CN100408613C - Polymer extraction methods - Google Patents
Polymer extraction methods Download PDFInfo
- Publication number
- CN100408613C CN100408613C CNB038238365A CN03823836A CN100408613C CN 100408613 C CN100408613 C CN 100408613C CN B038238365 A CNB038238365 A CN B038238365A CN 03823836 A CN03823836 A CN 03823836A CN 100408613 C CN100408613 C CN 100408613C
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- China
- Prior art keywords
- polymkeric substance
- solvent
- biomass
- pha
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 229920000642 polymer Polymers 0.000 title claims abstract description 56
- 238000000605 extraction Methods 0.000 title description 29
- 239000002904 solvent Substances 0.000 claims abstract description 219
- 239000002028 Biomass Substances 0.000 claims abstract description 171
- 238000000034 method Methods 0.000 claims abstract description 112
- 239000000126 substance Substances 0.000 claims description 143
- 238000001556 precipitation Methods 0.000 claims description 98
- 239000003795 chemical substances by application Substances 0.000 claims description 89
- 230000008569 process Effects 0.000 claims description 50
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical group CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 150000002148 esters Chemical class 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 13
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 11
- 229940043232 butyl acetate Drugs 0.000 claims description 9
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 9
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- 238000003756 stirring Methods 0.000 description 25
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- 230000000452 restraining effect Effects 0.000 description 1
- RGFNRWTWDWVHDD-UHFFFAOYSA-N sec-butyl ester of butyric acid Natural products CCCC(=O)OCC(C)C RGFNRWTWDWVHDD-UHFFFAOYSA-N 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- CIZOCKPOEXXEHB-UHFFFAOYSA-N tetradecan-3-ol Chemical compound CCCCCCCCCCCC(O)CC CIZOCKPOEXXEHB-UHFFFAOYSA-N 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
The invention features methods of separating a polymer from a biomass containing the polymer. In one aspect, the method includes contacting the biomass with a solvent system to provide a residual biomass and a solution. The solvent system includes a solvent for the polymer and a precipitant for the polymer, and the solution includes the polymer, the solvent for the polymer and the precipitant for the polymer. Applying a centrifugal force to the solution from the residual biomass to separate at least some of the solution from the residual biomass. In another aspect, the method includes contacting the biomass with a solvent system to provide a residual biomass and a solution including the polymer and the solvent system; adding a precipitant for the polymer to the solution; and a separating at least some of the solution from the residual biomass after adding the precipitant for the polymer.
Description
Technical field
The present invention relates to the extracting process of polymkeric substance.
Background technology
PHA (" PHA ") can extract from the biomass with the cell that contains PHA.Usually, this technology relates to biomass and the solvent that is used for PHA, then heating and stirring.This generally provides and comprises the biphase system, and one mutually for containing the solution of solvent and PHA, and another contains residual biomass mutually, and this residual biomass has the cell of the PHA that contains reduction.Usually, separate this two-phase, from solvent, remove PHA then.
General introduction
This invention relates generally to the extracting process of polymkeric substance.
On the one hand, the invention is characterized in from the method for the biomass isolating polymer that contains polymkeric substance.This method comprises makes biomass contact with solvent system, so that residual biomass and solution to be provided.Solvent system comprises the solvent (solvent for the polymer) of polymkeric substance and the precipitation agent (precipitant for the polymer) of polymkeric substance, and solution comprises the solvent of polymkeric substance, polymkeric substance and the precipitation agent of polymkeric substance.This method also comprises to solution and residual biomass and applies centrifugal force, to isolate some solution at least from residual biomass.
On the other hand, the invention is characterized in the method for isolating polymer from the biomass that contain polymkeric substance.This method comprises makes biomass contact with solvent system, and so that residual biomass and solution to be provided, this solution comprises polymkeric substance and solvent system, and isolates at least some solution from residual biomass.This method also comprises the precipitation agent that adds polymkeric substance in this solution, to remove at least some polymkeric substance from solvent system.
On the other hand, the invention is characterized in the method for from the biomass that contain polymkeric substance, separating this polymkeric substance.This method comprises contacts so that residual biomass and the solution that comprises polymkeric substance and solvent system to be provided biomass with solvent system.The polymer concentration of this solution be at least about 2% and its viscosity up to about 100 centipoises.This method also comprises from residual biomass isolates at least some solution.
On the one hand, the invention is characterized in the method for isolating polymer from the biomass that contain polymkeric substance.This method comprises contacts so that residual biomass and solution to be provided biomass with solvent system.Solvent system comprises the solvent of polymkeric substance, and solution comprises the solvent of polymkeric substance and polymkeric substance.The boiling point of the solvent of polymkeric substance can be higher than 100 ℃.This method also comprises from the residual biomass isolating polymer.
On the other hand, the invention is characterized in the method for isolating polymer from the biomass that contain polymkeric substance.This method comprises contacts residual biomass being provided and comprising the solution of the solvent of polymkeric substance and polymkeric substance biomass with the solvent system of certain volume, and separate at least some solution from residual biomass.This method also comprises the precipitation agent that adds the polymkeric substance of certain volume in isolated solution, to remove at least some polymkeric substance from solution.With respect to the volume of solvent system, the volume of the precipitation agent of adding is less than about 2 parts.
On the other hand, the invention is characterized in the method for isolating polymer from the biomass that contain this polymkeric substance and biomass impurity.This method comprises makes biomass contact with the precipitation agent of polymkeric substance, to remove at least some biomass impurity from the biomass that contain this polymkeric substance and biomass impurity, provides the biomass that contain this polymkeric substance of purifying thus.This method comprises that also the biomass that make purifying contact with solvent system, so that residual biomass and the solution that comprises the solvent of polymkeric substance and polymkeric substance to be provided.
On the other hand, the invention is characterized in the method for isolating polymer from the biomass that contain polymkeric substance and biomass impurity.This method comprises that the Chemical Pretreatment biomass to remove at least some biomass impurity from the biomass that contain biomass and impurity, provide the biomass that contain this polymkeric substance of purifying thus.Chemical treatment comprise additional chemical exist or not in the presence of, control pH, temperature and duration of contact, described chemical for example tensio-active agent, washing composition, enzyme maybe can help to remove the analogous material of biomass impurity.This method comprises that also the biomass that make purifying contact with solvent system so that residual biomass and the solution that comprises the solvent of polymkeric substance and polymkeric substance to be provided.
On the one hand, the invention is characterized in the method for isolating polymer from the biomass that contain this polymkeric substance.This method comprises makes biomass contact under counter-current condition with solvent system.
On the other hand, the invention is characterized in the method for isolating polymer from the biomass that contain polymkeric substance.This method comprises uses formation PHA with a step process of residual biomass phase biomass to be contacted with solvent system mutually.The volume of the solvent system that exists in mutually at PHA and the ratio of the volume of the solvent system that contacts with biomass are at least about 0.8.
On the other hand, the invention is characterized in the method for isolating polymer from the biomass that contain polymkeric substance.This method comprises uses formation PHA with a step process of residual biomass phase biomass to be contacted with solvent system mutually.The volume of the solvent system that exists in mutually in residual biomass and the ratio of the volume of the solvent system that contacts with biomass are up to about 0.2.
In specific implementations, this method can be with high relatively productive rate extraction polymkeric substance (for example PHA) from biomass.In some embodiments, can not use multistep rapid (for example using single-step process) from biomass extraction phase to the polymkeric substance (for example PHA) of high yield.
In some embodiments, this method can extraction phase to pure polymkeric substance (for example PHA).
In specific implementations, this method can be used solvent and/or precipitation agent with relative efficient manner.For example, can reclaim a high proportion of relatively solvent and/or the precipitation agent (for example, being used for utilizing again) that uses in the method.
In some embodiments, this method can have the environmental influence of minimizing.
In specific embodiment, this method can be with high relatively air speed (for example, high yield, and have overall low residence time in processing unit) extraction polymkeric substance.
In specific embodiment, this method can cause the unwanted byproduct of reaction (for example organic acid) of relatively small amount.This can for example reduce the possibility to corrosion or other undesirable infringement of used system in present method, and/or prolongs the work-ing life of this system.
In some embodiments, this method can provide the output (for example by using single-step process) of high relatively volume.
In specific embodiment, this method can provide high relatively solvent recuperation.
In specific embodiment, this method can use single step device (for example, adverse current centrifuge contactor) to carry out.
In some embodiments, (for example form low viscous relatively residual biomass, use counter-current condition), it can strengthen follow-up processing, for example strips residual solvent and thickened solid content (solidscontent) (for example by evaporation, filtration or dry).
In addition, feature of the present invention, purpose and advantage are embodied in specification sheets, accompanying drawing and the claim.
Description of drawings
Fig. 1 is the schema of the embodiment of the method for extraction PHA from the biomass with the cell that contains PHA;
Fig. 2 is the embodiment part schema of the method for extraction PHA from the biomass with the cell that contains PHA; With
Fig. 3 illustrates the viscosity of EXAMPLE III and the figure of polymer content.
