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Timestamp: 2014-10-26 08:07:41
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Matched Legal Cases: ['Application No. 07008768', 'Application No. 00917888', 'Application No. 07008768', 'Application No. 514253', 'Application No. 514253', 'Application No. 2004200701', 'Application No. 38794', 'Application No. 2004200701', 'Application No. 38794', 'Application No. 2004200701', 'Application No. 38794', 'Application No. 00804895', 'Application No. 00804895', 'Application No. 00917888', 'Application No. 00917888', 'Application No. 200580008137']

Patent US7601865 - Introducing tertiary amine and CO2 to dilute salt solution to form acid ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA method is disclosed for the recovery of an organic acid from a dilute salt solution in which the cation of the salt forms an insoluble carbonate salt. A tertiary amine and CO2 are introduced to the solution to form the insoluble carbonate salt and a complex between the acid and an amine. A water immiscible...http://www.google.com/patents/US7601865?utm_source=gb-gplus-sharePatent US7601865 - Introducing tertiary amine and CO2 to dilute salt solution to form acid/amine complex and insoluble carbonate salt, introducing water immiscible solvent to dilute salt solution to form reaction phase, continuously drying reaction phase and forming productAdvanced Patent SearchPublication numberUS7601865 B2Publication typeGrantApplication numberUS 11/046,206Publication dateOct 13, 2009Filing dateJan 28, 2005Priority dateJan 29, 2004Fee statusPaidAlso published asCN1938257A, EP1708984A1, EP1708984A4, US8048655, US20050256337, US20100187472, US20120112127, WO2005073161A1Publication number046206, 11046206, US 7601865 B2, US 7601865B2, US-B2-7601865, US7601865 B2, US7601865B2InventorsDan W. Verser, Timothy J. EggemanOriginal AssigneeZeachem, Inc.Export CitationBiBTeX, EndNote, RefManPatent Citations (90), Non-Patent Citations (67), Referenced by (111), Classifications (17), Legal Events (6) External Links: USPTO, USPTO Assignment, EspacenetIntroducing tertiary amine and CO2 to dilute salt solution to form acid/amine complex and insoluble carbonate salt, introducing water immiscible solvent to dilute salt solution to form reaction phase, continuously drying reaction phase and forming productUS 7601865 B2Abstract A method is disclosed for the recovery of an organic acid from a dilute salt solution in which the cation of the salt forms an insoluble carbonate salt. A tertiary amine and CO2 are introduced to the solution to form the insoluble carbonate salt and a complex between the acid and an amine. A water immiscible solvent, such as an alcohol, is added to extract the acid/amine complex from the dilute salt solution to a reaction phase. The reaction phase is continuously dried and a product between the acid and the solvent, such as an ester, is formed.
a. introducing a tertiary amine and CO2 to the dilute salt solution to form an acid/amine complex and the insoluble carbonate salt;
b. introducing a water immiscible solvent to the dilute salt solution to form a reaction phase comprising the acid/amine complex and the water immiscible solvent;
c. continuously drying the reaction phase; and
2. The method, as claimed in claim 1, wherein the water immiscible solvent is an alcohol.
3. The method, as claimed in claim 1, wherein the water immiscible solvent is an alcohol and the acid/solvent product is an ester.
4. The method, as claimed in claim 3, wherein the water immiscible solvent has a distribution coefficient of at least about 0.5.
5. The method, as claimed in claim 1, wherein the alcohol is selected from the group consisting of n-octanol, n-hexanol, n-pentanol, and n-butanol.
6. The method, as claimed in claim 1, wherein the water immiscible solvent is a mixed solvent comprising a solvent reactive with the acid portion of the acid/amine complex to form an acid/solvent product and a solvent that is inert with the acid portion of the acid/amine complex.
7. The method, as claimed in claim 1, wherein the water immiscible solvent has a distribution coefficient of at least about 0.5.
8. The method, as claimed in claim 1, wherein the water immiscible solvent has a distribution coefficient of at least about 0.75.
