WO2007046859A1 - Extraction and fractionation of biopolymers and resins from plant materials - Google Patents
Extraction and fractionation of biopolymers and resins from plant materials Download PDFInfo
- Publication number
- WO2007046859A1 WO2007046859A1 PCT/US2006/015025 US2006015025W WO2007046859A1 WO 2007046859 A1 WO2007046859 A1 WO 2007046859A1 US 2006015025 W US2006015025 W US 2006015025W WO 2007046859 A1 WO2007046859 A1 WO 2007046859A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- solvent
- rubber
- extraction
- plant material
- resin
- Prior art date
Links
- 239000011347 resin Substances 0.000 title claims abstract description 133
- 229920005989 resin Polymers 0.000 title claims abstract description 133
- 238000000605 extraction Methods 0.000 title claims abstract description 121
- 239000000463 material Substances 0.000 title claims abstract description 81
- 229920001222 biopolymer Polymers 0.000 title claims abstract description 21
- 238000005194 fractionation Methods 0.000 title abstract description 15
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 125
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- LOVYCUYJRWLTSU-UHFFFAOYSA-N 2-(3,4-dichlorophenoxy)-n,n-diethylethanamine Chemical compound CCN(CC)CCOC1=CC=C(Cl)C(Cl)=C1 LOVYCUYJRWLTSU-UHFFFAOYSA-N 0.000 claims abstract description 45
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- 238000000194 supercritical-fluid extraction Methods 0.000 claims description 13
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
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- 239000005909 Kieselgur Substances 0.000 claims description 2
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- 238000000926 separation method Methods 0.000 abstract description 18
- 238000000746 purification Methods 0.000 abstract description 6
- 238000003815 supercritical carbon dioxide extraction Methods 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 88
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
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- 238000002474 experimental method Methods 0.000 description 11
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- 244000043261 Hevea brasiliensis Species 0.000 description 8
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 8
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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- 238000006460 hydrolysis reaction Methods 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000004816 latex Substances 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N monofluoromethane Natural products FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
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- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
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- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
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- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241001495454 Parthenium Species 0.000 description 1
- AVFIYMSJDDGDBQ-UHFFFAOYSA-N Parthenium Chemical compound C1C=C(CCC(C)=O)C(C)CC2OC(=O)C(=C)C21 AVFIYMSJDDGDBQ-UHFFFAOYSA-N 0.000 description 1
- 241001555021 Pedilanthus Species 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C2/00—Treatment of rubber solutions
- C08C2/02—Purification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0203—Solvent extraction of solids with a supercritical fluid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0215—Solid material in other stationary receptacles
- B01D11/0219—Fixed bed of solid material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0288—Applications, solvents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/02—Solvent extraction of solids
- B01D11/0292—Treatment of the solvent
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09F—NATURAL RESINS; FRENCH POLISH; DRYING-OILS; OIL DRYING AGENTS, i.e. SICCATIVES; TURPENTINE
- C09F1/00—Obtaining purification, or chemical modification of natural resins, e.g. oleo-resins
-
- 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
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S528/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S528/93—Guayule rubber
Definitions
- This invention relates in general to the extraction, separation, fractionation and purification of resins and biopolymers from plant materials using supercritical solvent extractions. Specifically, the invention relates to a process for the separation of resins and rubber from the guayule shrub (Parthenium argentatum) using supercritical solvent extraction, for example, supercritical carbon dioxide extraction. Additionally, co-solvents can be used with supercritical carbon dioxide to enhance the selective extraction of resins and rubbers from the plant material. Finally, subcritical water extraction may also be used according to this invention.
- Guayule is a desert shrub native to the southeastern United States and northern Mexico and which produces polymeric isoprene essentially identical to that made by Hevea rubber trees (e.g., Hevea brasiliensis) in Southeast Asia. As recently as 1910 it was the source of half of the natural rubber used in the U.S. Since 1946, however, its use as a source of rubber has been all but abandoned in favor of cheaper Hevea rubber and synthetic rubbers. However, demand for natural rubber is expected to produce shortages of that material in the future and rubber prices are expected to rise significantly. Natural rubber having lower heat hysteresis is required for many kinds of tires and amounts to about 35% of U.S. rubber use.
- Guayule Parthenium argentatum
- Guayule normally yields one half ton to one ton of rubber per acre in cultivation when, after two years, the entire plant is harvested and processed. Guayule plants store latex in tiny inclusions in the bark, making harvest of the outer fibrous layers, or bagasse, of the plant, desirable.
- plant material is prepared by initially grinding it into small particles. Generally, the entire plant is fed whole, that is, with the leaves thereon as well as dirt or foreign debris, into a grinding apparatus, for example, a hammermill. The ground material can be flaked, that is, crushed, by adding to a two-roll mill or other conventional equipment, which ruptures the rubber-containing cells. The communited plants are subjected to a resin-rubber solvent system.
- the solvent system contains one or more solvents which extract the resin as well as the rubber from the guayule-type shrub.
- single-solvent systems include halogenated hydrocarbons having from 1 to 6 carbon atoms, such as chloroform, perchloroethylene, chlorobenzene, and the like; and aromatic hydrocarbons and alkyl- substituted aromatic hydrocarbons having from 6 to 12 carbon atoms, such as benzene, toluene, xylene, and the like.
- This solvent system typically contains one or more polar resin solvents as well as one or more hydrocarbon rubber solvents.