Detailed Description Of The Invention
Fig. 1 is the schema from the embodiment of the method for the biomass extraction PHA with the cell that contains PHA.The slurry that contains biomass and water (slurry) is provided.Solvent system is joined the mixture that contains this slurry and solvent system in the slurry with formation.Stir this mixture (for example stirring) and comprise the biphase combination to provide.One forms (" PHA mutually ") by containing the solution of PHA with solvent system and trace biology matter.Second forms (" residual biomass mutually ") by residual biomass, the water of the cell of the polymer content with reduction and the solvent system that stays part.Use proper device to separate the two-phase that is included in this combination, this device utilizes centrifugal force to promote to separate (for example disk centrifugal separator, bowl centrifuge, settling centrifuge, hydraulic vortex flow devices, adverse current centrifuge contactor).Randomly, one or more solvents can be joined and utilize centrifugal force to promote in the isolating device.The precipitation agent of PHA is joined PHA contain PHA mutually and the mixture of precipitation agent with formation in mutually.Stir (for example stirring) this mixture and contain the combination of sedimentary PHA, solvent system and precipitation agent with formation.In specific implementations, solvent system and precipitation agent are miscible, this obtain having two-phase (for example, contain the phase of sedimentary PHA, with contain solvent system and precipitation agent one mutually) combination (sedimentary PHA, solvent system and precipitation agent).Separate (for example by filtering or use centrifugal force) this combination (sedimentary PHA, solvent system and precipitation agent) to remove the PHA of this isolating extraction.
The technology of Fig. 1 can be called single-step process.Usually, single-step process is in the technology of only using a centrifugation step from the process of biomass isolating polymer (for example PHA).Usually, multistep technology refers in the technology of using from the process of biomass isolating polymer (for example PHA) more than a centrifugation step (referring to other following explanation).For example, can handle and the final centrifugal residual biomass that in the technology of Fig. 1, forms, produce thus two step process (referring to, for example, Fig. 2 and following explanation).
In some embodiments, this technology obtains the PHA of relative high yield.For example, in some embodiments, that the ratio of the dry weight of the PHA that initially contains in the dry weight of the PHA of extraction and the biomass is at least is about 0.9 (for example, be at least approximately 0.95, be at least approximately 0.97, be at least about 0.98).In specific embodiment, can need not to use multistep technology (for example using single-step process) to obtain the PHA of relative high yield.
In specific embodiment, can use a large amount of relatively solvents of transferring to the PHA phase to carry out this technology.For example, in some embodiments, PHA mutually in the ratio of recovered solvent volume and the solvent volume that contacts with biomass be at least about 0.8 (for example 0.85, be at least approximately 0.9, be at least approximately 0.95, be at least approximately 0.98, be at least about 0.99).In some embodiments, can for example use in the process of isolating polymer from biomass (for example PHA), counter-current condition is transferred to the PHA phase with a large amount of relatively solvents.
In specific embodiment, can use the solvent of transferring to the residual biomass phase of relatively small amount to carry out this technology.For example, in some embodiments, residual biomass mutually in recovered solvent volume and the volume of the solvent that contacts biomass ratio up to about 0.2 (for example, up to about 0.15, up to about 0.1, up to about 0.05, up to about 0.02, up to about 0.01).In some embodiments, can for example use in the process of isolating polymer from biomass (for example PHA), counter-current condition is transferred to the residual biomass phase with the solvent of relatively small amount.
Can provide slurry in any required mode.Usually, contain the fermenting broth (broth) of water and biomass, and from fermenting broth, remove portion water and slurry is provided by formation.Can be by for example, filter (for example micro-filtration, membrane filtration) and/or anhydrate by decantation and/or by using centrifugal force to remove.In specific embodiment, can in being provided, the technological process of slurry remove biomass impurity (for example cell walls and cytolemma impurity).These impurity can comprise protein, lipid (for example triglyceride level, phosphatide and lipoprotein) and lipopolysaccharides.
Can change the PHA content (for example, the PHA content of dry biomass comprises its polymer content, in weight %) of biomass as required.As an example, biomass are to come from the embodiment of microorganism (microbial origin) therein, and the PHA content of biomass can be at least about 50 weight % and (for example, be at least about 60 weight %, be at least about 70 weight %, be at least about 80 weight %).As another example, biomass are to come from the embodiment of plant therein, and the PHA content of biomass can be for less than about 50 weight % (for example less than about 40 weight %, less than about 30 weight %, less than about 20 weight %).
In some embodiments, the solids content of slurry (for example dry biomass comprises its PHA content, with respect to the weight of the total weight in wet base of slurry) is about 25 weight %～about 40 weight % (for example about 25 weight %～about 35 weight %).
Biomass can be formed by in the multiple entity (entities) one or more.This entity for example comprises, produce microorganism strains (for example, the Alcaligenes eutrophus (Alcaligenes eutrophus) (rename and be Alkaligenes (Ralstonia eutropha)) of PHA, Alcaligenes latus (Alcaligenes latus), Azotobacter (Azotobacter), Aeromonas (Aeromonas), Comamonas (Comamonas), Rhodopseudomonas (Pseudomonads)), be used to produce the engineered organism (Rhodopseudomonas for example of PHA, Ralstonia, intestinal bacteria (Escherichia coli), Klebsiella (Klebsiella)), the families of plant that are used to produce the yeast of PHA and are used to produce PHA.This entity for example is disclosed in, Lee, Biotechnology﹠amp; Bioengitieering
49: 1-14 (1996); People such as Braunegg (1998), J.Biotechnology
65: 127-161; Madison and Huisman, 1999; With Snell and Peoples2002, Metabolic Engineering
4: 29-40 is hereby incorporated by them.
Contain in the embodiment of microorganism cells in biomass, the size that is included in the microorganism cells in the biomass also can change as required.Usually, microorganism cells (for example bacterial cell) has one dimension at least, and it is of a size of at least about 0.2 micron (for example, be at least about 0.5 micron, be at least about 1 micron, be at least about 2 microns, be at least about 3 microns, be at least about 4 microns, be at least about 5 microns).In specific embodiment, it is favourable using big relatively microorganism cells (for example, big relatively bacterial cell) in the biomass, and this is because this can promote the separation of biomass, to form biomass slurry.
Usually, form PHA by one or more monomeric units of polymerization (for example enzymatic polymerization).The example of this monomeric unit comprises, for example, 3-butyric ester, 3-hydroxy propionate, 3-hydroxyl valerate, 3-hydroxycaproic ester, 3-hydroxyl heptanoate, 3-Hydroxyoctanoic acid ester, 3-hydroxyl pelargonate, 3-hydroxydecanoic acid ester, 3-hydroxyl dodecanoic acid ester, 3-hydroxyl dodecylene acid esters, 3-hydroxyl tetradecane acid ester, 3-hydroxy-palmitic acid ester, 3-hydroxyl octadecyl ester, 4 hydroxybutyric acid ester, 4-hydroxyl valerate, 5-hydroxyl valerate and 6 hydroxycaproic acid ester.
In some embodiments, PHA has at least a chemical formula and is-OCR
1R
2(CR
3R
4)
nThe monomeric unit of CO-.N is 0 or integer (for example, 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15, etc.).R
1, R
2, R
3And R
4Respectively the do for oneself group (for example, the alkyl of replacement) or the unsubstituted group (for example, unsubstituted alkyl) of hydrogen atom, saturated hydrocarbyl, unsaturated alkyl, replacement.The examples of groups that replaces comprises that group that halogen replaces (for example, the alkyl that halogen replaces), the group of hydroxyl-replacement (for example, the alkyl of hydroxyl-replacement), the group of halogen group, nitrogen-replacement (for example, the alkyl of nitrogen-replacement) and the group of oxygen-replacement (for example, the alkyl of oxygen-replacement).The group that replaces for example comprises the saturated alkyl of replacement and the unsaturated alkyl of replacement.R
1With R
2, R
3And R
4Each is identical or different.R
2With R
1, R
3And R
4Each is identical or different.R
3With R
1, R
2And R
4Each is identical or different.R
4With R
1, R
2And R
3Each is identical or different.
In some embodiments, PHA contains the unitary multipolymer of two or more different monomers.The example of this multipolymer comprises poly--3-butyric ester-altogether-the 3-hydroxy propionate, poly--the 3-butyric ester-altogether-the 3-hydroxyl valerate, poly--the 3-butyric ester-altogether-the 3-hydroxycaproic ester, poly--the 3-butyric ester-altogether-the 4 hydroxybutyric acid ester, poly--the 3-butyric ester-altogether-the 4-hydroxyl valerate, poly--the 3-butyric ester-altogether-the 6 hydroxycaproic acid ester, poly 3-hydroxy butyrate-altogether-3-hydroxyl heptanoate, poly--the 3-butyric ester-altogether-3-Hydroxyoctanoic acid ester, poly--the 3-butyric ester-altogether-3-hydroxydecanoic acid ester, poly--the 3-butyric ester-altogether-3-hydroxy-dodecanoic acid ester, poly--the 3-butyric ester-altogether-3-Hydroxyoctanoic acid ester-altogether-3-hydroxydecanoic acid ester, poly--3-hydroxydecanoic acid ester-as to be total to-3-Hydroxyoctanoic acid ester and poly--3-butyric ester-altogether-3-hydroxyl octadecane acid esters.
