WO2013044081A1 - Procédé de fermentation efficace en termes d'énergie intégré avec un procédé d'extraction utilisant un fluide supercritique - Google Patents

Procédé de fermentation efficace en termes d'énergie intégré avec un procédé d'extraction utilisant un fluide supercritique Download PDF

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Publication number
WO2013044081A1
WO2013044081A1 PCT/US2012/056644 US2012056644W WO2013044081A1 WO 2013044081 A1 WO2013044081 A1 WO 2013044081A1 US 2012056644 W US2012056644 W US 2012056644W WO 2013044081 A1 WO2013044081 A1 WO 2013044081A1
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supercritical
ethanol
fermentation
aerogel
gaseous
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PCT/US2012/056644
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English (en)
Inventor
Rafael Januario Calabrese
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E. I. Du Pont De Nemours And Company
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Publication of WO2013044081A1 publication Critical patent/WO2013044081A1/fr

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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels
    • 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
    • C12F3/02—Recovery of by-products of carbon dioxide
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • This invention relates to an energy efficient fermentation process integrated with an extraction process that uses a supercritical fluid.
  • bacteria cells used for fermentation exhibit reduced activity at carbohydrate concentrations higher than about 10 wt%.
  • undesirable bacteria cells become more active at higher carbohydrate concentrations, catalyze undesirable reactions in the fermenter, and thereby compromise selectivity of the reaction to the product of interest.
  • One approach to controlling the concentration of carbohydrates in a fermentation reaction is to dilute the reaction mixture with water. This not only uses large volumes of water, but makes recovery of the fermentation product more difficult in view of the need to separate the product from the water. Use of large volumes of water also increases the amount of stillage and other waste material left behind after completion of the fermentation reaction, and disposal of such waste material in a cost-effective, environmentally benign manner is difficult.
  • the source of water to be added to the fermentation reaction is a fresh water source such as a river, the water must typically be treated with a biocide to limit the growth of undesirable bacteria in the fermenter.
  • Aerogels are nanoporous materials that have the lowest known thermal conductivity and the highest insulation value. Even though aerogel insulation could significantly reduce energy losses in buildings, appliances, vehicles and other parts of the cold chain, the high cost of manufacturing aerogels has previously reduced their attractiveness because the payback time for investment in their use is quite long.
  • the high cost of the aerogel is due primarily to the high cost of raw materials needed to make the sol (the precursor to the gel), and the high cost associated with the supercritical drying of the alcogel, which relies on the presence of CO 2 to displace the solvent contained in the alcogel.
  • Supercritical drying with CO2 is usually required to prevent the pore structure of an aerogel from collapsing due to capillary forces.
  • an integrated manufacturing process comprising a fermentation process integrated with an extraction process that uses a supercritical fluid.
  • the process further comprises the steps: a) fermenting a carbohydrate to produce a fermentation product and gaseous CO2;
  • Figure 1 illustrates an aerogel process
  • FIGS 2, 4A and 4B illustrate a conceptual schematic of certain embodiments of the methods hereof.
  • Figure 3 illustrates a schematic of the integration fermentation process in concert with the manufacturing of aerogels.
  • Figure 5 illustrates a flow sheet of a fermentation process that converts sugar must to ethanol.
  • Figure 6 illustrates the entering and leaving streams to and from the heat exchanger employed in a typical sugar mill to control the temperature of the fermenter.
  • Figure 7 illustrates the flow diagram for a chiller and the heat exchanger used to cool the fermenter.
  • Figure 8 illustrates the energy, raw materials and equipment requirements in an organic aerogel manufacturing process that is set up as a standalone unit without the advantage of energy and material integration with a fermentation based manufacturing process.
  • Figure 9 illustrates a flow sheet for the gelation process used for this example.
  • Figure 10 illustrates a distillation column used to separate the water and concentrate the ethanol stream.
  • Figures 1 1 A, 1 1 B, and 12 illustrate a process flow sheet for heating and compressing the liquid CO2.
  • Figure 13 illustrates a simplified process diagram highlighting the pertinent process streams involved in cooling the fermentation vessel in the ethanol plant.