- Typical polar resin solvents include alcohols having from 1 to 8 carbon atoms, such as methanol, ethanol, isopropanol and the like; esters having from 3 to 8 carbon atoms such as the various formates, the various acetates and the like; ketones having from 3 to 8 carbon atoms, such as acetone, methyl ethyl ketone, and the like.
- Typical non-polar hydrocarbon rubber solvents include alkanes having from 4 to 10 carbon atoms, such as pentane, hexane, and the like; and cycloalkanes having from 5 to 15 carbon atoms, such as cyclohexane, decalin, the various monoterpenes, and the like.
- alkanes having from 4 to 10 carbon atoms, such as pentane, hexane, and the like
- cycloalkanes having from 5 to 15 carbon atoms, such as cyclohexane, decalin, the various monoterpenes, and the like.
- the two types of solvents can form a two-phase system, they often form a single phase when utilized in proper proportions.
- One manner of adding different type solvents to the shrub is separately, but simultaneously. However, they are generally prepared as a mixture and added as such.
- a specific solvent system is an azeotropic composition of approximately 80% by weight of pentane, more specifically 78.1% by weight, and 20% by weight of acetone, more specifically 21.9% by weight.
- the ratio by weight of solvent to the amount of shredded shrub can be any amount sufficient to generally extract most of the rubber and resin, as for example from about 1 part by weight of solvent up to about 20 parts by weight of solvent for each 1 part by weight of shrub, and preferably about 3 parts by weight of solvent to 1 part by weight of shrub.
- the rubber-resin miscella so obtained typically contains about 1 to 25% by weight of total solids, that is resin plus rubber, and preferably about 9 to 18% by weight of total solids with the amount of resin by weight being from about 1 to about 3 parts for every 1 part by weight of rubber.
- the present invention utilizes supercritical solvents, such as carbon dioxide, optionally in combination with other co-solvents, for the separation, fractionation and purification of low molecular weight resins and high molecular weight biopolymers, such as rubber, from plant materials, such a guayule.
- supercritical solvents such as carbon dioxide
- One embodiment uses supercritical carbon dioxide for the simultaneous extraction, separation, fractionation and purification of rubber and resins from guayule plant materials.
- Alternate embodiments of the present invention comprise the steps of resin and rubber extraction with supercritical carbon dioxide, separation, fractionation and purification of rubber and resins in succession rather than simultaneously.
- the present invention is a method of extracting high molecular weight biopolymers, for example, rubber, and resin from plant material using supercritical fluid at medium to high pressures, hi at least one embodiment, carbon dioxide gas is compressed into a dense liquid, this liquid is then pumped into a cylindrically-shaped high-pressure vessel containing the guayule shrub, the extract laden liquid is then pumped into a separation chamber, where the extract is separated from the gas, and the gas is recovered for reuse.
- carbon dioxide gas is compressed into a dense liquid
- this liquid is then pumped into a cylindrically-shaped high-pressure vessel containing the guayule shrub
- the extract laden liquid is then pumped into a separation chamber, where the extract is separated from the gas, and the gas is recovered for reuse.
- Guayule-type plants which can be utilized to prepare rubber-containing miscellae include guayule, gopher plant (Euphorbia lathyris), mariola (Parthenium incanw ⁇ ), rabbitbrush ⁇ Chrysothanmus nauseosus), candelilla (Pedilanthus macrocarpus), Madagascar rubbervine (Cryptostegia grandiflor ⁇ ), milkweeds ⁇ Asclepias syriaca, speciosa, subulata, et al.), goldenrods ⁇ Solidago altissima, graminifolia, rigida, et al.), Russian dandelion ⁇ Taraxacum, kok-saghyz), mountain mint (Pycnanthemum incanum), American germander (Teucreum canadense), and tall bellflower ⁇ Campanula americana).
- Plant materials may be obtained using a variety of conventional and experimental harvesting processes. Generally, plants are cultivated, harvested and bailed using standard farming practices. Various portions of a plant may be used to obtain plant materials, including leaves, bark, stems, root systems or root balls. [0022] The plant need not be de-leafed because the metal ions such as manganese, iron and copper in the leaves that could promote oxidative degradation of the rubber are not extracted into the rubber solvents.
- processing the plant including the leaves, may add to the quality of the bagasse because the leaves contain mineral, nitrogenous and carbohydrate components that could enhance the quality of the bagasse for certain postprocessing applications. Further, in this embodiment of the invention, the process results in three products: total shrub rubber, total shrub resin and total shrub bagasse.
- the plants may be processed by de-leafing or de-barking using mechanized shearing or hand shearing, or may be processed with leaves and washed without de-leafing or de-barking; Removal of the leaves from the harvested shrub prior to the disclosed supercritical extraction process would permit the leaf wax to be isolated and sold separately. Defoliation will also eliminate the wax as a possible contaminant hi the resin and rubber solvents.
- Initial processing of plant materials may consist of a high pressure water system to strip the bark or leaves off the plant.
- Plant materials may be processed at a processing facility by conveyor, and any leftover plant material transported away for further refining or disposal.
- Secondary processing prior to extraction may further comprise grinding, hammermilling, or forcibly fractionating whole or partial plant materials into smaller pieces.
- the plant material may also be ground and then pelleted.
- Plant material may also be pre-treated by enzymatic degradation of either whole or partial plants.
- the bagasse may then be further extracted according to the methods disclosed herein.
