into the facility through a fully automated receiving station.
- the waste material is then dumped onto a bulk conveyor.
- the recyclable materials such as valuable bulk items, ferrous metals, non-ferrous metals such as aluminum, glass, plastic, and rubber and the are then recovered. Methods for recovering such items are well known and disclosed, for example, in U.S. Patent Nos.
- the scrap tire materials are segregated onto a separate bulk conveyor which leads to a scrap tire processing and rubber recovery system, where the scrap tires are shredded and the rubber, steel and fiber are removed.
- a remote controlled magnetic crane is used to remove any oversized, bulky ferrous materials from the solid waste conveyor. These oversized materials are then processed through a shredder which reduces the material to a workable size. The material is then sent to a recycling bin to await baling. The waste material remaining after the oversized material is removed is then classified by the use of a trommel or other screening mechanism which disrupts any bags and yields two separate processing streams. By appropriate classification, one stream will contain primarily cellulosic and metallic products of a particular size, while the other stream will contain rubber, glass and most of the organics.
- the waste materials are processed through several magnetic separations to remove any ferrous metals.
- the waste is then passed through an eddy current separator to remove any non-ferrous metals.
- the ferrous and non- ferrous metals are both conveyed to bins to await baling.
- the waste is then shredded and processed in the ethanol production system which accepts the waste material and processes it to obtain ethanol to be sold commercially.
- a portion of the byproducts from the ethanol process may be sold commercially and/or used to cogenerate electricity to aid in the operation of the facility.
- the insoluble material obtained after hydrolysis of the cellulosic component of MSW is primarily composed of lignin, a natural aromatic organic polymer found in all vascular plants.
- Any non-organic materials remaining after the aforementioned screening process may be pelletized and used commercially as additives for construction materials.
- the present invention is entirely automated, requiring only routine maintenance at the end of each shift of operation.
- Fully automated screening techniques eliminate the need for unsanitary, hand sorting.
- the present invention allows for a completely zero discharge facility. All buildings may be fully enclosed. All air and water pollutants may be captured and summarily treated. All materials entering the facility may be treated and converted into commercially workable materials.
- Table I details the composition of dry municipal solid waste (MSW) as determined by the Environmental Protection Agency.
- the present invention is designed to receive solid waste such as detailed in Table 1 as well as municipal solid wastes that are recovered from land fills (which might have a slightly different composition).
- the rate at which the solid waste may be processed through the system is greatly dependent on the size of the community that the present invention will serve.
- the system may handle from 25 tons per hour up to 125 tons or more per hour.
- the equipment may be sized accordingly.
- the materials that are not treatable are hazardous waste, explosives and infectious wastes.
- the system is able to process refrigerators, washers, dryers, ranges, automobile scrap metal, large materials, small industrial waste and standard municipal solid waste.
- the present system is designed to recover plastics, non-ferrous metals and ferrous metals from the solid waste.
- the trucks discharge the municipal solid waste onto a bulk conveyor such as may be obtained from E&H Systems which traverses the length of the initial shredder building.
- a remote controlled magnetic crane is then used to remove any large metallic objects. These removed objects are placed into an automated pre-shredder for size reduction. Once the size reduction is completed, the waste is reintroduced into the system, into holding bins for baling on a standard baler.
- a trommel screen as commonly available from such sources as
- MacLanahan Corporation is then used to automatically open bags, remove small impurities and crush any glass materials.
- the material in the ethanol stream is conveyed through a series of five magnetic separators which will remove substantially all ferrous metals. That is to say, the waste stream which consists primarily of metallic and cellulosic components is delivered from the trommel to a series of inclined conveyors, each having a magnetic separator device, such as a drum or belt, as is well known in the art.
- the outlet end of each conveyor is supported at a height above the inlet of each succeeding conveyor such that the material passing the magnetic screen is subjected to gravitational agitation from one conveyor to the next, thereby enhancing magnetic recovery of remaining ferrous metals by a subsequent magnetic separator.
- the conveyor design is such that it will allow for the fully automated extraction of ferrous metals into a centralized area. This conveyor design also allows for the mixing of the materials to ensure 98% removal of all ferrous metals.
- the extracted ferrous metals fall down a vertical chute and are conveyed out of the facility to a holding bin for recycling.
- the remaining material is then conveyed to an eddy current separator such as an Eriez Ferrous Metal Separator.
- the eddy current separator is utilized for the automated removal of the non-ferrous metal materials including batteries.
- the eddy current separator is placed after the magnetic separators to ensure that no ferrous metals will damage the eddy current separator equipment.
- the presence of any ferrous metal materials in or on the eddy current separator will result in serious and expensive damage to the eddy current separator.
- the remaining waste materials are fed by the conveyor into a hammermill shredder which reduces the material to about a minus 3" to minus 4" size. The reduction in size of the material aids in the ethanol production process.
- the hammermill shredder will include an explosion proof shroud to eliminate any potential dust related explosions.
- the material flow may be divided into two distinct paths; the ethanol production process and a humus production path.
- the distribution of the waste between the two systems depends on the exact volume of waste coming into the facility.
- the level of heavy metals found in the cellulosic component of MSW can vary significantly depending upon the source of the waste. For instance the hydrolyzate generated from the cellulosic component of some samples of MSW obtained from urban or highly industrialized areas have been shown to be contaminated with heavy metals to an extent that the subsequent yeast fermentation process would be inhibited. Therefore, these types of MSW samples may be treated to reduce their heavy metal content prior to hydrolyzation to avoid contaminating the fermentation liquor. On the other hand, it has been discovered that the removal of heavy metals from less contaminated samples can be accomplished via an efficient ion exchange process after the hydrolysis of the cellulosic feedstock.
- the following discussion describes two processes which can be utilized to reduce the heavy metal content of the cellulose component of MSW. One which reduces the heavy metal content prior to hydrolyzation, and the other after hydrolyzation. Which process is used can be determined based upon the level of heavy metal contamination found in the MSW feedstock.
- the purpose of the Pre-treatment Process is to separate the heavy metals that may inhibit fermentation of the hydrolyzed cellulosic component of MSW by mixing the incoming shredded cellulosic component with dilute sulfuric acid. The solids are then pressed and the liquids are treated with lime, creating a byproduct, gypsum. The gypsum is then removed and the remaining solids are prepared to be broken down into sugars in the Hydrolysis System.
- MSW has levels of cadmium and iron which moderately inhibit the fermentation of yeast, and levels of lead, zinc and copper which severely inhibit the fermentation of yeast.
- the reduction of heavy metals in MSW is critical to achieve the efficient fermentation of sugars obtained from such MSW.
- a sample treated according to the pre-treatment process which has substantially no trace metals is one which has at least about a 70% reduction of these metals.
- Raw Feedstock Silos receive feedstock of about 85%-90% pure organic material in a pre-shredded state of -2" (5/8" x 2") particulate size. Each Silo holds about 25 tons of material, roughly equivalent to a 2-1/2 days supply of feedstock. Materials having no detectable heavy metal content do not require pre-treatment so they are stored separately in Silo IB.
- Material is conveyed from Silo 1A by bulk conveyor to a Metering Silo (Ref. 2).
- the Metering Silo dispenses the untreated feedstock to a Pre- Treatment Chamber (Ref. 3) while dilute sulfuric acid (about 1 to 10% by weight) is mixed with the feedstock at about 40 to 100 °C. This allows for the dissolution of heavy metals and chlorides (metal chlorides and possibly organic chlorides) from the feedstock.
- the material is then conveyed by a screw conveyor to Screw Presses (Ref. 5A and 5B) enabling the removal of about 60% -80% of the liquid content, thereby removing the soluble component from the insoluble component.
- a secondary wash is required to eliminate any trace acid (Ref. 5B).
- the solids from the Screw Press are then fed into a Conveyor Dryer (Ref. 6) with a feed rate of about 3.25 tons per hour.
- the Conveyor Dryer further reduces the moisture content of the feedstock to about 5%-10%.
- the dried insoluble component having a light, fluffy consistency, is pneumatically conveyed to a Feed Process Storage Silo (Ref. 7).
- an alternative ion exchange process for removing essentially the heavy metals involves carrying out the hydrolyzation step outlined below and recovering the aqueous-insoluble lignin. It has been discovered that essentially all of the heavy metals are bound to the lignin.