9. The method, as claimed in claim 1, wherein the water immiscible solvent has a distribution coefficient of at least about 1.
10. The method, as claimed in claim 1, wherein the water immiscible solvent has a selectivity value of at least about 8.
11. The method, as claimed in claim 1, wherein the water immiscible solvent has a selectivity value of at least about 15.
12. The method, as claimed in claim 1, wherein the water immiscible solvent has a selectivity value of at least about 20.
13. The method, as claimed in claim 1, wherein the tertiary amine is selected from the group consisting of tributylamine and dicyclohexyl methyl amine.
14. The method, as claimed in claim 1, wherein the organic acid is selected from the group consisting of acetic acid, lactic acid, propionic acid, butyric acid, succinic acid, citric acid, 3-hydroxypropionic acid, glycolic acid, and formic acid.
15. The method, as claimed in claim 1, wherein the step of continuously drying the reaction phase comprises a process selected from the group of removing water as an azeotrope with the solvent by azeotropic distillation and removing water by contacting the reaction phase with a water adsorbent.
16. The method, as claimed in claim 1, wherein the solvent is an alcohol and the step of forming the acid/solvent product comprises forming an ester between the acid and the alcohol by the production of water.
17. The method, as claimed in claim 1, wherein the water immiscible solvent is an alcohol and wherein the step of forming the acid/solvent product comprises adding a strong acid catalyst selected from the group consisting of a Lewis acid and a Br�nsted acid catalyst to the solvent.
18. The method, as claimed in claim 1, wherein the water immiscible solvent is an alcohol and wherein the step of forming the acid/solvent product comprises adding a strong acid catalyst to the solvent, wherein the strong acid catalyst is selected from the group consisting of acid catalysts having a pKa less than the organic acid.
19. The method, as claimed in claim 18, wherein the strong acid catalyst is selected from the group consisting of sulfuric acid, hydrochloric acid and methane sulfonic acid.
20. The method, as claimed in claim 1, further comprising separating the acid/solvent product, the tertiary amine and the solvent.
21. The method, as claimed in claim 20, wherein the separated tertiary amine is used as the tertiary amine in step (a).
22. The method, as claimed in claim 20, wherein the separated solvent is used as the solvent in step (b).
23. The method, as claimed in claim 20, wherein the step of separating comprises distilling the acid/solvent product from the tertiary amine and the solvent.
24. The method, as claimed in claim 23, wherein the step of separating comprises distilling the solvent from the tertiary amine.
25. The method, as claimed in claim 20, wherein the solvent is an alcohol and the acid/solvent product is an ester and the method further comprises hydrogenating the ester to form an alcohol of the acid and regenerate the solvent alcohol.
26. The method, as claimed in claim 25, further comprising dehydrating the alcohol of the acid to form an olefin product.
27. The method, as claimed in claim 25, wherein the regenerated solvent is used as the solvent in step (b).
28. The method, as claimed in claim 25, wherein the solvent is an alcohol and the acid/solvent product is a first ester and the method further comprises transesterifying the first ester with a second alcohol to form a second ester.
29. The method, as claimed in claim 20, wherein the solvent is an alcohol and the acid/solvent product is an ester and the method further comprises hydrolyzing the ester to form the acid and regenerate the solvent alcohol.
30. The method, as claimed in claim 29, wherein the regenerated solvent is used as the solvent in step (b).
31. A method for recovery of an organic acid from a dilute salt solution comprising a calcium salt of an organic acid, comprising:
a. introducing a tertiary amine and CO2 to the dilute salt solution to form an acid/amine complex and calcium carbonate;
b. mixing the dilute salt solution with a water immiscible alcohol having a distribution coefficient of at least about 0.5, whereby the acid/amine complex is extracted into the water immiscible alcohol;
c. continuously drying the water immiscible alcohol; and
d. forming an ester from the acid and the water immiscible alcohol to produce a mixture comprising the ester, residual water immiscible alcohol, and the tertiary amine.