  • the methods hereof take advantage of the fact that, although CO2 is a byproduct of the fermentation process, it is nevertheless a chemical compound that itself has several valuable uses. Therefore, the fermentation process combined with an extraction process utilizes the CO2 to produce a low cost aerogel.
  • a typical aerogel process requires large amounts of a solvent such as ethanol in the washing step, and large amounts of CO 2 and energy in the supercritical drying step.
  • supercritical drying step in an aerogel process requires the use of a large compressor to compress the CO2 to be used to obtain effective drying of the alcogel.
  • One embodiment of the methods hereof thus, involves the operation of a fermentation process in concert with the manufacturing process of aerogels.
  • a schematic of the integration can be seen in Figures 2 and 3.
  • a solvent such as ethanol, CO2 and excess energy (steam and electricity) can be obtained from a fermenter such as a sugar mill/bio-fuel plant.
  • Fermentation processes suitable for such purpose can use switch grass, corn products such as corn stover or corn cobs, or other cellulosic materials as the carbohydrate feedstock.
  • Such carbohydrates can be fermented by the action of bacteria such as Saccharomyces or
  • Lactobacillus Other aspects of such a fermentation process are described in USP 2010/0139154, which is by this reference incorporated in its entirety as a part hereof for all purposes.
  • a compressor as used for the compression of CO2 to form a supercritical CO2 stream for use in the supercritical drying of the alcogel can be used to treat some or all of the outflow stream coming from the fermenter.
  • the compression process will be able to separate a
  • the fermentation product such as ethanol and water from the CO2 stream, cycle the original stream less CO2 back to the fermenter, and route the clean CO2 stream for use in the supercritical cycle of the aerogel plant.
  • the CO2 that is not used in the aerogel plant can also be used or sold for other applications.
  • the decompression step in the supercritical CO2 cycle is similar to a refrigeration cycle with sufficient energy load to cool the fermenter to a preferred temperature.
  • FIG. 2 A schematic of a manufacturing plant where a solvent such as bio- ethanol and aerogels are produced by methods that achieve energy integration is shown in Figures 2, 4A and 4B.
  • the benefits to the aerogel plant include
  • the benefits to the biorefinery include:
  • a method of preparing supercritical CO 2 comprising (a) fermenting a carbohydrate to prepare a fermentation product, CO 2 and a waste material, (b) separating the waste material from the fermentation product, (c) burning the waste material to yield thermal energy, and (d) applying the thermal energy to compress the CO 2 .
  • Step (d) can comprise burning the waste material to generate electricity, and powering a compressor with the electricity.
  • a method of separating a fermentation product from water comprising (a) fermenting a carbohydrate to prepare a fermentation product in a mixture with water, (b) providing a supercritical CO 2 , (c) cooling the supercritical CO 2 to reduce the temperature thereof and extract thermal energy therefrom, and (d) applying the extracted thermal energy to heat the mixture of the fermentation product and water to separate the components of the mixture.
  • the method can also comprise preparing CO 2 in the fermentation process and compressing the CO 2 produced in the
  • a method of cooling a fermentation process comprising (a) fermenting a carbohydrate to prepare a fermentation product, (b) providing a supercritical CO 2 , (c) cooling the supercritical CO 2 to reduce the temperature thereof and extract thermal energy therefrom, and (d) applying the extracted thermal energy to cool the fermentation process.
  • Step (d) can also comprise heating, with the extracted thermal energy, a mixture of a refrigerant and an absorbent in an absorption chiller to separate refrigerant, in vapor form, from the absorbent, and increase the pressure of the refrigerant vapor.
  • the method can also comprise preparing gaseous CO 2 in the fermentation process and compressing the CO 2 produced in the fermentation process to provide the supercritical CO 2 .
  • a method of cooling a fermentation process that liberates thermal energy comprising (a) providing a supercritical CO 2 , and (b) releasing the pressure on the supercritical CO 2 to absorb the thermal energy as liberated by the fermentation process.