In specific embodiment, PHA is a homopolymer.The example of this multipolymer comprises poly--4 hydroxybutyric acid ester, poly--the 3-hydroxy propionate, poly--the 3-butyric ester, poly--the 3-hydroxycaproic ester, poly--3-hydroxyl heptanoate, poly--3-Hydroxyoctanoic acid ester, poly--3-hydroxydecanoic acid ester and poly--3-hydroxyl dodecanoic acid ester.
The suitable weight-average molecular weight of the polystyrene of PHA is at least about 500 (for example be at least about 10,000, be at least about 50,000) and/or less than about 2,000,000 (for example less than about 1,000,000, less than about 800,000).
Usually, the solvent system amount that joins slurry can change as required.In specific embodiment, the certain amount of solvent system is joined slurry, so that after centrifugal, the PHA solids content of PHA phase is (for example less than about 8 weight %, less than about 6 weight %, less than about 5 weight % less than about 10 weight %, less than about 4 weight %, less than about 3 weight %).
Solvent system comprises the solvent of one or more PHA, and can randomly comprise the precipitation agent of one or more PHA.Be not intended to be bound by theory, it is believed that the precipitation agent that comprises PHA in the solvent system can reduce the viscosity of the solution that contains polymkeric substance and solvent system and/or strengthen selectivity in the technology of the required PHA of extraction.
Usually, the solvent of given polymkeric substance can dissolve polymer, is formed on the solution of molecule or the basic homogeneous of ion yardstick level.Usually, the precipitation agent of given polymkeric substance can induced polymer the dissolving power of solvent of precipitation and/or reduction polymkeric substance.
Given PHA to be purified is depended in the selection of solvent and/or precipitation agent usually.Do not wish to be limited by theory, it is believed that and to select the used appropriate solvent of given polymkeric substance by the basic coupling of the appropriate solvent parameter (solvationparameters) (for example dispersion force (dispersive force), hydrogen bond force (hydrogen bonding forces) and/or polarity) that makes given polymkeric substance and solvent.These solvation parameters for example are disclosed in, Hansen, Solubility Parameters-A User ' s Handbook, CRC Press, NY, NY (2000).
PHA is that poly--3-hydroxybutyric acid ester copolymer (for example gathers-the 3-butyric ester-be total to-the 3-hydroxy propionate therein, poly--the 3-butyric ester-altogether-the 3-hydroxyl valerate, poly--the 3-butyric ester-as to be total to-3-hydroxycaproic ester and/or poly--3-butyric ester-altogether-the 4 hydroxybutyric acid ester, poly--the 3-butyric ester-altogether-3-Hydroxyoctanoic acid ester-altogether-3-hydroxydecanoic acid ester-altogether-3-hydroxy-dodecanoic acid ester) specific implementations in, wherein the major part of monomeric unit is that (for example be at least about 50% monomeric unit is the 3-butyric ester to the 3-butyric ester, being at least about 60% monomeric unit is the 3-butyric ester), solvent can be selected from ketone, ester and/or have the alcohol of at least 4 carbon atoms, and precipitation agent can be selected from paraffinic hydrocarbons, methyl alcohol and ethanol.
In PHA some embodiments for poly--3-Hydroxyoctanoic acid ester, solvent can be selected from ketone, ester, have the alcohol or the paraffinic hydrocarbons (for example hexane) of at least 4 carbon atoms therein.
Usually, ketone can be ring-type or non-annularity, straight chain or branching and/or replacement or unsubstituted.The example of non-annularity ketone and cyclic ketone comprises methyl iso-butyl ketone (MIBK) (" MIB K "), 3-methyl-2 pentanone (butyl methyl ketone), 4-methyl-2 pentanone (methyl iso-butyl ketone (MIBK)), 3-methyl-2-butanone (methyl isopropyl Ketone), 2 pentanone (methyl n-propyl ketone), diisobutyl ketone, methyl-n-butyl ketone (methyl n-butyl ketone), propione (metacetone), 2-methyl-3-heptanone (butyl nezukone), 3-heptanone (ethyl normal-butyl ketone), methyln-hexyl ketone (methyl n hexyl ketone), 5-methyl-3-heptanone (ethyl pentyl group ketone), 5 methy 12 hexanone (methyl isoamyl ketone), heptanone (amyl methyl ketone), cyclopentanone, pimelinketone.
Usually, ester can be ring-type or non-annularity, straight chain or branching and/or replacement or unsubstituted.Non-annularity and cyclic ester comprise ethyl acetate, propyl acetate, butylacetate, pentyl acetate, butyl isobutyrate, methyl butyl, butyl propionate, butyl butyrate, methyl valerate, Valeric acid ethylester, methyl caproate, ethyl butyrate, ethyl acetate, gamma-butyrolactone, γ-Wu Neizhi.
Usually, the alcohol with at least 4 carbon atoms can be ring-type or non-annularity, straight chain or branching and/or replacement or unsubstituted.The example of this class ring-type and acyclic alcohol comprises methyl isophthalic acid-butanols, ethyl-1-butanols, 3-methyl isophthalic acid-butanols (amylalcohol), 2-methyl-1-pentene alcohol, 2-methyl-2-butanols (amylalcohol), 3-methyl-2-amylalcohol (methyl isobutyl carbinol), methyl-2-amylalcohol, 4-methyl-2-amylalcohol, butanols, amylalcohol, hexanol, enanthol, hexalin, the pure and mild potato spirit of the methyl-cyclohexyl (mixture of higher alcohols, it generally is pure distillatory by product, and mainly is amylalcohol (methyl butanol) usually).
Usually, paraffinic hydrocarbons can be ring-type or non-annularity, straight chain or branching and/or replacement or unsubstituted.In some embodiments, this paraffinic hydrocarbons comprises straight-chain paraffin and has 5 or more a plurality of carbon atom (for example heptane, hexane, octane, nonane and dodecane).In specific embodiment, paraffinic hydrocarbons comprises isoalkane (for example methylheptane, methyloctane, dimethyl heptane).In specific embodiment, can use
100 (mixture of the isoparaffin of C9-C11 is available from being positioned at Houston, the Chevron Phillips Chemical Company of TX).
Usually, the quantity of solvent that exists in the solvent system can change as required.In some embodiments, solvent system has and is at least about 5 parts (for example, be at least about 10 parts, be at least about 15 parts) solvent/part PHA and/or less than about 50 parts (for example less than about 30 parts, less than about 25 parts) solvents/part PHA.
In some embodiments, the solvent right and wrong of PHA are halogenated.It may be favourable using non-halogenated solvent, and this is can reduce the negative impact of solvent to environment because of this, reduction and the danger of use solvent associated health, and/or reduce and storage, processing and/or the relevant cost of disposal solvent.
In specific embodiment, the solvent of PHA can have low relatively density.For example, in the time of 20 ℃, the density of the solvent of PHA can be for less than about 0.95 kg/liter (for example, less than about 0.9 kg/liter, less than about 0.8 kg/liter, less than about 0.7 kg/liter).Do not wish to be bound by theory, it is believed that the low-density relatively solvent of use can increase the quality of the PHA phase that is separated out from residual biomass.
In some embodiments, the solvent of PHA has low relatively solubleness in water.For example, in the time of 20 ℃, the solubleness of the solvent of PHA in water is less than about 1% (for example less than about 0.5%, less than about 0.2%).The solvent that has relative low solubility in water is preferred, because this solvent is not easy to mix with water.This can improve the accessibility that two separation phases are provided in technological process, reduce cost thus and/or process complexity.
In specific embodiment, the solvent of PHA is a non-hydrolysable basically.For example, the same with the ethyl acetate at the most hydrolyzable of solvent.Use the solvent of basic non-hydrolysable can reduce the possibility that unwanted by product (for example chemical reactivity material, for example organic acid) forms.This can reduce sectional interest (for example pipeline) corrosive amount and/or speed, carries out the PHA extraction in this system.
In some embodiments, the relatively easy stripping from water of the solvent of PHA.For example, in the time of 100 ℃, solvent phase is at least for the logK value of water and about 1.5 (for example be at least approximately 1.8, be at least about 2, be at least about 2.2), according to people Ind.Eng.Chem.Res. such as Hwang, Vol.31, No.7, pp.1753-1767 (1992) measures, and it is hereby incorporated by.Use easily that steam stripped solvent may be an ideal from water, this be because be not easy to steam stripped other solvent phase ratio from water, such solvent is easy to be recovered and circulate.
In specific embodiment, the boiling point of the solvent of PHA is higher than 100 ℃.
In specific embodiment, the appropriate solvent right and wrong are halogenated, consider the reactivity of hydrolysis and/or consideration and polymkeric substance, have the water solubility and relative low reactivity of low relatively (for example low than ethyl acetate).
In some embodiments, in the time of 20 ℃, the solubleness of PHA in precipitation agent is about 0.2% (for example less than about 0.1%) less than PHA.
In specific embodiment, volume with respect to the solvent system that joins slurry, with the precipitation agent of relative smaller size smaller join PHA mutually in, for example, the precipitation agent volume that joins the PHA phase with the ratio that joins the solvent system volume in the slurry less than about 0.2 (for example less than about 0.1, less than about 0.07, less than about 0.05).