32. A method for recovery of an organic acid selected from the group consisting of acetic acid, lactic acid, and propionic acid from a fermentation broth comprising a calcium salt of the organic acid, comprising:
a. introducing a tertiary amine selected from the group consisting of tributylamine and dicyclohexyl methyl amine and CO2 to the dilute salt solution to form an acid/amine complex and calcium carbonate;
b. mixing the dilute salt solution with a water immiscible alcohol selected from the group consisting of octanol, hexanol, pentanol, and butanol, whereby the acid/amine complex is extracted into the water immiscible alcohol;
c. continuously drying the water immiscible alcohol;
d. forming an ester from the acid and the water immiscible alcohol to produce a mixture comprising the ester, residual water immiscible alcohol, and the tertiary amine;
e. separating the ester, the tertiary amine and the water immiscible alcohol;
f. using the separated tertiary amine as the tertiary amine in step (a);
g. using the separated water immiscible alcohol as the water immiscible alcohol in step (b);
h. treating the ester by a process selected from the group consisting of
i. hydrogenating the ester to form an alcohol of the acid and regenerate the solvent alcohol; p2 ii. transesterifying the ester with a second alcohol to form a second ester;
iii. hydrolyzing the ester to form the acid and regenerate the solvent alcohol.
33. A method for recovery of an organic acid from an acid/amine complex in an aqueous solution, comprising:
a. introducing a water immiscible solvent to the aqueous solution to form a reaction phase comprising the acid/amine complex and the water immiscible solvent and an aqueous phase;
b. continuously drying the reaction phase; and
c. forming a product of the acid and the water immiscible solvent.
34. The method, as claimed in claim 17, wherein the acid catalyst is selected from the group consisting of a cationic ion exchange resin, a strong mineral acid, and a strong organic acid.
35. A method for recovery of an organic acid from a dilute salt solution comprising an organic acid salt, the cation of which forms an insoluble carbonate salt, comprising:
b. introducing n-butanol to the dilute salt solution to form a reaction phase comprising the acid/amine complex and the n-butanol;
d. forming an ester of the acid and the n-butanol by adding a strong reactive acid catalyst to the solvent, said strong reactive acid catalyst selected from the group consisting of sulfuric acid, hydrochloric acid and methane sulfonic acid.
CROSS-REFERENCE TO RELATED APPLICATIONS The present application claims priority from U.S. Provisional Patent Application Ser. No. 60/540,606, filed Jan. 29, 2004, and from U.S. Provisional Patent Application Ser. No. 60/550,659, filed Mar. 5, 2004, and from U.S. Provisional Patent Application Ser. No. 60/570,134, filed May 10, 2004. All three provisional applications are incorporated herein by reference in their entirety.
GOVERNMENT SUPPORT This invention was supported in part with funding provided by Grant No. DE-FG36-03GO13010, awarded by the United States Department of Energy. The government may have certain rights to this invention.
BACKGROUND OF THE INVENTION Organic acids are valuable products in their own right as food and feed ingredients, for example, or as intermediates. Organic acids can be converted chemically to alcohols, which can subsequently be converted to olefins. Such a process could be envisioned as the basis for a biorefinery to convert biomass resources into a range of products for the energy and chemical industries. Organic acids can be produced by fermentation at very high carbon yield from a wide range of biomass resources.
One reason why fermentation routes have failed to compete is that the micro-organisms used to produce these acids are inhibited by low pH. In order to achieve high yields, the pH of the fermentation step has to be kept near neutral by the addition of a base such as ammonia, sodium hydroxide or calcium hydroxide. In addition, even at neutral pH, the acids generally inhibit the growth of the organisms used in the fermentation and limit the broth to low concentrations of the acid salt. Thus, the fermentation routes typically produce a dilute aqueous solution of the organic acid salt rather than the organic acid in its protonated form. The salts are highly water-soluble, have a negligible vapor pressure and the carbonyl group is unreactive. These properties make recovery of the salt difficult since distillation, extraction, crystallization and other common industrial separation methods for large-scale production are either technically or economically infeasible.