- the purpose of the Hydrolyzation Process is to break down the molecular structure of the feedstock into sugars by mixing the material with concentrated (about 65 to 93%, preferably, about 70%) sulfuric acid.
- the sugar/acid/water solution is cooked for a determined period of time after which the solids are removed.
- the solution is sent to the Acid Recovery System for separation.
- Pre-treated feedstock is metered from the Storage Silo (Ref. 7 or Ref.
- a ratio of about 1:1 includes compositions comprised of a 60:40 to 40:60 by weight mixture.
- the ratio of concentrated sulfuric acid to pre-treated feed stock is about 45:55 to 55:45 by weight.
- Material from the Holding Vessel is then filtered for example by pumping it into a Filter Press (Ref. 15) which removes the suspended solids to give a filtrate.
- the solids may be pulverized, washed and returned to the Dryer (Ref. 6) for use as boiler fuel.
- the filtrate is then pumped from the Filter Press to the Acid Recovery Storage Vessel (Ref. 16).
- Municipal waste water from the Waste Water Storage Vessel may be used as a substitute for fresh water in the Hydrolysis System (Ref. 12). All pathogens inherent in the waste water are eliminated in the Hydrolysis System. The high nitrogen content of the waste water is retained, virtually eliminating the need for the addition of nitrogen containing compounds such as ammonia (a yeast nutrient useful in the fermentation process).
- nitrogen containing compounds such as ammonia (a yeast nutrient useful in the fermentation process).
- the purpose of the Acid Recovery Process is to recover the sulfuric acid from the sugar/acid/water solution to give an acid-containing solution and a sugar-containing solution.
- the concentrated sulfuric acid and water are then reused in the system. Once the sugars and water have been removed from the solution it is piped into the Fermentation Tanks to be fermented into ethanol.
- the aqueous stream may be passed through an activated charcoal filter to retain the sugars, and washed with water to rinse the remaining acid.
- the adsorbed sugar may then be eluted by washing with heated alcohol. See, M.R. Moore and J.W. Barrier, "Ethanol from Cellulosic Residues and Crops," Annual Report, DOE/SERI Contract No. DK-6-06103- 1, Tennessee Valley Authority, Muscle Shoals, Alabama, October 1987, pp. 27-49, the contents of which are incorporated by reference herein.
- this method for separating the sulfuric acid from the sugars is not preferred, as the alcohol must be evaporated from the resulting sugar solution before fermentation, which adds another step requiring energy input. Problems may also be encountered with acid carryover between the adsorption and desorption cycles which can be ameliorated by use of a nitrogen surge between the cycles. Problems may also be encountered with the effluent alcohol (ethanol) not being saturated at 70 °C, resulting in a lower sugar capacity. Lower ethanol flow rates and increased desorption cycle times enhance the desorption of the sugars to give effluent streams which are 95-100% saturated with sugar. More preferably, ion exchange resins may be used to separate the acid and sugar into an acid containing stream and a sugar containing stream.
- Such resins include the Amberlite strongly acidic cation exchanger resins of the "GEL” type, e.g. IR 120 PLUS sulfuric acid functionality, which is commercially available from the Aldrich Chemical Company.
- GEL Amberlite strongly acidic cation exchanger resins of the "GEL” type, e.g. IR 120 PLUS sulfuric acid functionality, which is commercially available from the Aldrich Chemical Company.
- the sugar is adsorbed on the strongly acidic resin giving an acid containing stream which can be recycled.
- the adsorbed sugars are then recovered by eluting the resin with pure water. See, M.R. Moore and J.W. Barrier, "Ethanol from Cellulosic Residues and Crops," Annual Report, DOE/SERI Contract No. DK-6-06103-1, Tennessee Valley Authority, Muscle Shoals, Alabama, October 1987, pp. 30-39, the contents of which are incorporated by reference herein.
- the separation may be carried out on a Karr reciprocating-plate extraction column.
- the column has receiving vessels at each end for solvent and hydrolyzate separation. Mixing is accomplished by teflon plates coupled to a motor.
- the acid-sugar solution is added to the top of the column which travels down the column where the aqueous solution is intimately admixed with the solvent.
- the solvent is added to the bottom of the column.
- aqueous solution containing the sugar is drawn off the bottom of the column while the acid containing solvent solution is drawn off the top.
- the acid may then be recovered from the solvent, for example, by distillation of the solvent or by washing the solvent with distilled water.
- An apparatus and solvent for the continuous separation of acid from aqueous sugar solutions is available, for example, from Glitsch, Inc., Parsippany, NJ.
- the sugar stream obtained from any of these separation processes will contain residual acid.
- the residual acid is then neutralized with lime or ammonia to a pH of about 6.
- Liquid containing about 10% sugar, 10% acid, and 80% water is pumped from the Acid Recovery Storage Vessel (Ref. 16) to the Acid Recovery System (Ref. 17) which separates the liquid into an acid/ water solution and a sugar/ water solution.
- the sugar/ water solution is pumped to a Holding Vessel (Ref. 19); the recovered acid/water solution is pumped to an Evaporator (Ref. 18) where water is removed from the acid by evaporated and returned to the Water Storage Vessel (Ref. 29 A). Removing the water brings the acid concentration to its original level of about 70%. This allows for the return of the acid from the Evaporator to the Concentrated Acid Storage Vessel (Ref. 30) for reuse into the system.
- the purpose of the Fermentation Process is to concentrate the sugar solution and blend it with yeast for the production of an ethanol/water solution.
- the sugar solution may be concentrated to about 12-14% by evaporation (e.g., by application of heat and/or a vacuum) or with a reverse osmosis filter.
- the ethanol is recovered.
- the yeast may or may not be removed prior to recovery of the ethanol.
- the ethanol may be recovered by distillation or, in the alternative, may be recovered by solvent extraction with a solvent which is non-toxic to the fermentation microorganisms. See, U.S. Patent No. 5,036,005, the contents of which are fully incorporated by reference herein.
- the yeast may also be removed by centrifiigation. See, U.S. Patent No. 4,952,503, the contents of which are fully incorporated by reference herein.
- the remaining yeast is first removed and the fermented liquid is pumped to the Distillation
- the purpose of the ethanol recovery is to separate the ethanol from the ethanol/water solution by means of evaporation and condensation. This results in the production of pure ethanol as well as the by-product stillage.
- Fermented stock is metered to the Distillation Column (Ref. 26). Depending on the original feedstock, the yield may range from 60 to 120 gallons of 180-190 proof ethanol per ton of input material.
- the ethanol from the Distillation Column is pumped to the Ethanol Storage Vessel (Ref. 28).
- the Ethanol Storage Vessel (Ref. 28) will have a storage capacity of 12,000 gallons of ethanol, roughly equivalent to a 12 to 14 day supply of ethanol manufactured in the process.
- a by-product of the distillation process is stillage. Stillage is a starchy residue that can be sold as cattle feed.
- the present invention further relates to an efficient process for the post-hydrolysis removal of heavy metals from the cellulosic component of MSW.
- the steps for processing MSW are similar to the ones described herein above with the exception that the removal of the heavy metals from the pre- shredded feed stock is delayed until after the hydrolysis step.
- the step involving the pretreatment of the cellulosic material with dilute sulfuric acid can be eliminated, thereby eliminating the need for a secondary wash and the time-consuming, energy-intensive, step of drying the pretreated feedstock. Therefore, rather than pretreating the preshred feedstock with dilute sulfuric acid, it is directly fed into the hydrolysis system where about
- 70% concentrated sulfuric acid is automatically introduced at about a 1:1 (acid/sample) ratio.
- This suspension is then blended at around 30-80 °C for preferably about 2-20 minutes, or more preferably about 2-15 minutes, then fed into cooking vessels where the suspension is diluted with water having a temperature of about 80 to 100 °C until the liquid-to-solid ratio 5:1 and the sulfuric acid concentration is about 12%.
- This material is agitated while maintaining a constant temperature of about 80-100°C for about 1-4 hours. Under these conditions the conversion of cellulose and hemicellulose to glucose and xylose is 87-100% complete.
- the cooking vessels are evacuated into a holding vessel, thereby allowing the cooking vessel to be recharged.
- the holding vessels stabilize the temperature of the hydrolyzate and regulates its flow to the filter press where suspended solids are removed to give a filtrate.
- the filtrate is separated into an acid containing solution and a sugar containing solution and the sugar containing solution processed to produce ethanol.