Solvent system contains in the embodiment of precipitation agent of the solvent of one or more PHA and one or more PHA therein, solvent and precipitation agent etc. the mole bubble point, under atmospheric pressure, the relative volatility of solvent and precipitation agent can be at least about 2 (for example be at least about 3, be at least about 4).
In some embodiments, wherein solvent system contains the solvent of one or more PHA and the precipitation agent of one or more PHA, and solvent and precipitation agent do not form azeotrope.Using the solvent and the precipitation agent that do not form azeotrope may be ideal, because with respect to the solvent and the precipitation agent that form azeotrope, it may be easier to separation and recovery solvent and precipitation agent and be used for utilizing again.
In specific implementations, wherein solvent system contains the solvent of PHA and the precipitation agent of PHA, the solution that is formed by PHA and solvent system contains the precipitation agent less than about 25 volume % (for example less than about 20 volume %, less than about 15 volume %, less than about 10 volume %).
Usually, heating contains the mixture of solvent system and slurry to strengthen the interaction of solvent system and PHA, makes thus PHA is removed from biomass.
Usually, during the stirring, the temperature of solvent system and slurry mix can change as required.In some embodiments, this temperature is less than about 160 ℃ (for example less than about 125 ℃, less than about 95 ℃, less than about 65 ℃) and/or be at least about 20 ℃.In specific embodiment, this temperature is that room temperature is to about 95 ℃ (for example about 40 ℃～about 80 ℃, about 60 ℃～about 70 ℃).In specific implementations, pressure can be adjusted to greater than normal atmosphere to promote the extraction (for example, greater than 1 normal atmosphere, up to 20 normal atmosphere) under the high temperature.
Shearing force when usually, stirring solvent system and slurry mix can change as required.In specific implementations, stir solvent system and slurry mix by stirring, so that reduce dissolution time.In some embodiments, in order to help dissolving, can use high-shear impeller and agitator (for example flat blade impeller, for example 6 straight leaf disc turbines), its end speed is for example about 5 meter per seconds or higher (for example reaching about 10 meter per seconds).In some embodiments, can use the have little profile blade high speed dispersion device of (profile blade), its end speed is for example about 10 meter per seconds or higher (for example about 15 meter per seconds or higher, about 20 meter per seconds～about 25 meter per seconds), usually this high speed dispersion utensil has the blade of little profile blade or jagged edges, to produce high-shear under the end speed that improves.In specific embodiment, use the rotor/stator system that produces relative high-shear (for example end speed up to about 50 meter per seconds under) in the slit between high speed rotor, this rotor is at the slotted stator internal rotation.The shape that can change rotor and stator usually is adapting to specific application, and many designs are commercially available.
Usually, stir PHA that solvent system and slurry mix have a required PHA solids content until the centrifuged sample of mixture mutually.In some embodiments, stir solvent system and slurry mix less than about 3 hours (for example less than about 2 hours) and/or be at least about 1 minute (for example be at least about 10 minutes, be at least about 30 minutes).
In specific embodiment, with respect to PHA mutually in the amount of dissolved PHA, PHA contains the biomass less than about 0.5 weight % (for example less than about 0.25 weight %, less than about 0.1 weight %) mutually.
In some embodiments, biomass contain less than about 25 weight % mutually (for example less than about 20 weight %, less than about 15 weight %) solvent (this solvent initially is present in the solvent system) and/or be at least the solvent (this solvent initially is present in the solvent system) of about 1 weight % (for example be at least about 5 weight %, be at least about 10 weight %).
In some embodiments, PHA has low relatively viscosity mutually.For example, the viscosity of this phase can be for less than about 100 centipoises (for example less than about 75 centipoises, less than about 50 centipoises, less than about 40 centipoises, less than about 30 centipoises).Do not wish to be limited by theory, it is believed that preparation PHA mutually so that its have low relatively viscosity can cause PHA from residual biomass mutually good relatively separation.Particularly, it is believed that the speed that is separated during centrifugal is inversely proportional with PHA viscosity mutually, so for given centrifugation time, have the specific system of viscosity higher mutually with respect to PHA wherein, what the viscosity that reduces the PHA phase caused improving is separated.
In specific embodiment, PHA has high relatively polymer concentration mutually.For example, the polymer concentration of PHA phase can be at least about 2% (for example be at least about 2.5%, be at least approximately 3%, be at least approximately 3.5%, be at least approximately 4%, be at least approximately 4.5%, be at least about 5%).
Can use various types of devices that utilize centrifugal force.As an example, use in some embodiments disc formula centrifugal device (disc stack) (SC-6 type for example, from being positioned at Northvale, the Westfalia Separator US of NJ, Inc.) carry out centrifugal.In specific implementations, use decantor (CA-220 type for example, from Northvale, the Westfalia Separator US of NJ, Inc.) carry out centrifugal.In some embodiments, can use hydraulic vortex flow devices.
In specific implementations, can use adverse current centrifuge contactor (for example Podbielniak centrifuge contactor, Luwesta centrifuge contactor, Taylor-Couette centrifuge contactor).Usually, by making two kinds of (or may be multiple) liquid streams contact with each other and use the adverse current centrifuge contactor.A kind of liquid stream (solvent streams) beginning is as the solvent-laden fluid stream of relative rich.Another kind of liquid stream (biomass stream) beginning is as the fluid stream that is rich in PHA relatively.Under counter-current condition, make this two kinds of liquid stream contact, make the minimum biomass stream part of the maximum solvent streams of solvent part and PHA contact (with increase, for example optimizing reclaims PHA from biomass stream), and/or make the maximum biomass stream part of PHA partly contact (with increase, for example concentration of PHA in the optimizing solvent streams) with the solvent streams that is rich in most PHA.In specific embodiment, this is to realize by the flowing opposite (counter current condition) that makes solvent streams and biomass stream.The adverse current centrifuge contactor can be available from for example, B﹠amp; P Process Equipment (Saginaw, MI) and Quadronics.The example of commercially available adverse current centrifuge contactor comprises Podbielniak A-1 adverse current centrifuge contactor (B﹠amp; PProcess Equipment) and Podbielniak B-10 adverse current centrifuge contactor (B﹠amp; P ProcessEquipment).
Usually, being used for centrifugal condition (for example power, time) can change as required.
Use in the embodiment of disc formula centrifugal device at some, can use be at least about 5,000RCF (relative centrifugal force) (for example be at least about 6,000RCF, be at least about 7,000RCF, be at least about 8,000RCF) and/or less than about 15,000RCF is (for example less than about 12,000RCF, less than about 10,000RCF) carry out centrifugal.In using the specific implementations of decanting vessel, can use be at least about 1,000RCF (for example be at least about 1,500RCF, be at least about 2,000RCF, be at least about 2,500RCF) and/or less than about 5,000RCF (for example less than about 4,000RCF, less than about 3,500RCF) carry out centrifugal.In the specific implementations of using the adverse current centrifuge contactor, can use at least about 1,000RCF (for example be at least about 1,500RCF, be at least approximately 2,000RCF is at least about 2,500RCF) and/or less than about 5,000RCF (for example less than about 4,000RCF, less than about 3,500RCF) carry out centrifugal.
Use in the embodiment of disc formula centrifugal device at some, centrifugal can carrying out less than about 1 hour (for example less than about 30 minutes, less than about 10 minutes, less than about 5 minutes, less than about 1 minute) and/or at least about 10 seconds (for example be at least about 20 seconds, be at least about 30 seconds).In using some embodiment of decanting vessel, centrifugally can carry out less than about 1 hour (for example less than about 30 minutes, less than about 10 minutes, less than about 5 minutes, less than about 1 minute) and/or be at least about 10 seconds (for example be at least about 20 seconds, be at least about 30 seconds).In the specific implementations of using the adverse current centrifuge contactor, centrifugal can carrying out less than about 1 hour (for example less than about 30 minutes, less than about 10 minutes, less than about 5 minutes, less than about 1 minute) and/or be at least about 10 seconds (for example be at least about 20 seconds, be at least about 30 seconds).
After centrifugal, add the precipitation agent of PHA to form mixture in mutually to isolated PHA.Solvent system contains in the embodiment of precipitation agent of one or more PHA therein, and joining the precipitation agent of isolated PHA in mutually can be identical or different with precipitation agent contained in solvent system.
Usually, joining the precipitation agent of isolated PHA in mutually can change as required.In some embodiments, the amount that joins the precipitation agent among the isolated PHA is at least about 0.1 parts by volume and (for example is at least about 0.25 part, be at least about 0.5 part) precipitation agent, with respect to the volume of the solvent of PHA in mutually and/or less than about 2 parts by volume (for example less than about 1.5 parts, less than about 1 part, less than about 0.75 part) precipitation agent, with respect to the solvent volume of PHA in mutually.