Recovery of fermentation-derived acetate has been summarized by Busche (Busche, R. M., �Recovering Chemical Products from Dilute Fermentation Broths�, Biotechnology and Bioengineering Symp. No. 13, p. 597-615, 1983 and co-workers at Du Pont (Busche et al., �Recovery of Acetic Acid from Dilute Acetate Solution�, Biotechnology and Bioengineering Symp. No. 12, p. 249-262, 1982) and by Partin and Heise, 1993.
Once the organic acid has been produced in solution in its protonated form by direct acidification, various means can be used for its recovery from the broth (Othmer, �Acetic Acid Recovery Methods�, Chemical Engineering Progress, Vol. 54, No. 7, July, 1958, Baniel et al., U.S. Pat. No. 4,275,234). For example, solvent extraction of organic acids from dilute solution has been studied in detail. (King, et al., �Solvent Equilibrium for Extraction of Carboxylic Acids from Water�, Journal of Chemical and Engineering Data, Vol. 23, No. 2, 1978). Baniel (U.S. Pat. No. 5,780,276) also mentions the use of enhancers in extraction of amines including small amounts of alcohols. However, Baniel (U.S. Pat. No. 5,780,276) provides processes for the recovery of the small amount (10%) of enhancer alcohol and does not suggest its reaction with the organic acid.
Although not considered by Busche (Busche, 1983), reactive distillation converts a carboxylic acid (a high boiler) into volatile ester (a low boiler), thus sidestepping the energy penalty associated with boiling water. (Xu and Chuang, �Kinetics of Acetic Acid Esterification over Ion Exchange Catalysts�, Can. J. Chem. Eng., pp. 493-500, Vol. 74, 1996, Scates et al, �Recovery of Acetic Acid from Dilute Aqueous Streams Formed During a Carbonylation Process�, U.S. Pat. No. 5,599,976, Feb. 4, 1997).
Many advances have been made in membrane processes during the last two decades. Crossflow microfilters and ultrafilters are routinely used to clarify broths by removing cell mass and insoluble materials. Further clarification by nanofiltration removes high molecular weight soluble impurities such as proteins and residual carbohydrates, and provides the additional benefit of concentrating the organic acid salt prior to downstream recovery. Bipolar electrodialysis can be used to acidify the broth. A patent assigned to Chronopol, Inc. (Miao, �Method and Apparatus for the Recovery and Purification of Organic Acids�, U.S. Pat. No. 5,681,728, Oct. 28, 1997) gives an example of how to sequence the various membrane units to recover and acidify lactic acid from a fermentation broth. Economics for membrane-based processes are favorable today for high value, low volume products. Scale-up of capital cost is nearly linear, so membrane systems are not always competitive for large-scale production of bio-commodities unless high flux is achieved. This is especially true when considering the more complex membrane processes such as bipolar electrodialysis.
Work at DuPont (Yates, �Removal and Concentration of Lower Molecular Weight Organic Acids From Dilute Solutions�, U.S. Pat. No. 4,282,323, Aug. 4, 1981 and Busche et. al., 1982) discusses the use of carbon dioxide as an acidulant to convert fermentation-derived acetate salts into acetic acid and subsequent solvent extraction. Researchers at Cargill (Baniel et. al., �Lactic Acid Production, Separation, and/or Recovery Process�, U.S. Pat. No. 5,510,526, Apr. 23, 1996) have investigated a related method for recovery of lactate by acidification with CO2 and concurrent extraction with an amine. However, this reaction requires high pressure and produces multiple phases (4) at the same point in the process.