- the insoluble component collected from the filter press is dried, optionally mixed with the non-chlorinated plastic component of MSW, and utilized as a boiler fuel to produce energy, e.g., to cogenerate electricity, which can be sold or used in the operation of the processing facility, such as in the distillation process. If required, the level of heavy metals associated with the insoluble component can be reduced prior to burning by treatment with a 1-10% salt solution followed by a rinse with water.
- MSW samples were mixed together to form a composite sample.
- Four samples were then taken from the composite sample and analyzed for cellulose, lignin, and ash using the following procedure.
- the composite MSW samples were dried to less than 1 % moisture in a microwave oven, and then ground to pass a 20 mesh screen.
- the samples were then mixed with an equal amount (weight) of 10% sulfuric acid and heated for two hours at about 100°C. After heating, the liquid was removed by filtration and the solids were collected, washed, dried, and weighted. The weight loss resulting from the treatment with 10% sulfuric acid represents the hemicellulose content of the MSW sample.
- the collected solids were then mixed with 70% sulfuric acid and placed in a reactor containing 5 parts water to 1 part solids and heated at about 100 °C for 3 hours in a microwave oven. The solids were then filtered from the slurry and the glucose content determined. The filtered solids were then dried, heated at about 600 °C, and the ash content determined. The lignin content of each sample was determined by the difference in the weight of ash contained in the sample and the total weight of the sample.
- the slurry was then heated at about 100°C for about 2-3 hours to complete the hydrolysis process. Once completed, the hydrolyzate liquid and the residual solids were separated and analyzed for carbohydrate and heavy metal content.
- the hydrolyzate liquid was neutralized with a known volume of sodium hydroxide.
- the neutralized sample was then analyzed for glucose content using a YSI model 20 glucose analyzer..
- the results of this procedure reveal that the hydrolyzate contained about 10% sugar (corrected for dilution).
- the theoretical yield of sugar is 10.4%. Error in analysis and decomposition of some of the glucose most likely accounts for the difference.
- the original composite MSW sample, the hydrolyzate residual solids, and the hydrolyzate liquid were analyzed to determine levels of copper, zinc, chromium, nickel, and iron. These heavy metals were found in previously analyzed prehydrolysis MSW samples at levels which may hinder fermentation. The results of this analysis are presented in Table 7.
- the original prehydrolysis MSW feedstock contained about the expected levels of heavy metals.
- the insoluble residue obtained after the hydrolysis step contained much higher concentrations of heavy metals than expected based upon the pretreatment studies. While the inventors do not wish to be bound by any particular theory, it appears that the residual solids may have been partially oxidized during the hydrolysis reaction converting them into low-grade ion-exchange resins which bind the heavy metals. The residue retained over 90% of the copper, 55 % of the chromium, and 20-30% of the zinc, nickel, and iron. The two heavy metals that interfere most with fermentation are copper and chromium.
- a sample treated according to the present ion-exchange process which has essentially all of the heavy metals removed from the hydrolyzate is one which has about 90% of the copper, about 55% of the chromium, and about 20-30% of the zinc, nickel, and iron retained in the insoluble component.
- the fermentation experiment was repeated with the exception that the sulfate salts of the heavy metals normally found in MSW were added at 10 and 20 times the concentrations shown for the hydrolyzate in Table 7. Under these conditions the amount of glucose consumed was 92% -93% and 61%- 65% for the fermentation solution containing 10 and 20 times the heavy metal concentrations shown for the hydrolyzate in Table 7, respectively. Similar to the effect on hydrolysis, the results obtained with the fermentation experiment show that heavy metal concentrations up to 10 times those expected in the MSW hydrolyzate do not significantly effect the rate or extent of glucose fermentation. Moreover, the fermentation rate was not decreased until heavy metal levels reached 20 times the concentration expected in the MSW hydrolyzate.
- the level of heavy metals associated with the insoluble component obtained after hydrolysis can be reduced prior to burning by the following procedure.
- the insoluble component was collected and washed with a 1% NaCl solution at room temperature. Once washed, the insoluble component was separated from the NaCl solution and amount of associated heavy metals measured. The heavy metals associated with the insoluble component were reduced according to the results presented in Table 9.
- ISEP LC200 employing the resin Finex CS16G, 310 micron mean size, obtained from Advanced Separation Technologies Incorporated, Lakeland FL, was used to separate the sugars from sulfuric acid of a 4.5% sugar/4.2% acid (wt.) solution.
- the resin volume was 1.22 ft 3 .
- the feed of sugar/acid solution was 0.082 BV (bed volumes)/hr.
- the resin was washed with 1.65 gal water/gal of feed. The results were as follows:
- the ISEP equipment is able to efficiently separate the sugars from the sulfuric acid, allowing the sulfuric acid to be recycled in the process.
- feedstock composed of 85% - 90% pure organic material.
- Materials that may be used as feedstock include processed cottonseed waste, switch grass, paper pulp, textile bag house residue, agricultural waste, sugar beet waste, sugar cane waste, the cellulosic component of municipal solid waste (MSW), and any other similar feedstocks having the desired organic content.
- the cellulosic component of MSW or any other feedstock composed of large particles will be shredded to -2" or (5/8" x 2") particulate size.
- each silo will store about
- the Ethanol Production System is designed to process 10 tons per day of feedstock. While the silos will receive material in a batch process, on average, the rate of delivery will be 41.7 Ibs/min (8 hours/day, 5 days/week). Output:
- Raw Feedstock Storage Silos are constructed of 10' high modules.
- the modules are constructed of 12 gauge sheet welded steel and will be bolted together for various volume requirements.
- Each silo has an approximate 2-1/2 day storage area (using 15 lbs/ft 3 as a standard). Storage capacity may vary depending on the feedstock present in the silo.
- Material from the Raw Feedstock Storage Silos (Ref 1A) is metered at a rate of 41.7 pounds per minute to the Pre-treatment Chamber (Ref. 3) by a variable speed auguring system (material from storage silo IB will not require pre-treatment).
- the Metering Vessel allows for the precise control of feedstock volume being fed to the Pre-Treatment Chamber (Ref. 3).
- the Metering Vessel is constructed of 12 gauge sheet welded steel and consist of a feed hopper with a screw conveying system to allow for uniform flow into the Pre-Treatment Chamber (Ref. 3).
- the Metering Vessel has an approximate capacity of 670 ft 3 (1/2 day using 15 lbs/ft 3 as a standard density).
- Storage capacity may vary depending on the feedstock present in the silo.
- Raw feedstock is metered into the Pre-Treatment Chamber at a rate of 41.7 pounds per minute.
- Dilute sulfuric acid (l %-2% concentration) is injected from the Dilute Sulf ric Acid Storage Vessel (Ref. 4) at 40 to 100°C into the chamber at a rate of 250 pounds per minute, simultaneously mixing with the feedstock.
- the mix ratio is about 4:1 to 6:1 (four to six pounds of l %-2% concentrated sulfuric acid to every one pound of feedstock).
- a ten (10) minute retention time in the mixing chamber is maintained to allow the separation of heavy metals from the raw feedstock.
- the treated feedstock is continuously metered to the Primary Screw Press (Ref. 5 A) at a rate of 291.7 pounds per minute.
- Input- Feedstock 41.7 lbs/min (8 hours/day, 5 days/week).
- the Pre-Treatment Chamber consists of a screw conveyor with a leak proof trough.
- the Chamber is constructed of acid resistant materials and corrosion proof seals.
- the material being conveyed has a 10 minute retention time in the Pre-Treatment Chamber and is sized accordingly (about 20 feet long).
- the Pre-Treatment Chamber has an approximate capacity of 66.7 ft 3
- the capacity may vary depending on the feedstock present in the silo.
- the Dilute Sulfuric Acid Storage Vessel is equipped with a bleeder valve in order to remove a portion of the solution and pipe it at a rate of 27.4 lbs/min to the Dilute Sulfuric Acid Neutralization Vessel (Ref. 8).
- the Dilute Sulfuric Acid Storage Vessel is designed to hold about 8000 gallons.
- Liquid to Pre-Treatment Chamber (Ref. 3): 250 lbs/min (8 hours/day, 5 days week).
- Liquid to Dilute Sulfuric Acid/Lime Neutralization Vessel (Ref. 8): 27.4 lbs/min (8 hours/day, 5 days/week).