- the extraction process disclosed herein can be carried out on a large scale using industrial extraction equipment, or on a small scale using typical laboratory scale units such as the Spe-ed SFE-2 from Applied Separations, 930 Hamilton Street, Allentown, PA, 18101.
- SCFs supercritical fluids
- solvents or supercritical fluids (SCFs)
- SCFs supercritical fluids
- the solvating powers can be adjusted by changing the pressure or temperature, separation and fractionation of resins and rubber is fast and easy.
- fractionation can be improved and extraction enhanced for high molecular weight components by adding modifiers or co-solvents, making SCFs a highly-versatile solvent to utilize with improved separation/fractionation capabilities when compared to conventional organic liquid solvent extraction processes.
- SCFs are fluids that exist at the transition between liquids and gases, and share some qualities of each.
- a pure SCF is any compound at a temperature and pressure above the critical values (e.g., a fluid is termed 'super-critical' when the temperature and the pressure exceed the critical pressure point of a vapor-liquid coexistence curve). More specifically, a fluid is termed supercritical when the temperature and pressure are higher than the corresponding critical values.
- the critical temperature of a fluid is the temperature above which liquefaction is not possible at any pressure.
- Critical pressure is further defined as the pressure required to liquefy a gas at the critical temperature. At temperatures and pressures above those at the critical point, fluids are at supercritical conditions. A supercritical fluid is characterized by physical and thermal properties that are between those of the gas and pure liquid. The fluid density is a strong function of the temperature and pressure. Above the critical temperature of a compound, the pure gaseous component cannot be liquefied regardless of the pressure applied. The CP is the vapor pressure of the gas at the critical temperature. In the supercritical state, only one phase exists. This phase retains solvent power approximating liquids as well as the transport properties common to gases. [0029] For example a comparison of typical values for density, viscosity, and diffusivity of gases, liquids and SCFs is as follows:
- pressure and temperature may be manipulated using a combination of isobaric changes in temperature with isothermal changes in pressure.
- SCFs it is possible to convert a pure component from a liquid to a gas (and vice versa) via the supercritical region without incurring a phase transition.
- the behavior of a fluid in the supercritical state can be described as that of a very mobile liquid, and the solubility behavior approaches that of the liquid phase while penetration into a solid matrix is facilitated by the gas-like transport properties.
- SCF extraction is known to be dependent on the density of the fluid, which in turn may be manipulated through control of the system pressure and temperature. Further, the dissolving power of SCF increases with isothermal increase in density or an isopyonic (i.e., constant density) increase in temperature.
- Supercritical fluids are an alternative to organic solvents in industrial purification and re-crystallization operations, because they provide a more environmentally-friendly process and eliminate some of the dangers to workers that are associated with traditional organic methods. SCF-based extraction processes do not produce the VOC and ODC emissions that are the by-products of traditional organic processes. Supercritical fluids are commonly used to extract analytes from samples.
- SFE supercritical fluid extraction
- SCF processes are commonly used in the food industry, e.g., for coffee and tea decaffeination and for beer brewing. SCF processes are also used in polymer, pharmaceutical, lubricant, and fine chemical industries and are valued for their potential to increase product performance levels over traditional processing technologies.
- SCFs are used in the recovery of organics from oil shale, separations of biological fluids, bio-separation, petroleum recovery, crude de-asphalting and de-waxing, coal processing, selective extraction of fragrances, oils and impurities, pollution control, and combustion.
- Supercritical fluids provide the advantage that they are inexpensive, extract the analytes faster and are more environmentally friendly than organic solvents.
- SCFs have solvating powers similar to liquid organic solvents but with higher diffusivities, lower viscosity, and lower surface tension.
- the solvating power can also be adjusted easily by changing the pressure or temperature for efficient separation of analytes.
- carbon dioxide is used as the supercritical solvent.
- solvents including, but not limited to, ammonia, water, nitrous oxide, xenon, krypton, methane, ethane, ethylene, propylene, propane, pentane, methanol, ethanol, isopropanol, isobutanol, chlorotrifluoromethane, monofluoromethane, cyclohexanol, toluene and other solvents known in the art.
- Supercritical fluid carbon dioxide has the gas-like physical properties of very low surface tension, low viscosity and high diffusivity, which allow a supercritical fluid solvent to penetrate an ultra low porosity substrate, such as a bed of finely ground bagasse, in a fixed bed extractor vessel and dissolve the compounds of interest.
- Supercritical carbon dioxide appears to have sufficient polarity at medium to high pressures and temperatures to be an adequate solvent of the resinous materials (but is a poor solvent for the rubber).
- supercritical carbon dioxide because of its low surface tension, low viscosity and high diffusivity, can penetrate the bed of ground bagasse at a very high percolation rate, which allows for a very quick extraction when compared to hydrocarbon solvents.
- Using supercritical CO 2 is advantageous over other extraction methods and has the potential to be the superior process for resin and rubber extraction on a commercial scale.
- the plant material is contacted with carbon dioxide near or above the supercritical conditions for a sufficient time to solubilize the resin and/or rubber components, forming a supercritical solution.
- a collection process in which the resins and rubber, which precipitate out from the supercritical solution, are collected when the pressure is reduced to atmospheric level.
- the pressures used for extraction can range from about 1,500 psi to about 10,000 psi, depending on the temperature, for the supercritical carbon dioxide and for the carbon dioxide with modifier co-solvent systems.
