method for purification of isoprene from a fermenter gaseous effluent and composition

专利摘要:
isoprene purification from renewable resources. Methods and apparatus for purifying isoprene are presented, such as purifying a bioisoprene composition from fermenter gas effluent. The apparatus includes two columns that process the fermenter gaseous effluent, which includes isoprene and various impurities. A solvent is added to the gaseous effluent in the first column, and the isoprene is rectified from the solvent in the second column. An additional jusane purification process is also presented. Also shown are the resulting purified isoprene compositions.
公开号:BR112012014736B1
申请号:R112012014736
申请日:2010-12-15
公开日:2018-09-18
发明作者:D Ploetz Christopher；J Feher Frank；Kaluen Kan John；C Mcauliffe Joseph；J Pickert Lawrence；Rodewald Stephan；H Wong Tang；f mccall Thomas；A Sabo Timothy
申请人:Danisco Us Inc；Goodyear Tire & Rubber；
IPC主号:

专利说明:

(54) Title: METHOD FOR PURIFICATION OF ISOPRENE FROM A GASEOUS EFFLUENT FROM THE FERMENTER AND COMPOSITION (51) Int.CI .: C07C 7/04; C07C 11/18; B01D 11/04; B01D 11/00; C07C 7/00 (30) Unionist Priority: 12/18/2009 US 61 / 288,142 (73) Holder (s): DANISCO US INC .. THE GOODYEAR TIRE & RUBBER COMPANY (72) Inventor (s): FRANK J. FEHER ; JOHN KALUEN KAN; JOSEPH C. MCAULIFFE; THOMAS F. MCCALL; STEPHAN RODEWALD; TIMOTHY A. SABO; TANG H. WONG; LAWRENCE J. PICKERT; CHRISTOPHER D. PLOETZ (85) National Phase Start Date: 06/15/2012
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Descriptive Report of the Invention Patent for METHOD FOR PURIFICATION OF ISOPRENE FROM A GASEOUS EFFLUENT OF THE FERMENTER AND COMPOSITION.
FIELD OF THE INVENTION
This description refers to the production of isoprene. BACKGROUND
Isopropene (2-methyl-1,3-butadiene) is an important organic compound used in a wide variety of applications. For example, isoprene is used as an intermediate or starting material in the synthesis of numerous chemical compositions and polymers. Isopropene is also an important biological material that is naturally synthesized by many plants and animals, including humans.
Isopropene became an important monomer for use in the synthesis of c / 's-1,4-polyisoprene, when its stereoregulated polymerization became commercially possible in the early 1960s. The c / s-1,4 polyisoprene produced by these stereoregulated polymerizations it is similar, in terms of structure and properties, to natural rubber. Although not identical to natural rubber, it can be used as a substitute for natural rubber in many applications. For example, c / s-1,4-polyisoprene synthetic rubber is widely used in the manufacture of vehicle tires and other rubber products. This demand for c / s-1,4-polyisoprene synthetic rubber consumes most of the isoprene available on the world market. The remaining isoprene is used in the manufacture of other synthetic rubbers, block copolymers and other chemicals. For example, isoprene is used in the manufacture of butadiene isoprene rubbers, styrene-isoprene copolymer rubbers, styrene-isoprene-butadiene rubbers, styrene-isoprene-styrene block copolymers and styrene-isoprene block copolymers.
Over the years, many synthetic routes for isoprene production have been investigated. For example, the synthesis of isoprene by reacting isobutylene with formaldehyde in the presence of a catalyst is described in US patents No. 3,146,278, US No. 3,437,711, US No. 3,621,072,
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US No. 3,662,016, US No. 3,972,955, US No. 4,000,209, US No. 4,014,952, US No. 4,067,923 and US No. 4,511,751. US patent No. 3,574,780 discloses another process for the manufacture of isoprene by passing a mixture of methyl tert-butyl ether and air over mixed oxide catalysts. The methyl tert-butyl ether is then cracked in isobutylene and methanol on the catalyst. The methanol produced is oxidized to formaldehyde, which then reacts with isobutylene on the same catalyst to produce isoprene. US patent No. 5,177,290 discloses a process for producing dienes, including isoprene, which involves reacting a reaction mixture of a tertiary alkyl ether and an oxygen source. On two functionally distinct catalysts, under sufficient reaction conditions to produce a high yield of dienes with minimal recycling of tertiary alkyl ether and decomposition products of tertiary alkyl ether.
The isoprene used in industrial applications is typically produced as a by-product of thermal cracking of oil or naphtha or is otherwise extracted from petrochemical currents. This is a relatively expensive and energy-intensive process. With the steady increase in world demand for petrochemical products, the cost of isoprene is expected to rise to much higher levels in the long run, and its availability is limited, anyway. There is concern that future supplies of isoprene obtained from sources based on petrochemicals will be inadequate to meet projected needs, and that prices will rise to unprecedented levels. Consequently, there is a need to obtain an isoprene source from a renewable, low-cost and environmentally friendly source.
Several recent advances have been made in the production of isoprene from renewable sources (see, for example, international patent application publication No. W02009 / 076676). These production techniques often result in isoprene compositions containing varying amounts of impurities as part of the fermentation process. For example, fermentation can generate more volatile components, such as
3/74 water vapor, from the fermentation medium, carbon dioxide as a breathing product and residual oxygen in the case of aerobic metabolism, as well as other organic biological by-products. Oxygen can initiate unwanted chemical reactions of isoprene, reducing productivity and generating undesirable reaction products. Carbon dioxide is a known inhibitor for subsequent catalytic reactions for converting and applying isoprene, such as isoprene to polymers, such as dimers, trimers, and even polymers with very long chains, such as synthetic rubber. Water vapor and other residual biological by-products are also undesirable for many applications using isoprene. Consequently, purification techniques and methods are desirable for isoprene compositions produced from renewable resources.
The descriptions of all publications, patents, patent applications and published patent applications mentioned in this document are hereby incorporated by reference, in their entirety. SUMMARY
The present description presents, among others, methods and apparatus for purifying isoprene from renewable or similar resources, as well as the resulting purified isoprene compositions.
In one aspect, a method for purifying isoprene from a gaseous effluent from the fermenter is presented, the gaseous effluent comprising isoprene, volatile impurity and biological by-product impurity, and the said method comprising: placing the gaseous effluent from the fermenter in contact with a solvent in an apparatus that includes a first column, to form: an isoprene-rich solution comprising the solvent, a major portion of the isoprene and a major portion of the biological by-product impurity, and a vapor comprising a major portion of the volatile impurity, transfer the isoprene-rich solution from the first column to a second column, and rectify the isoprene from the isoprene-rich solution in the second column, to form: an isoprene-poor solution, comprising a major portion of the biological by-product impurity , and a composition of
4/74 purified isoprene. In some embodiments, the gaseous effluent is a bioisoprene composition.
In any of these modalities, the volatile impurity comprises a compound selected from H ₂ O, CO ₂ , N ₂ , H ₂ , CO and O ₂ . In some embodiments, the volatile impurity comprises H ₂ O, CO ₂ and N ₂ . In some embodiments, the volatile impurity comprises from about 25 to about 80 mol% CO ₂ , from about 45 to about 99 mol% N ₂ and optionally comprises less than about 50 mol% of O ₂ . In some embodiments, the volatile impurity comprises from about 40 to about 60 mol% CO ₂ , from about 65 to about 99 mol% N ₂ and optionally comprises less than about 25 mol% of O ₂ .
In any of these embodiments, the biological by-product impurity comprises a polar, non-polar or semipolar impurity. In some embodiments, the biological by-product impurity comprises one, two, three or more compounds selected from ethanol, acetone, methanol, acetaldehyde, methacrolein, methyl vinyl ketone, 3-methylfuran, 2-methyl-2-vinylvinyloxane, cis and ions-3- methyl-1,3-pentadiene, a C5 prenyl alcohol (such as 3-methyl-3-buten-1-ol or 3-methyl-2-buten-1-ol), 2-heptanone, 6-methyl-5-hepten2 - one, 2,4,5-trimethylpyridine, 2,3,5-trimethylpyrazine, citronelal, methanethiol, methyl acetate, 1-propanol, diacetyl, 2-butanone, 2-methyl-3-buten-2-ol, acetate ethyl, 2-methyl-1-propanol, 3-methyl-1-butanal, 3-methyl-2-butanone, 1butanol, 2-pentanone, 3-methyl-1-butanol, ethyl isobutyrate, 3-methyl-2butenal , butyl acetate, 3-methyl butyl acetate, 3-methyl-3buten-1-yl acetate, 3-methyl-2-buten-1-yl acetate, (E) -3,7-dimethyl-1, 3,6-octatriene, (Z) -3,7-dimethyl-1,3,6-octatriene, (E, E) -3,7,11-trimethyl-1,3,6,10-dodecatetraene and (E ) -7,11-dimethyl-3-methylene-1,6,10-dodecatriene, 3-hexen-1-ol, acetate
3-hexen-1-yl, limonene, geraniol (trans-3,7-dimethyl-2,6-octadien-1-ol), citronelol (3,7-dimethyl-6-octen-1-ol), (E ) -3-methyl-1,3-pentadiene, (Z) -3-methyl1,3-pentadiene. In some embodiments, the amount of biological by-product in relation to the amount of isoprene in the fermented gaseous effluent is greater than about 0.01% (weight / weight), or greater than about 0.05% (weight / weight).
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In either of these modalities, the solvent is a non-polar solvent with a high boiling point. In some embodiments, the solvent has a boiling point greater than about 177 ° C (350 ° F), or greater than about 191 ° C (375 ° F). In some embodiments, the solvent has an Ostwald coefficient for CO ₂ at 54 ° C (130 ° F) less than about 1.25, or less than about 1.1. In some embodiments, the solvent has a Kauri-butanol value of less than about 50, or from about 20 to about 30, or from about 23 to about 27. In some embodiments, the solvent has an aniline point greater than about 66 ° C (150 ° F), or from about 79 ° C (175 ° F) to about 93 ° C (200 ° F). In some embodiments, the solvent has a kinematic viscosity at 40 ° C less than about 2.5 x 10 ⁶ m / s ² (2.5 centistokes (cSt)), or less than about 1.75 x 10 ' ⁶ m / s ² (1.75 centistokes (cSt)). In some embodiments, the solvent has a surface tension at 25 ° C of about 20 to 30 dynes / cm, or about 23 to 27 dynes / cm. In some embodiments, the solvent has an average molecular weight of about 125 to about 225, or from about 140 to about 200. In some embodiments, the solvent is selected from a terpene, a paraffin, a monoaromatic hydrocarbon , a polyaromatic hydrocarbon or a mixture thereof. In some embodiments, the solvent is a paraffin (for example, a C10-C20 paraffin, such as a C12-C14 paraffin). In some embodiments, the solvent is an isoparaffin, such as isoparaffin C12C14. In some embodiments, the solvent is selected from a solvent substantially similar to Isopar ™ L, Isopar ™ H and Isopar ™ M. In some embodiments, the solvent is selected from Isopar ™ L, Isopar ™ H and Isopar ™ M. In some embodiments , the solvent is substantially similar to Isopar ™ L. In some embodiments, the solvent is Isopar ™ L. In some embodiments, the solvent additionally comprises a polymerization inhibitor. In some embodiments, the polymerization inhibitor is selected from 2,2,6,6-tetramethyl piperidin 1-oxyl (TEMPO), 4-hydroxy-2,2,6,6tetramethyl piperidin 1-oxyl (TEMPOL), bis sebacate (1-oxyl-2,2,6,6tetramethyl piperidin-4-yl) (TEMPO with bridge), and t-butyl catechol. In some embodiments, the concentration of the polymerization inhibitor is about
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0.001% to about 0.1% (weight / weight) in relation to the isoprene concentration.
In any of these modalities, the temperature of the gaseous effluent from the fermenter is reduced before it enters the solvent in the first column.
In any of these modalities, the gaseous effluent from the fermenter is transferred to an isolation unit capable of stabilizing the pressure of the fermenter before it contacts the solvent in the first column.
In either of these modalities, the gaseous effluent from the fermenter is at least partially condensed before coming into contact with the solvent in the first column.
In any of these modalities, the step of putting the fermenter's gaseous effluent in contact with a solvent in a first column comprises cooling the solvent being fed. The poor solvent stream is cooled or cooled before being supplied to the first column, for example, up to 4 ° C (40 ° F).
In some embodiments, the bottom current from the first (or second) column is referred to a temperature greater than about 66 ° C (150 ° F), or greater than about 91 ° C (200 ° F). In some embodiments, this bottom current is referred to a temperature of about 93 ° C (200 ° F) to about 135 ° C (275 ° F), or about 110 ° C (230 ° F) to about 121 ° C (250 ° F). Refervura removes CO ₂ , which is a volatile impurity, from the isoprene-rich solvent.
In any of these modalities, the step of putting the fermenter's gaseous effluent in contact with a solvent in a first column further comprises adding steam to the first column as an alternative to the bottom current, which is necessary under certain operating conditions.
In either of these embodiments, the step of rectifying the isoprene from the isoprene-rich solution in the second column comprises adding steam to the second column as an alternative to re-whitening.
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In any of these modalities, the method additionally comprises transferring the purified isoprene-poor solution to the first column for reuse. In some embodiments, the method additionally comprises: purifying the isoprene-poor solution to remove a major portion of the biological by-product impurity, and transferring the purified isoprene-poor solution to the first column for reuse. In some embodiments, purifying the low isoprene solution comprises treating the low isoprene solution with an adsorption system. In some embodiments, the adsorption system comprises activated carbon, alumina, silica or Selexsorb® (available from BASF). In some embodiments, the adsorption system comprises silica. In some embodiments, purifying the low isoprene solution comprises distillation. In some embodiments, purifying the isoprene-poor solution involves liquid-liquid extraction.
In either of these modalities, the temperature of the isoprene-poor solution is reduced before removing a major portion of the biological by-product impurity. In some embodiments, the temperature of the low isoprene solution is reduced to less than about 66 ° C (150 ° F), or to less than about 38 ° C (100 ° F), or to less than about 24 ° C (75 ° F).
In either of these embodiments, the method comprises further purifying the purified isoprene composition. In some embodiments, purifying the isoprene comprises distillation (for example, after the purified isoprene composition is transferred from the second column to a reflux condenser). In some embodiments, further purifying the purified isoprene composition comprises treating the purified isoprene composition with an adsorption system. In some embodiments, the adsorption system comprises activated carbon, alumina, silica or Selexsorb®. In some embodiments, the adsorption system comprises silica.
In any of these modalities, the method additionally comprises removing a minor portion of the isoprene from the steam, if
8/74 is present. In some embodiments, removing a minor portion of the isoprene, if present, involves treating the steam with an adsorption system. In some embodiments, the adsorption system comprises activated carbon, alumina, silica or Selexsorb®. In some embodiments, the adsorption system comprises activated carbon.
In any of these modalities, the gaseous effluent from the fermenter is supplied to the first column at a pressure greater than atmospheric pressure.
In either of these embodiments, the purified isoprene composition has a purity greater than about 90%, or greater than about 95%, or greater than about 99%.
In either of these embodiments, the purified isoprene composition comprises less than about 25%, or less than about 10%, or less than about 5% of biological by-product impurity in relation to the biological by-product impurity of the fermenter gaseous effluent .
In any of these modalities, the purified isoprene composition comprises less than about 2.5% water and 0.25% CO ₂ , O ₂ and N ₂ as volatile impurities, in relation to the volatile impurity of the fermenter gaseous effluent, or less than about 0.10%, or less than about 0.05% of these impurities.
In another aspect, a purified isoprene composition prepared by any of the methods described herein is presented. In some embodiments, a purified isoprene composition prepared by any of the methods described herein is provided.
In another aspect, an isoprene composition is shown. In some embodiments, the composition comprises isoprene and biological by-product impurity, the biological by-product impurity comprising C5 hydrocarbons, and there is more than about 99.94% isoprene (weight / weight) in relation to the weight of the hydrocarbons C5, and less than about 0.05% of biological by-product (weight / weight) in relation to the weight of the isoprene. In some modalities, the by-product
Biological 9/74 comprises one or more compounds as mentioned above, and even those selected from the group consisting of 2-heptanone, 6methyl-5-hepten-2-one, 2,4,5-trimethylpyridine, 2,3,5-trimethylpyrazine , citronelal, acetaldehyde, methanethiol, methyl acetate, 1-propanol, diacetyl, 2-butanone,
2-methyl-3-buten-2-ol, ethyl acetate, 2-methyl-1-propanol, 3-methyl-1-butanal, 3-methyl-2-butanone, 1-butanol, 2-pentanone, 3-methyl- 1-butanol, ethyl isobutyrate, 3-methyl-2-butenal, butyl acetate, 3-methyl butyl acetate, acetate
3-methyl-3-but-1-enyl, 3-methyl-2-but-1-enyl acetate, (E) -3,7-dimethyl-1,3,6octatriene, (Z) -3,7- dimethyl-1,3,6-octatriene and 2,3-cycloheptenol pyridine. In some embodiments, the composition comprises less than about 5% volatile impurity, relative to the weight of the composition. In some embodiments, the composition comprises more than about 95% isoprene in relation to the weight of the composition.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a diagram of a process, and the equipment associated with it, for isoprene purification as described in the present invention.
Figure 2 is a graph of the efficiency in absorbing isoprene.
Figure 3 is an analysis of the isoprene / solvent composition.
Figure 4 shows details of figure 3.
Figure 5 is a graph of the isoprene recovered from a solution.
Figure 6 is a diagram of a process, and the equipment associated with it, to further purify the isoprene.
Figure 7 is a graph of impurities in the isoprene.
Figure 8 is a graph of a concentration of the dimethyl disulfide impurity over time.
Figure 9 is another graph of the dimethyl disulfide concentration over time.
DETAILED DESCRIPTION
This description presents, among others, methods and devices for purifying isoprene from renewable resources. These methods
10/74 can use one or more columns to remove volatile and / or biological by-product impurities resulting from fermentation.
The inventors have determined methods for purifying the isoprene present in a fermenter gaseous effluent generated from renewable resources using solvents (for example, non-polar solvents) with absorption and rectification processes that can provide isoprene with significantly improved purity. The purified isoprene compositions described herein are particularly suitable for use in applications that conventionally use petroleum based isoprene, as polymerization and use as a starting material in the synthesis of numerous desirable chemical compositions.