  • the fermentation process can be conducted in a fermenter, and step (b) can comprise releasing pressure on the supercritical CO 2 proximate to a thermal energy transfer medium that is proximate also to the fermenter or a feed thereto.
  • a method of preparing an alcogel comprising (a) fermenting a carbohydrate to prepare a fermentation product, and (b) contacting a hydrogel with the fermentation product to expel water from the hydrogel and give an alcogel.
  • the fermentation product can comprise an alcohol.
  • a method of displacing a volatile chemical from a substrate comprising (a) fermenting a carbohydrate to produce a fermentation product and gaseous CO 2 , (b) separating the gaseous CO 2 from the fermentation product, and (c) contacting the substrate with the gaseous CO 2 as produced from fermentation to expel the volatile chemical from the substrate.
  • the method can further comprise compressing the gaseous CO 2 before contact with the substrate.
  • the substrate can comprise an alcogel, and a solvent can be expelled from an alcogel to give an aerogel.
  • a method of displacing a volatile chemical from a substrate comprising (a) compressing CO 2 to form a supercritical CO 2 ,(b) exposing the supercritical CO 2 to a thermal energy transfer medium to provide a cooled CO 2 , (c) further compressing the cooled CO 2 , (d) contacting the substrate with the further compressed CO 2 to expel the volatile chemical from the substrate, and (e) releasing the pressure on the CO2 in proximity to the thermal energy transfer medium to absorb thermal energy therefrom.
  • a method of providing a purified CO 2 comprising (a) fermenting a carbohydrate to produce a fermentation product in a mixture with water and gaseous CO2, and (b) compressing the mixture to separate water and/or the fermentation product from the CO2.
  • a method of providing a supercritical CO 2 comprising (a) fermenting a carbohydrate to produce a fermentation product in a mixture with water and CO2, (b) separating the CO2 from the mixture, and (c) compressing the CO2 forming supercritical CO2.
  • An integrated manufacturing process comprising a fermentation process integrated with an extraction process that uses a supercritical fluid.
  • a supercritical fluid is defined as a fluid that is near or above both its critical pressure and critical temperature.
  • the preparation and properties of supercritical fluids are well known in the art; see for example "Supercritical Fluids", Kirk-Othmer Encyclopedia of Chemical Technology, Tomasko and Guo, 14 APR 2006, John Wiley & Sons, Inc.
  • a particularly suitable fluid is CO2.
  • supercritical CO2 is defined as being above about 800° C and 20 PSI (0.59 MPa).
  • extraction processes include but are not limited to the separation of azeotropic mixtures, such as ethanol and water, extracting materials such as flavors and fragrances from food and natural plant materials, removal of caffeine from products such as coffee and tea, purification of pharmaceuticals, polymers, or environmental materials, and removal of long chain alcohols from sugar cane crude wax (a byproduct of sugar cane production).
  • azeotropic mixtures such as ethanol and water
  • extracting materials such as flavors and fragrances from food and natural plant materials
  • removal of caffeine from products such as coffee and tea
  • purification of pharmaceuticals, polymers, or environmental materials and removal of long chain alcohols from sugar cane crude wax (a byproduct of sugar cane production).
  • Also described is an integrated manufacturing process comprising: a) fermenting a carbohydrate to produce a fermentation product and gaseous CO2,
  • the mixture can be a gel, and the component can be a continuous phase.
  • an aerogel is formed after the separation of the component from the mixture.
  • the fermentation product and the component is ethanol.
  • the process further comprises after step b: contacting a hydrogel with the ethanol to remove water from the hydrogel to form the gel.
  • a gel is typically an interconnected colloidal state in which a dispersed phase has combined with a continuous phase to produce a viscous product.
  • the gel can be an alcogel (in which the continuous phase is an alcohol) or a hydrogel (in which the continuous phase is water).
  • Also described is an integrated manufacturing process comprising: a) fermenting a carbohydrate to produce a fermentation product gaseous CO 2 and thermal energy;
  • an aerogel is formed after the separation of the component from the mixture. Also described is an integrated manufacturing process comprising: a) fermenting a carbohydrate to produce a fermentation product, gaseous CO 2 , and thermal energy wherein the thermal energy is transferred to a cooled water stream forming a heated water stream;
  • the process further comprises recycling the cooled water stream in step c) to step a).