- the guayule shrub is first extracted with supercritical carbon dioxide at high temperatures and pressures and the temperature and pressure conditions are lowered or changed to precipitate the various insoluble fractions.
- fractionation can be carried out by extracting guayule shrub at different temperatures and pressures, going from low to high, and collecting each fraction, a novel way to make different melting point resins.
- this method of extraction can be used to fractionate the resins and rubber in a single system and with a single solvent.
- steps of the disclosed method are capable of being performed in various orders or, in some cases, as noted, at approximately the same time.
- simultaneous extraction of resin and rubber using a non-polar co- solvent is followed by fractionation in a supercritical fluid system, for example, using supercritical CO 2 , into a rubber fraction and a resin fraction.
- the present invention discloses a method of rubber and resin extraction in at least the following alternate and non-limiting ways: (1) approximately simultaneous extraction of rubber and resin using a supercritical solvent, such as supercritical CO 2 without use of any co-solvents; (2) approximately simultaneous extraction of resin and rubber using a non-polar co-solvent, followed by fractionation in a supercritical fluid system, for example, using supercritical CO 2 , into a rubber fraction and a resin fraction; or (3) high pressure supercritical fluid extraction at a specific narrow range of pressure and temperatures to remove the resin, followed by a high pressure solvent extraction in the same vessel, with cyclohexane or similar non-polar solvent to remove the rubber; or (4) high pressure solvent extraction at a specific range of temperature and pressure with cyclohexane or similar non-polar solvent to remove the rubber, followed by high pressure supercritical fluid extraction at a specific narrow range of pressure and temperatures to remove the resin.
- a supercritical solvent such as supercritical CO 2 without use of any co-solvents
- a supercritical fluid system for example,
- the method comprises a simultaneous resin and rubber extraction utilizing supercritical carbon dioxide at specific pressure, preferably between 1,500 and 10,000 psi, and more preferably between 5,000 and 10,000 psi, with a temperature range between 60-100 0 C.
- An alternate embodiment further includes using a non-polar co-solvent, preferably at a co-solvent ratio 3-10 times the feedstock weight, in order to simultaneously extract the resins and the rubber.
- non-polar co-solvents include, but are not limited to, hexane, hexene, octane, pentane, cyclohexane, iso-octane, and 1 -hexene.
- Another embodiment alternately includes using a polar co-solvent, for example, water, ethanol, methanol and acetone.
- the present disclosure includes a supercritical fluid extraction further including both a polar co-solvent and a non-polar co-solvent.
- the simultaneous extraction is followed by a fractionation step, utilizing a supercritical fluid system to fractionate the material into a rubber fraction and a resin fraction.
- the fractionation is then followed by a rinse of pure carbon dioxide, which removes the residual solvent from the bagasse.
- high pressure supercritical fluid extraction at a specific narrow range of pressure and temperatures to remove the resin is followed by a high pressure solvent extraction in the same vessel, with a non-polar solvent to remove the rubber.
- high pressure solvent extraction is carried out at a specific range of temperature and pressure with cyclohexane or similar non-polar solvent to remove the rubber, followed by high pressure supercritical fluid extraction at a specific narrow range of pressure and temperatures to remove the resin.
- one or more of the above processes are then optionally followed by a final rinse of supercritical carbon dioxide to remove the residual solvent from the bagasse.
- the removal of the resins and the second extraction is performed under pressure, which allows circumvention of the slow percolation problem, and provides a method capable of obtaining a high yield of rubber from the product.
- the final rinse with carbon dioxide allows for elimination of the environmental problem.
- Another version of this second process utilizes a polar solvent that is selective for resin such as alcohol or acetone to accelerate the removal of the resin and in some cases to suppress the extraction of the rubber for an even higher yield and purity of resin and rubber fraction.
- the present disclosure also envisions the use of subcritical liquid for the extraction process. Many variations of these process and conditions can be used such as different co-solvent systems, subcritical conditions to extract low molecular weight fractions, and the like, and these will be apparent to those skilled in the art.
- the subcritical method comprises contacting plant material with a compressed gas solvent, wherein the temperature and pressure of the solvent are at subcritical liquid conditions; maintaining the subcritical liquid for a sufficient time, wherein the biopolymer and the solvent form a subcritical liquid solvent solution; and extracting the biopolymer by percolation of the subcritical liquid through a bed of the plant material utilizing an inert percolation aid such as diatomaceous earth.
- plant material is stored prior to processing.
- storage comprises mixing the material in communited form with at least one essentially water-free organic liquid to form a slurry in which the material is protected from contact with oxygen and then storing said slurry for at least 24 hours.
- the organic liquid may be selected from (1) alcohols, ethers, esters and ketones having one to eight carbon atoms; (2) hydrocarbon solvents having a boiling range within about 20°- 100 0 C; (3) concentrated resin miscella; (4) hydrocarbon/guayule rubber/guayule resin miscella; (5) hydrocarbon/guayule rubber miscella comprising said hydrocarbon solvent and about 2-4% guayule rubber, or (6) mixtures thereof.
- the liquid is acetone or acetone/resin miscella and contains a stabilizer such as a para-phenylenediamine stabilizer.
- the storage of the plant material may comprise the entire non-defoliated plant and may be dried to a moisture content of about 5-25% before forming the slurry.
- the slurry is subjected to mild agitation.
- This storage method prevents development of offensive odors, due to the degradation, as well as prevents microfloral growth on the shrub.