- the Dilute Sulfuric Acid Storage Vessel is constructed of an acid resistant, premium/iso. resin, with top and side manways and an epoxy coated ladder with no cage.
- the Dilute Sulfuric Acid Vessel has a capacity of 1,070 ft 3 (8,000 gallons).
- Neutralized feedstock is discharged to the Primary Screw Press at a rate of 291.7 pounds per minute from the Pre-Treatment Chamber (Ref. 3).
- a controlled compression rate allows the removal of 60% - 80% of the dilute sulfuric acid at a rate of about 187.5 pounds per minute (based on a 75% moisture removal rate).
- the dilute sulfuric acid is then returned to the Dilute Acid Storage Vessel (Ref. 4) for reuse.
- the action of the Screw Press compresses the solids which are then pulverized and conveyed to the
- Liquid to Dilute Sulfuric Acid Storage Vessel 187.5 lbs/min (8 hours/day, 5 days/ week).
- Solids to Secondary Screw Press 104 lbs/min (8 hours/day, 5 days/week).
- the Primary Screw Press is constructed of corrosion resistant materials and shall have an approximate 10 minute retention time. A minimum of 60% liquid extraction is required.
- Neutralized feedstock is conveyed from the Primary Screw Press (Ref. 5 A) to the Secondary Screw Press at a rate of 104 pounds per minute.
- Water is piped from the Water Holding Vessel (Ref. 29B) into a screw conveyor at a rate of 187.5 pounds per minute and mixed with the solids from the Primary Screw Press (Ref. 5 A) to the Secondary Screw Press at a rate of 104 pounds per minute.
- Water is piped from the Water Holding Vessel (Ref. 29B) into a screw conveyor at a rate of 187.5 pounds per minute and mixed with the solids from the Primary
- Input- Solids from Primary Screw Press (Ref. 5A): 104 lbs/min (8 hours/day, 5 days/week).
- Solids to Dryer (Ref. 6): 104 lbs/min (8 hours/day, 5 days/ week).
- Water to Water Holding Vessel (Ref. 29B): 187.5 lbs/min (8 hours/day, 5 days/ week).
- the Secondary Screw Press is constructed of corrosion resistant materials and shall have an approximate 10 minute retention time. A minimum of 60% liquid extraction is required.
- the dryer has a flow and capacity rating of 4.00 tons per hour, producing a product with a moisture content of about 5% - 10%.
- the dried material has a light fluff consistency.
- the dried material is then pneumatically conveyed to the Processed Feedstock Storage Vessel (Ref. 7).
- Solids from Secondary Screw Press (Ref. 5B): 104 lbs/min (8 hours/day, 5 days/ week).
- Solids to Processed Feedstock Storage Silo (Ref. 7): 45.0 lbs/min (8 hours/day, 5 days/ week).
- Liquid Lost to Drying Process 59.1 lbs/min (8 hours/day, 5 days/week). Specifications:
- Processed feedstock is pneumatically conveyed from the Dryer (Ref. 6) to the storage vessel at a rate of 45.0 pounds per minute.
- the vessel is designed to hold 25 tons of feedstock (about a two and one half (2-1/2) day supply). Material is metered to the Hydrolysis System (Ref. 12) at the precise rate of 27.8 pounds per minute.
- Solids from Dryer (Ref. 6): 45.0 lbs/min (8 hours/day, 5 days/week).
- Solids to Hydrolysis System (Ref. 12): 27.8 lbs/min (24 hours/day, 5 days/ week, alternating one hour operating and one hour resting).
- the Processed Feedstock Storage vessel is constructed of corrosion resistant, 12 gauge sheet welded steel and has a capacity of about 2-1/2 day storage area (using 15 lbs/ft 3 as a standard). Storage capacity may vary depending on the density of the feedstock present in the silo. The silo will maintain the 5% to 10% moisture level required in the feedstock.
- Dilute sulfuric acid (1% - 2% concentration) along with the contaminants is piped from the bottom of the Dilute Sulfuric Acid Storage Vessel (Ref. 4) into the Dilute Sulf ric Acid Neutralization Vessel at a rate of 27.5 pounds per minute.
- the contaminated acid solution is treated with 1020 pounds of lime.
- the lime reacts with the acid, capturing the heavy metals, forming gypsum.
- the liquid is piped to the Gypsum Belt Press (Ref. 10) at a rate of 142.8 pounds per minute.
- Lime from Lime Holding Vessel (Ref 9): 1,020 lbs of lime is manually added to the vessel once a week. While all 1,020 lbs is added at once, on average, the lime is added at 2.1 lbs/min (8 hours/day, 1 day on weekend).
- This vessel holds lime for the periodic neutralization and capture of heavy metals from the dilute sulfuric acid.
- the lime in either a liquid or dry form, is manually added to the Dilute Sulfuric Acid Neutralization Vessel (Ref. 8) at an approximate rate of 2.1 pounds per minute (1,020 pounds per week).
- the vessel holds 1 ,500 pounds of lime in a dry, form with a manual discharge chute.
- Liquid is pumped from the Dilute Sulfuric Acid Neutralization Vessel (Ref. 8) to the Gypsum Belt Press at a rate of 142.8 pounds per minute.
- the gypsum is separated from the neutralized liquid and conveyed to a holding vessel at a rate of 3.91 pounds per minute.
- the neutralized liquid is piped at a rate of 136.6 pounds per minute to the Neutralized Water Storage Vessel (Ref. 11).
- Gypsum 3.9 lbs/min (8 hours/day, 1 day on weekend).
- Water to Neutralized Water Storage Vessel (Ref. 11): 138.9 lbs/min (8 hours/day, 1 day on weekend).
- the Neutralized Water Storage Vessel has a capacity of 3000 gallons.
- the purpose of the Hydrolysis System is to break down the solid feedstock into cellulose and hemicellulose. Feedstock is metered from either storage vessel (Ref 7 or IB) at a rate of 27.8 pounds per minute.
- Concentrated sulfuric acid (70% concentration) is automatically injected into the Hydrolyzer at a rate of 27.8 pounds per minute from the Concentrated Sulfuric Acid Storage Vessel (Ref. 30).
- the feedstock and acid are continuously blended for a resident time of about ten minutes. The two materials form a gel which is discharged from the
- the Hydrolyzer at a rate of 55.6 pounds per minute to the Cooking Vessels (Ref. 13).
- the Hydrolyzer is automatically flushed with 88 °C water to clean the unit and transfer any remaining residue to the Cooking Vessel. It takes about one hour to meter the feedstock through the Hydrolysis System, flush the system and fill the Cooking Vessel (Ref. 13).
- the Hydrolysis System operates one hour and fills one Cooking Vessel. The system then sits idle for one hour before beginning its process again to fill the second Cooking Vessel.
- Feedstock from Storage Vessels (Ref. 7 or IB): 27.8 lbs/min (24 hours/day, 5 days/week, alternating one hour operating and one hour resting).
- Concentrated Sulfuric Acid from Concentrated Sulfuric Acid Storage (Ref. 7 or IB): 27.8 lbs/min (24 hours/day, 5 days/week, alternating one hour operating and one hour resting).
- Vessel (Ref. 30): 27.8 lbs/min (24 hours/day, 5 days/week, alternating one hour operating and one hour resting).
- the Hydrolysis System consists of a screw conveyor with a leak proof trough.
- the chamber is constructed of acid resistant materials and corrosion proof seals.
- the material being conveyed has a 10 minute retention time in the Hydrolysis System and is sized accordingly (about 15 feet long).
- the Hydrolysis System has an approximate capacity of 55.6 lbs/min. Cooking Vessel (Quantity 2) (Ref. No. 13)
- Each Cooking Vessel is operated independently, constructed of polyethylene resins and sized at 1250 gallons each (about 6' in diameter by 6' - 8" in height). Each tank is equipped with agitators and heat tracing to maintain the 95 °C - 99°C approximate temperature required for reaction. Each tank is covered with 2" thick polyurethane insulation to minimize heat loss. The hydrolyzed material is deposited into 790 gallons of 88°C water. The water flows into the Cooking Vessel from the Water Heater (Ref. 32) at a rate of 111 pounds per minute (13.3 gallons per minute). The ratio of product in the Cooking Vessel is two to four parts water, one part 70% concentrate sulfuric acid and one part feedstock.
- the residence time in the Cooking Vessel is two hours, plus one hour fill time and one hour discharge time.