Consequently, in one aspect a method for purifying isoprene from a fermenter gaseous effluent is presented, comprising: placing the fermenter gaseous effluent in contact with a solvent in a column to form: an isoprene-rich solution comprising the solvent and a major portion of the isoprene, and a vapor comprising a major portion of the volatile impurity. In some embodiments, the method additionally comprises: rectifying the isoprene from the isoprene-rich solution in a second column, to form: an isoprene-poor solution, comprising a major portion of the biological by-product impurity, and a purified isoprene composition. Purified isoprene compositions are also presented.
Except where otherwise stated in this document, all technical and scientific terms used in the present invention have the same meaning commonly understood by the person skilled in the art to which this invention belongs.
For use in the present invention, the singular terms one, one, o and a include the reference to the plural, unless the context clearly indicates otherwise.
The intention is that each maximum numerical limit mentioned in this specification includes each of the lower numerical limits, as if such lower numerical limits were expressly
11/74 registered in this document. Each minimum numerical limit mentioned in this specification includes each of the upper numerical limits, as if such upper numerical limits were expressly registered in this document. Each number range mentioned in this specification includes each more restricted number range that is within that broader number range, as if such more restricted number ranges were expressly recorded in this document.
The term isoprene refers to 2-methyl-1,3-butadiene (CAS No. 7879-5). Isopropene can be produced as the direct and final product of volatile C5 hydrocarbon, from the elimination of 3,3-dimethyl allyl pyrophosphate pyrophosphate (DMAPP), and does not involve the binding or polymerization of one or more IPP molecules to one or more DMAPP molecules. The term isoprene is not intended, in general, to be limited to its method of production, except where otherwise indicated in the present invention.
For use in the present invention, biologically produced isoprene or bioisoprene refers to isoprene produced by any biological means, as produced by genetically engineered cell cultures, as well as microorganisms, plants or natural animals. A bioisoprene composition generally contains less hydrocarbon impurities than isoprene produced from petrochemical sources, and often requires minimal treatment to be in a degree of polymerization. A bioisoprene composition also has a different impurity profile than a petrochemical produced isoprene composition.
Although isoprene can be obtained by fractioning oil, purifying this material is expensive and time-consuming. Cracking oil from the C5 hydrocarbon chain produces only about 15% isoprene. Isopropene is also produced naturally by a variety of microbial, plant and animal species. In particular, two routes have been identified for the biosynthesis of the
12/74 isoprene: the mevalonate route (MVA) and the non-mevalonate route (DXP). Genetically engineered cell cultures, placed in bioreactors, have produced isoprene more efficiently, in greater quantities, with higher levels of purity and / or with exclusive impurity profiles, for example as described in the international patent application publication No. W02009 / 076676, in US patent applications No. 12 / 496,573, 12 / 560,390, 12 / 560,317, 12 / 560,370, 12 / 560,305 and 12 / 560,366, and in US provisional patent applications No. 61 / 187,930, 61 / 187,934 and 61 / 187,959.
Crude bioisoprene compositions are distinguished from isoprene derived from petroleum compositions (mentioned in the present invention as petroisoprene) by the fact that bioisoprene compositions are substantially free of any contamination by unsaturated C5 hydrocarbons that are generally present in compositions of petroisoprene, for example, but not limited to, 1,3cyclopentadiene, trans-A, 3-pentadiene, cis-1,3-pentadiene, 1,4-pentadiene, 1pentino, 2-pentino, 3-methyl-1-butino, pent-4-en-1-yn, trans-pent-3-en-1-yn and s / pent-3-en-1-yn. If any contamination by unsaturated C5 hydrocarbons is present in the starting material of the bioisoprene composition described here, they will be present at lower levels than in the petrochemical compositions. Crude bioisoprene may have higher levels of certain C5 hydrocarbons than highly purified petroisoprene. Some of these impurities are particularly problematic, due to their structural similarity to isoprene and the fact that they can act as poisons in the polymerization catalyst. As detailed below, biologically produced isoprene compositions can be substantially free of any contamination by unsaturated C5 hydrocarbons, without having to undergo extensive purification.
In addition, bioisoprene is distinguished from petroisoprene through carbon identification (fingerprinting). In one respect, bioisoprene has a higher content of radioactive carbon-14 ( ¹⁴ C), or a higher ratio between ¹⁴ C / ¹² C, compared to petroisoprene. Bioisoprene is
13/74 produced from renewable carbon sources, so the ¹⁴ C content or the ¹⁴ C / ¹² C ratio in bioisoprene is the same as that in the present atmosphere. Petroisoprene, on the other hand, is derived from fossil fuels deposited between thousands and millions of years, so the ¹⁴ C content or the ¹⁴ C / ¹² C ratio is decreased due to radioactive decay. As discussed in more detail in the present invention, fuel products derived from bioisoprene have a higher content of ¹⁴ C or a higher ratio between ¹⁴ C / ¹² C than fuel products derived from petroisoprene. In one embodiment, a bioisoprene derived fuel product described here has a ¹⁴ C content or a ¹⁴ C / ¹² C ratio similar to that found in the atmosphere. In another aspect, bioisoprene can be analytically distinguished from petroisoprene by the ratio of stable carbon isotopes ( ¹³ C / ¹² C), which can be recorded as delta values represented by the symbol Õ ¹³ C. For example, for isoprene derived from extractive distillation of C ₅ streams from oil refineries, õ ¹³ C is about -22% o to about -24% o. This range is typical for petroleum-based unsaturated light hydrocarbons, and petroleum-based isoprene products typically contain isoprene units with the same õ ¹³ C. The bioisoprene produced by fermentation of glucose derived from corn (õ ¹³ C of -10, 73% o) with minimal amounts of other carbon-containing nutrients (for example, yeast extract) produces an isoprene that can be polymerized in polyisoprene with Õ ¹³ C of -14.66% oa -14.85% o. Products produced from these bioisoprene are expected to have δ ¹³ C values that are less negative than those derived from petroleum based isoprenes.
In addition, the bioisoprene compositions are distinguished from the petroisoprene composition by the fact that the bioisoprene compositions contain other biological by-products, comprising, for example, polar impurities, which are not present or are present in much lower levels in the petroisoprene compositions, such as alcohols, aldehydes, ketones and the like. The biological by-product may include, but is not limited to, ethanol, acetone, methanol, acetaldehyde,
14/74 methacrolein, methyl vinyl ketone, 3-methylfuran, 2-methyl-2-vinyloxyrane, cis and trans-3-methyl-1,3-pentadiene, a C5 prenyl alcohol (such as 3-methyl-3-buten1-ol or 3-methyl ~ 2-buten-1-ol), 2-heptanone, 6-methyl-5-hepten-2-one, 2,4,5-trimethylpyridine, 2,3,5-trimethylpyrazine, citronellal, methanethiol, acetate methyl, 1-propanol, diacetyl, 2-butanone, 2-methyl-3-buten-2-ol, ethyl acetate, 2-methyl-1-propanol, 3-methyl-1-butanal, 3-methyl-2-butanone, 1-butanol, 2-pentanone, 3-methyl-1-butanol, ethyl isobutyrate, 3-methyl-2-butenal, butyl acetate, 3-methyl butyl acetate, 3-methyl-3-buten-1-yl acetate , 3-methyl-2-buten-1-yl acetate, (E) -3,7-dimethyl-1,3,6-octatriene, (Z) -3,7-dimethyl-1,3,6octatriene, 2 , 3-cycloheptenol pyridine, 3-hexen-1-ol, 3-hexen-1-yl acetate, limonene, geraniol (trans-3,7-dimethyl-2,6-octadien-1-ol), citronelol ( 3,7-dimethyl6-octen-1-ol) or a linear isoprene polymer (such as a linear isoprene dimer or a linear isoprene trimer derived from the polymer multiple isoprene units). As described in the present invention, bioisoprene compositions can additionally comprise significant amounts of one or more volatile impurities (for example, O ₂ , N ₂ , H ₂ O, CO ₂ ) acquired during fermentation. The removal of one or more of these compounds (e.g., polar compounds and / or volatile impurities) from the bioisoprene, as described in the methods of the present invention, may be desirable.
Unless otherwise stated based on the context in which it is used, the term majority portion refers to an amount greater than 50% (by weight). For example, a major portion of isoprene means more than 50% of the mentioned isoprene. In some modalities, the majority portion is greater than 60%, 70%, 75%, 80%, 90%, 95% or 99%, by weight.
For use in the present invention, a purified isoprene composition refers to an isoprene composition that has been separated from at least a portion of one or more components that are present in the gaseous effluent from the fermenter (for example, a portion of volatile impurity and / or impurity of biological by-product). A purified isoprene composition can exist in any phase or mixture of phases, such as a complete gas phase (for example, isoprene gas with one or more
15/74 additional components), a complete liquid phase (for example, a solution comprising isoprene with 0, 1, 2 or more components), a solid phase, or mixtures thereof. In some embodiments, the purified isoprene composition is at least about 20% by weight, free of components other than isoprene. In various embodiments, the purified isoprene composition is at least or about 25%, 30%, 40%, 50%, 60%, 70%, 75%, 80%, 90%, 95%, 98% or 99% , by weight, pure. Purity can be tested by any suitable method, for example, by column chromatography, HPLC analysis or GCMS analysis.
For use in the present invention, the term biological by-product or biological by-product impurity refers to one or more organic compounds, excluding isoprene and methane, associated with biological fermentation processes and obtained together with isoprene in the said gaseous effluent from the fermenter.
For use in the present invention, the term volatile impurity means methane and / or one or more inorganic compounds found in the said gaseous effluent from the fermenter, in a gaseous state under standard atmospheric conditions.
Except where otherwise stated, the meanings of all technical and scientific terms used herein are those commonly understood by those versed in the technique to which this invention belongs. Singleton, et al., Dictionary of Microbiology and Molecular Biology, 2a. Edition, John Wiley and Sons, New York, USA (1994) and Hale & Marham, The Harper Collins Dictionary of Biology, Harper Perennial, NY, USA (1991), provide the technical expert with a general dictionary of many of the terms used here . It should be understood that this invention is not limited by the methodology, protocols and specific reagents described, as these may vary. The person skilled in the art will also understand that any methods and materials similar or equivalent to those described herein can also be used to practice or test the invention.
The titles presented here do not represent limitations of the
16/74 various aspects or modalities of the invention that can be taken by reference to the specification as a whole.
For use in the present invention, except where clearly indicated otherwise, the use of the terms one, one and the like refers to one or more.
The reference to about a value or parameter in the present invention includes (and describes) modalities that address that value or parameter itself. For example, the description referring to about X includes the description of X. Numeric ranges include the numbers that define the range.
It should be understood that the aspects and modalities of the invention described herein include aspects and modalities comprising, consisting of and consisting essentially of.
Purification of isoprene
Methods for enriching and / or purifying isoprene are presented here. In some embodiments, the isoprene comes from a gaseous effluent from the fermenter. In one aspect, a method for purifying isoprene from a gaseous effluent from the fermenter is presented, the gaseous effluent comprising isoprene and volatile impurity. In one embodiment, a method for purifying isoprene from a gaseous effluent from the fermenter is presented, with the gaseous effluent comprising isoprene and volatile impurity, and the method comprising: placing the gaseous effluent from the fermenter in contact with a solvent in a column to form: an isoprene-rich solution comprising the solvent and a major portion of the isoprene, and a vapor comprising a major portion of the volatile impurity.
In one aspect, a method for purifying isoprene from a solution comprising isoprene and biological by-product impurity is presented. In one embodiment, a method is presented for purifying isoprene from a solution comprising isoprene and biological by-product impurity, the method comprising: rectifying an isoprene from the solution in a column, to form: a
17/74 isoprene-poor solution, comprising a major portion of the biological by-product impurity, and a purified isoprene composition.
In one aspect, a method for purifying isoprene from a gaseous effluent from the fermenter is presented, with the gaseous effluent comprising isoprene, volatile impurity and biological by-product impurity, and said method comprising: (a) placing the gaseous effluent from the fermenter in contact with a solvent in a first column, to form: an isoprene-rich solution comprising the solvent, a major portion of the isoprene and a major portion of the biological by-product impurity, and a vapor comprising a major portion of the impurity volatile, (b) transfer the isoprene-rich solution from the first column to a second column, and (c) rectify the isoprene from the isoprene-rich solution in the second column to form: an isoprene-poor solution, comprising a major portion impurity of biological by-product, and a purified isoprene composition.
Figure 1 illustrates an exemplifying method for isoprene purification, as well as an exemplifying apparatus. The gaseous effluent from the fermenter comprising isoprene can be generated from renewable resources (for example, carbon sources) by any method in the art, for example as described in provisional US patent application No. 61 / 187,944, the content of which is incorporated herein by reference, particularly with regard to methods for generating gaseous effluent from the fermenter comprising isoprene. The fermenter gaseous effluent generated from one or more individual fermenters 12 (for example, 1, 2, 3, 4, 5, 6, 7, 8 or more fermenters connected in series and / or in parallel) can be directed to a first column 14. As described below, the gaseous effluent from the fermenter can be directed through an isolation unit 16 and / or compressed by a compression medium, such as a compression system 18. Additionally, the temperature of the gaseous effluent from the fermenter can optionally be reduced to any point, for example to form a condensate or a
18/74 partial condensate before coming into contact with the solvent (which can help solubilize one or more components of the gaseous effluent, such as isoprene). The gaseous effluent from the fermenter can be contacted (for example, absorbed) in column 14 with a solvent (for example any solvent described herein, such as a non-polar solvent with a high boiling point). Volatile impurities with a lower propensity for absorption in the solvent (particularly with non-polar solvents with a high boiling point) are separated from the rest of the solvent / gaseous mixture from the fermenter, resulting in a vapor comprising a majority of the volatile impurity (eg example, leaving port 20) and an isoprene-rich solution with a major portion of the isoprene and a major portion of the biological by-product impurity (for example, at port 22). A stream of steam for grinding can be provided by any suitable means (for example, by steam injection or by a refueling unit 23 below the point of fermentation gaseous effluent in the first column), which can help to separate the impurity of the remaining solution. The steam can be directed through the column (at any suitable location, shown in figure 1) to provide an extensive vapor phase, which can assist in the removal of the volatile impurity.
The isoprene-rich solution that has a major portion of the isoprene and a major portion of the biological by-product impurity (for example, at port 22) can be directed to a second column 24. The second column may be isolated from the first column 14 (as shown in figure 1) or it can be part of a single column comprising both the first and second columns (for example, a tandem column in which the solvent enters the first column at, or near, one end and exits the second column at, or near, an opposite end). The isoprene can be rectified from the isoprene-rich solution in the second column to generate a purified isoprene composition (for example, at port 26) and a isoprene-poor solution comprising a major portion of the impurity of
19/74 biological by-product (for example, on port 28). Steam can be added to the second column, which can help to rectify the isoprene from the remaining solution. The steam can be directed through the column (at any suitable location, such as the opposite end of the entry point of the isoprene-rich solution, and / or near the exit end of the isoprene-poor solution, as shown in figure 1).
As described in the present invention, the columns can be conventional and of any suitable size. Exemplary column types are commercially available from manufacturers including Koch Modular Process Systems (Paramus, NJ, USA), Fluor Corporation (Irving, TX, USA), and Kuhni USA (Mount Holly, NC, USA). In general, the columns are designed to maximize the contact between steam and liquid, in order to obtain the desired efficiency. This is achieved by filling the column with a filling material, or with trays spaced at regular intervals along the column. Suitable filler materials include both random and structured types based on metal, glass, polymer and ceramic materials. Examples of random fill types include Raschig rings, Pall rings, A-PAK rings, saddle rings, Pro-Pak, Heli-Pak, ceramic saddles and FLEXIRINGS®. Structured fillers include wire mesh and perforated metal plate materials. Specialized column filling manufacturers include ACS Separations & Mass-Transfer Products (Houston, TX, USA), Johnson Bros. Metal Forming Co. (Berkeley, IL, USA) and Koch Glitsch, Inc. Knight Div. (East Canton, OH, USA). The efficiency of a gas rectifying column is expressed in terms of the theoretical plate height and the total number of plates in the column. In general, the greater the number of theoretical plates present, the greater the efficiency of the column. Laboratory-scale columns can be purchased from Ace Glass (Vineland, NJ, USA), Sigma-Aldrich (St. Louis, MO, USA) and Chemglass (Vineland, NJ, USA). Suitable types of glass column include Vigreux, Snyder, Hemple and perforated plate columns. Columns can include filling materials, or they can contain features designed to
20/74 maximize the vapor / liquid contact. A laboratory scale gas purifier unit (catalog number CG-1830-10) is available from Chemglass and consists of a filled glass column, a solvent reservoir and a pump for solvent recirculation.
The purified isoprene composition obtained from the second column 24 (for example, exiting through port 26) can be further purified by any suitable means (for example, using a reflux condenser 34 and / or an adsorption system 36, as a silica-based adsorption system). Reflux reduces the composition of the solvent in the isoprene product. The low isoprene solution can be recycled back to the first column for reuse (for example, as shown in figure 1 on port 30). The isoprene-poor solution can be purified by any suitable means (for example, by liquid-liquid extraction and / or by an adsorption system 32, such as a silica-based adsorption system) before recycling to the first column 14, to reduce the amount of biological by-product. In addition, the temperature of the isoprene-poor solution can be reduced by any suitable means before recycling to the first column 14 (for example before, simultaneously with, and / or after optionally purifying that of isoprene). Figure 1 shows an example of reducing the temperature of the low isoprene solution in port 40, before the purification of the low isoprene solution (in this case, with the use of refrigerant to reduce the temperature).
In one embodiment, a cooling unit is coupled immediately downstream of system 32 to provide additional cooling. In addition, the isoprene-poor solvent in the second column 24 can be separated in phases to remove water, before the solution is cooled and returned to the top of the first column 14, and this unit for phase separation would be attached immediately below the door. 40. In addition, the mixture of water and isoprene condensed from condenser 34 can similarly be separated in phases to remove water by a similar phase separator unit, coupled
21/74 immediately downstream of condenser 34. In this way, only the isoprene phase is returned to the second column. In each case, the water from the phase separation units is a waste stream.