- This method also allows communited guayule/organic solvent slurry to be pumped from one processing unit to another, avoiding undue exposure of the material to air.
- the invention permits partial or essentially complete extraction of useful products from the shrub during storage, thus reducing costs, time and equipment required.
- Another alternate additional step is pretreatment of the plant material to increase the efficiency of the supercritical extraction process and/or increase the yield of rubber and resin produced in the extraction.
- the pretreatment step comprises the application of a guanidine salt solution to the plant material, to soften the plant cell tissue and denature the protein coat that surrounds each globule of rubber, in order to facilitate the release of rubber into solution.
- the bagasse recovered from the solvent extraction process is relatively free of water and could be used as a fuel to supply the power requirements of the disclosed system and method, or as a separate marketable product.
- the resins which are extracted from the shrub are also recoverable and are a mixture of terpenes, terpenoids, parthenoids and glycerides of fatty acids.
- the resin component also contains a valuable hard wax similar to carnauba wax.
- the resins can be used as an adhesive in plywood and as a component in varnishes. Further, resin can also be used as a tackifying resin in the manufacture of reinforced composite rubber articles such as tires and car radiator hoses. Examples
- the ASE system used for determining rubber and resin extracted using the disclosed method comprises the following: a polypropylene centrifuge tube, 50 ml, with skirt; aluminum weighing dish, 70 mm diameter, with tab; a drying oven, Thelco Model 130DM (or equivalent); a centrifuge, Dynac Model 420101 (or equivalent); an analytical balance, Mettler Toledo AG 104 (or equivalent) with resolution of 0.01 mg; a vacuum oven, VWR Model 1400E (or equivalent); and an Accelerated Solvent Extractor (A. S. E.), Dionex Model 200 with solvent controller; extraction cells, 11 ml with filter discs; Borosillicate vials, 40 ml, with septa and lids; and a coffee grinder.
- the following reagents are used: acetone; cyclohexane, methyl alcohol; nitrogen; and Ottawa sand.
- the analysis of the extract begins by placing the plant material, such as the whole guayule shrub or coarsely or finely ground guayule shrub, in a supercritical fluid extraction (SFE) pressure vessel.
- the guayule shrub is chopped into small pieces.
- the guayule shrub is shredded or finely ground first.
- the sample of plant material is prepared by weighing the entire fresh sample and then cutting the branch tissue into 2 cm lengths. The plant material is also reduced through a chipper using a 3/8" round-hole screen to achieve the same particle size. Once reduced in size, the plant material is again weighed. The plant material is then dried in a suitable oven at 8O 0 C. Once dried, the plant material is again weighed. Next, the plant material is ground in a coffee grinder or other suitable apparatus. Then, the sample material is stored in jars or vials in a refrigerator. [0056] The analysis is performed according to the following method. First, a 1.5g prepared plant material sample is placed into a tared aluminum dish.
- sand (approximately 2.5- 3g) is mixed with the sample, transferred to a cell (screw on bottom, place a filter inside), and screw on top of cell. Additional sand is added to fill. The top and bottom are checked for tightness to prevent the run from aborting due to solvent leak. [0057] The cell is then loaded into top tray of ASE. A "blank" cell (filled with only sand) is then loaded in the first position. The labeled vials are then loaded into bottom tray and empty vials are placed in the R1-R4 positions. The system is checked to verify that there is enough solvent in the bottles. The gas is turned on followed by the ASE.
- the following program schedule comprises three cycles of 20 minutes each with an oven temperature at 140 0 C.
- a 100% methyl alcohol flush is used with a 60 second purge and a 50% acetone/50% cyclohexane rinse.
- the samples are then loaded and the run is started.
- the vials are placed into a freezer until ready to centrifuge.
- the vials are shaken gently (not stirred).
- About 20 ml of the sample mixture is poured or pipetted into the centrifuge tube and an equal amount of methyl alcohol is added.
- the vial is capped and is centrifuged at 3,500 rpm for 20 minutes.
- Example 1 50ml extraction of natural rubber with pure CO 2 (5,000 psi, 60 ° C)
- the extract sample has a resin concentration in the CO 2 of 16.20% and is among the lowest concentration of resin; however, the yield at 8.04% of feedstock is higher than previous experiments.
- the percentage of rubber in the extract is 4.98% of the feedstock.
- Example 3 50ml extraction with hexane co-solvent (5,000 psi, 100°C) [0069] 15.00g of guayule shrub feedstock is placed in an extraction vessel and extracted with carbon dioxide and llOg of hexane co-solvent at a pressure of 5,000 psi and a temperature of 100 ° C. The flow rate is 3 liters/minute. The extraction is run for forty-five minutes. 0.71g of dark green film is extracted (4.73% of feedstock). An additional 14.89g of primarily hexane is collected in the cold trap. Supercritical carbon dioxide at these processing conditions shows good extraction capability for rubber. The extract sample has a low resin concentration of 15.44% and a high yield of 4.73% feedstock.
- the percentage of rubber in the extract is 9.40% of the feedstock.
- These process conditions indicate that the presence of relatively high concentration of hexane co-solvent promote the extraction of rubber and slightly increase the extraction of resin.
- the analysis of the residue shows that the concentration of residual resin is 2.0%, and the concentration of rubber in the residue is 0.8%.
- This example further illustrates the increased rubber yield using one embodiment of the disclosed method, namely supercritical solvent extraction including a non-polar co- solvent.