Stir PHA phase/precipitant mix thing to strengthen the interaction of PHA and PHA precipitation agent.This makes PHA be precipitated out from mixture, causes the combination that is formed by following: sedimentary PHA and the mixture that contains the PHA precipitation agent of solvent system and adding.Usually, at room temperature stir PHA phase/precipitant mix thing, but can use other temperature if desired.In some embodiments, use high-shear device, for example high-shear impeller (for example 6 straight leaf disc turbines), high speed dispersion device and rotor/stator high-shear online (in-line) or jar interior (in-tank) agitator mix PHA phase/precipitant mix thing.End speed by various devices is determined shearing rate, and can change between about 5 meter per seconds～about 50 meter per seconds (for example about 10 meter per seconds～about 25 meter per seconds) for example.Be not wishing to be bound by theory, it is believed that high shear mixing under given conditions can improve the quality of sedimentary polymkeric substance.
The PHA of precipitation separation from the liquid (for example solvent system and precipitation agent) of remnants then.This separation can be undertaken by for example filtration or centrifugal (for example use centrifugal basket drier, use vacuum band-type filter machine).
Generally, the PHA of washing precipitation removes unwanted impurity, for example residual solvent and/or precipitation agent with help then.In some embodiments, can use the solvent solvent of new system (for example relatively) washing copolymer, this solvent for example, the mixture of PHA solvent and PHA precipitation agent (for example any ratio between 0-100%).Usually the composition of selecting to be used to wash is with dissolving once more of reduction (for example minimizing) polymkeric substance and/or removing of enhancing (for example maximization) impurity.In specific embodiment, proper proportion may depend on the particular polymers composition and/or can determine by standard test (detersive efficiency).In some embodiments, this washing step can carry out under high temperature and suitable residence time, with further promotion washing with remove impurity.
Generally, the sedimentary PHA of dry washing (for example under about 40 ℃～about 100 ℃ temperature).Can under vacuum (for example, to help the recovery of promotion), carry out drying to residual solvent.In some embodiments, may need direct extruding still to contain the sedimentary polymkeric substance of solvent, for example, exhaust (devolatilizing) forcing machine.Can for example under near the temperature of melting point polymer, carry out this extruding, and can directly from forcing machine, reclaim solvent.Randomly can be under pressure water be injected vented extruder (for example produce steam, promote effective stripping of trace residue solvent and remove) with original position.Gas stream (for example air, CO
2Or steam) can randomly be injected into (for example, to promote solvent to remove) in the forcing machine.Extrude and operation (for example granulation) dry and the formation product can be combined into single unit (single unit), economize on the use of funds simultaneously and the technological operation cost.
Further residual processing liquid (solvent system and precipitation agent), thus can reuse the component of liquid (solvent and/or precipitation agent).For example, can distillating liquid, to separate solvent and precipitation agent.In some embodiments, isolated solvent and/or precipitation agent can be reused (for example as the solvent in the solvent system, as the precipitation agent in the solvent system, as joining the precipitation agent of PHA in mutually) in above-mentioned technology.In some embodiments, reuse isolated solvent and/or precipitation agent (for example as the solvent in the solvent system, as the precipitation agent in the solvent system, as joining the precipitation agent of PHA phase) in the technology that can in Fig. 2, describe (face is described as follows).
In specific embodiment, can carry out this technology (or part technology) in continuous and/or online mode.As an example, this technology can comprise the online rotor/stator depositing technology of the online rotor/stator dissolution process of PHA and/or PHA and/or online vented extruder (for example Werner and Pfleiderer ZSK forcing machine, by Coperion Corporation of Ramsey, NJ provides), be used for except that desolvating and forming PHA solid (for example pellet).
In some embodiments, this technology is used solvent with relative efficient manner.For example, the solvent that initially uses in the recovery solvent is used for utilizing at least about 90 volume % (for example at least about 95 volume %, at least about 97 volume %, at least about 98 volume %) again.
In some embodiments, this technology is used precipitation agent with relative efficient manner.For example, reclaim initial precipitation agent that uses in the solvent and the total amount that joins the precipitation agent of PHA in mutually be used for utilizing again at least about 90 volume % (for example be at least about 95 volume %, be at least about 97 volume %, be at least about 98 volume %).
Fig. 2 is the schema of embodiment that shows second step of two step process, this technology can be used for by extraction be present in residual biomass phase (Fig. 1) to small part PHA, improve the efficient of PHA extraction.As shown in Figure 2, solvent system is joined biomass and contain biomass mutually and the mixture of solvent system to provide in mutually.Stir the mixture (for example using above-mentioned) about stirring the condition of slurry and solvent system mixture comprise that to provide PHA (mainly contains solvent system and PHA) and the biomass combination of (solvent system that mainly contains biomass, water and carry secretly) mutually mutually.Use centrifugation PHA phase and biomass phase (for example using above-mentioned relevant centrifugal PHA phase and biomass condition mutually).Can handle PHA phase (for example by adding precipitation agent, stirring, separation, washing, the drying of PHA) as mentioned above, perhaps PHA can be added in the above-mentioned slurry and solvent mixture.Can use standard technique from the biomass of remnants mutually the component (for example solvent and/or precipitation agent) of stripping solvent system.Can reclaim the residual solvent that contains in the biomass by variety of way, for example at suitable tower, (for example routine is used for behind extraction oil to desolventize moisture eliminator, that reclaims residual solvent from soyflour desolventizes roaster (desolvantizer toaster)) in stripping, or convection drying and reclaim solvent (for example vacuum drier, have the fluidized bed dryer of rare gas element circulation and solvent condenses).In some embodiments, the biomass that contain solvent can be dry altogether with compatible animal-feed (for example gluten feed, distiller's dried grain, oil grain powder (oil seed meal)) in moisture eliminator, and the suitable setting of this moisture eliminator is to handle and to reclaim and/or to eliminate safely (for example adsorbing or burning) residual solvent.In whole technologies in Fig. 2, show the first step among Fig. 1, and showed for second step among Fig. 2.In some embodiments, randomly after removing residual solvent as mentioned above, residual biomass can be used as the nutrition (for example using the zymic ethanol fermentation) of fermentation.In some embodiments, can be used for fermentation to improve its nutrition distribution by hydrolyzing biomass (for example, handling) with proteolytic enzyme, lytic enzyme by at high temperature being exposed to acidic conditions.
Though described from some method of biomass extraction PHA, also had other embodiment.
As an example, can use dry biomass.In some embodiments, dry biomass can combine so that slurry to be provided with water.
As another example, can be before adding solvent system the precipitation agent of PHA be joined in the slurry.In some embodiments, the amount of the precipitation agent of adding is at least about 0.5 volume (for example about 0.5 volume～about 2 volumes) of slurry.
Before adding solvent system, add precipitation agent and can cause forming the PHA (for example purity is at least approximately 99%, and it is about 99.5% that purity is at least, and purity is at least about 99.9%) of pure relatively, isolating, extraction.Can be by the matter sample that depolymerizes of butanols under acidic conditions, to form the butyl ester of PHA monomeric unit, and behind the butyl ester of lipid and lipoid fatty acid residue, analyze definite polymkeric substance purity by gas-chromatography (GC) and (for example use Hewlett Packard 5890Series II GC, the Supelco 24044SBP-1 post that it is equipped with 30m x0.32mm ID has 0.25 micron membranes).Use the suitable standard substance of lipid acid and alcohol acid (for example palmitinic acid, stearic acid, oleic acid, linolic acid and 3-hydroxybutyric acid) to demarcate and stdn and the response of quantification chromatogram.This can be used to quantize polymer content and foreign matter content.Can quantize inorganic impurity by ashing.
Do not wish to be bound by theory, it is believed that before adding solvent system that precipitation agent with PHA joins and to help to remove the biomass impurity that is present in the biomass (for example phosphatide, neutral lipid, lipoprotein) in the slurry.If when the PHA solids content in the biomass is high relatively (for example the PHA solids content is at least approximately 65%, is at least about 75%), this may be particularly advantageous.
As other example, for example (for example pH is about 8.5～10, about 8.5～about 9, about 9～about 9.5, about 9.5～about 10) Chemical Pretreatment biomass and/or slurry under gentle relatively causticity condition then neutralizes before adding solvent system.This can cause forming the PHA (for example, it is about 99% that purity is at least, and is at least about 99.5%) of pure relatively, isolating, extraction.Can use one or more materials of alkalescence relatively, for example, potassium hydroxide, sodium hydroxide and/or ammonium hydroxide obtain the condition of causticity.
As another example, can be in the process of Chemical Pretreatment step elevated temperature (for example any temperature between room temperature and about 95 ℃) and can add other chemical for example tensio-active agent, washing composition and/or enzyme, form the PHA (for example purity is at least approximately 99%, is at least about 99.5%) of pure relatively, isolating, extraction with further promotion.
Be not wishing to be bound by theory, it is believed that chemical treatment before adding solvent system (for example gentle relatively caustic alkali is handled) slurry can help to remove the biomass impurity that is present in the biomass (for example lipid, phosphatide, lipoprotein).When the PHA solids content is high relatively in the biomass (for example the PHA solids content is at least approximately 65%, is at least about 75%), this may be particularly advantageous.
As another example, this method can be included in from residual biomass be separated PHA mutually after but the precipitation agent that adds PHA to PHA mutually before, concentrate (for example evaporating) PHA phase.This can reduce the volume of solution, reduces precipitation agent thus.