The vapor comprising a major portion of the volatile impurity (for example the steam coming out of port 20 in figure 1) may comprise a minor portion of isoprene (for example residual isoprene that was not left in the isoprene-rich solution). The residual isoprene can be collected again for use from the vapor that comprises a majority of the volatile impurity, by any suitable means (for example by an adsorption system 38, such as an adsorption system based on activated carbon) and, in some cases as shown in figure 1, can be combined with the purified isoprene composition (for example, before, during or after further purification, as an adsorption system similar to system 36). Figure 1 also shows an optional capture device 42 (for example, a thermal oxidizer and / or a CO ₂ capture system) capable of reducing the amount of undesirable components released into the atmosphere (for example, CO ₂ ) to from the steam.
Gaseous effluent from the fermenter
Techniques for producing gaseous effluent from the fermenter comprising isoprene that can be used in the methods of the present invention are described, for example, in International Patent Application Publication No. W02009 / 076676, in US Patent Applications No. 12 / 496,573, 12 / 560,390, 12 / 560,317, 12 / 560,370, 12 / 560,305 and 12 / 560,366, and in US provisional patent applications No. 61 / 187,930, 61 / 187,934 and 61 / 187,959. In particular, these compositions and methods increase the rate of isoprene production, and increase the amount of isoprene that is produced.
As described in more detail below, the gaseous effluent from the fermenter can be produced by cells in culture. In some embodiments, cultured cells are capable of producing more than about 400 nmols of isoprene / gram of cells for the wet weight of cells / hour (nmol / g _wcm / h) of isoprene. In some embodiments, cells
22/74 have a heterologous nucleic acid that (i) encodes an isoprene synthase polypeptide and (ii) is functionally linked to a promoter. In some embodiments, cells are grown in a culture medium that includes a carbon source, for example, but not limited to, a carbohydrate, glycerol, glycerin, dihydroxy acetone, source of a carbon, oil, animal fat , animal oil, fatty acid, lipid, phospholipid, glycerolipid, monoglyceride, diglyceride, triglyceride, renewable carbon source, polypeptide (for example, a protein or peptide of microbial or plant origin), yeast extract, component of a yeast extract, or any combination of two or more of the items mentioned above. In some embodiments, cells are grown under conditions of limited glucose.
Suitable materials and methods for the maintenance and growth of bacterial cultures are well known in the art. Exemplary techniques can be found in the Manual of Methods for General Bacteriology, by Gerhardt et al., Editors), American Society for Microbiology, Washington, DC, USA, (1994), or in Brock in Biotechnology: A Textbook of Industrial Microbiology, Second Edition (1989), Sinauer Associates, Inc., Sunderland, MA, USA, each of which is incorporated herein by reference, in its entirety, particularly with respect to cell culture techniques.
Standard conditions for cell culture can be used for cell culture {see, for example, the international patent publication WO 2004/033646 and the references cited therein, each of which is incorporated herein by reference, in its entirety , particularly with regard to cell culture and fermentation conditions). The cells are cultured and maintained at a suitable temperature, gas mixture and pH (such as from about 20 to about 37 ° C, from about 6% to about 84% CO2, and at a pH between about 5 and about 9). In some embodiments, cells are grown at 35 ° C in a suitable cell medium. In some embodiments, for example, cultures are grown at approximately 28 ° C in a suitable medium in cultures under
23/74 stirring or fermenters, until the desired amount of isoprene production is obtained. In some embodiments, the pH ranges for fermentation are between about pH 5.0 and about pH 9.0 (such as about pH 6.0 to about pH 8.0 or about 6.5 to about of 7.0). The reactions can be carried out under aerobic, anoxic or anaerobic conditions, based on the requirements of the host cells. The exemplary culture conditions for a given filamentous fungus are known in the art, and can be found in the scientific literature and / or at the source of the fungi, such as the American Type Culture Collection and Fungai Genetics Stock Center.
In various embodiments, cells are cultured using any known fermentation mode, such as batch, batch fed or continuous processes. In some embodiments, a batch fermentation method is used. Classic batch fermentation is a closed system in which the composition of the medium is adjusted at the beginning of the fermentation and is not subjected to artificial changes during fermentation. Thus, at the beginning of the fermentation, the cell medium is inoculated with the desired host cells, and the fermentation is allowed to occur without any addition to the system. Typically, however, batch fermentation is batch in relation to the addition of the carbon source, and attempts are often made to control factors such as pH and oxygen concentration. In batch systems, the metabolite and biomass compositions of the system constantly change until the time when fermentation is stopped. Within batch cultures, cells moderate through a static delay phase to a high growth log phase and, finally, a stationary phase in which the growth rate is slowed or stopped. In some embodiments, cells in the log phase are responsible for the volume of isoprene production. In some embodiments, cells in a stationary phase produce isoprene.
In some embodiments, cultured cells are capable of converting more than about 0.002% of the carbon into isoprene in a cell culture medium. In some embodiments, cells have a nucleic acid
Heterologous which (i) encodes an isoprene synthase polypeptide and (ii) is functionally linked to a promoter. In some embodiments, the cells are grown in a culture medium that includes a carbon source, for example, but not limited to, a carbohydrate, glycerol, glycerin, dihydroxy acetone, source of a carbon, oil, animal fat, oil of animal origin, fatty acid, lipid, phospholipid, glycerolipid, monoglyceride, diglyceride, triglyceride, renewable carbon source, polypeptide (for example, a protein or peptide of microbial or vegetable origin), yeast extract, component of an extract of yeast, or any combination of two or more of the items mentioned above. In some embodiments, cells are grown under conditions of limited glucose.
In some embodiments, cells in culture comprise a heterologous nucleic acid that encodes an isoprene synthase polypeptide. In some embodiments, the cells have a heterologous nucleic acid that (i) encodes an isoprene synthase polypeptide and (ii) is functionally linked to a promoter. In some embodiments, the cells are grown in a culture medium that includes a carbon source, for example, but not limited to, a carbohydrate, glycerol, glycerin, dihydroxy acetone, source of a carbon, oil, animal fat, oil of animal origin, fatty acid, lipid, phospholipid, glycerolipid, monoglyceride, diglyceride, triglyceride, renewable carbon source, polypeptide (for example, a protein or peptide of microbial or vegetable origin), yeast extract, component of an extract of yeast, or any combination of two or more of the items mentioned above. In some embodiments, cells are grown under conditions of limited glucose.
In some embodiments, cultured cells are capable of producing an amount of isoprene (such as the total amount of isoprene produced, or the amount of isoprene produced per liter of juice per hour per OD ₆ oo), during the stationary phase, which is greater than or about 2 or more times the amount of isoprene produced during the
25/74 growth for the same period of time. In some embodiments, cells in culture are able to produce isoprene only in the stationary phase. In some embodiments, cultured cells are capable of producing isoprene in both the growth and stationary phases. In various modalities, cultured cells are capable of producing an amount of isoprene, during the stationary phase, which is greater than or about 2, 3, 4, 5, 10, 20, 30, 40, 50 or more times the amount of isoprene produced during the growth phase for the same period of time.
In some embodiments, the cells in culture come from a system that includes a reactor chamber in which the cells are capable of producing more than about 400, 500, 600, 700, 800, 900, 1,000, 1,250, 1,500, 1,750 , 2,000, 2,500, 3,000, 4,000 or 5,000 nmols / g _wcm / h isoprene, or more. In some embodiments, the system is not a closed system. In some embodiments, at least a portion of the isoprene is removed from the system. In some embodiments, the system includes a gas phase comprising isoprene. In various embodiments, the gas phase comprises any of the compositions described herein.
In some embodiments, cultured cells produce isoprene at a xxx greater than or about 400, 500, 600, 700, 800, 900, 1,000, 1,250, 1,500, 1,750, 2,000, 2,500, 3,000, 4,000, or 5,000 nrnols / g _wcm / h, or more. In some embodiments, cultured cells convert to isoprene more than or about 0.002, 0.005, 0.01, 0.02, 0.05, 0.1, 0.12, 0.14, 0.16, 0, 2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.2, 1.4, 1.6% or more of carbon present in the cell culture medium. In some embodiments, cells in culture produce more isoprene than or about 1, 10, 25, 50, 100, 150, 200, 250, 300, 400, 500, 600, 700, 800, 900, 1,000, 1,250, 1,500, 1,750, 2,000, 2,500, 3,000, 4,000, 5,000, 10,000 or 100,000 ng isoprene / gram of cells for wet cell weight / h (ng / g _W cm / h), or more. In some embodiments, cells in culture produce a cumulative titration (total amount) of isoprene greater than or about 1, 10, 25, 50, 100, 150, 200, 250, 300, 400, 500, 600, 700,
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800, 900, 1,000, 1,250, 1,500, 1,750, 2,000, 2,500, 3,000, 4,000, 5,000, 10,000, 50,000, 100,000 or more isoprene / L broth (mg / L _caido , the broth volume including cell volume and cell medium). Other examples of isoprene production rates and total amounts of isoprene production are shown in the present invention.
In some embodiments of either aspect, the cultured cells additionally comprise a heterologous nucleic acid that encodes an IDI polypeptide. In some embodiments, the cells additionally comprise an insert of a copy of an endogenous nucleic acid that encodes an IDI polypeptide. In some embodiments, the cells additionally comprise a heterologous nucleic acid that encodes a DXS polypeptide. In some embodiments, the cells additionally comprise an insert of a copy of an endogenous nucleic acid that encodes a DXS polypeptide. In some embodiments, cells additionally comprise one or more nucleic acids that encode an IDI polypeptide and a DXS polypeptide. In some embodiments, a nucleic acid encodes the isoprene synthase polypeptide, the IDI polypeptide and the DXS polypeptide. In some embodiments, a vector encodes the isoprene synthase polypeptide, the IDI polypeptide and the DXS polypeptide. In some embodiments, the vector comprises a selective marker, such as an antibiotic-resistant nucleic acid.
In some embodiments, the heterologous isoprene synthase nucleic acid is functionally linked to a T7 promoter, such as a T7 promoter contained in a medium or high copy plasmid. In some embodiments, the heterologous isoprene synthase nucleic acid is functionally linked to a Trc promoter, such as a Trc promoter contained in a medium or high copy plasmid. In some embodiments, the heterologous isoprene synthase nucleic acid is functionally linked to a Lac promoter, such as a Lac promoter contained in a low copy plasmid. In some embodiments, the heterologous isoprene synthase nucleic acid is functionally linked to an endogenous promoter, such as an endogenous serine protease promoter
27/74 alkaline. In some embodiments, the heterologous isoprene synthase nucleic acid integrates with a cell chromosome without a selective marker.
In some embodiments, one or more of the MVA, IDI, DXP or isoprene synthase nucleic acids are placed under the control of a promoter or factor that is more active in the stationary phase than in the growth phase. For example, one or more of the MVA, IDI, DXP or isoprene synthase nucleic acids routes can be placed under the control of a stationary phase sigma factor, such as RpoS. In some embodiments, one or more of the MVA, IDI, DXP or isoprene synthase nucleic acids are placed under the control of an inducible promoter in the stationary phase, as a promoter inducible by an active response regulator in the stationary phase.
In some embodiments, at least a portion of the cells in culture maintain the heterologous isoprene synthase nucleic acid for at least or about 5, 10, 20, 40, 50, 60, 65 or more cell divisions in a continuous culture (such as a continuous culture without dilution). In some embodiments, the nucleic acid comprising isoprene synthase, IDI or DXS nucleic acid also comprises a selective marker, such as an antibiotic-resistant nucleic acid.
In some embodiments, the cultured cells further comprise a heterologous nucleic acid that encodes a polypeptide of the MVA route (such as a polypeptide of the MVA route obtained from Saccharomyces cerevisia or Enterococcus faecalis). In some embodiments, the cells additionally comprise insertion of a copy of an endogenous nucleic acid that encodes a polypeptide of the MVA route (such as a polypeptide of the MVA route obtained from Saccharomyces cerevisia or Enterococcus faecalis). In some embodiments, the cells comprise an isoprene synthase nucleic acid, DXS and MVA route. In some embodiments, the cells comprise an isoprene synthase nucleic acid, a DXS nucleic acid, an IDI nucleic acid and an MVA route nucleic acid (in addition to the IDI nucleic acid).
In some embodiments, the isoprene synthase polypeptide is
28/74 a naturally occurring polypeptide from a plant such as Pueraria (for example, Pueraria montaria or Pueraria lobata).
In some embodiments, the cultured cells are bacterial cells, such as gram-positive bacterial cells (for example, Bacillus cells, such as Bacillus subtilis cells or Streptomyces cells, such as Streptomyces lividans, Streptomyces coelicolor or Streptomyces griseus). In some embodiments, the cultured cells are gram-negative bacterial cells (for example, Escherichia cells, such as Escherichia coli cells or Pantoea cells, such as Pantoea citrea cells). In some embodiments, cultured cells are fungal cells, like filamentous fungus cells (for example, Trichoderma cells, like Trichoderma reesei cells, or Aspergillus cells, like Aspergillus oryzae and Aspergillus niger cells), or yeast (for example, Yarrowia cells, such as Yarrowia lipolytica cells).
In some embodiments, the carbon source of the microbial polypeptide includes one or more polypeptides obtained from yeast or bacteria. In some embodiments, the vegetable polypeptide carbon source includes one or more polypeptides obtained from soybeans, corn, canola, jatropha, palm, peanut sunflower, coconut, mustard, rapeseed, cotton seed, palm kernel, olive, safflower , sesame or flaxseed.
As previously mentioned, the gaseous effluent from the fermenter described here can be derived from renewable resources (for example, carbon, biological and / or vegetable sources). Exemplary renewable resources are described, for example, in US provisional patent application No. 61 / 187,944 (the contents of which are incorporated by reference) and include cheese whey permeate, corn steeping water, sugar beet molasses , barley malt and components of any of the above. Exemplary renewable carbon sources also include acetate, glucose, hexose, pentose and xylose present in biomass, such as corn, switchgrass (Panicum virgatum), sugarcane, cell debris from
29/74 fermentation and protein by-products from the grinding of soy, corn or wheat. In some embodiments, the biomass carbon source is a lignocellulosic, hemicellulosic or cellulosic material such as, but not limited to, a grass, wheat, wheat straw, bagasse, sugarcane bagasse, softwood pulp, corn, corncobs or husks, corn kernels, fiber obtained from corn kernels, corn husks, switchgrass (Panicum virgatum), rice husk product, or a dry or wet grain milling by-product (eg corn , sorghum, rye, triticale, barley, wheat and / or distillery grains). Exemplary cellulosic materials include wood waste, paper and pulp, herbaceous plants and fruit pulp. In some embodiments, the carbon source includes any part of the plant, such as stems, grains, roots or tubers. In some modalities, all or part of any of the following plants are used as a carbon source: corn, wheat, rye, sorghum, triticale, rice, millet, barley, cassava, vegetables such as beans and peas, potatoes, sweet potatoes , bananas, sugar cane and / or tapioca. In some embodiments, the carbon source is a biomass hydrolyzate, such as a biomass hydrolyzate that includes both xylose and glucose, or that includes both sucrose and glucose.
In some modalities of the methods described here, the gaseous effluent from the fermenter is derived from renewable resources. In some embodiments, the gaseous effluent from the fermenter comprises bioisoprene. In some embodiments, the gaseous effluent from the fermenter comprises more than or about 98.0, 98.5, 99.0, 99.5 or 100% isoprene, by weight, compared to the weight of all C5 hydrocarbons present in the gaseous effluent from the fermenter. In some embodiments, the gaseous effluent from the fermenter comprises more than or about 99.90, 99.92, 99.94, 99.96, 99.98 or 100% isoprene, by weight, compared to the weight of all C5 hydrocarbons present in the gaseous effluent from the fermenter. In some embodiments, the gaseous effluent from the fermenter produces a relative detector response greater than or about 98.0, 98.5, 99.0, 99.5 or 100% for isoprene, compared to the response of
30/74 detector for all C5 hydrocarbons present in the fermenter's gaseous effluent, when analyzed by gas chromatography with flame ionization detection (GC / FID). In some embodiments, the gaseous effluent from the fermenter produces a relative detector response greater than or about 99.90, 99.91, 99.92, 99.93, 99.94, 99.95, 99.96, 99 , 97, 99.98, 99.99 or 100% for isoprene, compared to the detector response for all C5 hydrocarbons present in the fermenter gas effluent, when analyzed in a similar way. In some embodiments, the gaseous effluent from the fermenter comprises from about 98.0 to about 98.5, from about 98.5 to about 99.0, from about 99.0% by weight of all C5 hydrocarbons present in the gaseous effluent from the fermenter. In some embodiments, the gaseous effluent from the fermenter comprises from about 99.90 to about 99.92, from about 99.92 to about 99.94, from about 99.94 to about 99.96, from about 99.96 to about 99.98, about 99.98 to 100% isoprene, by weight, compared to the weight of all C5 hydrocarbons present in the gaseous effluent from the fermenter.
In some embodiments of the methods described here, the gaseous effluent from the fermenter comprises less than or about 2.0, 1.5, 1.0, 0.5, 0.2, 0.12, 0.10, 0.08 , 0.06, 0.04, 0.02, 0.01, 0.005, 0.001, 0.0005, 0.0001, 0.00005 or 0.00001% of C5 hydrocarbons in addition to isoprene (such as 1,3-cyclopentadiene , c / 's-1,3-pentadiene, trans-1,3-pentadiene, 1,4 pentadiene, 1-pentino, 2-pentino, 1-pentene, 2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butino, pent-4-en-1-ino, trans-pent-3-en-1-ino, or c / s-pent3-en-1-ino), by weight, compared to weight of all C5 hydrocarbons present in the gaseous effluent from the fermenter. In some embodiments, the gaseous effluent from the fermenter has a relative detector response less than or about 2.0, 1.5, 1.0, 0.5, 0.2, 0.12, 0.10, 0 , 08, 0.06, 0.04, 0.02, 0.01, 0.005, 0.001, 0.0005, 0.0001, 0.00005 or 0.00001% for C5 hydrocarbons in addition to isoprene, compared to the response detector for all C5 hydrocarbons present in the gaseous effluent from the fermenter. In some embodiments, the gaseous effluent from the fermenter has a relative detector response less than or about 2.0, 1.5,
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1.0, 0.5, 0.2, 0.12, 0.10, 0.08, 0.06, 0.04, 0.02, 0.01, 0.005, 0.001, 0.0005,
0.0001, 0.00005 or 0.00001% for 1,3-cyclopentadiene, w / s-1,3-pentadiene, trans-1,3-pentadiene, 1,4-pentadiene, 1-pentino, 2-pentino , 1-pentene, 2-methyl-1-butene, 3-methyl-1-butino, pent-4-en-1-ino, trans-pent-3-en-1-ino or c / s-pent-3-en -1-ino, compared to the detector response for all C5 hydrocarbons present in the gaseous effluent from the fermenter. In some embodiments, the initial composition of highly pure isoprene comprises from about 0.02 to about 0.04%, from about 0.04 to about 0.06%, from about 0.06 to 0.08 %, from about 0.08 to 0.10%, or from about 0.10 to about 0.12% of C5 hydrocarbons in addition to isoprene (such as 1,3-cyclopentadiene, c / 's-1,3 -pentadiene, trans-1,3-pentadiene, 1,4-pentadiene, 1-pentino, 2-pentino, 1-pentene, 2-methyl-1-butene, 3-methyl-1-butine, pent-4-en-1-ino , trans-pent-3-en-1-ino or c / s-pent-3-en-1-ino), by weight, compared to the total weight of all C5 hydrocarbons present in the fermenter gas effluent.