- Example 5 50ml extraction with hexane co-solvent (9,900 psi, 80°C) [0071] 12.98g of guayule shrub feedstock is placed in an extraction vessel and extracted with carbon dioxide and 115.38g of hexane co-solvent at a pressure of 9,900 psi and a temperature of 80 ° C. The flow rate is 3 liters/minute. The extraction is run for thirty minutes. 0.6Og of dark green film is extracted (4.62% of feedstock). An additional 0.26g of primarily hexane is collected in the cold trap. Supercritical carbon dioxide at these processing conditions shows very good selectivity for rubber. The extract sample has a 12.35% concentration of resin and a 4.62% yield of feedstock.
- the percentage of rubber in the extract is 8.97% of the feedstock and indicates that rubber is extractable at these process conditions. These process conditions further indicate that the presence of hexane co-solvent promotes the extraction of rubber. Using the ASE method, the residue has a 2.3% concentration of resin and a 1.1% concentration of rubber.
- Example 7 50ml extraction with 1-hexene co-solvent (9,800 psi, 100 ° C) [0073] 13.0Og of guayule shrub feedstock is placed in an extraction vessel and extracted with carbon dioxide and 114.16g of 1-hexene co-solvent at a pressure of 9,800 psi and a temperature of 100 ° C. The flow rate is 3 liters/minute. The extraction is run for one hour. 0.68g of dark green film is extracted (5.85% of feedstock). An additional 0.44g of primarily hexene is collected in the cold trap. Supercritical carbon dioxide at these processing conditions shows very good selectivity for rubber. The extract sample has a combined average resin concentration of 11.4% and a 5.85% feedstock yield.
- the percentage of rubber in the extract is 13.4% of the feedstock, indicating that rubber is highly extractable at these process conditions. These process conditions indicate that the presence of 1-hexene co-solvent promotes the extraction of rubber.
- the residue has a 2.0% concentration of resin and a 1.1% concentration of rubber.
- Example 8. 50ml extraction with cyclohexane co-solvent (9,500 psi, 100°C) [0074] 13.00 g of guayule shrub feedstock is placed in an extraction vessel and extracted with carbon dioxide and 109.8Og of cylohexane co-solvent at a pressure of 9,500 psi and a temperature of 100°C. The flow rate is 3 liters/minute.
- the extract sample of >30.1% resin is high, as is the total yield of feedstock at 5.46%.
- the percentage of rubber in the extract is 3.9% of the feedstock, which was moderate compared to most other organic non-polar co-solvent experiments, indicating that iso-octane is not as efficacious a co- solvent for extracting rubber as hexane, 1-hexene, or cyclohexane.
- the residue has a 2.5% concentration of resin and a 4.5% concentration of rubber.
- the percentage of rubber in the extract is only 0.83% of the feedstock.
- These process conditions show a very high selectivity for resin and a relatively low selectivity for rubber, indicating the presence of water promotes the extraction of resin and depresses the extraction of rubber.
- These process conditions are suitable for a two-step commercial process that selectively extracts resin and leaves behind the rubber for subsequent extract.
- the material in the cold trap is much lower in resin and rubber concentration than in the collection vessel. Using the ASE method, the residue has a 2.3% concentration of resin, and a 5.7% concentration of rubber.
- the percentage of rubber in the extract is reported at only 0.37% of the feedstock which is among the lowest amount when compared to other process conditions. These process conditions show that the presence of water suppresses the extraction of the rubber, but that the higher pressure conditions are more conducive for the extraction of resin.
- the material in the cold trap has extremely low concentrations of resin and rubber compared to that in the collection vessel. Using the ASE method, the residue had a 2.6% concentration of resin, and a 5.8% concentration of rubber.
- Ig of guayule shrub feedstock is placed in an extraction vessel and extracted with carbon dioxide at a pressure of 2,000 psi and a temperature of 9.2 ° C.
- the extract vessel and pre-heater vessel are both placed in a container with ice to perform a cold extraction, however, we are unable to achieve flow and no extract is collected.
- the guayule feedstock at least at the particle size at which the test was performed, does not have an adequate percolation rate to perform the extraction.
- the slow percolation rate of the liquid carbon dioxide causes the bed to compress and form a plug, which prevents extraction.
- Liquid carbon dioxide requires the use of a specialized extractor, pelletizing of the feedstock, or a much larger particle size, in order for this liquid carbon dioxide process to work effectively.
- Example 13 50ml extraction with ethanol co-solvent, (7,250 psi, 80°C) [0081] 15.04g of guayule shrub feedstock is placed in an extraction vessel and extracted with carbon dioxide and 15g of ethanol co-solvent at a pressure of 7,250 psi and a temperature of 80 ° C. The flow rate is 3 h ' ters/mitmte. The time of extraction is 45 minutes. 0.58g of solid yellow material and dark green film is extracted (3.85% of feedstock). Supercritical carbon dioxide at these processing conditions shows average selectivity for resins. The extract sample at 30.09% concentration of resin is not as high as other experiments.
- Example 15 50ml extraction with hexane co-solvent, (5,000 psi, 60°C) [0085] 16.12g of guayule shrub feedstock is placed in an extraction vessel and extracted with carbon dioxide and 15g of hexane co-solvent at a pressure of 5,000 psi and a temperature of 60 ° C. The flow rate is 3 liters/minute. The time of extraction is forty- five minutes. 0.53g of solid yellow material and dark green film is extracted (3.28% of feedstock). Supercritical carbon dioxide at these processing conditions shows very good selectivity for resins. The extract sample at 34.69% concentration of resin is among the highest of the experiments; however, the yield at 3.28% of feedstock is not as high as several other experiments.