As further example, can carry out this technology in some embodiments and do not add the precipitation agent of PHA in mutually to PHA.
And, can form solvent system, and contact with biomass then, or biomass can contact with all components that is less than solvent system, then add the solvent system (for example order adds or once adds all) of rest part.For example, solvent system comprises that slurry can contact with solvent, then add precipitation agent, or vice versa in the embodiment of precipitation agent of the solvent of PHA and PHA therein.As selection, can merge solvent and precipitation agent to form solvent system, then contact biomass.
In addition, extract single PHA though described from biomass, this technology can be used for from the multiple PHA of biomass extractions (for example 2,3,4,5,6).This technology may relate to uses multiple solvent, precipitation agent and/or solvent system.
In addition, though described the solvent system of the single precipitation agent of the single solvent that contains PHA and optional PHA, can use the multiple solvent (for example 2,3,4,5,6) of PHA and/or the multiple precipitation agent of PHA (for example 2,3,4,5,6).
As another example, in some embodiments, can stir slurry/solvent system mixture and need not the heating.Selectively, can under pressurization and heating, stir slurry/solvent system mixture.
As further example, this method can comprise the solvent system/precipitant mix thing of distillation formation (for example distillation) with separated portion (for example precipitation agent of the solvent of PHA, PHA), so that can utilize in the component one or more again.
The following examples are indicative and are not intended to limit the present invention.In these embodiments, (Milwaukee, WI), overhead stirrer (overheadstirrer) is chemical from Aldrich Chemical Co.Inc.
-werke Eurostar power control-visc overhead stirrer (Ika Work Inc., Wilmington, NC) and whizzer be Sorvall RC 5B plus whizzer.
Example I
The a collection of intestinal bacteria biomass slurry that contains 70% polymkeric substance (butt) is divided into three parts, and following processing, wherein polymkeric substance consist of poly butyric ester with 4 hydroxybutyric acid ester of 25%-altogether-4 hydroxybutyric acid ester:
The a spraying drying is also collected 30 dry biomass that restrain.
B. spraying drying is collected the biomass of 30 grams and is used deionization (DI) water rewetting to 100g.
C. the initial slurry of unmodified 100 grams that contains 30 gram dry biomass.
Each batch used 400ml n-butyl acetate extraction 2 hours under the overhead stirring of room temperature, 500rpm.With gained slurry under 5000g centrifugal 20 minutes and reclaim the PHA phase.By use hexane as precipitation agent from PHA mutually precipitation PHA, then dried overnight under the temperature of the vacuum of 1 mmhg and 40 ℃, mensuration PHA content.The polymkeric substance that reclaims shows 32% starting polymer dissolving (scheme 1), 43% starting polymer dissolving (scheme 2) and greater than 97% starting polymer dissolving (scheme 3).
Example II
In test side by side, relatively from contain the one dimension size greater than the meat soup of the escherichia coli fermented broth of 2 microns cell with contain the Alkaligenes that overall dimension is 0.5 micron cell (Ralstoniaeutropha).In the Eppendorf 5415C Eppendorf centrifuge, determine under 12000rpm, to use the 1.5mL centrifuge tube that is filled with 1mL meat soup to obtain the time of limpid supernatant liquor.Under the situation of intestinal bacteria meat soup, obtain limpid supernatant liquor at the centrifugation time that is less than 1 minute, and Alkaligenes need be greater than 5 minutes time for similar clarity.
EXAMPLE III
By using the step of example I c, at butylacetate (Aldrich Chemical Co.Inc., Milwaukee, WI) the intestinal bacteria biomass slurry preparation that dissolving contains 70% polymkeric substance (butt) in contains the polymers soln (to represent with respect to total solution weight) of 5 weight % polymkeric substance, the 4 hydroxybutyric acid ester of the poly butyric ester that the consisting of of this polymkeric substance contained the 25%4-butyric ester-altogether.(MA) viscosity that records gained solution is 365 centipoises (cP) for Brookfield Engineering Laboratories Inc., Stoughton to use Brookfield LVF Viscometer.For the solution of viscosity less than 100cP, use No. 1 pivoted lever (spindle), for the solution of viscosity, use No. 2 pivoted lever greater than 100cP.This solution further is diluted to 4% and 3% polymkeric substance of total solution weight with other butylacetate.Find that gained viscosity is respectively 150cP and 40cP.
(WI) 5% polymers soln in some butylacetates of preparing above of dilution is to prepare the solution of 4.5 weight %, 4.3 weight %, 4.1 weight % and 3.9 weight % for Aldrich Chemical Co.Inc., Milwaukee then to use hexane.Measure the viscosity of these solution as mentioned above, and be defined as 215cP, 37.5cP, 5cP and 27.5cP respectively.
Viscosity when having described 5% polymers soln in butylacetate among Fig. 3 and diluting and comparison with the viscosity of hexane (precipitation agent of PHA under the room temperature) dilution with other butylacetate (PHA solvent).Has non-linear and required influence with the precipitation agent dilution to reducing viscosity.Be diluted to the observed viscosity of the polymkeric substance of 3.9 weight % in the solution with hexane and increase that to precipitate from solution with polymkeric substance under the level of adding hexane be consistent.
EXAMPLE IV
In the fed-batch fermentation, utilize glucose, use recombination bacillus coli to prepare poly 3-hydroxy butyrate-common-4 hydroxybutyric acid ester (the 30%4-butyric ester is based on volumetric molar concentration) as main carbon source.After fermentation was finished, Bacillus coli cells expand into greater than 2 microns in unidimensional size at least.Biomass have accumulated 70% polymkeric substance (dry weight).Then use centrifugal harvesting biomass,, do not contain dissolved impurity substantially to make humidogene material pellet.
The 100 gram humidogene material pellets (48% dried solid) that contain the poly 3-hydroxy butyrate-common 4 hydroxybutyric acid ester of 70% (butt) are filled with the 500ml ethyl acetate, and at room temperature stir 1 hour with overhead stirrer.Polymkeric substance consists of 30%4-butyric ester (volumetric molar concentration).Be increased to further mixing effectively after the degree of mixing material in viscosity, stop to mix.Collect 350ml slurry altogether, and under 5000g centrifugal 20 minutes altogether (Sorvall RC 5B plus whizzer, Kendro LaboratoryProducts, Newtown CT).Calculate according to mass balance, the theoretical amount of the ethyl acetate that should reclaim from the 350mL slurry is 300mL.
The PHA content of PHA phase is about 5.3%.By reclaiming 220 milliliters PHA phase, account for about 73 volume % of the callable ethyl acetate altogether of slurry before centrifugal at centrifugal back decant.
EXAMPLE V
Repeat the embodiment of front, difference be to use butylacetate (Aldrich Chemical Co.Inc., Milwaukee, WI) rather than ethyl acetate.Polymkeric substance in the solution is about 4.3%.Emulsion layer appears in the place at centrifugal rear interface.By reclaiming 250 milliliters of PHA phases, account for about 83% of the callable butylacetate altogether that exists in the slurry before centrifugal at centrifugal back decant.
Example VI
Repeat the embodiment of front, difference be to use MIBK (Aldrich Chemical Co.Inc., Milwaukee, WI) rather than butylacetate.Polymkeric substance in the solution is about 4.2%.By reclaiming 290 milliliters of PHA phases, account for about 97% of the callable MIBK altogether that exists in the slurry before centrifugal at centrifugal back decant.
Example VII A
Containing the wet intestinal bacteria biomass of 28% dried solid 100 grams sticks with paste, it contains the 75% poly 3-hydroxy butyrate-common 4 hydroxybutyric acid ester of 35% (based on dried solid) 4 hydroxybutyric acid ester, this is stuck with paste and 200 hexane (the Aldrich Chemical Co.Inc. that restrain, Milwaukee, WI) contact, and by overhead stirring at room temperature (
-werke Eurostar power control-visc overhead stirrer, Ika Work Inc., Wilmington, NC) extraction is 2 hours.
By 3, separated the hexane supernatant liquor in centrifugal 20 minutes under the 500g, and after decantation hexane supernatant liquor, reclaim solid grain.Then at room temperature, utilize overhead stirring (
-werke Eurostar powercontrol-visc overhead stirrer, Ika Work Inc., Wilmington, NC), (WI) the extraction pellet is 3 hours for Aldrich Chemical Co.Inc., Milwaukee to use 425 MIBK that restrain.3, centrifugal 20 minutes separation of supernatant (solution of polymkeric substance in MIBK) and by adding the hexane precipitation polymers of 355 grams under the 500g.Be arranged with filter paper (the VWR Scientific Products of rib ditch by use, West Chester, PA) funnel filters and reclaims sedimentary polymkeric substance, and in the B ü chi rotatory evaporator (rotavap) at 45 ℃ under the vacuum of 1mm Hg dried overnight, obtain 13 gram exsiccant polymkeric substance.Make this exsiccant polymer poly compound under 180 ℃, carry out hotting mask compacting (hot film pressing).The PHA of appropriate amount (being generally 0.5 gram) is placed between 2 PET sheets that separated by pad, forms thickness and be 100 microns film.This film assembling thing (i.e. 2 sheets, pad and PHA) is placed on the pressing machine of heating (180 ℃), and (Wabash IN) between the piece (block), and applies 10 tons load 30 seconds for Carver Hydraulic Press Model#3912, Carver Inc..Then this film is cooled off between aluminium block, and observe color and clarity.This has produced limpid substantially film, and this film does not have smoke cured or disgusting taste basically under 180 ℃ service temperature in the press cycle process.