In some embodiments of the methods described herein, the gaseous effluent from the fermenter comprises less than or about 50, 40, 30, 20, 10, 5, 1, 0.5, 0.1, 0.05, 0.01 or 0.005 pg / L of a compound that inhibits the polymerization of isoprene, for any compound present in the gaseous effluent from the fermenter that inhibits the polymerization of isoprene. In some embodiments, the gaseous effluent from the fermenter comprises from about 0.005 to about 50, such as from about 0.01 to about 10, from about 0.01 to about 5, from about 0.01 to about from 1, from about 0.01 to about 0.5, or from about 0.01 to about 0.005 pg / L of a compound that inhibits the polymerization of isoprene, for any compound present in the fermenter gaseous effluent that inhibit polymerization of isoprene. In some embodiments, the gaseous effluent from the fermenter comprises less than or about 50, 40, 30, 20, 10, 5, 1, 0.5, 0.1, 0.05, 0.01 or 0.005 pg / L of a hydrocarbon in addition to isoprene (such as 1,3-cyclopentadiene, c / s-1,3 pentadiene, trans-1,3-pentadiene, 1,4-pentadiene, 1-pentino, 2-pentino, 1 pententene, 2-methyl-1 -butene, 3-methyl-1-butino, pent-4-en-1-ino, trans-pent-3-en1-ino or c / 's-pent-3-en-1-ino). In some modalities, the gaseous effluent
32/74 of the fermenter comprises from about 0.005 to about 50, from about 0.01 to about 10, from about 0.01 to about 5, from about 0.01 to about 1, from about 0.01 to about 0.5, or about 0.01 to about 0.005 pg / L of a hydrocarbon in addition to isoprene. In some embodiments, the gaseous effluent from the fermenter comprises less than or about 50, 40, 30, 20, 10, 5, 1, 0.5, 0.1, 0.05, 0.01 or 0.005 pg / L of a protein or fatty acid (such as a protein or fatty acid that is naturally associated with natural rubber).
In some embodiments of the methods described herein, the gaseous effluent from the fermenter comprises less than or about 10, 5, 1, 0.8, 0.5, 0.1, 0.05, 0.01 or 0.005 ppm of alpha- acetylenes, piperylenes, acetonitrile or 1,3-cyclopentadiene. In some embodiments, the gaseous effluent from the fermenter comprises less than or about 5, 1, 0.5, 0.1, 0.05, 0.01 or 0.005 ppm of sulfur or alenes. In some embodiments, the gaseous effluent from the fermenter comprises less than or about 30, 20, 15, 10, 5, 1, 0.5, 0.1, 0.05, 0.01 or 0.005 ppm of all acetylenes ( 1pentino, 2-pentino, 3-methyl-1-butino, pent-4-en-1-ino, trans-pent-3-en-1-ino and c / s-pent-3-en-1-ino) . In some embodiments, the gaseous effluent from the fermenter comprises less than or about 2,000, 1,000, 500, 200, 100, 50, 40, 30, 20, 10, 5, 1, 0.5, 0.1, 0.05 , 0.01 or 0.005 ppm of isoprene dimers, such as cyclic isoprene dimers (for example, C10 cyclic compounds derived from the dimerization of two isoprene units). Impurity of biological by-product in gaseous effluent
The biological by-product of the gaseous effluent from the fermenter can comprise any compound or any combination of compounds described herein. In some embodiments, the biological by-product of the gaseous effluent from the fermenter comprises one or more polar compounds. The polarity can be determined using methods known in the art, for example by measuring the solubility in water, the potential for hydrogen bonding, the dielectric constant and / or an oil / water separation coefficient. In some embodiments, one or more compounds of the biological by-product have a total polarity greater than the
33/74 isoprene polarity, for example as measured by having a dielectric constant greater than 2.1 at 25 ° C (77 ° F). In some embodiments, more than about any of 20%, 30%, 50%, 60%, 70%, 80%, 90% or 95% (weight / weight) of the biological by-product consists of one or more compounds that have a total polarity greater than the isoprene polarity. In some embodiments, one or more of the compounds of the biological by-product has a dielectric constant greater than about 2, or greater than about 3, or greater than about 5, or greater than about 7.5, or greater than about 10, at 20 ° C. In some embodiments, more than about any of 20%, 30%, 50%, 60%, 70%, 80%, 90% or 95% (weight / weight) of the biological by-product consists of one or more compounds that have a dielectric constant greater than about 2, or greater than about 3, or greater than about 5, or greater than about 7.5, or greater than about 10, at 20 ° C.
In some embodiments, the gaseous effluent from the fermenter includes one or more of the following compounds in the biological by-product; an alcohol, an aldehyde or a ketone (like any of the alcohols, aldehydes or ketones described herein). In some embodiments, the gaseous effluent from the fermenter includes (i) an alcohol and an aldehyde, (ii) an alcohol and a ketone, (iii) an aldehyde and a ketone, (iv) an alcohol, an aldehyde and a ketone, or (v) esters.
The gaseous effluent from the fermenter may comprise any or any combination of one or more of the following compounds in the biological by-product; ethanol, acetone, methanol, acetaldehyde, methacrolein, methyl vinyl ketone, 2-methyl-2-vinyloxyrane, 3-methylfuran, cis and irans-S-methyl-1,3-pentadiene, a C5 prenyl alcohol (such as 3-methyl -3buten-1-ol or 3-methyl-2-buten-1-ol), 2-heptanone, 6-methyl-5-hepten-2-one, 2,4,5-trimethylpyridine, 2,3,5- trimethylpyrazine, citronelal, methanethiol, methyl acetate, 1-propanol, diacetyl, 2-butanone, 2-methyl-3-buten-2-ol, ethyl acetate, 2-methyl-1-propanol, 3-methyl-1- butanal, 3-methyl-2-butanone, 1-butanol, 2-pentanone, 3-methyl-1-butanol, ethyl isobutyrate, 3-methyl-2-butenal, butyl acetate, 3-methyl butyl acetate, 3 acetate -methyl-3-buten-1-yl, acetate
34/74 of 3-methyl-2-buten-1-yl, (E) -3,7-dimethyl-1,3,6-octatriene, (Z) -3,7-dimethyl-1,3,6octatriene, 2,3-cycloheptenol pyridine, 3-hexen-1-ol, 3-hexen-1-yl acetate, limonene, geraniol (trans-3,7-dimethyl-2,6-octadien-1-ol), citronelol (3,7-dimethyl6-octen-1-ol).
In some embodiments, the gaseous effluent from the fermenter includes any or any combination of one or more of the following compounds in the biological by-product: 2-heptanone, 6-methyl-5hepten-2-one, 2,4,5-trimethylpyridine, 2 , 3,5-trimethylpyrazine, citronelal, acetaldehyde, methanethiol, methyl acetate, 1-propanol, diacetyl, 2-butanone,
2-methyl-3-buten-2-ol, ethyl acetate, 2-methyl-1-propanol, 3-methyl-1-butanal, 3-methyl-2-butanone, 1-butanol, 2-pentanone, 3-methyl- 1-butanol, ethyl isobutyrate, 3-methyl-2-butenal, butyl acetate, 3-methyl butyl acetate, acetate
3-methyl-3-buten-1-yl, 3-methyl-2-buten-1-yl acetate, (E) -3,7-dimethyl-1,3,6octatriene, (Z) -3,7- dimethyl-1,3,6-octatriene, 2,3-cycloheptenol pyridine, or a linear isoprene polymer (such as a linear isoprene dimer or a linear isoprene trimer derived from the polymerization of multiple isoprene units). In some embodiments, the gaseous effluent from the fermenter comprises one or more of the following compounds in the biological by-product: ethanol, acetone, methanol, acetaldehyde, methacrolein, methyl vinyl ketone, 3-methylfuran, 2-methyl-2-vinyloxirane, cis and frans -3-methyl-1,3-pentadiene, a C5 prenyl alcohol (such as 3-methyl-3-buten-1-ol or 3-methyl-2buten-1-ol).
In some embodiments of the methods described herein, the gaseous effluent from the fermenter comprises more than or about 0.005, 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 20, 30, 40, 60 , 80, 100 or 120 pg / L of biological by-product (for example, biological by-product comprising one or more compounds selected from ethanol, acetone, methanol, acetaldehyde, methacrolein, methyl vinyl ketone, 3-methylfuran, 2-methyl-2-vinyloxyrane , cis and trans-3-methyl-1,3-pentadiene and a C5 prenyl alcohol (such as 3-methyl-3-buten1-ol or 3-methyl-2-buten-1-ol)). In some embodiments, the gaseous effluent from the fermenter comprises more than or about 0.005, 0.01, 0.05, 0.1, 0.5, 1, 5, 10, 20, 30, 40, 60, 80, 100 or 120 pg / L of one or more compounds
35/74 in the biological by-product (for example, one or more compounds selected from ethanol, acetone, methanol, acetaldehyde, methacrolein, methyl vinyl ketone, 3-methifuran, 2-methyl-2-vinyloxyrane, cis and ans-3-methyl- 1,3 pentadiene and a C5 prenyl alcohol (such as 3-methyl-3-buten-1-ol or 3-methyl-2buten-1-ol)). In some embodiments, the gaseous effluent from the fermenter comprises from about 0.005 to about 120, such as from about 0.01 to about 80, from about 0.01 to about 60, from about 0.01 to about 40, about 0.01 to about 30, about 0.01 to about 20, about 0.01 to about 10, about 0.1 to about 80, about 0.1 to about 60, about 0.1 to about 40, about 5 to about 80, about 5 to about 60, or about 5 to about 40 pg / L biological by-product (for example, biological by-product comprising one or more compounds selected from ethanol, acetone, methanol, acetaldehyde, methacrolein, methyl vinyl ketone, 3-methylfuran, 2-methyl-2-vinyloxirane, cis and frans-3-methyl-1 , 3-pentadiene and a C5 prenyl alcohol (such as 3-methyl-3-buten1-ol or 3-methyl-2-buten-1-ol)). In some embodiments, the gaseous effluent from the fermenter comprises from about 0.005 to about 120, such as from about 0.01 to about 80, from about 0.01 to about 60, from about 0.01 to about 40, about 0.01 to about 30, about 0.01 to about 20, about 0.01 to about 10, about 0.1 to about 80, about 0.1 to about 60, about 0.1 to about 40, about 5 to about 80, about 5 to about 60, or about 5 to about 40 pg / L one or more compounds of the biological by-product (for example, one or more compounds selected from ethanol, acetone, methanol, acetaldehyde, methacroleine, methyl vinyl ketone, 3-methylfuran, 2-methyl-2-vinyl vinyloxane, cis and frans-3-methyl-1 , 3-pentadiene and a C5 prenyl alcohol (such as 3-methyl-3-buten-1-ol or 3-methyl-2-buten-1-ol)).
In various modalities of the methods described here, the amount of biological by-product and / or the amount of one or more compounds of the biological by-product in relation to the amount of isoprene in percentage units by weight (that is, the weight of the biological by-product divided by isoprene weight times 100) is greater than or about 0.01,
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0.02, 0.05, 0.1, 0.5, 1, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 or 110% (weight / weight). In some embodiments, the relative detector response for the biological by-product and / or one or more compounds of the biological by-product, compared to the detector response for isoprene, is greater than or about 0.01, 0.02, 0, 05, 0.1, 0.5, 1.5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 or 110%. In various embodiments, the amount of biological by-product and / or the amount of one or more compounds of the biological by-product, in relation to the amount of isoprene in weight percentage units (ie, the weight of the biological by-product or the weight of one or more compounds divided by the weight of the isoprene times 100) is about 0.01 to about 105% (weight / weight), like about 0.01 to about 90, about 0.01 to about 80, about 0.01 to about 50, about 0.01 to about 20, about 0.01 to about 10, about 0.02 to about 50, about 0.05 at about 50, from about 0.1 to about 50, or from 0.1 to about 20% (weight / weight).
In some embodiments, the gaseous effluent from the fermenter contains one or more of the following compounds in the biological by-product: methanol, ethanol, methanethiol, 1-butanol, 3-methyl-1-propanol, acetone, acetic acid, 2-butanone, 2- methyl-1-butanol or indole. In some embodiments, the gaseous effluent from the fermenter contains 1 ppm or more of one or more of the following compounds: methanol, acetaldehyde, ethanol, methanethiol, 1butanol, 3-methyl-1-propanol, acetone, acetic acid, 2-butanone, 2-methyl-1-butanol or indole. In some embodiments, the concentration of biological by-product and / or one or more compounds of the biological by-product (for example, one or more of the following: methanol, acetaldehyde, ethanol, methanethiol, 1-butanol, 3-methyl-1-propanol , acetone, acetic acid, 2-butanone, 2-methyl-1-butanol or indole) is about 1 to about 10,000 ppm in the gaseous effluent from the fermenter. In some embodiments, the gaseous effluent from the fermenter includes one or more of the following: methanol, acetaldehyde, ethanol, methanethiol, 1-butanol, 3-methyl-1-propanol, acetone, acetic acid, 2-butanone, 2-methyl-1- butanol or indole, at a concentration of about 1 to about 100 ppm, such as from about 1 to about 10 ppm, from about 10 to
37/74 about 20 ppm, about 20 to about 30 ppm, about 30 to about 40 ppm, about 40 to about 50 ppm, about 50 to about 60 ppm, about from 60 to about 70 ppm, from about 70 to about 80 ppm, from about 80 to about 90 ppm, or from about 90 to about 100 ppm. In some embodiments, the amount of biological by-product present in the gaseous effluent from the fermenter is at a concentration of about 1 to about 100 ppm, like from about 1 to about 10 ppm, from about 10 to about 20 ppm, about 20 to about 30 ppm, about 30 to about 40 ppm, about 40 to about 50 ppm, about 50 to about 60 ppm, about 60 to about 70 ppm, from about 70 to about 80 ppm, from about 80 to about 90 ppm, or from about 90 to about 100 ppm. The biological by-product from cell cultures (such as volatile organic compounds in the free space above cell cultures) can be analyzed using standard methods such as those described herein or other standard methods such as proton transfer reaction mass spectrometry ( see, for example, Bunge et al., Applied and Environmental Microbiology, 74 (7): 2179-2186, 2008, which is incorporated herein by reference, in its entirety, particularly with regard to the analysis of volatile organic compounds ).
Volatile impurity of gaseous effluent
The optimal ranges of the various components during isoprene fermentation to obtain adequate production levels and safe operation (for example, based on flammability characteristics) are described, for example, in provisional US patent application 61 / 187,944, whose content is hereby incorporated by reference. As a result, the gaseous effluent from fermentation may contain volatile impurity (for example, volatile impurity comprising water vapor, CO ₂ , N ₂ and O ₂ ). It may be desirable to remove this volatile impurity from the isoprene before commercial use. Consequently, in one aspect, the methods described herein decrease or remove the volatile impurity of the isoprene-containing fermenter gaseous effluent.
In some embodiments, the volatile impurity of the gaseous effluent
38/74 of the fermenter includes one, two or more compounds selected from H ₂ O, CO ₂ , CO, N ₂ , CH ₄ , H ₂ and O ₂ . In some embodiments, the volatile impurity comprises H ₂ O, CO ₂ and N ₂ . In some embodiments, the volatile impurity comprises H ₂ O, CO ₂ , N ₂ and O ₂ . In some embodiments, the volatile impurity comprises an inorganic gas under standard temperature and pressure.
In some embodiments, the gaseous effluent from the fermenter comprises volatile impurity (for example, where the volatile impurity comprises a compound such as H ₂ O, CO ₂ , CO, N ₂ , CH ₄ , H ₂ and / or O ₂ ) at a content of at least about 2, 5, 10, 50, 75 or 100 times less than the amount of isoprene. In some embodiments, the volatile impurity of the gaseous effluent from the fermenter comprises one or more compounds (for example H ₂ O, CO ₂ , CO, N ₂ , CH ₄ , H ₂ and / or O ₂ ) at a content of at least about 2, 5, 10, 50, 75 or 100 times less than the amount of isoprene. In some embodiments, the portion of gaseous effluent in addition to the isoprene comprises from about 0% to about 100% (volume) of oxygen, from about 0% to about 10%, from about 10% to about 20 %, from about 20% to about 30%, from about 30% to about 40%, from about 40% to about 50%, from about 50% to about 60%, from about 60 % to about 70%, from about 70% to about 80%, from about 80% to about 90%, or from about 90% to about 100% (volume) of oxygen. In some embodiments, the portion of gaseous effluent in addition to isoprene comprises from about 0% to about 99% (volume) of nitrogen, from about 0% to about 10%, from about 10% to about 20 %, from about 20% to about 30%, from about 30% to about 40%, from about 40% to about 50%, from about 50% to about 60%, from about 60 % to about 70%, from about 70% to about 80%, from about 80% to about 90%, or from about 90% to about 99% (volume) of nitrogen. In some embodiments, the portion of gaseous effluent in addition to the isoprene comprises from about 0% to about 99% (volume) of H ₂ O, from about 0% to about 10%, from about 10% to about 20%, about 20% to about 30%, about 30% to about 40%, about 40% to about 50%, about 50% to about 60%, about from 60% to about 70%, from
39/74 about 70% to about 80%, about 80% to about 90%, or about 90% to about 99% (volume) of H ₂ O. In some embodiments, the portion of gaseous effluent in addition to isoprene comprises from about 1% to about 50% (volume) of CO ₂ , as from about 1% to about 10%, from about 10% to about 20%, from about 20 % to about 30%, from about 30% to about 40%, or from about 40% to about 50% (volume) of CO ₂ .