- the present method of using supercritical carbon dioxide eliminates or greatly decreases the use of organic solvents which are ozone depleting and environmentally unfriendly, while providing a more effective method of separating, fractionating and purifying rubber and resins from plant materials.
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Abstract
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2006302814A AU2006302814B2 (en) | 2005-10-12 | 2006-04-21 | Extraction and fractionation of biopolymers and resins from plant materials |
EP06750916A EP1948715B1 (en) | 2005-10-12 | 2006-04-21 | Extraction and fractionation of biopolymers and resins from plant materials |
ES06750916T ES2424681T3 (en) | 2005-10-12 | 2006-04-21 | Extraction and fractionation of biopolymers and resins from plant materials |
MX2008004857A MX2008004857A (en) | 2005-10-12 | 2006-04-21 | Extraction and fractionation of biopolymers and resins from plant materials. |
BRPI0617402-7A BRPI0617402A2 (en) | 2005-10-12 | 2006-04-21 | Method for removing a biopolymer from plant material, Method for removing rubber and resin from plant material, Commercial accelerated solvent extraction process and Instrument for selectively extracting a biopolymer from plant materials |
IL190815A IL190815A (en) | 2005-10-12 | 2008-04-13 | Extraction and fractionation of biopolymers and resins from plant materials |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/249,884 US7259231B2 (en) | 2004-10-12 | 2005-10-12 | Extraction and fractionation of biopolymers and resins from plant materials |
US11/249,884 | 2005-10-12 |
Publications (1)
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WO2007046859A1 true WO2007046859A1 (en) | 2007-04-26 |
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ID=37962804
Family Applications (1)
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PCT/US2006/015025 WO2007046859A1 (en) | 2005-10-12 | 2006-04-21 | Extraction and fractionation of biopolymers and resins from plant materials |
Country Status (10)
Country | Link |
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US (3) | US7259231B2 (en) |
EP (1) | EP1948715B1 (en) |
AU (1) | AU2006302814B2 (en) |
BR (1) | BRPI0617402A2 (en) |
ES (1) | ES2424681T3 (en) |
IL (1) | IL190815A (en) |
MX (1) | MX2008004857A (en) |
TR (1) | TR200804341T1 (en) |
WO (1) | WO2007046859A1 (en) |
ZA (1) | ZA200804003B (en) |
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Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5171592A (en) * | 1990-03-02 | 1992-12-15 | Afex Corporation | Biomass refining process |
US5849854A (en) * | 1994-06-01 | 1998-12-15 | The Proctor & Gamble Company | Process for recovering polyhydroxyalkanotes using air classification |
Family Cites Families (25)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3616222A (en) | 1969-05-08 | 1971-10-26 | Exxon Research Engineering Co | Process for saccharification of cellulosic and woody tissues by fungi or enzymes from fungi |
US3812012A (en) | 1970-11-07 | 1974-05-21 | Hoechst Ag | Method of degrading natural plant material with an enzyme preparation |
AT313039B (en) | 1971-05-07 | 1974-01-25 | Studiengesellschaft Kohle Mbh | Process for obtaining caffeine from green coffee |
US4104409A (en) | 1971-06-03 | 1978-08-01 | Studiengesellschaft Kohle Mbh | Production of hop extracts |
US3972775A (en) | 1974-06-28 | 1976-08-03 | The United States Of America As Represented By The United States Energy Research And Development Administration | Conversion of cellulosic materials to sugar |
JPS5839517B2 (en) | 1974-09-20 | 1983-08-30 | カブシキガイシヤ バイオリサ−チセンタ− | Cellulose Scala Alcohol |
US3990945A (en) | 1975-04-28 | 1976-11-09 | Bio Research Center Company Limited | Enzymatic hydrolysis of cellulose |
US4009075A (en) | 1975-08-22 | 1977-02-22 | Bio-Industries, Inc. | Process for making alcohol from cellulosic material using plural ferments |
US4089745A (en) | 1976-12-27 | 1978-05-16 | Standard Brands Incorporated | Process for enzymatically converting cellulose derived from corn hulls to glucose |
US4094742A (en) | 1977-03-04 | 1978-06-13 | General Electric Company | Production of ethanol from cellulose using a thermophilic mixed culture |
US4097333A (en) | 1977-06-22 | 1978-06-27 | The Great Western Sugar Company | Enzymatic method of producing glucose from ethylene treated cellulose |
US4308200A (en) * | 1980-07-10 | 1981-12-29 | Champion International Corporation | Extraction of coniferous woods with fluid carbon dioxide and other supercritical fluids |
DE3207914A1 (en) * | 1982-03-04 | 1983-09-15 | Skw Trostberg Ag, 8223 Trostberg | METHOD FOR EXTRACTIVELY OBTAINING HIGH QUALITY NATURAL WAXES |