  • the process further comprises recycling the liquid phase CO 2 formed in step e to step b).
  • an aerogel is formed after the separation of the component from the mixture.
  • range includes the endpoints thereof and all the individual integers and fractions within the range, and also includes each of the narrower ranges therein formed by all the various possible combinations of those endpoints and internal integers and fractions to form subgroups of the larger group of values within the stated range to the same extent as if each of those narrower ranges was explicitly recited.
  • range of numerical values is stated herein as being greater than a stated value, the range is
  • This example shows the performance of a typical fermenter in a sugar mill ethanol plant and the cooling loop employed to control the temperature in the fermenter.
  • Figure 5 shows a flow sheet of a fermentation process that converts sugar must to ethanol.
  • the size of fermentation plant can vary over a wide range but all calculations presented to demonstrate the present invention are based on a fermentation plant that produces 90,000 m 3 of ethanol per year. Those skilled in the art of producing ethanol from sugar will know that the chosen plant size is typical in the ethanol industry.
  • Table 1 shows the size, composition and temperature of the major process streams in the sugar to ethanol fermentation plant.
  • Sugar must, water and yeast are added to the fermentation vessel. Since aerobic fermentation process is exothermic, the temperature in the fermenter can rise to undesirable levels.
  • part of the wine from the fermenter is sent to a plate heat exchanger where it is cooled with help of process water from the cooling towers.
  • the rest of the wine exiting the fermenter is sent to a centrifuge where the yeast is separated from the wine and is recycled back to the fermenter.
  • the ethanol water solution is sent to the beer well and then to the distillation column where ethanol is separated from water.
  • the ethanol rich stream from the distillation condenser is sent to a molecular sieve column, where it is further purified to yield almost anhydrous ethanol.
  • the waste or stillage from the distillation column is collected and disposed.
  • Sugar cane is predominantly produced in temperate and tropical regions of the world where, during the sugar cane season, the ambient wet bulb temperatures can be high.
  • typical wet bulb temperature in Brazil during the sugar and ethanol production season may be around 30° C.
  • the cooling water from the cooling towers can be 30° C or higher.
  • Figure 6 shows the entering and leaving streams to and from the heat exchanger employed in a typical sugar mill to control the temperature of the fermenter.
  • Table 2 shows the size, temperature and enthalpy of the streams entering and leaving the heat exchanger.
  • the net energy exchanged in the heat exchanger for this example is 10,640 MM Btu/hr. It can also be seen that the temperature of the fermenter can be no lower than 32° C.
  • This example shows the energy used in separating ethanol from water in the distillation train of a typical sugar mill ethanol plant.
  • This example shows the improvement in ethanol yield possible if the fermenter can be cooled to 30° C.
  • Dedini S/A Sao Paulo, Brazil evaluated the advantages of cooling the ethanol fermentation process to temperatures below 32° C.
  • the study was carried out on a semi industrial scale fermentation process comprising a 100 m 3 fed batch fermenter, a lithium bromide absorption chiller and 315 m 3 /hr evaporative cooling tower. Results from the study were published by Oliverio et. al., in the Proceedings of the International Society of Sugar Cane Technology (Vol. 27, 2010). In this study the fermentation unit was run at different temperatures at and below 32° C and its effect was evaluated by measuring a number of dependent variables including the concentration of ethanol in the fermentation broth and the total yield of ethanol from the plant.
  • Table 3 shows that ethanol yields in the plant were improved from 85.05% to 86.79% when the temperature of the fermenter was reduced from 32° C to 30° C.
  • This example shows the size of a chiller and the additional heat exchange needed to cool the fermenters in order to improve ethanol yield of the plant that produces 90,000 m 3 of ethanol per year.
  • Example 1 it was shown that by using water from cooling towers, the temperature of the sugar must being recycled back to the fermenter can only be cooled to 32° C.