Example VII A I
Repeat the embodiment of front, difference be to use heptane (Aldrich Chemical Co.Inc., Milwaukee, WI) rather than hexane.This technology produces limpid substantially film, and this film does not have smoke cured or disgusting taste substantially.
Example I X
Repeat the embodiment of front, difference is to use Soltrol
100 (C
9-C
11The mixture of isoalkane is available from being positioned at Houston, the Chevron Phillips Chemical Company of TX) rather than hexane.This technology produces limpid substantially film, and this film does not have smoke cured or disgusting taste substantially.
Embodiment X
With effective 0.02N NaOH (Aldrich Chemical Co.Inc., Milwaukee, WI) stuck with paste 20 minutes 65 ℃ of wet intestinal bacteria biomass of handling 100 grams down, this paste has 28% dried solid, this solid contains the 4 hydroxybutyric acid ester of 75% the poly 3-hydroxy butyrate of 35% (based on dried solid) 4 hydroxybutyric acid ester-altogether, is quickly cooled to room temperature in 5 minutes afterwards.Use 85% phosphoric acid (WI) the gained slurry is neutralized pH is 7 for Aldrich ChemicalCo.Inc., Milwaukee, centrifugal then (and 3,500g) 20 minutes, and with the deionized water wash of 2 volumes.Abandoning supernatant, and use 425 the gram MIBK at room temperature use overhead stirring (
-werke Eurostar power control-visc overhead stirrer, Ika Work Inc., Wilmington NC) will stick with paste extraction 3 hours.By 3, centrifugal 20 minutes separation of supernatant (solution of polymkeric substance in MIBK) and by adding the 355 alkane precipitation polymers of restraining oneself under the 500g.By this sedimentary polymkeric substance of filtered and recycled and dry in B ü chi B-171 rotatory evaporator (65 ℃ and 1mm Hg vacuum 8 hours), to obtain 12 gram exsiccant polymkeric substance.Under 180 ℃, this exsiccant polymkeric substance is carried out the hotting mask compacting.This is only had very slight decolouring/opaque film.
Embodiment XI
The embodiment of repetition front, but do not handle 20 minutes and quick refrigerative step with NaOH at 65 ℃.So the PHA that reclaims produces the film with strong yellow decolouring and opacity in the hotting mask pressing process.The evidence that also has thermal destruction in process of the test is as by being fuming in film test pressure cycling (pressure of 180 ℃ and 10 tons is during 30 seconds) and proving.
Embodiment XII
Be to use the embodiment of the single-step process of adverse current centrifuge contactor below.
The biomass that contain the dried solid 11kg of 26% intestinal bacteria stick with paste with 38.6kg methyl iso-butyl ketone (MIBK) (4-methyl-2 pentanone or MIBK) in the time of 30 ℃, contact is 3 hours in the dissolving vessel of the agitator that is equipped with sea usefulness impeller (marine impeller), to keep the mixture of homogeneous.Biomass contain poly--3-butyric ester-common 4 hydroxybutyric acid ester (the 4 hydroxybutyric acid ester of 22% volumetric molar concentration) (butt) of 71 weight %.After 3 hours, MIBK that obtains by centrifugal sample from dissolving vessel and the supernatant soln of PHA contain the PHA of 4.1 weight %, the dissolving of expression 91.2%.
With the speed of 635ml/min, cell is stuck with paste and the mixture of MIBK infeeds A-1 pilot scale Podbielniak extractor (B﹠amp; P Process Equipment, Saginaw, MI) (HLI) as heavy liquid charging (heavy liquid in).Simultaneously, fresh MIBK is infeeded as light weight fluid charging (LLI), to carry out the extraction that countercurrent washing and the cell in the Podbielniak contactor are stuck with paste.Supply LLI to keep charge proportion HLI with the speed of 175ml/min: LLI is 3.6: 1.During 90 minutes, infeed the HLI of 49.6kg and the LLI of 12.8kg altogether.Collected altogether the residual cells of 8.9kg and stuck with paste, and in during 90 minutes, collected PHA solution among the 53.6kg MIBK as light weight fluid discharging (LLO) as heavy liquid discharging (HLO).LLO contains 3.75 weight %PHA in the solution, and this is by the sample determination of dry this material.Reclaim the PHA of 2.0kg among the LLO altogether, stuck with paste the PHA (98.4% total yield) that contains 2.04kg in the charging at the HLI cell by comparison.
Mass balance is measured and is shown, in the limpid PHA of MIBK solution (LLO), has reclaimed more than 98% of whole MIBK that contains in bonded HLI and LLI.Centrifugal being presented in laboratory forms very limpid interface after centrifugal 1 minute under the 3000g.Keep limpid 90 minutes test periods also to confirm aggregation by LLO without any the interface.
The PHA rate of recovery (98.4%) of the improvement of Podbielniak extractor compare with the rate of recovery that obtains with single step dissolving (91.2%) confirmed with the fresh solvent counter current contact to improve the validity of the PHA rate of recovery.The viscosity that residual biomass is stuck with paste also significantly reduces by counter current contact, and this is the result who almost all removes PHA.
Embodiment XIII
Be to use the embodiment of pimelinketone extraction PHA below.
Under 90 ℃, the wet intestinal bacteria biomass of 90 grams are stuck with paste pimelinketone (the Aldrich Chemical Co. that joins 400 grams, Inc., Milwaukee, WI), this paste has 28% dried solid, and 80% poly 3-hydroxy butyrate that this solid contains 12%4-butyric ester (based on dried solid) is total to 4 hydroxybutyric acid ester (PHA).30,000rpm, use the hand-held homogenizer be equipped with single groove rotor stator combination (NY) this solution of homogenizing is 5 minutes for Virtis, Gardiner, use then overhead stirrer (
-werkeEurostar power control-visc overhead stirrer, Ika Work Inc., Wilmington NC) stirred 30 minutes.During the solvent contact procedure, temperature is controlled at 90 ± 5 ℃.Use Sorvall RC 5B plus whizzer (Kendro Laboratory Products by decantation then, Newtown, CT) centrifugal biomass paste/cyclohexanone mixture 5 minutes under 3000g is stuck with paste pellet separation of supernatant (solution of polymkeric substance pimelinketone) from residual biomass.
Then supernatant liquor is heated to 80 ± 5 ℃ once more in beaker, and during 5 minutes, isopyknic heptane (keep at room temperature) is slowly joined in this solution, use simultaneously overhead stirrer (
-werke Eurostar power control-visc overhead stirrer, Ika Work Inc., Wilmington, NC) violent stirring remains on temperature between 70 ℃ and 80 ℃ simultaneously with precipitation polymers.Be arranged with filter paper (the VWR Scientific Products of rib ditch by use, West Chester, PA) funnel filters and reclaims sedimentary polymkeric substance, and in chemical fuming cupboard air-dry overnight, to produce the white polymer particles (80% total yield) of 16 grams.
By between 2 PET sheets that separate by pad, placing the polymkeric substance of about 0.5 gram, be 100 microns film to form thickness, and prepare film.This film assembling thing (i.e. 2 sheets, pad and PHA) is placed on the pressing machine of heating (180 ℃), and (Wabash IN) between the piece (block), and applies 10 tons load 30 seconds for Carver Hydraulic Press Model#3912, CarverInc..Then this film is cooled off between aluminium block, and observe color and clarity.This has produced limpid substantially film, and this film does not have smoke cured or disgusting taste basically under 180 ℃ service temperature in the press cycle process.
Embodiment XIV
Be the embodiment of PHBH extraction below.
Use engineered Alcaligenes strain (as people such as Kichise, (1999), Intl.J.Biol.Macromol.25:69-77) preparation is described) and Naylor at US patent No.5,871, use fructose of describing in 980 and lauric acid are as the zymotechnique of carbon source, the wet cell of preparation Alkaligenes (Ralstoniaeutropha) is stuck with paste (27 weight % biomass solids in the water), this paste contains about 65% poly 3-hydroxy butyrate 3-hydroxycaproic ester (PHBH) (based on dry biomass) altogether, it consists of the hydroxycaproic ester (people such as Kichise of 5-7% volumetric molar concentration, (1999), Intl.J.Biol.Macromol.25:69-77).These biomass are joined the MIBK of appropriate amount, obtain 5% solution (w/w) of PHBH in solvent.30,000rpm, use the hand-held homogenizer be equipped with single groove rotor stator combination (NY) this solution of homogenizing is 5 minutes for Virtis, Gardiner, use then overhead stirrer (
-werke Eurostar powercontrol-visc overhead stirrer, Ika Work Inc., Wilmington NC) stirred 30 minutes.During the solvent contact procedure, temperature is controlled at 80 ± 5 ℃.Then, (Kendro Laboratory Products, Newtown is CT) by centrifugal and separating obtained biomass/solvent mixture to use Sorvall RC 5B plus whizzer.Under 3000g with centrifugal 5 minutes of biomass paste/cyclohexanone mixture, to stick with paste separation of supernatant (solution of polymkeric substance in pimelinketone) the pellet from residual biomass by decant.