- the purpose of the two hour residence time is to further break down the feedstock material and to convert the cellulose into sugars.
- the vessel is emptied at a rate of 166.7 pounds per minute into Holding Vessel #1 (Ref. 14). After being emptied, the vessel is then ready to receive product from the Hydrolysis System (Ref. 12).
- Water from Water Heater (Ref. 32): 111 lbs/min (24 hours/day, 5 days/week, alternating one hour operating and one hour resting).
- Each Cooker Vessel evacuates to this tank at a rate of 166.7 pound per minute for one hour. Due to the 2 hour residence time of the Cooking Vessel (Ref 13), there is a one hour lag time between fills for Holding Vessel #1.
- the Holding Vessel allows the material to cool and enables the Cooking Vessel to be charged with new material.
- the tank has a 600 gallon capacity, constructed of polyethylene and has no insulation. The tank is sized to discharge at a steady flow rate of 83.333 pounds per minute to the Filter Press (Ref. 15).
- Liquid from Cooking Vessel (Ref. 13): 166.7 lbs/min (24 hours/day, 5 days/week, alternating one hour operating and one hour resting).
- Liquid to Filter Press (Ref. 15): 83 lbs/min (24 hours/day, 5 days/ week).
- Material from the Holding Vessel #1 (Ref. 14) is piped to the Filter Press at a rate of 83 pounds per minute.
- the membrane filter press is employed to remove the suspended solids from the liquid mixture.
- the resulting solids have about 30 to 50% moisture content and are deposited at a rate of 5.2 pounds per minute into the Lignin Holding Vessel (Ref. A) to await washing.
- the liquid material from the press is piped at a rate of 78 pounds per minute to the Acid Recovery Storage Vessel (Ref. 16).
- Liquid from Holding Vessel #1 (Ref. 14): 83 lbs/min (24 hours/day, 5 days/ week).
- Solids to Lignin Holding Vessel (Ref. A): 5.2 lbs/min (24 hours/day, 5 days/week).
- Liquid to Acid Recovery Storage Vessel (Ref. 16): 78 lbs/min (24 hours/day, 5 days/ week).
- a membrane filter press to accept 83 lbs/min of liquid. Complete with press frame, PLC control system, drip trays, membrane plates pack with manifold - automatic controls including panel, wiring, etc.
- the liquids from the Filter Press (Ref. 15) are pumped to the Acid Recovery Storage Vessel at a rate of 78 pounds per minute.
- the Acid Recovery Storage Vessel allows the Acid Recovery System (Ref. 17) to operate 24 hours a day, seven days a week (the Pre-Treatment Stage and the Hydrolysis Process operates 5 days a week).
- the Acid Recovery Storage Vessel is designed to hold 19,000 gallons (2 days worth) of liquid product for the Acid Recovery System (Ref. 17). A storage vessel of this size simply allows the Acid Recovery System (Ref. 17) to operate on weekends.
- the liquid product is piped to the Acid Recovery System (Ref. 17) at a rate of 55.8 pounds per minute.
- Liquid to Acid Recovery System (Ref. 17): 55.8 lbs/min (24 hours/day, 7 days/ week).
- the liquids from the Acid Recovery Storage Vessel (Ref. 16) are pumped to the Acid Recovery System at a flow rate of 55.8 pounds per minute. Water is also piped into the Acid Recovery System from the Water Storage Vessel (Ref. 29 A) at a rate of 118 pounds per minute. In the Acid Recovery System, about 96-99% of the sulfuric acid and about 92-99% of the sugars are recovered and separated into two distinct product streams.
- the sulfuric acid solution (now concentrated to 5 % sulfuric acid) is pumped at a rate of 116.2 pounds per minute to the Evaporator (Ref. 18). If the Pre- Treatment Process is operating, the acid solution is piped to the Dilute Sulfuric Acid Storage Vessel (Ref. 4) at a rate of 36.0 pounds per minute and to the Evaporator at a rate of 80 pounds per minute.
- the sugar solution is piped to the Dilute Sulfuric Acid Storage Vessel (Ref. 4) at a rate of 36.0 pounds per minute and to the Evaporator at a rate
- Acid Solution to Evaporator (Ref. 18): 116.2 lbs/min (from hours 8 - 24, 5 days/week and 24 hours a day on weekends).
- Liquid from Acid Recovery Storage Vessel (Ref. 16): 55.8 lbs/min (24 hours/day, 7 days/ week).
- Acid Solution to Evaporator (Ref. 18): 80 lbs/min (from hours 0 - 8, 5 days/ week).
- Acid Solution to Dilute Acid Storage Vessel (Ref. 4): 36 lbs/min (from hours 0 - 8, 5 days/week).
- Ion-exchange system designed to process the sugar/acid/water solution for 24 hours/day, 7 days/week, is available from Advanced Separation
- the acid solution is pumped at a rate of 116.2 pounds per minute from the Acid Recovery System (Ref. 17). Water is evaporated from the sulfuric acid, allowing the acid concentration to return to 70% (its original state). The concentrated acid is pumped at a rate of 8.3 pounds per minute to the Concentrated Sulfuric Acid Storage Vessel (Ref. 30) for reuse. The evaporated water is captured and condensed by the Evaporator and piped at a rate of 107.9 pounds per minute to the Water Storage Vessel (Ref. 29) for system reuse. During the 8 hours when the PreTreatment Process is operating, the volumes at this station are follows: 1) acid solution input: 80 pounds per minute, 2) concentrated acid output: 5.7 pounds per minute,
- Acid Solution from Acid Recovery System (Ref. 17): 116.2 lbs/min (from hours 8 - 24, 5 days/ week and 24 hours a day on weekends).
- Vessel (Ref. 30): 8.30 lbs/min (from hours 8 - 24, 5 days/week and 24 hours a day on weekends).
- Input- Acid Solution from Acid Recovery System (Ref. 17): 80 lbs/min (from hours 0 - 8, 5 days/ week).
- the sugar solution is piped from the Acid Recovery System (Ref. 17) at a rate of 58.1 pounds per minute to Holding Vessel #2.
- the vessel is designed to receive the sugar/water solution from the Acid Recovery System
- the sugar solution is piped from Holding Vessel #2 (Ref. 19) to the Reverse Osmosis Filter at a rate of 58.1 pounds per minute.
- the purpose of the Reverse Osmosis Filter is to increase the sugar concentration in the solution.
- the filter increases the sugar concentration form 9% sugar to about 15% sugar (the optimum sugar concentration for fermentation).
- the sugar solution is then piped to the Ammonia and pH Balancing System at a rate of 34.1 pounds per minute.
- the extracted water is pumped to the Water Storage Vessel (Ref. 29 A) at a rate of 24.0 pounds per minute.
- a nano-filtration system designed specifically to concentrate the sugar/water solution.
- the Ammonia and pH Balance System is comprised of an ammonia storage vessel and in-line injectors for the introduction of ammonia into the sugar solution.
- the sugar solution is piped to the Ammonia and pH Balancing System at a rate of 34 pounds per minute from the Reverse Osmosis Filter
- Ammonia from Ammonia Storage Vessel 0.1 lbs/min (24 hours/day, 7 days/week).
- Unit includes pH balance sensors to monitor the pH balance informing the control injector to add proper balance of ammonia to the stream.
- the Yeast Injection System is an on-line system similar to the Ammonia and pH Balancing System (Ref. 21).
- the Yeast Injection System is comprised of a yeast storage vessel and an in-line injector for the introduction of yeast into the sugar/ammonia solution.
- the sugar solution is piped to the Yeast Injection System at a rate of 34 lbs/min from the Ammonia and pH Balancing System (Ref. 21).
- Precise amounts of yeast are automatically injected into the solution at an approximate rate of 0.853 pounds per minute.
- the entire yeast injection process takes place as the solution flows at a rate of 35 pounds per minute to Holding Vessel #3 (Ref. 23). lnput:
- Yeast from Yeast Storage Vessel 0.853 lbs/min (24 hours/day, 7 days/week).
- Make-up Yeast Required As yet undetermined. If all yeast can be recaptured by the Yeast Filter (Ref. 25), very little make-up yeast will be required.
- a value control unit to inject precise amounts of yeast in the flow line of sugar and water for fermentation 1000 gallon capacity, 6' I.D. x 5' 6" High, iso. resin, flat bottom, closed top, epoxy coated ladder (no cage).