  • Figure 7 shows the flow diagram for a chiller and the heat exchanger used to cool the fermenter.
  • Table 4 shows the size, temperature and enthalpy of the streams when a chiller is installed and the heat load required for the chiller.
  • Example 3 showed the increase in ethanol yield if the fermentation process could be run at 30° C. This example shows additional savings in energy and reduction in waste stillage if the fermentation process can be cooled to 30° C.
  • Examples 6 and Figure 8 are presented to demonstrate the energy, raw materials and equipment requirements in an organic aerogel manufacturing process that is set up as a standalone unit without the advantage of energy and material integration with a fermentation based manufacturing process. Aerogels of both inorganic and organic
  • compositions are well known. See, for example, the Aerogel Handbook (Editors Leventis and Koebel, 201 1 , Springer) and Aerogels (Husing and Schubert, Ullman's Encyclopedia of Industrial Chemistry, 15 Dec 2006 DOI: 10.1002/14356007.c01_c01 .pub2). All aerogel processes requiring supercritical extraction will benefit from integration with a fermentation process. But in order to demonstrate the advantages of an integrated process all of the examples presented hereafter assume an aerogel manufacturing plant that produces an organic aerogel formed by the reaction between phenol and formaldehyde. The size of the aerogel manufacturing plant is assumed to be such that it produces 90,000 m 3 of aerogel/year.
  • a flow sheet for a typical phenol formaldehyde aerogel process is shown Figure 8.
  • Phenol and formaldehyde are reacted in an aqueous solution, in the presence of a base catalyst to form a low molecular weight phenol formaldehyde resin precursor.
  • the precursor in dilute form is further reacted in the presence of an acid catalyst to form a hydrogel.
  • the water in the hydrogel is removed by washing with the help of another solvent such as ethanol.
  • the resulting phenol formaldehyde gel rich in ethanol is transferred to a super critical extraction unit where the ethanol is removed from the gel thus producing a phenol formaldehyde aerogel.
  • This example shows the energy used to convert an organic phenol formaldehyde solution to a hydrogel in a phenol formaldehyde aerogel manufacturing process.
  • Figure 8 and Figure 9 show a flow sheet for the gelation process used for this example. Phenol and dilute formaldehyde solution are reacted in the presence of acid catalyst to form a crosslinked hydrogel.
  • a particle formation process may be integrated with the gelation process in order to convert the hydrogel being formed into discrete gel beads.
  • energy needs to be supplied to the gelation process.
  • gelation may be carried out over a wide range of temperature. However, for this example gelation is assumed to be carried out at 65° C. Thus 4550 kg/hr of condensate steam at 85° C is supplied to heat the gelation vessel .
  • This example demonstrates the distillation process and the energy needed to concentrate and recycle the ethanol stream back to the washing unit.
  • Figure 10 shows a distillation column used to separate the water and concentrate the ethanol stream.
  • Table 6 shows the composition and enthalpy of the different streams entering and leaving the distillation column. Aspen model based
  • This example shows the energy required to prepare the liquid CO 2 needed for supercritical extraction in the aerogel manufacturing process.
  • liquid CO 2 In a standalone aerogel plant, liquid CO 2 will need to be shipped from an external source. Liquid CO2 is usually stored and shipped at 24 atm and -
  • a 90,000 m 3 ethanol plant will generate about 85,000 ton of CO 2 that can be liquefied and sold in the market with minor investments and operational costs.
  • Example 3 the advantage of cooling the fermentation process in a standalone sugar mill ethanol plant was presented.
  • Example 4 showed the size of a separate refrigeration unit required and the energy used to operate the refrigeration unit. This example shows that the same desired cooling of the fermentation process can be achieved by energy and material integration of process streams in the ethanol and aerogel process without the operation of a separate refrigeration unit with considerable savings in energy cost.
  • FIG 13 shows a simplified process diagram highlighting the pertinent process streams involved in cooling the fermentation vessel in the ethanol plant.