In some embodiments, the volatile impurity of the gaseous effluent from the fermenter comprises from about 10 to about 90, or from about 20 to about 80, or from about 40 to about 60, or from about 10 to about 20, or about 20 to about 30, or about 30 to about 40, or about 40 to about 50, or about 50 to about 60, or about 60 to about 70, or about 70 to about 80, or about 80 to 90, or about 90 to about 99 mol% of N ₂ . In some embodiments, the volatile impurity comprises about 10 to about 90, or about 20 to about 80, or about 40 to about 60, or about 10 to about 20, or about about 20 to about 30, or about 30 to about 40, or about 40 to about 50, or about 50 to about 60, or about 60 to about 70, or about from 70 to about 80 or from about 90, or from about 90 to about 99 mol% of carbon dioxide. In some embodiments, the volatile impurity comprises about 10 to about 90, or about 20 to about 80, or about 40 to about 60, or about 10 to about 20, or about about 20 to about 30, or about 30 to about 40, or about 40 to about 50, or about 50 to about 60, or about 60 to about 70, or about from 70 to about 80 or about 90, or from about 90 to about 99 mol% of carbon monoxide. In some embodiments, the volatile impurity comprises about 10 to about 90, or about 20 to about 80, or about 40 to about 60, or about 10 to about 20, or about about 20 to about 30, or about 30 to about 40, or about 40 to about 50, or about 50 to about 60, or about 60 to about 70, or about 70 to about 80 or about
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90, or about 90 to about 99, or less than 50, or less than 40, or less than 30, or less than 20, or less than 10, or less than 5, or equal to zero, or greater than 80, or greater than 90, or greater than 95 mol% of O2. In some embodiments, the volatile impurity comprises about 10 to about 90, or about 20 to about 80, or about 40 to about 60, or about 10 to about 20, or about about 20 to about 30, or about 30 to about 40, or about 40 to about 50, or about 50 to about 60, or about 60 to about 70, or about from 70 to about 80 or about 90, or from about 90 to about 99 mol% of hydrogen. In some embodiments, the volatile impurity comprises less than about 50, or less than about 40, or less than about 30, or less than about 20, or less than about 10, or less than about 5, or less than about 3 mol% of methane.
In some embodiments, the volatile impurity of the gaseous effluent from the fermenter comprises from about 25 to about 80 mol% CO ₂ , from about 45 to about 99 mol% N ₂ and, optionally, comprises less than about 50% by mol of O ₂ . In some embodiments, the volatile impurity comprises from about 40 to about 60 mol% CO ₂ , from about 65 to about 99 mol% N ₂ and optionally comprises less than about 25 mol% of O ₂ .
Although the gaseous effluent from the fermenter derived from renewable resources originates from the fermentation of the gaseous phase, the gaseous effluent can exist as described in the present invention in any phase or mixture of phases, such as a complete gas phase, a partial gas phase and a phase partial liquid (like a condensate), or in a complete liquid phase. In some embodiments, at least a portion of the gaseous effluent from the fermenter derived from renewable resources is in a gaseous phase. In some modalities, at least a portion of the gaseous effluent from the fermenter derived from renewable resources is in a liquid phase (such as a condensate). In some embodiments, at least a portion of the gaseous effluent from the fermenter derived from renewable resources is in a solid phase. In some modalities, the effluent
41/74 fermenter gas has undergone one or more purification steps before use in the methods described here. In some embodiments, the gaseous effluent from the fermenter did not undergo purification before use in the methods described here. In some embodiments, at least a portion of the gaseous effluent from the fermenter derived from renewable resources is absorbed on a solid support, such as a support that includes silica and / or activated carbon before use in the methods described herein. In some embodiments, the gaseous effluent from the fermenter is mixed with one or more solvents before use in the methods described herein. In some embodiments, the gaseous effluent from the fermenter is mixed with one or more gases before use in the methods described herein.
In some embodiments of the methods described here, the temperature of the gaseous effluent from the fermenter is reduced before it comes into contact with the solvent in the first column. Reducing the temperature of the gaseous effluent from the fermenter can help solubilize one or more components of the gaseous effluent (such as isoprene) in the solvent (for example, a hydrophobic solvent with a high boiling point). The temperature can be reduced by any suitable means (for example, using a refrigerant). In some embodiments, reducing the temperature of the gaseous effluent from the fermenter results in a partial or complete condensation of the gaseous effluent from the fermenter. In some embodiments, the temperature of the gaseous effluent from the fermenter is reduced to less than any of about 95%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20% or 10% of the temperature of the gaseous effluent, in ° C, when leaving the fermenters. In some embodiments, the temperature of the gaseous effluent from the fermenter is reduced to less than any of about 150 ° C, 125 ° C, 100 ° C, 90 ° C, 80 ° C, 70 ° C, 60 ° C, 50 ° C, 45 ° C, 40 ° C, 35 ° C, 30 ° C, 25 ° C, 20 ° C, 15 ° C, 10 ° C, 5 ° C or 0 ° C. In some embodiments, the temperature of the gaseous effluent from the fermenter is reduced to anywhere from about 0 ° C to about 150 ° C, from about 0 ° C to about 125 ° C, from about 0 ° C to about from 100 ° C, from about 0 ° C to about 75 ° C, from about 0 ° C to about 30 ° C,
42/74 from about 0 ° C to about 20 ° C, from about 0 ° C to about 10 ° C, from about 0 ° C to about 7.5 ° C, or about 5 ° C .
In some embodiments of the methods described here, the pressure of the gaseous effluent from the fermenter is increased before it comes into contact with the solvent in the first column. The pressure can be increased by any suitable means (for example, compression systems known in the art). The increase in pressure can help solubilize one or more components of the gaseous effluent (such as isoprene) in the solvent (for example, a hydrophobic solvent with a high boiling point). In some embodiments, the pressure of the fermenter's gaseous effluent is increased by more than any of about 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 95% of the pressure of the gaseous effluent (in kPa (PSIA - pounds per square inch) absolute) when leaving the fermenters. In some embodiments, the pressure of the gaseous effluent from the fermenter is increased to more than any of about 68.9 kPa (10 PSIA), 138 kPa (20 PSIA), 207 kPa (30 PSIA), 276 kPa (40 PSIA), 345 kPa (50 PSIA), 414 kPa (60 PSIA), 483 kPa (70 PSIA), 552 kPa (80 PSIA), 621 kPa (90 PSIA), 689 kPa (100 PSIA), 758 kPa (110 PSIA), 827 kPa (120 PSIA), 896 kPa (130 PSIA), 965 kPa (140 PSIA) or 1034 kPa (150 PSIA). In some embodiments, the pressure of the gaseous effluent from the fermenter is increased to anywhere from about 34.5 kPa (5 PSIA) to about 1034 kPa (150 PSIA), from about 68.9 kPa (10 PSIA) to about from 689 kPa (100 PSIA), from about 103 kPa (15 PSIA) to about 517 kPa (75 PSIA), from about 138 kPa (20 PSIA) to about 448 kPa (65 PSIA), from about 172 kPa (25 PSIA) to about 414 kPa (60 PSIA), about 207 kPa (30 PSIA) to about 345 kPa (50 PSIA), or about 241 kPa (35 PSIA) to about 310 kPa ( 45 PSIA).
Insulation unit
The gaseous effluent from the fermenter can be routed through an isolation unit before reaching a column. The isolation unit can serve to prevent the fermentation process from being influenced by the downstream purification process.
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In addition, the isolation unit can serve to provide a stable intermediate pressure to the column (for example with a current compensation flow of recycled gas, fresh atmospheric air and / or other added gas, such as nitrogen). The foam formed and the entrained liquid (for example, the medium) can also be collected by the isolation unit and prevented from reaching the column. In some embodiments of any of the methods described here, the gaseous effluent from the fermenter is transferred to an isolation unit (the same or a different isolation unit), before the gaseous effluent from the fermenter comes into contact with the solvent in the first column. In some of these modalities, the isolation unit is able to stabilize the pressure of the gaseous effluent.
Solvents
Any suitable solvent can be used in the methods described herein. The solvent can be a pure solvent or a mixture of two or more solvents. In some cases, the solvent is capable of absorbing a major portion of the isoprene from the gaseous effluent from the fermenter (or a major portion of the isoprene and a major portion of the biological by-product), and is not capable of absorbing a major portion of the volatile impurity of the gaseous effluent from the fermenter under the same conditions. In some modalities of the methods described here, the solvent is able to absorb more than about 2, 5, 10, 20, 50, 100, 200 or 500 times more isoprene (weight / weight), compared to the volatile impurity, under the same conditions. In some modalities of the methods described here, the solvent is capable of only a relatively low absorption of CO2 (for example, as defined by its Ostwald coefficient). Consequently, in some embodiments the solvent is a solvent with low absorption of carbon dioxide. For use in the present invention, unless otherwise specified, a solvent with low carbon dioxide absorption refers to a solvent that has an Ostwald coefficient of less than 2 at 54.4 ° C (130 F) and under standard pressure . In some embodiments, the solvent is a solvent with low absorption of carbon dioxide
44/74 carbon that has an Ostwald coefficient for CO ₂ less than any of about 1.75, about 1.5, about 1.25, about 1.1, or about 1.0 to 54 ° C (130 ° F) and under standard pressure.
The solvent can have a relatively high boiling point. For use in the present invention, unless otherwise specified, a solvent with a high boiling point refers to a solvent that has a boiling point greater than 121 ° C (250 ° F) at 101 kPa (1 atm). In some embodiments of the methods described here, the solvent is a solvent with a high boiling point, having a boiling point greater than about 121 ° C (250 F), greater than about 135 ° C (275 ° F), greater than about 149 ° C (300 F), greater than about 163 ° C (325 ° F), greater than about 121 ° C (350 F), greater than about 191 ° C (375 ° F), or greater than about 204 ° C (400 ° F), or greater than about 177 ° C (420 ° F), or greater than about 232 ° C (450 ° F), or greater than about 246 ° C ( 475 ° F) at 101.3 kPa (1 atm). In some embodiments, the solvent has a boiling point of about 121 ° C (250 ° F) to about 149 ° C (300 ° F), or 135 ° C (275 ° F) to about 163 ° C (325 ° F), or from about 149 ° C (300 ° F) to about 177 ° C (350 ° F), or from about 163 ° C (325 ° F) to about 149 ° C (375 ° F), or about 135 ° C (350 ° F) to about 204 ° C (400 ° F), or about (191 ° C (375 ° F) to about (218 ° C (425 ° F), or from about 204 ° C (400 ° F) to about 232 ° C (450 ° F), or from about 218 ° C (425 ° F) to about 246 ° C (475 ° F) ) at 101.3 kPa (1 atm).
In some embodiments of the methods described herein, the solvent is relatively non-polar. The polarity of the solvent can be determined by any method known in the art (for example, water solubility, hydrogen bonding potential, dielectric constant and / or an oil / water separation coefficient). In some embodiments, the solvent is a non-polar solvent. For use in the present invention, unless otherwise specified, a non-polar solvent refers to a solvent that has a dielectric constant less than 15 to 20 ° C. In some embodiments, the solvent is a non-polar solvent that has a dielectric constant less than about 12, or less than about 10, or less than about 7.5, or less than about 5, or less than about
45/74 of 3, or less than about 2, or less than about 1 to 20 ° C. In some embodiments, the solvent has a water solubility of less than about 5%, or less than about 3%, or less than about 2%, or less than about 1%, or less than about 0.5 %, or less than about 0.25%, or less than about 0.1%, or less than about 0.05%, or less than about 0.025% under standard conditions.
The solvent used in the methods described here can be characterized by its Kauri-butanol value (Kb value) as measured in the technique. In some embodiments of the methods described here, the solvent has a Kb value less than 75, or less than 50, or less than 40, or less than 30, or less than 20, or less than 10. In some embodiments, the solvent has a Kb value of about 10 to about 40, or about 15 to about 35, or about 20 to about 30, or about 23 to about 27, or about 25.
The solvent used in the methods described herein can be characterized by its aniline point, as measured in the art. In some embodiments of the methods described herein, the solvent has an aniline point greater than about 52 ° C (125 ° F), or greater than about 66 ° C (150 ° F), or greater than about 79 ° C (175 ° F), or greater than about 91 ° C (200 ° F). In some embodiments, the solvent has an aniline point of about 66 ° C (150 ° F) to about 121 ° C (250 ° F), or about 79 ° C (175 ° F) to about 93 ° C (200 ° F), or from about 82 ° C (180 ° F) to about 91 ° C (195 ° F).
The solvent used in the methods described here can be characterized by its kinematic viscosity, as measured in the art. In some embodiments of the methods described here, the solvent has a kinematic viscosity at 40 ° C less than about 3.00 x 10 ' ⁶ (3), or less than about 2.75 x 10' ⁶ (2.75) , or less than about 2.25 x 10 ' ⁶ (2.25), or less than about 2.0 x 10' ⁶ (2.0), or less than about 1.75 x 10 ' ⁶ ( 1.75), or less than about 1.5 x 10 ' ⁶ (1.5), or less than about 1.25 x 10' ⁶ m / s ² (1.25 centistokes (cSt)).
The solvent used in the methods described here can be
46/74 characterized by its surface tension, as measured in the technique. In some embodiments of the methods described herein, the solvent has a surface tension at 25 ° C of about 15 to about 35 dyne / cm, or from about 17 to about 32 dyne / cm, or from about 20 to about from 30 dynes / cm, or from about 23 to about 27 dynes / cm, or from about 25 dynes / cm.
The solvent used in the methods described herein can be characterized by its molecular weight (or a weight average molecular weight in the case of a mixed solvent system). In some embodiments of the methods described herein, the solvent has an average molecular weight of about 100 to about 250, or about 125 to about 225, or about 140 to about 200, or about 150 to about 175.
The solvent used in the methods described herein can have any one, or a combination of two or more, among the properties described herein. For example, in some embodiments the solvent used in the methods described herein may be a non-polar solvent with a high boiling point (i.e., a non-polar solvent which is also a solvent with a high boiling point). In some embodiments, the solvent used in the methods described herein may be a non-polar solvent with low absorption of carbon dioxide, or a solvent with a high boiling point and low absorption of carbon dioxide, or a non-polar solvent with a high absorption point boiling and low carbon dioxide absorption. In some embodiments of the methods described here, the solvent is characterized as having a boiling point greater than about 177 ° C (350 ° F), a water solubility of less than about 3% and a lower Ostwald coefficient for CO ₂ than about 1.25 to 54 ° C (130 F). In some of these embodiments, the solvent has an average molecular weight of about 125 to about 225. In other embodiments of the methods described herein, the solvent is characterized as having a boiling point greater than about 191 C (375 ° F) , a water solubility of less than about 1% and an Ostwald coefficient for CO ₂ less than about 1.1 to 54 ° C (130 ° F). In some of these embodiments, the solvent has an average molecular weight of about 140 to about 200.
47/74
In some embodiments of the methods described herein, the solvent is selected from a terpene, a paraffin, a monoaromatic hydrocarbon, a polyaromatic hydrocarbon or a mixture thereof. In some embodiments, the solvent is a paraffin (for example, a C10-C20 paraffin, such as a C12-C14 paraffin) or an isoparaffin as described above. In some embodiments, the solvent is a terpene. In some embodiments, the solvent is a monoaromatic hydrocarbon. In some embodiments, the solvent is a polyaromatic hydrocarbon. In some embodiments, the solvent is an Isopar ™ solvent (available commercially from Exxon) or its equivalent, as a solvent substantially similar to any solvent described in Table 1 (for example, solvent 1, 2, 3, 4, 5, 6, 7 and / or 8). In some embodiments, the solvent has any one or more properties substantially similar to any solvent described in Table 1 (e.g., solvent 1,
2, 3, 4, 5, 6, 7 and / or 8). In some embodiments, the solvent is selected from Isopar ™ L (Table 1, solvent 6), Isopar ™ H (Table 1, solvent 4) and
Isopar ™ M (Table 1, solvent 7). In some embodiments, the solvent is
Isopar ™ L (Table 1, solvent 6). In some embodiments, the solvent is
Isopar ™ H (Table 1, solvent 4). In some embodiments, the solvent is
Isopar ™ M (Table 1, solvent 7).