- the Sugar/ Ammonia/Yeast solution is piped into Holding Vessel #3 from the Yeast Injection System (Ref. 22) at a rate of 35 pounds per minute.
- the Holding Vessel is designed to store 3,000 gallons of solution.
- the size of the Holding Vessel makes it possible to fill the Fermentation Vessel (Ref. 24) with an entire days worth of solution in 12 hours.
- the solution is piped from Holding Vessel #3 to the Fermentation Vessel (Ref. 24) at a rate of 70 pounds per minute for 12 hours.
- the fermented beer solution is piped to the Yeast Filter and Distillation Holding Vessel (Ref. 25) at a rate of 419.8 pounds per minute for about 2 hours.
- the Fermentation Vessel is then steam cleaned and prepared for another batch. Input:
- the Yeast Filter and Distillation Holding Vessel consists of a trap filter to capture the yeast and return it to the Yeast Injection system (Ref. 22) and a Distillation Holding Vessel to regulate flow into the Distillation Column (Ref. 26) and provide a short evacuation time for the
- Fermentation Vessels (Ref. 24) (about 2 hours).
- the fermented beer solution is piped from the Fermentation Vessel (Ref. 24) to the Yeast Filter at a rate of 419.8 pounds per minute.
- the trap filter removes the yeast from the fermented beer and pumps the yeast to the Yeast Injection System (Ref. 22) at a rate of 10.2 pounds per minute.
- the remaining fermented beer solution is piped into the Distillation Holding Vessei at a rate of 409.6 pounds per minute.
- the Yeast Filter and Distillation Holding Vessel regulates the flow of fermented beer solution into the Distillation Column (Ref. 26) at a rate of 34 pounds per minute. Inpu
- Fermented Beer from Fermentation Vessel (Ref. 23): 419.8 lbs/min (2 hours/day, 7 days/week).
- Fermented Beer to Distillation Column (Ref. 26): 34 lbs/min (21 hours/day, 7 days/week).
- the Distillation Column accepts the fermented beer at 12% - 14% ethanol (by volume) and concentrates the ethanol to 99.7% ethanol (by volume).
- the first step of the distillation process concentrates the ethanol to about 94% by volume.
- the second step removes almost all of the remaining water with a desiccant.
- the Distillation Column consists of a beer still, dehydration column and entrainer recovery column. With this particular application, the dehydration column is used to provide 60% of the heat required for the beer still. The system is designed to allow for the beer still and the dehydration column to be run independently.
- the ethanol is piped from the
- Distillation Column to the Ethanol Storage Vessel (Ref. 28) at a rate of 4.6 pounds per minute (based on a standard output of 100 gallons per ton of dry feedstock).
- the output flow rate will vary from 60-120 gallons per ton dry feedstock, depending on the quality of the feedstock used.
- the remaining stillage from the Distillation Column is pumped at a rate of 1.5 pounds per minute to a holding area to await sale as cattle feed.
- the water in the solution is evaporated off at a rate of 28 pounds per minute. In the future, the evaporated water may be captured and condensed for reuse.
- Ethanol to Ethanol Storage Vessel (Ref. 28): 4.6 lbs/min (24 hours/day, 7 days/ week). Stillage to Holding Area: 1.5 lbs/min (24 hours/day, 7 days/ week).
- Distillation Column consists of the following equipment: Degasser Condenser, Degasser Reboiler, Feed Preheater, Beer Still, Dehydration
- Maximum input shall be 9 gallons per minute. Size: 16 inch stripper and rectifier.
- Ethanol to be used as fuel shall have less than .5% water.
- Chiller Coil (Ref. No. 27)
- the Chiller Coil is a basic heat exchanger for the heating and removal of heat from the Fermentation Vessels (Ref. 24).
- the coil utilizes steam heat from the boiler to begin the fermentation reaction.
- the Chillier Coil utilizes cool water from a lagoon for heat removal from the Fermentation Vessels.
- the Chiller Coil maintains the temperature of the Fermentation Vessel (Ref. 21) at 36°C.
- the water requirements for the Chiller Coil are delivered as required.
- Ethanol from the Distillation Column (Ref. 26) is piped to the Ethanol Storage Vessel at a rate of 4.6 pounds per minute (using 100 gallons per ton dry feedstock as standard).
- the Ethanol Storage Vessel is emptied every week to a tanker truck at an approximate rate of 340 pounds per minute. All storage tanks are ASME certified and exceed any and all state and local codes and industrial regulations as well as EPA and all other environmental agencies. Because of the material contained, a 110% containment barrier as set forth by codes and regulations to capture any spill or purgement of material is specified.
- Ethanol from Distillation Column (Ref. 26): 4.6 lbs/min (24 hours/day, 7 days/week).
- Ethanol to Tanker Truck 340 lbs/min (2 hours/day, once a week).
- Water to Water Heater (Ref. 32): 111 lbs/min (24 hours/day, 5 days/ week alternating one hour operating, one hour resting).
- the water is used to remove any trace heavy metals and acid left in the pre-treated feedstock.
- the water is piped to the Secondary Screw Press (Ref. 5B) at a rate of 187.5 pounds per minute.
- the water is then returned from the Secondary Screw Press at a rate of 187.5 pounds per minute.
- the water may need to be neutralized with about 20 pounds of lime. Testing will determine the exact number of days between neutralization.
- the Concentrated Sulfuric Acid Vessel serves as a storage vessel for the 70 % concentrated sulfuric acid used in the process.
- the vessel accepts concentrated acid from the Evaporator (Ref. 18) at a rate of 5.7 pounds per minute during the 8 hours of operation of the Pre-Treatment System and 8.30 pounds per minute during the remaining 16 hours of operation and on weekends.
- the concentrated sulfuric acid is piped from the Concentrated Sulfuric Acid Storage Vessel to the Hydrolysis System (Ref. 12) at a rate of 27.8 pounds per minute, alternating one hour pumping and one hour resting.
- the Concentrated Acid Storage Vessel is ASME certified and exceeds any and all state and local codes and industrial regulations as well as EPA and all other environmental agencies. Because of the material contained, a 110% containment barrier as set forth by codes and regulations to capture any spill or purgement of material, is specified
- Concentrated Sulfuric Acid from Evaporator (Ref. 18): 5.7 lbs/min (from hours 0 - 8, 5 days/ week).
- Concentrated Sulfuric Acid from Evaporator (Ref. 18): 8.30 lbs/min (from hours 8 - 24, 5 days/ week and on weekends).
- Concentrated Sulfuric Acid to Hydrolysis System (Ref. 30): 27.8 lbs/min (24 hours/day, 5 days/week, alternating one hour operating and one hour resting).
- Waste Water Storage Vessel (Optional) (Ref. No. 30)
- Municipal waste water or sewage may be used as a substitute for water added to the Cooking Vessels (Ref. 13). All bacteria and pathogens are destroyed by the sulfuric acid and >93°C temperature. Any solids present in the waste water are minimal and in turn will not reduce the BTU rating of the lignin.
- the high nitrogen content of the waste water not only acts as a fertilizer for the yeast, but also reduces the amount of ammoma (a source of nitrogen) required for proper fermentation.
- the waste water (if used) will be piped to the Water Heater (Ref. 32) at a rate of 111 pounds per minute.
- Waste Water from Source Delivered in bulk as required. If Waste Water was used exclusively with no clean water as make-up, requirements would be 400,000 lbs/week. On average, the rate of delivery would be 55.6 lbs/min (24 hours/day, 5 days/week).
- Waste water to Water Heater (Ref. 32): 111 lbs/min (24 hours/day, 5 days/week, alternating one hour pumping and one hour resting).
- Clean water from the Water Storage Vessel (Ref. 29A) is piped to the Water Heater at a rate of 111 pounds per minute (if waste water is used, the liquid will be piped from the Waste Water Storage Vessel (Ref. 31) at the same rate).
- the water is heated to about 88 °C and piped to the Cooking Vessels (Ref. 13) at a rate of 111 pounds per minute, pumping one hour and resting one hour.
- Input :
- Water to Cooking Vessel (Ref. 12): 111 lbs/min (24 hours/day, 5 days/week, alternating one hour pumping and one hour resting).
- Indirect Fired Hot Water Storage Heater 36" dia. x 52" lg. vertical ASME tank designed for 125 PSIG with a copper coat internal lining and insulation with jacket. Tank capacity is 200 gal.