  • the use part of the water from the cooling tower (streams 17 and 18) exchanging heat (through the heat exchanger HEX3) with the liquid carbon dioxide (streams 9, 16 and 19) that is pumped to be used in the supercritical extraction is shown.
  • the temperature for pumping the liquid carbon dioxide is 5 °C and the temperature required for the supercritical extraction is 30 °C so this temperature difference can be used to cool down the cooling water. This water will be used to complement the fermentation cooling.
  • Ethanol supply (ethanol will be used as a catalyst and can be all recovered) 3 MMBtu/h Energy required to heat CO 2 .

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Abstract

La présente invention concerne un procédé de fabrication intégré, dans lequel un procédé de fermentation est intégré avec un procédé d'extraction qui utilise un fluide supercritique. Le procédé fermente un glucide pour produire un produit de fermentation et du CO2 gazeux, puis comprime le CO2 gazeux pour former un CO2 supercritique en utilisant le CO2 supercritique en tant qu'agent d'extraction pour séparer un composant d'un mélange.
PCT/US2012/056644 2011-09-21 2012-09-21 Procédé de fermentation efficace en termes d'énergie intégré avec un procédé d'extraction utilisant un fluide supercritique WO2013044081A1 (fr)

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US201161537426P 2011-09-21 2011-09-21
US61/537,426 2011-09-21
US201261661888P 2012-06-20 2012-06-20
US61/661,888 2012-06-20

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001028675A1 (fr) * 1999-10-21 2001-04-26 Aspen Systems, Inc. Procede de production rapide d'aerogel
US20100139154A1 (en) 2008-12-04 2010-06-10 E.I. Du Pont De Nemours And Company Process for fermentive preparation of alcohols and recovery of product
WO2011021856A2 (fr) * 2009-08-18 2011-02-24 Kim Young-Il Agent de déshuilage et procédé et appareil pour la préparation de celui-ci
EP2361741A1 (fr) * 2010-02-25 2011-08-31 The Procter & Gamble Company Procédé de séparation de particules polymères superabsorbantes d'une composition thermoplastique solidifiée comprenant des polymères

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001028675A1 (fr) * 1999-10-21 2001-04-26 Aspen Systems, Inc. Procede de production rapide d'aerogel
US20100139154A1 (en) 2008-12-04 2010-06-10 E.I. Du Pont De Nemours And Company Process for fermentive preparation of alcohols and recovery of product
WO2011021856A2 (fr) * 2009-08-18 2011-02-24 Kim Young-Il Agent de déshuilage et procédé et appareil pour la préparation de celui-ci
EP2361741A1 (fr) * 2010-02-25 2011-08-31 The Procter & Gamble Company Procédé de séparation de particules polymères superabsorbantes d'une composition thermoplastique solidifiée comprenant des polymères

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
HUSING; SCHUBERT: "Ullman's Encyclopedia of Industrial Chemistry", 15 December 2006, article "Aerogels"
KHOSRAVI-DARANI K; VASHEGHANI-FARAHANI E: "Application of supercritical fluid extraction in biotechnology", CRITICAL REVIEWS IN BIOTECHNOLOGY, vol. 25, 2005, pages 231 - 242, XP008158772 *
LEVENTIS AND KOEBEL,: "Aerogel Handbook", 2011, SPRINGER
OLIVERIO ET AL., PROC. INT. SOC. SUGAR CANE TECHNOL., vol. 27, 2010
OLIVERIO, PROCEEDINGS OF THE INTERNATIONAL SOCIETY OF SUGAR CANE TECHNOLOGY, vol. 27, 2010
SOLEIMANI DORCHEH ET AL: "Silica aerogel; synthesis, properties and characterization", JOURNAL OF MATERIALS PROCESSING TECHNOLOGY, ELSEVIER, NL, vol. 199, no. 1-3, 1 November 2007 (2007-11-01), pages 10 - 26, XP022409626, ISSN: 0924-0136 *
TOMASKO; GUO: "Kirk-Othmer Encyclopedia of Chemical Technology", 14 April 2006, JOHN WILEY & SONS, INC., article "Supercritical Fluids"

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