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Table 1
CO Isopar ™ V | COCM 92.2 (198) I 129 (265) | 273 (523) | 312 (594) I 0.83 99.8 1 <0.5 1 ANDJC.ç.ΦZ r- V - 26.9 44.9 1 Excellent | Π5 CD O) CO σ> £ N. sH1_ΦCL 25 05 0500 COCO 00 0.79 99.9 <0.05 = 5_ççΦ V <2 26.4 52.2 çΦΦO O_ω 05 92, CMCM U)CM z LU (15 CO 2Hi_05 27 (185) st CMCO 1X5O > -r- 05σϊ O ANDΞ3JZç V V V <2 v ~tfí ooσ> “ #çΦΦ CLO_to 1X500 63.9 189 OCM O O) V <Dz CM C5XLJJ Φ LO l · - £ M— · Φ CO 21-05CL 27 0000 COx—CM 1X500,Γ- oooo 0.76 050505 <0.01 çΦ CM V V <2 24.2 50.1 çΦΦO ç O CM r- 1- 05 z LU Φ (Λ 00 1X5 > OCO X QC cn c T O £ ΦM— · Xj- 21-l_05Ω 26 00O> CM05 1X500,00 52oo 0.76 OO <0.01 Z5_ £ =ÇΦ <3 V V - 24.1 51.4 çΦΦO O CO CO r- oo z XLU _ω 00 1X5 V ^- O (15 CO O 05 £ <*> 2HdogQ. 27 0000 Ov— CM00,O M52-CD 0.75 OO T- “Odv 3XZçΦ V V "V OOCO1- - 23.8 51.6 CZΦΦO O CM V " CD z LU 00 M LU (15 CM 21-l_05 29 (167) LO Ό-Ç ^ 05r-cm. CMl · - OO O ANDZ3_çç CMV CMV O v—CM 0500 ÇΦΦ CLOP 75 CMK oo CO O V Φz ASS OXLU T- O5HdogΩ r-CM -3 (173) I | (81) 8 ' -8 (208) J 4 (219) J O> -O' OO OOv ANDZ3JCÇΦ COV 1 O 20.3 05ooM ΦçΦΦO Ow oor- (γ 05 OT ~ z XLU CO O O O O O M— 1X5 1X5 O ((of) CMLL OωO. CM CM çro OO O COL ± tJ-LL C0Φ m CO CD VF ^- • fc o dogOCO ro -Q (0 Ç- O LL and * £ Φ OO D05 çΈ O_O5 OO OO O52- E ^- ANDCLQ. CLCL CLCL andCL ΦO. % ~ 3 co tΦM— · T0COP tO alue of K 05<1> * + -Φ O> 05 O> co ΦO O ωO C0Í CLCL Or ωO CL ω .5 = T0 s O<uANDO TOOÇO TOOM- *çO O_ço53Φ O_çoi ^ 5 Φ COT0>C0 CD1X5©) TOCOΞ3-I— <(0 romantic «5OT0Ό s2 O <φCOO T0XΌ1-Φ Φ1_M—OXç sion ^r 7 ° F), O> coC / 5çΦ LLOr- ωANDφ Z > CL CL Q Io O ω < < O Z CL LU 1- the 1- Q
ASTM D1133, (2) ASTM D56, TTC, (3) ASTM D86, IBP, (4) ASTM D86, Dry spot, (5) ASDM D1250 ASTM D971
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The solvent used in the methods described herein may also contain a polymerization inhibitor to help reduce unwanted polymerization of isoprene. Consequently, in some embodiments the solvent additionally comprises a polymerization inhibitor (for example an isoprene polymerization inhibitor). Suitable inhibitors include, for example, 2,2,6,6-tetramethyl piperidine 1-oxyl (TEMPO), 4-hydroxy-2,2,6,6-tetramethyl piperidine 1-oxyl (TEMPOL), bis (1oxyl- 2,2,6,6-tetramethyl piperidin-4-yl) (TEMPO with bridge), and t-butyl catechol. In some embodiments of the methods described herein, the solvent comprises a suitable amount of a polymerization inhibitor to sufficiently prevent polymerization of the isoprene (for example to prevent more than 95%, or more than 97%, or more than 98%, or more than 99%, or more than 99.5% of the isoprene polymerizes, in comparison to the absence of the inhibitor). In some embodiments, the solvent comprises a polymerization inhibitor at a concentration of about 0.001% to about 0.1%, or from about 0.005% to about 0.075%, or from about 0.01% to about 0.05% (weight / weight) in relation to isoprene. In some embodiments, the solvent comprises a polymerization inhibitor at a concentration of about 0.001% to about 0.1%, or from about 0.005% to about 0.075%, or from about 0.01% to about 0.05% (weight / weight) in relation to the solvent. Removal of volatile gases
In some respects, the methods described herein include removing volatile gases from a gaseous effluent from the fermenter. In some of the modalities described here, the gaseous effluent from the fermenter is placed in contact with a solvent in a column. In some of these embodiments, the gaseous effluent from the fermenter is placed in contact with a solvent in a column to form: an isoprene-rich solution comprising the solvent and a major portion of the isoprene, and a vapor comprising a major portion of the volatile impurity. A stream of steam for rectification can be introduced in the column (for example, in the first column), below the feed point of the gaseous effluent from the fermenter, which can help to separate the volatile impurity from the solution
50/74 remaining. The steam for rectification can be introduced by any suitable means (for example, by steam or by a cooler at the bottom of the column). In some embodiments, the temperature of the current at the bottom of the column (for example, in the first column) is much higher than the temperature of the solvent before entering the column. In some embodiments, the current temperature at the bottom of the column (for example, in the first column) is higher at any of about 38 ° C (100 ° F), 52 ° C (125 ° F), 66 ° C (150 ° F), 79 ° C (175 ° F), 93 ° C (200 ° F), 109 ° C (225 ° F), 121 ° C (250 ° F), 135 ° C (275 ° F) or 149 ° C (300 ° F). In some embodiments, the solvent temperature in the column bottom stream (for example, in the first column) is about 66 ° C (150 ° F) to about 177 ° C (350 ° F), or about 79 ° C (175 ° F) to about 149 ° C (300 ° F), or about 93 ° C (200 F) to about 135 ° C (275 ° F), or about 110 ° C (230 ° F) at about 121 ° C (250 ° F), or from about 113 ° C (235 ° F) to about 118 ° C (245 ° F). The steam can be directed through the column (at any suitable location, such as near the inlet of the gaseous effluent and / or at the opposite end to the outlet of the volatile impurity), to offer an extensive vapor phase, which can assist in the removal of the volatile impurity . In some embodiments, steam is routed through the column (for example, through the first column). Removal of impurities from biological by-products
In some of the embodiments described here, the solution comprising isoprene and biological by-product impurities (for example, any isoprene-rich solution transferred from a first column) is transferred to a column (for example, a second column) in which the isoprene is rectified from the solution. In some of these embodiments, the rectification results in: an isoprene-poor solution, comprising a major portion of the biological by-product impurity, and a purified isoprene composition. In some embodiments, the second column is separated from the first column. In some embodiments, the first and second columns are combined into one column (for example, the functions of the first and second columns are combined into one column, like a joined tandem column, in which the
51/74 solvent enters the first column at, or close to, one end and leaves the second column at, or close to, an opposite end).
In some embodiments, the temperature of the solution in the column (for example, in the second column) is about 66 ° C (150 ° F) to about 177 ° C (350 ° F), or about 79 ° C ( 175 ° F) at about 149 ° C (300 ° F), or from about 93 ° C (200 ° F) to about 135 ° C (275 ° F), or about 110 ° C (230 ° F) at about 121 ° C (250 ° F), or from about 113 ° C (235 ° F) to about 118 ° C (245 ° F). Steam can be conducted through the column (at any suitable location, such as the opposite end of the isoprene-rich solution entry point, and / or near the outlet of the isoprene-poor solution) to provide an extensive vapor phase that can help recovering the isoprene from the solvent. In some embodiments, steam is routed through the column (for example, through the second column).
In some embodiments, rectifying the isoprene involves increasing the pressure of the solution in the column (for example, the second column). In some of these embodiments, the solution comprising isoprene and biological by-product impurity (for example, any isoprene-rich solution transferred from a first column) in the column (for example, the second column), has a pressure of more than any among about 34.5 kPa (5 PSIA), 68.9 kPa (10 PSIA), 138 kPa (20 PSIA), 207 kPa (30 PSIA), 276 kPa (40 PSIA), 345 kPa (50 PSIA), 414 kPa (60 PSIA), 483 kPa (70 PSIA), 552 kPa (80 PSIA), 621 kPa (90 PSIA), 689 kPa (100 PSIA), 758 kPa (110 PSIA), 827 kPa (120 PSIA), 896 kPa (130 PSIA) ), 965 kPa (140 PSIA) or 1034 kPa (150 PSIA). In some embodiments, the pressure is anywhere from about 34.5 kPa (5 PSIA) to about 1034 kPa (150 PSIA), from about 34.5 kPa (5 PSIA) to about 689 kPa (100 PSIA), from about 68.9 kPa (10 PSIA) to about 517 kPa (75 PSIA), from about 68.9 kPa (10 PSIA) to about 448 kPa (65 PSIA), from about 68.9 kPa ( 10 PSIA) at about 414 kPa (60 PSIA), from about 103 kPa (15 PSIA) to about 345 kPa (50 PSIA), from about 103 kPa (15 PSIA) to about 310 kPa (45 PSIA) , from about 103 kPa (15 PSIA) to about 241 kPa (35 PSIA), or from about 103 kPa (15 PSIA) to about 207 kPa (30 PSIA).
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Additional purification
The purified isoprene composition resulting from any of the methods described herein (for example, a purified isoprene composition rectified from the second column) can be further purified by any suitable means, for example as shown in figure 1 with reference to the adsorption system 36. For example, the purified isoprene composition can be further purified using conventional techniques, such as fractionation, additional gas rectification, adsorption / desorption, pervaporation, thermal or vacuum desorption of the isoprene from a solid phase, extraction counter-current liquid-liquid with a suitable solvent, or extraction of isoprene immobilized or absorbed in a solid phase with a solvent (see, for example, US patent No. 4,703,007 and US patent No. 4,570,029, each of which it is incorporated herein by reference, in its entirety, particularly with regard to methods for recovery and purification of is opreno). Suitable solvents include, but are not limited to, sodium hydroxide, sodium bicarbonate, sodium carbonate, potassium hydroxide, potassium bicarbonate, potassium carbonate, water, ionic liquids such as 1-ethyl-3-methyl imidazolium acetate , 1-ethyl 3-methyl imidazolium sulfate, choline acetate, 1-butyl-4-methyl pyridinium tetrafluoroborate, 1-hexyl-3-methyl imidazolium chloride, 1-ethyl-3-methyl imidazolium thiocyanate, and 1- ethyl-3-methyl imidazolium.
Additional gas rectification involves removing isoprene vapor continuously. This removal can be achieved in a number of different ways including, but not limited to, adsorption to a solid phase, partition to a liquid phase, or direct condensation. In some embodiments, membrane enrichment of a diluted isoprene vapor stream above the vapor dew point results in condensation of liquid isoprene. Further purification of the purified isoprene composition can involve one step or multiple steps.
In some embodiments, the isoprene resulting from any of the methods described here is further purified by treatment
53/74 with an adsorption system (for example, an adsorption system comprising activated carbon, alumina, silica and / or Selexsorb®.) Other suitable materials are zeolites and molecular sieves, see US patents 4,147,848 , 5,035,794 and 6,987,152. Filter housings suitable for this type of system include those used in the petrochemical industry to remove impurities present in crude hydrocarbon streams. Examples include those available from The Hilliard Corporation (Elmira, NY, USA) and ISO Corporation (Plano, TX, USA). In some embodiments, the isoprene resulting from any of the methods described herein is further purified by treatment with an adsorption system that comprises silica. In some embodiments, the isoprene resulting from any of the methods described herein is further purified by distillation (for example, reflux condensation), before or after any other optional purification added. In some embodiments, the isoprene resulting from any of the methods described herein is further purified by treatment with an adsorption and distillation system (for example, an adsorption system comprising silica and reflux condensation). Adsorption is typically conducted in a column-filled configuration, being applicable to isoprene in both vapor and liquid states. If the isoprene is fed in the form of steam, this is commonly done by feeding from the top of the column while, on the other hand, if it is fed in the form of liquid, this is usually done by feeding from the bottom. Suitable adsorbents include, but are not limited to, the following: activated carbon (eg NUCON G60, GC60, GC 4X8S for vapor filtration, TIGG 5CC 0408), activated alumina (eg Axens SAS 351, SAS 830, BASF Selexsorb CD), silica gel (Eagle Chemical grade 148, grade 140) and 3A, 5A or 13X molecular sieves. Solvent recirculation and purification
In any of the methods described herein, the resulting solution following the rectification of the isoprene from the second column (for example, the isoprene-poor solution comprising a portion
54/74 majority of the biological by-product impurity) can be recycled back to the first column for reuse. In some embodiments, the biological by-product is removed from the recycled solution before reuse (for example, before re-entering the first column). In some embodiments of any of the methods described herein, the method further comprises purifying the isoprene-poor solution to remove a major portion of the biological by-product impurity, and transferring the resulting solvent to the first column for reuse. In some embodiments, purifying the rectified solution before reuse comprises treating the solution with an adsorption system (for example an adsorption system comprising activated carbon, alumina, silica and / or Selexsorb®). This absorption can also be done using, for example, a filled column. In some embodiments, purifying the rectified solution before reuse involves treating the solution with a silica-based adsorption system. In some embodiments, the purification of the rectified solution before reuse comprises liquid-liquid extraction. In some embodiments, purifying the rectified solution before reuse involves treating the solution by distillation. In some embodiments, the purification of the rectified solution before reuse comprises treating the solution with an adsorption system (e.g., the silica-based adsorption system) and liquid-liquid extraction (in any order). In some embodiments, purifying the rectified solution before reuse involves treating the solution with an adsorption system (for example, a silica-based adsorption system), liquid-liquid extraction and distillation (in any order). In any of these modalities, the rectified solution (for example the low isoprene solution) can be purified by any of the described means (for example adsorption, liquid-liquid extraction and / or distillation), so that the amount of biological by-product in the solution rectified is reduced by more than any of about 5%, 10%, 15%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or 95%, following purification . In some embodiments, the temperature of the rectified solution (for example the solution low in isoprene
55/74 comprising a major portion of the biological by-product impurity) is reduced before reuse in the first column. In some embodiments, the rectified solution is purified, and the temperature is reduced before reuse in the first column. In some of these embodiments, the temperature is reduced before purification. In some of these modalities, the temperature is reduced after purification. In some embodiments, the temperature of the rectified solution is reduced to less than any of about 95%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20% or 10% of the temperature, in ° C (° F) of the second column, before reuse (for example, before re-entering the first column). In some embodiments, the temperature of the rectified solution is reduced to less than any of about 121 ° C (250 ° F), 107 ° C (225 ° F), 93 ° C (200 ° F), 79 ° C (175 ° F), 66 ° C (150 ° F), 52 ° C (125 ° F), 38 ° C (100 ° F), 24 ° C (75 ° F), 10 ° C (50 ° F) or - 4 ° C (25 ° F). In some embodiments, the temperature of the rectified solution is reduced to anywhere from about -4 ° C (25 ° F) to about 121 ° C (250 ° F), from about -4 ° C (25 ° F) to about 79 ° C (175 ° F), about -4 ° C (25 ° F) to about 66 ° C (150 ° F), about -4 ° C (25 ° F) to about 38 ° C (100 ° F), or from about -4 ° C (25 ° F) to about 24 ° C (75 ° F). Collection of residual isoprene from steam
In some cases, the steam removed from the first column (for example the steam comprising a majority portion of volatile impurity) may also comprise small desirable amounts of isoprene (for example the residual isoprene that was not left in the isoprene-rich solution). In some of the embodiments described herein, the vapor comprising a major portion of the volatile impurity additionally comprises a minor portion of isoprene. In any of the methods described herein, the method further comprises removing a minor portion of the isoprene from the vapor, if present. The residual isoprene can be collected for use from the steam that comprises a majority portion of volatile impurity, by any suitable means (for example, with an adsorption system). As described in the present invention for further purification of an
56/74 purified isoprene composition, any suitable technique such as fractionation, additional gas rectification, adsorption / desorption, pervaporation, thermal or vacuum desorption of isoprene from a solid phase, or extraction of immobilized or absorbed isoprene in a solid phase with a solvent (see, for example, US Patent No. 4,703,007 and US Patent No. 4,570,029, each of which is incorporated herein by reference in its entirety, particularly with regard to methods for isoprene recovery and purification) can be used to isolate residual isoprene from the vapor phase. As described, isoprene vapor can be removed continuously, for example, but not limited to, by adsorption to a solid phase, partition into a liquid phase, or direct condensation. The removal / purification of isoprene from the vapor phase can involve one step or multiple steps. In any of the modalities of the methods described herein, the method additionally comprises removing the isoprene (if present) from the vapor using an adsorption system (for example, an adsorption system comprising activated carbon, alumina, silica and / or Selexsorb®). In any of the modalities of the methods described here, the method additionally comprises removing isoprene (if present) from the steam using an activated carbon-based adsorption system. Capture device
The methods described here can optionally use a capture device (such as system 38 in figure 1) capable of reducing the total amount of undesirable components released into the atmosphere (for example, CO2) from the vapor. A generic coal-based adsorption unit, such as those used for solvent recovery and supplied by manufacturers including AMCEC Inc. (Lisle, IL, USA) and Nucon International Inc. (Columbus, OH, USA), would be suitable.
It is often desirable to capture the trace amount of isoprene or other components present in the fermentation gaseous effluent that is not recovered by the primary process, both for the value of the product and to minimize the release, in the environment, of components
57/74 undesirable as carbon dioxide. The trace levels of isoprene and high molecular weight organic compounds can be effectively captured by adsorption on a solid surface, such as activated carbon (for example, see NUCON G60, GC60, GC 4X8S for steam filtration, TIGG 5CC 0408). The capture of carbon dioxide is commonly carried out in a counter-current gas purifier / absorber, where the purification fluid is fed from the top of the liquid contactor, while the gas being purified is fed from the bottom. The liquid contactor will have enough contact surface or equilibrium stages to obtain the desired reduction in concentration. Common purification fluids include, but are not limited to, monoethanol amine (MEA), piperazine, water or a combination of all of these (see, for example, CO ₂ Absorption Rate and Solubility in Monoethanolamine / Piperazine / Water, by Hongyi Dang , et al., prepared for presentation at the First national carbon sequestration conference, held in Washington, DC, USA, May 14-17, 2001). Resulting compositions
In some respects, the methods described herein offer a purified isoprene composition, a purified isoprene composition being an isoprene composition that has been separated from at least a portion of one or more components that are present in the gaseous effluent from the fermenter. In some embodiments, the purified isoprene composition has a purity greater than about 75% (weight / weight). In some embodiments, the purified isoprene composition has a purity greater than any of about 80%, 85%, 90%, 95%, 97%, 98%, 99%, 99.5%, 99.5% or 99 , 95% (weight / weight).
In any of the embodiments described herein, the purified isoprene composition comprises no more than about 20% (w / w) impurity of biological by-product. In some embodiments, the purified isoprene composition comprises less than about 15%, 12%, 10%, 8%, 6%, 5%, 4%, 3%, 2%, 1%, 0.075%, 0.5 %, 0.25%, 0.1%, 0.05%, 0.02%, 0.01%, or 0.005% (weight / weight) of biological by-product impurity, in
58/74 in relation to the weight of isoprene. In some embodiments, the purified isoprene composition comprises less than about 50% (weight / weight) of biological by-product impurity in relation to the biological by-product impurity of the fermenter gaseous effluent. In some embodiments, the purified isoprene composition comprises less than any of about 40%, 35%, 30%, 25%, 20%, 15%, 10%, 7.5%, 5%, 2.5%, 1%, or 0.5% (weight / weight) of biological by-product impurity in relation to the biological by-product impurity of the gaseous effluent from the fermenter.