- the unit is furnished with P&T relief valve, pressure and temperature gages, single wall tank heater with non-ferrous tube sheet, self- operating steam control valve, inlet steam strainer, drip trap, and F&T trap. Capacity is 1000 GPH 16° to 88° C, at 100 PSIG steam. This unit will give 1000 GPH continuous duty and 200 gal storage capacity when not in use.
- Portable storage hoppers dimensions about 6' x 6' x 5' for a storage capacity of about 180 ft 3 .
- a simple holding vessel for the storage of pulverized lignin and wood chips and/or non-chlorinated plastic serves as boiler fuel.
- the Lignin is conveyed to the Boiler Feedstock Storage Vessel at a rate of 15.6 pounds per minute.
- the rate in which the boiler fuel is burned will be about 15.8 pounds per minute with a steam production of 3800 pounds of steam per hour.
- Wood Chips and non-chlorinated plastic As Required (depending on lignin output).
- Boiler feedstock storage hopper dimensions about 10' x 10' x 16' for a storage capacity of about 1600 ft 3 .
- a packaged boiler is used to generate steam and hot water for the system. Elements of the system requiring steam and hot water are the Cooking Vessel (Ref. 13), the Acid Recovery System (Ref. 17); the Fermentation Vessels (Ref. 24) and the Distillation Column (Ref. 26).
- the steam generating plant is designed to burn a maximum 950 pounds per hour of lignin wood chip fuel to produce about 3800 pounds of steam per hour delivered at 125 PSIG.
- Boiler Fuel from Boiler Feedstock Storage Vessel (Ref. B): 15.833 lbs/min (24 hours/day, 7 days/ week).
- Boiler System includes fuel feed system, tangential furnace system, HRT boiler pressure vessels, mechanical dust collector, induced draft fan and stack, condensate return and boiler feed system, boiler feed pump and control system, control panel and chemical feed system and water softener. Summary of Solid Waste Processing System
- the process for the treatment of solid waste, waste sludge and scrap tires and producing usable, commercial products is a zero discharge system.
- the process is fully enclosed and odor controlled. All water is filtered and purified after use and all odor and dust are collected and filtered.
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Organic Chemistry (AREA)
- Biotechnology (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Food Science & Technology (AREA)
- Biochemistry (AREA)
- Physiology (AREA)
- Mycology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Microbiology (AREA)
- Molecular Biology (AREA)
- Botany (AREA)
- Animal Husbandry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Processing Of Solid Wastes (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
Claims
Priority Applications (13)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
BR9408408A BR9408408A (en) | 1993-12-23 | 1994-12-16 | Process for the production of ethanol from municipal solid waste process for the removal of heavy metals and production of glucose from the cellulosic component of municipal solid waste |
UA96072679A UA41971C2 (en) | 1993-12-23 | 1994-12-16 | method for producing ethanol of cellulose-containing waste (variants), a method for preparing glucose of cellulose-containing waste |
DE69433942T DE69433942D1 (en) | 1993-12-23 | 1994-12-16 | INDUSTRIAL PROCESS FOR THE PRODUCTION OF ETHANOL |
EP95905989A EP0741794B1 (en) | 1993-12-23 | 1994-12-16 | Commercial ethanol production process |
NZ278230A NZ278230A (en) | 1993-12-23 | 1994-12-16 | Producing ethanol from municipal solid waste by a multistage process using fermentation of sugars extracted from hydrolysed separated cellulose |
AT95905989T ATE273396T1 (en) | 1993-12-23 | 1994-12-16 | INDUSTRIAL PROCESS FOR PRODUCING ETHANOL |
RO96-01273A RO117804B1 (en) | 1993-12-23 | 1994-12-16 | Process for producing ethanol from municipal solid waste |
HU9601722A HU222009B1 (en) | 1993-12-23 | 1994-12-16 | Commercial ethanol production process |
JP7517524A JPH09507386A (en) | 1993-12-23 | 1994-12-16 | Method for producing industrial ethanol |
AU14389/95A AU679828B2 (en) | 1993-12-23 | 1994-12-16 | Commercial ethanol production process |
FI962570A FI962570A (en) | 1993-12-23 | 1996-06-20 | Commercial ethanol production process |
NO962650A NO962650L (en) | 1993-12-23 | 1996-06-21 | Commercial ethanol production process |
PL94315171A PL182075B1 (en) | 1993-12-23 | 1996-07-25 | Method of obtaining ethyl alcohol of indutry quality |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US17220293A | 1993-12-23 | 1993-12-23 | |
US08/172,202 | 1993-12-23 | ||
US35101794A | 1994-12-07 | 1994-12-07 | |
US08/351,017 | 1994-12-07 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1995017517A1 true WO1995017517A1 (en) | 1995-06-29 |
Family
ID=26867846
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1994/014566 WO1995017517A1 (en) | 1993-12-23 | 1994-12-16 | Commercial ethanol production process |
Country Status (20)
Country | Link |
---|---|
EP (1) | EP0741794B1 (en) |
JP (1) | JPH09507386A (en) |
CN (2) | CN1085730C (en) |
AT (1) | ATE273396T1 (en) |
AU (1) | AU679828B2 (en) |
BR (1) | BR9408408A (en) |
CA (1) | CA2179615A1 (en) |
CZ (1) | CZ183096A3 (en) |
DE (1) | DE69433942D1 (en) |
FI (1) | FI962570A (en) |
HK (1) | HK1053660A1 (en) |
HU (1) | HU222009B1 (en) |
MX (1) | MX9500128A (en) |
NO (1) | NO962650L (en) |
PL (1) | PL182075B1 (en) |
PT (1) | PT741794E (en) |
RO (1) | RO117804B1 (en) |
RU (1) | RU2159816C2 (en) |
UA (1) | UA41971C2 (en) |
WO (1) | WO1995017517A1 (en) |
Cited By (24)
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CN1064711C (en) * | 1997-05-07 | 2001-04-18 | 昆明市环境科学研究所 | Alcohol extracting method from waste liquid containing sugar and acid |
GB2416776A (en) * | 2004-07-28 | 2006-02-08 | British Sugar Plc | Enhancement of the fermentability of carbohydrate substrates by chromatographic purification |
EP1860201A1 (en) * | 2006-05-25 | 2007-11-28 | BP p.l.c. | Conversion method |
DE202008001824U1 (en) | 2007-07-25 | 2008-11-27 | Lanxess Deutschland Gmbh | Apparatus for biodiesel production |
US8003352B2 (en) | 2004-07-16 | 2011-08-23 | Iogen Energy Corporation | Method of obtaining a product sugar stream from cellulosic biomass |
US8163517B2 (en) | 2008-10-02 | 2012-04-24 | Mitsubishi Heavy Industries, Ltd. | Organic material production system using biomass material and method |
US8247200B2 (en) | 2007-01-25 | 2012-08-21 | Iogen Energy Corporation | Method of obtaining inorganic salt and acetate salt from cellulosic biomass |
US8980060B2 (en) | 2008-02-01 | 2015-03-17 | Mitsubishi Heavy Industries Mechatronics Systems, Ltd. | Biomass hydrothermal decomposition apparatus, method thereof, and organic material production system using biomass material |
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US9328323B2 (en) | 2011-07-08 | 2016-05-03 | Aikan North America, Inc. | Systems and methods for digestion of solid waste |
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US9822420B2 (en) | 2013-03-18 | 2017-11-21 | Industrial Technology Research Institute | Method of separating carbohydrate |
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US9868932B2 (en) | 2010-03-10 | 2018-01-16 | Mitsubishi Hitachi Power Systems Environmental Solutions, Ltd | Biomass hydrothermal decomposition apparatus, temperature control method thereof, and organic raw material production system using biomass material |