Supernatant liquor is joined in the beaker, and during 5 minutes, isopyknic heptane is slowly joined in this solution, use simultaneously overhead stirrer (
-werke Eurostar power control-visc overhead stirrer, Ika Work Inc., Wilmington, NC) violent stirring is with precipitation polymers.In chemical fuming cupboard, after the dried overnight, reclaim the white polymer crystal powder.
Embodiment XV
Be the embodiment of PHBX extraction below.
As people such as Matsusakai (1999, Biomacromolecules
1: 17-22) described, the wet cell for preparing engineered pseudomonas kind (Pseudomonas sp) is stuck with paste, and on glucose, grow, it contains the 3-hydroxyl dodecylene acid esters (PHBX) of the 3-hydroxyl dodecanoic acid ester of the 3-hydroxydecanoic acid ester of the 3-Hydroxyoctanoic acid ester of about 50% poly 3-hydroxy butyrate-altogether-altogether-altogether-altogether based on dry biomass, consists of 92%3-butyric ester, 1%3-Hydroxyoctanoic acid ester, 3%3-hydroxydecanoic acid ester, 3%3-hydroxyl dodecanoic acid ester and 1%3-hydroxyl dodecylene acid esters (volumetric molar concentration).Biomass are joined among the MIBK of appropriate amount, obtain 5% solution (w/w) of PHBX in solvent.30,000rpm, use the hand-held homogenizer be equipped with single groove rotor stator combination (NY) this solution of homogenizing is 5 minutes for Virtis, Gardiner, use then overhead stirrer (
-werke Eurostar power control-visc overhead stirrer, Ika Work Inc., Wilmington NC) stirred 30 minutes.During the solvent contact procedure, temperature is controlled at 80 ± 5 ℃.Use Sorvall RC 5B plus whizzer (Kendro Laboratory Products, Newtown, CT) separating obtained biomass/solvent mixture.Centrifugal biomass paste/cyclohexanone mixture 5 minutes under 3000g is stuck with paste pellet separation of supernatant (solution of polymkeric substance pimelinketone) by decantation from residual biomass then.
Then supernatant liquor is joined in the beaker, and during 5 minutes, isopyknic heptane is slowly joined in this solution, use simultaneously overhead stirrer (
-werke Eurostar powercontrol-visc overhead stirrer, Ika Work Inc., Wilmington, NC) violent stirring is with precipitation polymers.In chemical fuming cupboard, after the dried overnight, reclaim the white polymer crystal powder.
Other embodiment in the claims.
Claims (31)
1. method of from the biomass that contain polymkeric substance, separating this polymkeric substance, this method comprises:
Biomass are contacted with solvent system, and this solvent system comprises the solvent of polymkeric substance and the precipitation agent of polymkeric substance, so that the solution of residual biomass with the precipitation agent of solvent that comprises polymkeric substance, polymkeric substance and polymkeric substance to be provided; With
This solution and residual biomass are applied centrifugal force to separate at least some described solution from residual biomass.
2. the process of claim 1 wherein that the density of solvent of polymkeric substance is less than 0.95 kg/liter.
3. the process of claim 1 wherein that the solvent right and wrong of polymkeric substance are halogenated.
4. the process of claim 1 wherein that the solubleness of solvent in water of polymkeric substance is less than 1%.
5. the process of claim 1 wherein that the solvent of polymkeric substance is non-hydrolysable basically basically.
6. the process of claim 1 wherein that the solvent phase of polymkeric substance is at least 1.5 for the logK value of 100 ℃ of water.
7. the process of claim 1 wherein that the boiling point of solvent is higher than 100 ℃.
8. the process of claim 1 wherein that the solvent of polymkeric substance is selected from ketone, ester and alcohol.
9. the process of claim 1 wherein that the solvent of polymkeric substance is selected from MIBK, butylacetate, pimelinketone and combination thereof.
10. the process of claim 1 wherein that the precipitation agent of polymkeric substance at room temperature dissolves the polymkeric substance less than 0.2%.
11. the process of claim 1 wherein the precipitation agent of the solvent of polymkeric substance and polymkeric substance etc. under the mole bubble point, the relative volatility of the solvent of polymkeric substance and the precipitation agent of polymkeric substance is at least 2.
12. the process of claim 1 wherein that the solvent of polymkeric substance and the precipitation agent of polymkeric substance do not form azeotrope.
13. the process of claim 1 wherein that precipitation agent comprises at least a alkane.
14. the process of claim 1 wherein that solution comprises the precipitation agent of the polymkeric substance that is at most 25 volume %.
15. the process of claim 1 wherein that the polymer concentration of solution is at least 2%.
16. the process of claim 1 wherein that the viscosity of solution is at most 100 centipoises.
17. the process of claim 1 wherein the biomass sources that contains this polymkeric substance in microorganism, and its polymer content is at least 50 weight %.
18. the process of claim 1 wherein the biomass sources that contains this polymkeric substance in plant, and its polymer content is less than 50 weight %.
19. the process of claim 1 wherein that the biomass that contain this polymkeric substance comprise the cell that contains polymkeric substance.
20. the method for claim 1 further comprises and remove at least some polymkeric substance from solution.
21. the method for claim 20 further comprises this polymkeric substance of removing of extruding so that polymkeric substance is dry and granulation.
22. the method for claim 20 is wherein removed polymkeric substance and is not comprised solution is exposed to hot water from solution.
23. the method for claim 20 is wherein removed polymkeric substance and is comprised second precipitation agent that adds polymkeric substance in solution from solution.
24. the method for claim 23, wherein first and second precipitation agents of polymkeric substance are identical.
25. the method for claim 20 further is included in and removes at least some polymkeric substance front evaporator part solution from solution.
26. the method for claim 1, comprise that further after solution was applied centrifugal force, second precipitation agent of the polymkeric substance of adding certain volume was to remove at least some polymkeric substance from solution, wherein with respect to the volume of solvent system, the volume of second precipitation agent is less than 2 parts.
27. the process of claim 1 wherein that polymkeric substance contains PHA.
28. the process of claim 1 wherein that solvent system contacts under counter-current condition with biomass.
29. the method for claim 28, wherein this method is a single step process.
30. the method for claim 28, wherein this method is a multistep processes.
31. the method for claim 28, wherein counter-current condition comprises the pressure that is at least 65psig.
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| US40149802P | 2002-08-06 | 2002-08-06 | |
| US60/401,498 | 2002-08-06 | ||
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| CN201110314892.9A Division CN102443159B (en) | 2002-08-06 | 2003-07-23 | Polymer extraction methods |
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| CN105189658A (en) * | 2012-12-18 | 2015-12-23 | 威立雅水务技术支持公司 | Method of producing polyhydroxyalkanoate compounded plastics having improved mechanical properties |
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| JP4759529B2 (en) * | 2007-03-06 | 2011-08-31 | 花王株式会社 | Method for producing microbial fermentation product |
| US8828474B2 (en) * | 2009-09-20 | 2014-09-09 | Medtronic Vascular, Inc. | Apparatus and methods for loading a drug eluting medical device |
| CN109575264B (en) * | 2018-10-26 | 2021-09-28 | 亿科优生物降解材料研究院(广东)有限公司 | Method for extracting polyhydroxyalkanoate by taking valerolactone as solvent |
| CN109517156A (en) * | 2019-01-02 | 2019-03-26 | 清华大学 | A kind of purification process of polyhydroxyalkanoate |
| CN112552500B (en) * | 2021-01-04 | 2022-12-20 | 珠海麦得发生物科技股份有限公司 | Method for removing endotoxin in PHAs by fermentation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO1998046782A1 (en) * | 1997-04-15 | 1998-10-22 | Monsanto Company | Methods of pha extraction and recovery using non-halogenated solvents |
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| US4324907A (en) * | 1979-05-08 | 1982-04-13 | Imperial Chemical Industries Limited | Extraction process |
| US4358583A (en) * | 1980-08-13 | 1982-11-09 | Imperial Chemical Industries Plc | Extraction of poly(β-hydroxy butyric acid) |
| US5942597A (en) * | 1995-08-21 | 1999-08-24 | The Procter & Gamble Company | Solvent extraction of polyhydroxyalkanoates from biomass |
| CN1328160A (en) * | 2000-06-13 | 2001-12-26 | 中国科学院微生物研究所 | One-stop separation method for extracting polyhydroxyl phytanate directly from fermented liquid |
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| WO1998046782A1 (en) * | 1997-04-15 | 1998-10-22 | Monsanto Company | Methods of pha extraction and recovery using non-halogenated solvents |
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| CN105189658A (en) * | 2012-12-18 | 2015-12-23 | 威立雅水务技术支持公司 | Method of producing polyhydroxyalkanoate compounded plastics having improved mechanical properties |
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