In any of the embodiments described herein, the purified isoprene composition comprises no more than about 20% (w / w) volatile impurity. In some embodiments, the purified isoprene composition comprises less than about 15%, 12%, 10%, 8%, 6%, 5%, 4%, 3%, 2%, 1%, 0.075%, 0.5 %, 0.25%, 0.1%, or 0.05% (weight / weight) of volatile impurity. In some embodiments, the purified isoprene composition comprises less than about 50% (weight / weight) of volatile impurity relative to the volatile impurity of the gaseous effluent from the fermenter. In some embodiments, the purified isoprene composition comprises less than any of about 40%, 35%, 30%, 25%, 20%, 15%, 10%, 7.5%, 5%, 2.5%, 1%, or 0.5% (weight / weight) of volatile impurity in relation to the volatile impurity of the gaseous effluent from the fermenter.
In any of the embodiments described herein, the purified isoprene composition comprises no more than about 20% (weight / weight) of one or more compounds selected from H ₂ O, CO ₂ , CO, N ₂ , CH ₄ , H ₂ and The ₂ . In some embodiments, the purified isoprene composition comprises no more than about 15%, 12%, 10%, 8%, 6%, 5%, 4%, 3%, 2%, 1%, 0.075%, 0, 5%, 0.25%, 0.1%, or 0.05% (weight / weight) of one or more compounds selected from H ₂ O, CO ₂ , CO, N ₂ , CH ₄ , H ₂ and O ₂ . In some embodiments, the purified isoprene composition comprises less than about 50% (weight / weight) of one or more compounds selected from H ₂ O, CO ₂ , CO, N ₂ , CH ₄ , H ₂ and O ₂ , in relation to the gaseous effluent from the fermenter. In some embodiments, the purified isoprene composition comprises less than any of about 40%,
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35%, 30%, 25%, 20%, 15%, 10%, 7.5%, 5%, 2.5%, 1%, or 0.5% (weight / weight) of one or more selected compounds among H ₂ O, CO ₂ , CO, N ₂ , CH4, H ₂ and O ₂ , in relation to the gaseous effluent from the fermenter.
In any of the embodiments described herein, the purified isoprene composition comprises no more than about 20% (w / w) CO ₂ . In some embodiments, the purified isoprene composition comprises no more than about 15%, 12%, 10%, 8%, 6%, 5%, 4%, 3%, 2%, 1%, 0.075%, 0, 5%, 0.25%, 0.1%, or 0.05% (weight / weight) of CO ₂ . In some embodiments, the purified isoprene composition comprises less than about 50% (weight / weight) of CO ₂ in relation to the amount of CO ₂ in the gaseous effluent from the fermenter. In some embodiments, the purified isoprene composition comprises less than any of about 40%, 35%, 30%, 25%, 20%, 15%, 10%, 7.5%, 5%, 2.5%, 1%, or 0.5% (weight / weight) of CO ₂ in relation to the amount of CO ₂ in the gaseous effluent from the fermenter.
In any of the embodiments described herein, the purified isoprene composition comprises no more than about 20% (w / w) O ₂ . In some embodiments, the purified isoprene composition comprises no more than about 15%, 12%, 10%, 8%, 6%, 5%, 4%, 3%, 2%, 1%, 0.075%, 0, 5%, 0.25%, 0.1%, or 0.05% (weight / weight) of O ₂ . In some embodiments, the purified isoprene composition comprises less than about 50% (weight / weight) of O ₂ relative to the amount of O ₂ in the gaseous effluent from the fermenter. In some embodiments, the purified isoprene composition comprises less than any of about 40%, 35%, 30%, 25%, 20%, 15%, 10%, 7.5%, 5%, 2.5%, 1%, or 0.5% (weight / weight) of O ₂ in relation to the amount of O ₂ in the gaseous effluent from the fermenter. Isopropene compositions
Also disclosed are compositions of purified isoprene (for example, compositions comprising purified bioisoprene). In some embodiments, a purified isoprene composition prepared by any of the methods described herein is provided. In some embodiments, a composition of purified isoprene is shown
60/74 prepared by any of the methods of the present invention described herein.
In some embodiments, an isoprene composition (e.g., bioisoprene) is presented comprising less than about 15%, 12%, 10%, 8%, 6%, 5%, 4%, 3%, 2%, 1% , 0.075%, 0.5%, 0.25%, 0.1%, 0.05%, 0.02%, 0.01%, or 0.005% (weight / weight) of biological by-product impurity in relation to isoprene weight. In some embodiments, an isoprene composition (e.g., bioisoprene) is presented comprising less than about 15%, 12%, 10%, 8%, 6%, 5%, 4%, 3%, 2%, 1% , 0.075%, 0.5%, 0.25%, 0.1%, or 0.05% (weight / weight) of volatile impurity. In some embodiments, an isoprene composition (e.g., bioisoprene) is presented comprising less than about 15%, 12%, 10%, 8%, 6%, 5%, 4%, 3%, 2%, 1% , 0.075%, 0.5%, 0.25%, 0.1%, 0.05%, 0.02%, 0.01%, or 0.005% (weight / weight) of biological by-product impurity in relation to isoprene weight, and less than about 15%, 12%, 10%, 8%, 6%, 5%, 4%, 3%, 2%, 1%, 0.075%, 0.5%, 0.25 %, 0.1%, or 0.05% (weight / weight) of volatile impurity in relation to the weight of the composition. In any of these modalities, the isoprene composition comprises more than any of about 80%, 85%, 90%, 95%, 97%, 98%, 99%, 99.5%, 99.5%, or 99, 95% (weight / weight) of isoprene in relation to the weight of the composition. In any of these modalities, the isoprene composition comprises more than about 99.94%, 99.94%, 99.95%, 99.96%, 99.97%, 99.98%, or 99.99% isoprene (weight / weight) in relation to the weight of all C5 hydrocarbons. In any of these compositions, the biological by-product impurity comprises one or more compounds selected from the group consisting of 2-heptanone, 6-methyl-5-hepten-2-one,
2.4.5- trimethylpyridine, 2,3,5-trimethylpyrazine, citronelal, acetaldehyde, methanethiol, methyl acetate, 1-propanol, diacetyl, 2-butanone, 2-methyl-3-buten-2-ol, ethyl acetate, 2-methyl-1-propanol, 3-methyl-1-butanal, 3-methyl-2-butanone, 1-butanol, 2-pentanone, 3-methyl-1-butanol, ethyl isobutyrate, 3-methyl-2-butenal, butyl acetate, 3-methyl butyl acetate, 3-methyl-3-but-1-enyl acetate, 3-methyl-2-but-1-enyl acetate, (E) -3,7-dimethyl-1 , 3,6-octatriene, (Z) -3,7-dimethyl1.3.6- octatriene and 2,3-cycloheptenol pyridine, or as indicated above.
61/74
In some embodiments, an isoprene composition (e.g., bioisoprene) is presented comprising less than about 5% (or 1%, or 0.5%, or 0.05%, or 0.005%) (weight / weight) of impurity of biological by-product in relation to the weight of the isoprene, less than about 10% (or 1%, or 0.1%, or 0.05%) (weight / weight) of volatile impurity in relation to the weight of the composition, and more than about 95% (or 98%, or 99%, or 99.95%) (weight / weight) of isoprene in relation to the weight of the composition, with the isoprene composition comprising more than about 99.9% (or 99.95%, or 99.97%, or 99.99%) of isoprene (weight / weight) relative to the weight of all C5 hydrocarbons. In some embodiments, an isoprene composition comprising less than about 1% (weight / weight) of biological by-product impurity in relation to the weight of the isoprene, less than about 5% (weight / weight) of volatile impurity in relation to is presented the weight of the composition, and more than about 98% (weight / weight) of isoprene in relation to the weight of the composition, the isoprene composition comprising more than about 99.95% of isoprene (weight / weight) in relation to the weight of all C5 hydrocarbons. In some embodiments, an isoprene composition comprising less than about 1% (weight / weight) of biological by-product impurity relative to the weight of the isoprene, less than about 5% (or 2%, or 1%, or 0.5%) CO ₂ (weight / weight) in relation to the weight of the composition, and more than about 98% (weight / weight) of isoprene in relation to the weight of the composition, with the isoprene composition comprising more than about 99.95% isoprene (weight / weight) relative to the weight of all C5 hydrocarbons.
In some embodiments of either composition, at least a portion of the isoprene is in a gaseous phase. In some embodiments, at least a portion of the isoprene is in a liquid phase (like a condensate). In some embodiments, at least a portion of the isoprene is in a solid phase. In some embodiments, at least a portion of the isoprene is adsorbed on a solid support, such as a support that includes silica and / or activated carbon.
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In any of the compositions described herein, the composition may comprise more than about 2 mg of isoprene, such as more than or about 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 200, 300, 400, 500, 600, 700, 800, 900 or 1,000 mg of isoprene. In some embodiments, the composition comprises more than or about 2, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 g of isoprene. In some embodiments, the amount of isoprene in the composition is from about 2 to about 5,000 mg, such as from about 2 to about 100 mg, from about 100 to about 500 mg, from about 500 to about 1,000 mg, from about 1,000 to about 2,000 mg, or from about 2,000 to about 5,000 mg. In some embodiments, the amount of isoprene in the composition is from about 20 to about 5,000 mg, from about 100 to about 5,000 mg, from about 200 to about 2,000 mg, from about 200 to about 1,000 mg , from about 300 to about 1,000 mg, or from about 400 to about 1,000 mg.
In some embodiments, the composition includes ethanol. In some embodiments, the composition includes between about 75 and about 90% by weight of ethanol, such as between about 75 and about 80%, about 80 to about 85%, or about 85 to about 90% by weight of ethanol. In some embodiments in which the composition includes ethanol, the composition also includes between about 4 and about 15%, by weight, of isoprene, such as between about 4 and about 8%, from about 8 to about 12% , or from about 12 to about 15%, by weight, of isoprene.
Additional methods and compositions are described in accordance with International Patent Application Publication No. W02009 / 076676, US Patent Applications No. 12 / 496,573, 12 / 560,390, 12 / 560,317, 12 / 560,370, 12 / 560,305 and 12 / 560,366, and provisional US patent applications No. 61 / 187,930, 61 / 187,934 and 61 / 187,959, all of which are incorporated herein by reference in their entirety, particularly with respect to compositions and methods for production of isoprene.
This invention is illustrated by the examples presented below, which are for the purpose of illustration only and which should not be considered as limiting the scope of the invention or the way
63/74 by which it can be practiced. Except where specifically stated otherwise, parts and percentages are provided by weight. Examples
Example 1 consists of recovering isoprene from the fermentation gaseous effluent, through absorption and rectification, including:
(1) Absorption of isoprene from fermentation gaseous effluent. The fermentation gaseous effluent comprising isoprene, biological by-product impurities and volatile impurities is introduced into a glass gas purifying unit (catalog number CG-1830-10, available from ChemGlass, Vineland, New Jersey, USA) a a flow of 4 L / mrn. The purifier reservoir contains 0.5 L of Isopar® M (ExxonMobil, TX, USA) which is recirculated at a rate of 2 L / min. The solvent is recirculated until equilibrium with the fermentation gaseous effluent is reached, as determined by GC / MS analysis of the fermentation gaseous effluent prior to its entry into the gas purifying unit, the isopene-rich Isopar solvent, and the gas tail that emerges from the gas purifying unit. The equilibrium occurs at the point where the concentration of isoprene in the feed gas is the same as that in the tail gas that emerges from the purifier. Another indication is the point at which the concentration of isoprene in the solvent reaches a stable state.
(2) Rectification and condensation of isoprene. The rectification of the isoprene from the isoprene-rich Isopar solvent is obtained by reconfiguring the gas purifying unit, so that steam is added to the gas purifying unit in place of the fermentation effluent, at a rate of 4 L / min. The solvent is recirculated at a rate of 2 L / min, and the isoprene vapor rectified from the solvent emerges from the top of the gas purifying unit, along with amounts of biological by-product impurities.
The isoprene vapor that emerges from the gas purifying unit is then condensed using a Graham condenser or similar glass condenser, cooled with a refrigerant at a temperature of 0 to 10 ° C. The isoprene condensate is collected and inhibited
64/74 by adding 150 ppm of f-butyl catechol. The purity of the liquid isoprene is determined by GC / MS, according to procedures known to the person skilled in the art.
Below are described two sets of exemplary columns for use in the present invention, suitable for large-scale (manufacturing) or small-scale (a pilot plant or testing apparatus) processes, as determined by simulation.
Example A, below, uses tray columns, with thirteen trays for the absorption column 14 and sixteen trays for the rectification column 24. Example B, below, uses structured filled columns, with ten stages (equivalent to the tray) for the absorption column 14 and eleven stages for the rectification column 24. The objective is 99.9% recovery of the isoprene. All of these parameters and examples are illustrative only.
Example A Solvent in L / s (gpm) / MSCFH gas supply Percentage of recovery of isoprene contained Concentration of isoprene in gas 0.024 (0.38) 89.0% of the fermenter: 0.0252 (0.40) 91.0% 0.0259 (0.41) 94.0% 0.12 molar fraction 0.0271 (0.43) 97.5% 0.21 fraction of weight 0.0297 (0.47) 99.9% Pounds of rectifying steam / Pounds of recovered isoprene @ 99.9% recovery 1.10 Purity of recovered isoprene 99.8% by weight Example B Solvent in L / s (gpm) / MSCFH gas supply Percentage of recovery of isoprene contained Concentration of isoprene in 0.0177 (0.28) 89.0% fermenting gas: 0.0183 (0.29) 91.0% 0.0196 (0.31) 94.0% 0.04 molar fraction 0.0208 (0.33) 97.5% 0.08 weight fraction 0.0259 (0.41) 99.9%
Pounds of rectifying steam / Pounds of recovered isoprene @ 99.9% recovery
2.79
Purity of recovered isoprene
99.8% by weight
Example 2 consists of recovering isoprene from
65/74 gaseous effluent from fermentation, using solvent, by a gas purifying unit on a laboratory scale, as described above.
The gaseous effluent from fermentation including isoprene, biological by-product impurities and volatile impurities was introduced into a laboratory-type glass gas purifying unit, which includes an absorption column (catalog number CG-1830-10, supplied by ChemGlass , from Vineland, New Jersey, USA), at a flow rate of 8 L / min. The isoprene concentration was in the range of 1.8 to 2.1% v / v, as determined by online mass spectrometry using a Hiden HPR-20 mass spectrometer (available from Hiden Analytical, UK ). The purifier reservoir contained 1 L of lsopar®L isoparaffinic solvent, as described above, and from this point onwards this document called solvent (available from ExxonMobil Chemical Co., Houston, Texas, USA) that was recirculated at a rate 2 L / min at room temperature (20 ° C). The concentration of isoprene in the Isopar solution was about 1% by volume during this process. The process continued until equilibrium with the fermentation gaseous effluent was obtained, as determined by in-line analysis of the mass spectrometer for the fermentation gaseous effluent before it entered the gas purifying unit and for the tail gas emerging from the gas purifying unit. These data were used to calculate the isoprene absorption efficiency (vertical axis) as a function of time (horizontal axis), as shown in the plot in figure 2.
The cumulative amount of isoprene collected was calculated by multiplying the total isoprene productivity by the average absorption efficiency over the duration of the process, as determined by the area extrapolated under the plot in figure 2. At an isoprene concentration of 2% v / gaseous effluent flow rate of 8 L / min, the total amount of isoprene produced by the fermenter over the 1.6 hour period was approximately 40 g, of which about 30% was collected, resulting in a theoretical concentration in the range of 10 to 12 g / L of isoprene in the solvent. Following the completion of the process, the solution was removed from the
66/74 gas purifier for subsequent analysis, rectification and condensation, to recover the pure liquid isoprene.
Example 3 consists of an analysis of the isoprene solution.
The isoprene solution generated by the gas absorption described above was analyzed to determine the isoprene content and the identity of the main impurities, using both the free space method and the liquid CG / EM (gas chromatography / mass spectrometry) method . The isoprene concentration was determined using a free space method, whereby 1 ml of the isoprene solution was placed in a flask containing 20 ml of free space, and incubated at 40 ° C for 5 minutes before an injection of 100 pL in free space. The GC / MS method used helium as the carrier gas at 1 mL / min, an inlet temperature of 230 ° C and a 100: 1 split ratio. A Zebron TM ZB-5 GC column (30 mx 0.25 mm x 0.25 pm, obtained from Phenomenex, Torrance, California, USA) was used, with the mass spectrometer detector working in SIM mode for monitoring am / z ions 41, 56, 68, 69, 71 and 86. Heating started at 50 ° C, was maintained for 2 minutes, followed by an increase to 75 ° C at a rate of 20 ° C / min and, then increased to 250 ° C at a rate of 35 ° C / min. The final temperature of 250 ° C was maintained for 0.75 minutes, for a total run time of 9 minutes. Under these conditions, the isoprene eluted at 1.68 minutes and the hydrocarbons derived from solvent L eluted between 5.5 and 6.5 minutes. The method was calibrated using isoprene / solvent standards in the concentration range from 1 mg / mL to 20 mg / mL. The concentration of the isoprene / solvent composition generated in Example 2 was determined to be 9.4 g / L, using this method.
For the identification of biological by-product impurities present in the isoprene solution, a liquid GC / MS method was used whereby a 1 pL sample was injected into a CG inlet maintained at 250 ° C with a 20: 1 division ratio , using helium as the carrier gas at a flow rate of 1 mL / min. The Zebron ZB-5 GC column (30 m x 0.25 mm x 0.25 um) was used, with the mass spectrometer detector
Q7Í7A operating in scan mode for ion monitoring between m / z 29 and 350. Heating started at 50 ° C, was maintained for 2 minutes, followed by an increase to 320 ° C at a rate of 20 ° C / min with a final maintenance time of 2.5 minutes for a total operating time of 18 minutes. Under these conditions, as shown in figure 3, the isoprene eluted at 1.69 minutes (horizontal axis) and the hydrocarbons derived from the solvent eluted between 5.5 and 9 minutes. Several impurities of biological by-product have been identified (see Table 2), in addition to low molecular weight saturated hydrocarbons derived from the solvent. Note that some of these impurities have, by themselves, commercial value and could be further isolated as biological by-products using well-known methods in an industrial scale version of the present purification process.