US10155952B2 (en) | 2013-10-23 | 2018-12-18 | Ajinomoto Co., Inc. | Method for producing target substance |
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- 1994-12-16 PT PT95905989T patent/PT741794E/en unknown
- 1994-12-16 CN CN94194894A patent/CN1085730C/en not_active Expired - Fee Related
- 1994-12-16 HU HU9601722A patent/HU222009B1/en not_active IP Right Cessation
- 1994-12-16 CZ CZ961830A patent/CZ183096A3/en unknown
- 1994-12-16 AU AU14389/95A patent/AU679828B2/en not_active Ceased
- 1994-12-16 JP JP7517524A patent/JPH09507386A/en active Pending
- 1994-12-16 AT AT95905989T patent/ATE273396T1/en not_active IP Right Cessation
- 1994-12-16 RU RU96115272/13A patent/RU2159816C2/en not_active IP Right Cessation
- 1994-12-16 BR BR9408408A patent/BR9408408A/en not_active Application Discontinuation
- 1994-12-16 CA CA002179615A patent/CA2179615A1/en not_active Abandoned
- 1994-12-16 RO RO96-01273A patent/RO117804B1/en unknown
- 1994-12-16 CN CNB021009031A patent/CN1161366C/en not_active Expired - Fee Related
- 1994-12-16 UA UA96072679A patent/UA41971C2/en unknown
- 1994-12-16 EP EP95905989A patent/EP0741794B1/en not_active Expired - Lifetime
- 1994-12-16 DE DE69433942T patent/DE69433942D1/en not_active Expired - Lifetime
- 1994-12-16 WO PCT/US1994/014566 patent/WO1995017517A1/en not_active Application Discontinuation
-
1995
- 1995-01-02 MX MX9500128A patent/MX9500128A/en unknown
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Cited By (32)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1064711C (en) * | 1997-05-07 | 2001-04-18 | 昆明市环境科学研究所 | Alcohol extracting method from waste liquid containing sugar and acid |
US8003352B2 (en) | 2004-07-16 | 2011-08-23 | Iogen Energy Corporation | Method of obtaining a product sugar stream from cellulosic biomass |
GB2416776A (en) * | 2004-07-28 | 2006-02-08 | British Sugar Plc | Enhancement of the fermentability of carbohydrate substrates by chromatographic purification |
US8637661B2 (en) | 2006-05-25 | 2014-01-28 | Petroliam Nasional Berhad | Conversion method |
EP1860201A1 (en) * | 2006-05-25 | 2007-11-28 | BP p.l.c. | Conversion method |
WO2007138256A2 (en) * | 2006-05-25 | 2007-12-06 | The Queen's University Of Belfast | Conversion method |
WO2007138256A3 (en) * | 2006-05-25 | 2008-01-24 | Bp Plc | Conversion method |
US8637660B2 (en) | 2006-05-25 | 2014-01-28 | Petroliam Nasional Berhad | Conversion method |
US8247200B2 (en) | 2007-01-25 | 2012-08-21 | Iogen Energy Corporation | Method of obtaining inorganic salt and acetate salt from cellulosic biomass |
DE202008001824U1 (en) | 2007-07-25 | 2008-11-27 | Lanxess Deutschland Gmbh | Apparatus for biodiesel production |
EP2019088A2 (en) | 2007-07-25 | 2009-01-28 | Lanxess Deutschland GmbH | Polyol cleaning |
DE102007034621A1 (en) | 2007-07-25 | 2009-01-29 | Lanxess Deutschland Gmbh | Polyolreinigung |
US9238827B2 (en) | 2008-02-01 | 2016-01-19 | Mitsubishi Heavy Industries Mechatronics Systems, Ltd. | Biomass hydrothermal decomposition apparatus and method |
US8980060B2 (en) | 2008-02-01 | 2015-03-17 | Mitsubishi Heavy Industries Mechatronics Systems, Ltd. | Biomass hydrothermal decomposition apparatus, method thereof, and organic material production system using biomass material |
US10792588B2 (en) | 2008-02-01 | 2020-10-06 | Mitsubishi Hitachi Power Systems Environmental Solutions, Ltd. | Organic material production system using biomass material and method |
US8163517B2 (en) | 2008-10-02 | 2012-04-24 | Mitsubishi Heavy Industries, Ltd. | Organic material production system using biomass material and method |
US8334113B2 (en) | 2008-10-02 | 2012-12-18 | Mitsubishi Heavy Industries Mechatronics Systems, Ltd. | Organic material production system using biomass material and method |
US9102956B2 (en) | 2010-03-10 | 2015-08-11 | Mitsubishi Heavy Industries Mechatronics Systems, Ltd. | Biomass hydrothermal decomposition apparatus, temperature control method thereof, and organic raw material production system using biomass material |
US9868932B2 (en) | 2010-03-10 | 2018-01-16 | Mitsubishi Hitachi Power Systems Environmental Solutions, Ltd | Biomass hydrothermal decomposition apparatus, temperature control method thereof, and organic raw material production system using biomass material |
US11236369B2 (en) | 2010-07-06 | 2022-02-01 | Mitsubishi Heavy Industries Power Environmental Solutions, Ltd. | Fermentation system and fermentation method using saccharide solution |
US9850511B2 (en) | 2010-07-09 | 2017-12-26 | Mitsubishi Hitachi Power Systems Environmental Solutions, Ltd. | Biomass processing system and saccharide-solution production method using biomass material |
US9422519B2 (en) | 2010-07-09 | 2016-08-23 | Mitsubishi Hitachi Power Systems Environmental Solutions, Ltd. | Biomass hydrothermal decomposition system and saccharide-solution production method using biomass material |
US9567558B2 (en) | 2010-07-09 | 2017-02-14 | Mitsubishi Hitachi Power Systems Environmental Solutions, Ltd. | Biomass hydrothermal decomposition system and saccharide-solution production method using biomass material |
US9404135B2 (en) | 2010-09-03 | 2016-08-02 | Mitsubishi Heavy Industries Mechatronics Systems, Ltd. | Biomass decomposition apparatus and method thereof, and sugar-solution production system using biomass material |
US9587217B2 (en) | 2011-03-24 | 2017-03-07 | Toray Industries, Inc. | Apparatus for producing saccharide solution that uses biomass as feedstock |
US9657262B2 (en) | 2011-03-24 | 2017-05-23 | Toray Industries, Inc. | Fermentation apparatus that uses biomass as feedstock |
US9328323B2 (en) | 2011-07-08 | 2016-05-03 | Aikan North America, Inc. | Systems and methods for digestion of solid waste |
US10174281B2 (en) | 2013-02-28 | 2019-01-08 | Mitsubishi Hitachi Power Systems Environmental Solutions, Ltd. | Biomass treatment system |
US9822420B2 (en) | 2013-03-18 | 2017-11-21 | Industrial Technology Research Institute | Method of separating carbohydrate |
US10155952B2 (en) | 2013-10-23 | 2018-12-18 | Ajinomoto Co., Inc. | Method for producing target substance |
US11384379B2 (en) | 2017-09-25 | 2022-07-12 | Ajinomoto Co., Inc. | Method for producing a protein and disaccharide using a Talaromyces cellulolyticus |
CN111172201A (en) * | 2020-01-16 | 2020-05-19 | 吉林大学 | Method for preparing cellulosic ethanol by alkali pretreatment |
Also Published As
Publication number | Publication date |
---|---|
CN1161366C (en) | 2004-08-11 |
BR9408408A (en) | 1997-08-05 |
PL182075B1 (en) | 2001-11-30 |
RO117804B1 (en) | 2002-07-30 |
NO962650D0 (en) | 1996-06-21 |
AU1438995A (en) | 1995-07-10 |
CN1085730C (en) | 2002-05-29 |
AU679828B2 (en) | 1997-07-10 |
JPH09507386A (en) | 1997-07-29 |
CZ183096A3 (en) | 1996-10-16 |
PT741794E (en) | 2004-10-29 |
HK1053660A1 (en) | 2003-10-31 |
EP0741794A4 (en) | 2000-08-30 |
HU9601722D0 (en) | 1996-08-28 |
CA2179615A1 (en) | 1995-06-29 |
FI962570A (en) | 1996-08-21 |
CN1142857A (en) | 1997-02-12 |
MX9500128A (en) | 1997-06-28 |
HUT76708A (en) | 1997-10-28 |
HU222009B1 (en) | 2003-03-28 |
EP0741794A1 (en) | 1996-11-13 |
ATE273396T1 (en) | 2004-08-15 |
FI962570A0 (en) | 1996-06-20 |
PL315171A1 (en) | 1996-10-14 |
DE69433942D1 (en) | 2004-09-16 |
NO962650L (en) | 1996-08-23 |
CN1397561A (en) | 2003-02-19 |
EP0741794B1 (en) | 2004-08-11 |
UA41971C2 (en) | 2001-10-15 |
RU2159816C2 (en) | 2000-11-27 |
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