US4684715A (en) | 1984-05-07 | 1987-08-04 | The Firestone Tire & Rubber Company | Extraction of rubber and/or resin from rubber containing plants with a monophase solvent mixture |
US4681929A (en) * | 1985-04-29 | 1987-07-21 | The Firestone Tire & Rubber Company | Use of rubber solvent-resin solvent and miscella mixtures for extraction-expression of rubber and resins from guayule shrub |
JPH04264035A (en) * | 1991-02-15 | 1992-09-18 | Jiyumoku Chiyuushiyutsu Seibun Riyou Gijutsu Kenkyu Kumiai | Extraction of magnolol from magnolol-containing plant |
US5252729A (en) * | 1991-10-23 | 1993-10-12 | Schering Corporation | Extraction of compounds from plant materials using supercritical fluids |
JPH09143489A (en) * | 1995-09-21 | 1997-06-03 | T Hasegawa Co Ltd | Extraction of flavor from raw material of animal and plant |
US6054525A (en) | 1996-09-16 | 2000-04-25 | The University Of Akron | Hypoallergenic natural rubber latex and a process for making the same |
DE19800330C2 (en) * | 1998-01-07 | 2002-09-26 | Delta 9 Pharma Gmbh | Pharmaceutical CO¶2¶ extract from Tanacetum parthenium |
DK199801456A (en) | 1998-11-10 | 2000-05-11 | Fls Miljoe A S | Process for impregnating or extracting a resinous wood substrate |
US8101862B2 (en) * | 1999-01-11 | 2012-01-24 | Southwire Company | Self-sealing electrical cable using rubber resins |
US6569375B1 (en) | 2000-04-11 | 2003-05-27 | Apex Medical Technologies, Inc. | Vulcanization of dip-molded rubber articles with molten media baths |
US20020155177A1 (en) * | 2000-09-29 | 2002-10-24 | Krasutsky Pavel A. | Process for extracting compounds from plants |
US7008528B2 (en) * | 2001-03-22 | 2006-03-07 | Mitchell Allen R | Process and system for continuously extracting oil from solid or liquid oil bearing material |
-
2005
- 2005-10-12 US US11/249,884 patent/US7259231B2/en active Active
-
2006
- 2006-04-21 ZA ZA200804003A patent/ZA200804003B/en unknown
- 2006-04-21 ES ES06750916T patent/ES2424681T3/en active Active
- 2006-04-21 AU AU2006302814A patent/AU2006302814B2/en not_active Ceased
- 2006-04-21 BR BRPI0617402-7A patent/BRPI0617402A2/en not_active Application Discontinuation
- 2006-04-21 MX MX2008004857A patent/MX2008004857A/en active IP Right Grant
- 2006-04-21 WO PCT/US2006/015025 patent/WO2007046859A1/en active Application Filing
- 2006-04-21 EP EP06750916A patent/EP1948715B1/en not_active Not-in-force
- 2006-04-21 TR TR2008/04341T patent/TR200804341T1/en unknown
-
2007
- 2007-07-16 US US11/778,589 patent/US20080015336A1/en not_active Abandoned
-
2008
- 2008-04-13 IL IL190815A patent/IL190815A/en not_active IP Right Cessation
-
2010
- 2010-10-04 US US12/897,735 patent/US20110021743A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5171592A (en) * | 1990-03-02 | 1992-12-15 | Afex Corporation | Biomass refining process |
US5849854A (en) * | 1994-06-01 | 1998-12-15 | The Proctor & Gamble Company | Process for recovering polyhydroxyalkanotes using air classification |
Non-Patent Citations (1)
Title |
---|
See also references of EP1948715A4 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2152511A1 (en) * | 2007-06-01 | 2010-02-17 | Yulex Corporation | Guayule rubber and resin wet-stick bioadhesives |
EP2152511A4 (en) * | 2007-06-01 | 2010-07-21 | Yulex Corp | Guayule rubber and resin wet-stick bioadhesives |
CN101848809A (en) * | 2007-06-01 | 2010-09-29 | 尤莱克斯公司 | Guayule rubber and resin wet-stick bioadhesives |
WO2009051606A1 (en) * | 2007-10-16 | 2009-04-23 | Yulex Corporation | Rapid expanded solvent extraction |
EP2205679A1 (en) * | 2007-10-16 | 2010-07-14 | Yulex Corporation | Guayule resin multipolymer |
US7790036B2 (en) | 2007-10-16 | 2010-09-07 | Yulex Corporation | Rapid expanded solvent extraction |
EP2205679A4 (en) * | 2007-10-16 | 2010-11-24 | Yulex Corp | Guayule resin multipolymer |
WO2016062753A1 (en) | 2014-10-22 | 2016-04-28 | Versalis S.P.A. | Integrated process for processing and utilising the guayule plant |
US9969818B2 (en) | 2014-10-22 | 2018-05-15 | Versalis S.P.A. | Integrated process for processing and utilising the guayule plant |
Also Published As
Publication number | Publication date |
---|---|
IL190815A0 (en) | 2008-11-03 |
ZA200804003B (en) | 2009-10-28 |
US20110021743A1 (en) | 2011-01-27 |
MX2008004857A (en) | 2008-09-11 |
ES2424681T3 (en) | 2013-10-07 |
IL190815A (en) | 2012-02-29 |
US20080015336A1 (en) | 2008-01-17 |
AU2006302814A1 (en) | 2007-04-26 |
US7259231B2 (en) | 2007-08-21 |
TR200804341T1 (en) | 2008-11-21 |
BRPI0617402A2 (en) | 2011-07-26 |
EP1948715A4 (en) | 2008-09-17 |
EP1948715B1 (en) | 2013-03-13 |
AU2006302814B2 (en) | 2012-03-22 |
US20060106183A1 (en) | 2006-05-18 |
EP1948715A1 (en) | 2008-07-30 |
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