Table 2
Compound Retention time (min) Ethanol 1.59 Acetone 2.65 3-methyl-3-buten-1-ol 3.02 3-methyl-2-buten-1-ol 3.48 3-methyl-2-buten-1-yl acetate 4.69
Figure 4 is an expansion of the left portion of the CG / EM spectrum of figure 3, from 1.6 minutes to 4.8 minutes (horizontal axis).
Example 4 consists of rectification and condensation of liquid isoprene from isoprene / solvent solutions.
Two methods (mentioned above) were used to recover liquid isoprene from generated isoprene / solvent solutions as described in Example 2:
(a) In a laboratory scale process, the rectification of the isoprene from the solvent was obtained by transferring the isoprene / solvent solution to a 1 L flask with a round bottom and 3 necks, equipped with a style distillation head Dewar type for laboratory and cooled by dry ice (catalog number CG-1251, available from Chemglass, Vineland, New Jersey, USA), a spreader inlet
68/74 gas and a stir bar. The condenser was equipped with a 50 mL receiving flask for the liquid isoprene product. The outlet of the device was passed through a cooling trap filled with dry ice and a bubbler to monitor the gas flow. The flask was heated to 80 ° C in an oil bath, and nitrogen gas bubbled through the solution at a rate of less than 1 L / minute. Over 2 hours, the liquid isoprene (about 4 mL) was collected in the receiving flask.
(b) The apparatus described in (a) above was modified by coupling a 3-stage Snyder distillation column, coupled between the 3-necked flask and the condenser. The temperature of the oil bath was raised to 120 ° C. In this case, steam was used instead of nitrogen gas, the flow of which was adjusted to maintain a temperature gradient in the distillation column, in the range of 100 ° C at the bottom to 34 ° C at the top. Over 2 hours, the liquid isoprene (about 6 mL) was collected in the receiving flask.
The analysis of the solvent following this distillation was performed using the free space and CG / MS method described in Example 3, in order to determine the extent to which the isoprene was rectified from the solvent. The results are shown in Table 3:
Table 3
Rectification method Concentration of isoprene in the solvent (g / L) Grinding efficiency Initial Final Nitrogen 8.55 5.52 41% Steam 9.38 3.84 55%
Example 5 is an analysis of liquid isoprene recovered by absorption / rectification using solvent.
The liquid isoprene generated as described in Example 4 was analyzed using the CG / FID (gas chromatography / flame ionization detector) and CG / EM methods, to assess general purity and to identify both biological by-products and other impurities gifts. The CG / FID analysis was performed using a DB-Petro column (100 m x 0.25 mm, with 0.50 µm film thickness, available from Agilent
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Technologies, Santa Clara, California, USA) maintained at 50 ° C for 15 minutes. The method used helium as the carrier gas at a flow rate of 1 mL / min. The injection port was maintained at 200 ° C and operated in non-split mode. An Agilent 5793N mass selective detector was operated in full scan mode from m / z 19 to m / z 250. Figure 5 is a CG / FID plot of the isoprene recovered from the solvent in this example. Under these conditions, the isoprene was observed to elute at 13.4 min, and the impurities of biological by-product and impurities derived from volatile solvent between 12.6 and 23.0 minutes. The solvent hydrocarbons eluted between 27 and 29.5 minutes.
Example 6 consists of removing polar impurities from the biological by-product of the solvent in a final purification process, as mentioned above.
The polar impurities of biological by-product present in the isoprene-solvent mixture were removed by passing over an adsorbent as described above, in particular adsorbents based on silica and alumina. For example, the solvent solution (100 ml_) obtained after the rectification of the isoprene (see Example 4) was pumped through a bed of Selexsorb CDX adsorbent (10 g of Selexsorb CDX, available from BASF) over 20 minutes , the filtered solvent being analyzed by CG / FID. The chromatogram (not shown) demonstrated that most of the biological by-product impurities were removed. Alternatively (see below), a silica-based adsorbent can be used.
Figure 6 shows an example of an adsorbent process apparatus (such as system 36 in figure 1) where the outlet of the isoprene solution from the upstream portion of the apparatus in figure 1 is initially maintained in the feed tank (reservoir) 80. A flow of nitrogen gas is supplied via flow line 82 to reservoir 80, to maintain a pressure of about 608 kPa (90 PSI (pounds per square inch, about 6 atmospheres) measured at pressure regulator P), for example through the V1 valve. The valve V2 admits the pressurized isoprene solution to the valves V3 and V4, between which a pump 90 is attached. The pumped solution is transported by the transfer line 94 via valve V5 to
70/74 a conventional adsorption bed 98, which is a bed of alumina, silica or other adsorbent, as described above, as Selexsorb CDX, housed in a conventional housing 100.
A second flow of nitrogen gas is provided through valves V8 and V6, with the interposition of rotameter 104 to measure the gas flow. This second flow of nitrogen gas is coupled to bed 98. As is conventional, the nitrogen gas in valve V6 and the isoprene solution in valve V5 are supplied alternately to allow purging with nitrogen gas from the adsorbent in bed 98. Pure remove the impurities present in the isoprene solution, which were adsorbed by the bed. This process allows impurities to be vented with the purging of nitrogen gas via the V5 valve, during this regeneration of the bed. The V9 and V10 valves connect a chiller / heater unit 108 to the bed 98, to keep both the purging nitrogen gas and the isoprene solution at their appropriate temperatures. Finally, the resulting purified isoprene solution leaves via transfer line 110 (which has a second pressure regulator P) and valve V7.
In a laboratory-scale example, the isoprene derived from a bioisoprene composition (1 ml_ with the addition of 150 ppm TBC) was treated with a microsphere (diameter 3 mm, ie 1/8, about 90 mg by weight ) of Selexsorb® CD or Selexsorb® CDX, in a CG bottle, for 1 hour with occasional stirring. Selexsorb® products changed color from white to yellow within 10 minutes. The samples were analyzed by gas chromatography / mass spectrometry, and the spectra were overlaid to highlight the degree to which impurities were removed. The extent of the removal of polar impurities has been determined, and the results are shown in Table 3A.
Table 3A
Compound Selexsorb® CD Selexsorb® CDX Ethanol > 90% > 90% Acetone > 90% > 90% Methacrolein > 90% > 90% Ethyl acetate > 90% > 90%
ΊΑΠΑ
Compound Selexsorb® CD Selexsorb® CDX 3-methyl-3-buten-2-ol > 90% > 90% Methyl vinyl ketone > 90% > 90% 2-vinyl-2-methyloxyrane > 90% > 90% 3-methyl-3-buten-1-ol 94% 96% 3-methyl-3-buten-1-yl acetate 68% 75%
Additional isoprene purification - liquid extraction
As explained above and shown in figure 6, it is desirable to further purify the isoprene solution, which typically contains a number of impurities of various types. In one embodiment, further purification was achieved using the liquid extraction method, mentioned above, to remove semipolar impurities.
It has been determined that a significant difference between conventional petroleum-derived isoprene and the present fermentation-derived bioisoprene is the presence, in the isoprene of the type obtained by fermentation, of large amounts of biological (bio) by-products, which are polar in nature refers to your chemistry. These impurities are in chemical classes that include acetates, alcohol, ketones and acids, as described above. These impurities interfere or inhibit the subsequent and necessary polymerization of the isoprene as described above and, therefore, need to be removed from the recovered isoprene, before the downstream polymerization step. The adsorbent process described with reference to figure 6 in general would not remove these polar impurities.
It has been found that placing the bioisoprene in contact with deionized water (Dl) or with a solution of deionized water and base (alkaline) removes a significant amount of these impurities. Multiple contacts with water or aqueous alkaline solution will reduce impurities to any desirable content. In yet another example, Table 4 shows (left column) the various impurities, the proportion of the impurity removed in this example by contacting an equal volume of aqueous alkaline solution (center column), and (right column) the proportion of the impurity removed through contact with an equal volume of deionized water.
Ί2Π4
Table 4
Impurity (0.1 M in n-hexane) Percentage removed (contact with equal volume of (10)% by weight of NaOH) Percentage removed(contact with equal volume of deionized water) 2-methylfuran 2.6% 0.4% Methanol 100.0% 100.0% Prenol 55.7% 18.3% Acetone 71.2% 90.1% Acetic Acid Coelute with hexane Methyl isobutyrate 89.3% 9.1% Methyl acetate 38.3% 24.2% Dimethyl disulfide 4.4% 2.6%
Thus, it was discovered that the water and base (alkaline) process in the second column of Table 4 was effective in removing all these impurities to a large extent, except for 2-methylfurane and dimethyl disulfide. Only a small proportion of these two impurities have been removed. However, it was found that 2-methylfuran is not significant in terms of preventing polymerization. Therefore, dimethyl sulfide is the remaining impurity of key importance. It is well known that dimethyl disulfide is a particularly potent polymerization poison.
An apparatus for performing this caustic washing process is conventional, and could include a suitable container to contain the caustic solution and into which a volume of isoprene solution is pumped. The container would be equipped with a suitable stirring or mixing device, since the isoprene solution is not miscible with water. This is due to the reference above regarding placing the isoprene solution in contact with the caustic solution for an interval long enough to obtain the desired extraction of impurities in the caustic solution. Then, the caustic solution is conventionally separated from the purified isoprene solution. This caustic washing process can be a conventional batch process or a continuous process. This caustic washing process can be carried out upstream or downstream
73/74 of the adsorption system of figure 6. Or, the caustic washing and adsorption can be carried out together, for example by impregnating the silica or alumina adsorbent with a suitable caustic compound, as is known in the art. .
In addition, an effective way to remove dimethyl disulfide consists of the adsorption technique as described above with reference to figure 6. Figure 7 is a graph of impurities present in the bioisoprene along the moment (horizontal axis), where the peak on the right shows the concentration of dimethyl disulfide after an elution time (in a laboratory-type adsorbent bed purification apparatus) indicated along the horizontal axis. As seen, the initial concentration of dimethyl disulfide was quite high and then dropped substantially after treatment with an adsorption system having alumina, and dropped further after treatment with silica adsorption, until it was almost imperceptible.
Figure 8 also refers to this adsorbent technique and shows the time along the horizontal axis and, along the left vertical axis and the graph associated with the left side, the proportion of dimethyl disulfide present in the silica as a percentage of the silica. , and along the right vertical axis and the graph associated with the right side, the percentage of dimethyl disulfide present in the feed stream that is not absorbed by silica over time. Consequently, the effectiveness of the adsorption process decreased markedly, starting in about 60 minutes, as the adsorbent bed was loaded (saturated) with dimethyl disulfide. According to the left graph, the bed becomes saturated with about 38% of dimethyl disulfide. Hence the need to periodically purge (regenerate) the bed, as described with reference to figure 6.
Additionally, figure 9 shows, in terms of relative concentrations, the presence of nitrogen, isoprene and dimethyl disulfide in the isoprene solution at various times during the performance of the adsorption technique, showing the same effect as in figure 8. This illustrates the composition
14Π4 initial gas (pre-treatment) in the lower graph, continuing until the end of a process cycle in the upper graph, in which the dimethyl disulfide was essentially eliminated while the quantities of the other two compounds, which are dissolved nitrogen and isoprene, remained essentially the same. Note that at 120 minutes the peak of dimethyl disulfide reappears, when the saturated bed allows the dimethyl disulfide to pass.
The above examples, which are intended to be purely exemplary of the invention and should therefore not be considered in any way as limiting the invention, also describe and detail aspects and modalities of the invention discussed above. Unless otherwise noted, the temperature is in degrees Celsius and the pressure is equal to or close to atmospheric pressure. The aforementioned examples and detailed description are offered by way of illustration and without limitation. All publications, patent applications and patents cited in this specification are incorporated herein by reference, as if each publication, patent application, or individual patent were specifically and individually indicated to be incorporated by reference. In particular, all publications cited herein are expressly incorporated by reference for the purpose of describing and presenting compositions and methodologies that could be used in connection with the invention. Although the aforementioned invention has been described in some detail by way of illustration and example, for the sake of clarity and understanding it will be readily apparent to those skilled in the art, in light of the teachings of the present invention, that certain changes and modifications can be made to it without departing from the spirit or scope of the attached claims.
1/4

权利要求:
Claims (20)
[1]
1. Method for purifying isoprene from a gaseous effluent from the fermenter (12) characterized by the fact that it comprises the steps of:
5 place a gaseous effluent from the fermenter (12), comprising isoprene, volatile impurity and biological by-product impurity, in contact with a solvent in a first column (14), to form:
an isoprene-rich solution comprising the solvent, a major portion of the isoprene and a major portion of the biological by-product impurity present in the gaseous effluent, and a vapor comprising a portion of the volatile impurity present in the gaseous effluent;
transferring the isoprene-rich solution from the first column (14) 15 to a second column (24); and rectify the isoprene from the isoprene-rich solution in the second column (24), to form:
an isoprene-poor solution comprising a portion of the biological by-product impurity present in the gaseous effluent, and
20 is a purified isoprene composition, wherein the solvent:
has a Kauri-butanol value less than about 50;
has an aniline point greater than about 66 ° C;
has a kinematic viscosity at 40 ° C less than about
25 2.5 x 10 ^-6 m / s ² (2.5 centistokes (cSt));
has a surface tension at 25 ° C of about 20 to 30 dyne / cm; and / or has an average molecular weight of about 125 to about 225.
[2]
2. Method according to claim 1, characterized by the fact that the impurity of biological by-product comprises a polar impurity.
[3]
3. Method according to claim 1, characterized by the
Petition 870180045878, of 05/29/2018, p. 6/13
2/4 the fact that the amount of impurity of biological by-product in relation to the amount of isoprene, in the gaseous effluent, is greater than about 0.01% (weight / weight).
[4]
4. Method according to claim 1, characterized by the fact that the solvent further comprises a polymerization inhibitor.
[5]
5. Method according to claim 1, characterized by the fact that placing the gaseous effluent from the fermenter (12) in contact with a solvent in a first column (14) comprises supplying rectification steam from the bottom of the first column ( 14).
10
[6]
6. Method according to claim 1, characterized by the fact that placing the gaseous effluent from the fermenter (12) in contact with a solvent in a first column (14) comprises, in addition, adding steam to the first column (14).
[7]
Method according to claim 1, characterized by the
15 the fact that rectifying the isoprene from the isoprene-rich solution in the second column (24) comprises adding steam to the second column (24).
[8]
8. Method, according to claim 1, characterized by the fact that it also comprises:
purify the low isoprene solution to remove a portion
20 majority of the impurity of biological by-product; and transfer the low isoprene solution to the first column (14) for reuse.
[9]
9. Method, according to claim 8, characterized by the fact that purifying the solution low in isoprene comprises treating the
25 isoprene-poor solution with an adsorption system (32, 36, 38).
[10]
10. Method according to claim 8, characterized in that purifying the isoprene-poor solution comprises distillation.
[11]
11. Method according to claim 8, characterized by the fact that purifying the isoprene-poor solution comprises liquid-liquid extraction.
[12]
12. Method according to claim 1, characterized
Petition 870180045878, of 05/29/2018, p. 7/13
3/4 because it further comprises purifying the purified isoprene composition by distillation or adsorption.
[13]
13. Method, according to claim 1, characterized by the fact that it also comprises removing from the steam a portion of the
5 isoprene.
[14]
14. Method according to claim 1, characterized by the fact that the gaseous effluent from the fermenter (12) is supplied to the first column (14) at a pressure greater than atmospheric pressure.
[15]
15. Method according to claim 17, characterized in that the further purification comprises bringing the purified isoprene composition into contact with water or with a base and water.
[16]
16. Purified isoprene composition, characterized by the fact that it is prepared by the method as defined in claim 1.
[17]
17. Composition prepared by the method as defined in claim 1, characterized by the fact that it comprises isoprene and biological by-product impurity, in which the biological by-product impurity comprises C5 hydrocarbons, and in which there is more than about 99.94% of isoprene (weight / weight) in relation to the weight of C5 hydrocarbons, and less than about 0.05% of biological by-product (weight / weight) in
20 in relation to the weight of isoprene.
[18]
18. Composition according to claim 17, characterized by the fact that the impurity of biological by-product comprises one or more compounds selected from the group consisting of: 2-heptanone, 6-methyl-5-hepten-2-one, 2, 4,5-trimethylpyridine, 2,3,525 trimethylpyrazine, citronellal, acetaldehyde, methanethiol, methyl acetate, 1propanol, diacetyl, 2-butanone, 2-methyl-3-buten-2-ol, ethyl acetate, 2-methyl1-propanol , 3-methyl-1-butanal, 3-methyl-2-butanone, 1-butanol, 2-pentanone, 3methyl-1-butanol, ethyl isobutyrate, 3-methyl-2-butenal, butyl acetate, 3 -methyl butyl, 3-methyl-3-but-1-enyl acetate, 3-methyl30 2-but-1-enyl acetate, (E) -3,7-dimethyl-1,3,6-octatriene, ( Z) -3,7-dimethyl-1,3,6-octatriene, (E, E) -3,7,11-trimethyl-1,3,6,10-dodecatetraene and (E) -7,11-dimethyl -3-methylene1,6,10-dodecatriene.
Petition 870180045878, of 05/29/2018, p. 8/13
ΑΙΑ
[19]
19. Composition according to claim 17, characterized in that it comprises even less than about 5% volatile impurity in relation to the weight of the composition.
[20]
20. Composition that is an isoprene-rich solution prepared 5 by the method as defined in reivication 1, characterized by the fact that it comprises:
a solvent; isoprene; and a biological by-product impurity being a smaller portion 10 of the solution than isoprene.
Petition 870180045878, of 05/29/2018, p. 9/13
1/9

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法律状态:
2018-03-13| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2018-07-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2018-09-18| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/12/2010, OBSERVADAS AS CONDICOES LEGAIS. |

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2021-10-13| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 11A ANUIDADE. |

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2022-02-01| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2649 DE 13-10-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |

优先权:

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申请号 | 申请日 | 专利标题

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US28814209P| true| 2009-12-18|2009-12-18|

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PCT/US2010/060552|WO2011075534A2|2009-12-18|2010-12-15|Purification of isoprene from renewable resources|

---