Researchers at CPC International (Urbas, �Recovery of Acetic Acid from a Fermentation Broth�, U.S. Pat. No. 4,405,717, Sep. 20, 1983 and Urbas, �Recovery of Organic Acids from a Fermentation Broth�, U.S. Pat. No. 4,444,881, Apr. 24, 1984) also discuss the use of carbon dioxide as an acidulant. Tributylamine (TBA) is normally immiscible with water, but the tributyl amine: acetic acid complex (TBA:HAc) is water soluble. When a dilute aqueous solution of calcium acetate at near neutral pH is mixed with TBA, and then carbon dioxide is bubbled through the mixture, the following reaction occurs at or near ambient temperatures:
Ca(Ac)2+H2O+CO2+2 TBA=>2 TBA:HAc+CaCO3 Use of a stoichiometric amount of TBA produces a single aqueous liquid phase containing the tributyl amine:acetic acid complex. The reaction is driven to the right since calcium carbonate precipitates upon formation. The amine must be suitably chosen such that its acid/amine complex is completely water soluble. Urbas (Urbas, U.S. Pat. No. 4,405,717) also mentions dicyclohexyl methyl amine.
The production of esters of organic acids is well known. Esters have been used as an intermediate in the recovery and purification of organic acids. Methods such as reactive distillation as mentioned previously can be used if the acid is in the protonated form, i.e., the free acid. (Benninga 1990, Scates) Various catalysts have been explored to facilitate this reaction including cationic ion exchange resins, strong mineral acids such as sulfuric, hydrochloric and nitric, and strong organic acids such as methane sulfonic acid or toluene sulfonic acid. (Xu and Chuang, 1996, Filachione et al., �Production of Esters�, U.S. Pat. No. 2,565,487, Aug. 28, 1951)
Direct esterification of acid/amine complexes have been reported by several groups (Filachione, 1951, Tung et al, �Sorption and Extraction of Lactic and Succinic Acids at pH>pKa, 2. Regeneration and Process Considerations�, Industrial and Engineering Chemistry, Vol. 33, pgs. 3224-3229, 1994, Sterzel et al, �Preparation of Lactates, U.S. Pat. No. 5,453,365, Sep. 26, 1995). Each of these references reports the esterification of the concentrated complex in which the bulk of the water is removed by evaporation or distillation overhead. Thus, these processes suffer from the energy penalty of vaporizing the water.
The hydrogenation or hydrogenolysis of esters to produce an alcohol from the organic acid moiety and to regenerate the alcohol of the ester is well known. McKee, WO 00/53791 Alcohols produced by hydrogenation of esters can also be converted to an olefin derived from the organic acid moiety. The dehydration of alcohols to olefins has been described (Tsao et al., �Dehydrate Ethanol to Ethylene�, Hydrocarbon Processing, 57(2), p. 133-136, February 1978). The process has been practiced at the commercial scale for ethanol dehydration to ethylene. The process is carried out in a fluidized bed with a phosphoric acid catalyst on an inert support.
SUMMARY OF THE INVENTION One embodiment of the present invention is a method for recovery of an organic acid from a dilute salt solution that includes an organic acid salt. The cation of the salt forms an insoluble carbonate salt. The method includes introducing a tertiary amine and carbon dioxide to the dilute salt solution to form an acid/amine complex, as well as the insoluble carbonate salt. A water immiscible solvent is introduced to the dilute salt solution to form a reaction phase that includes the acid/amine complex and the water immiscible solvent. The method further includes continuously drying the reaction phase and forming a product between the acid and the water immiscible solvent.
The step of forming the acid/solvent product can comprise forming an ester between the acid and an alcohol solvent by the production of water. Further, the step of forming the acid/solvent product can include adding a catalyst to the solvent. The catalyst can be a strong acid catalyst, such as acid catalysts having a pKa less than the organic acid and solid catalysts. The catalyst can be selected from sulfuric acid, hydrochloric acid and methane sulfonic acid.
BRIEF DESCRIPTION OF THE FIGURES FIG. 1 is a block flow diagram of an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION In one embodiment of the present invention, a method for recovery of an organic acid from a dilute salt solution is provided. The dilute salt solution includes an organic acid salt, the cation of which forms an insoluble carbonate salt. The process includes introducing a tertiary amine and CO2 to the salt solution to form an acid/amine complex and the insoluble carbonate salt. The process further includes introducing a water immiscible solvent to the dilute solution to form a reaction phase that includes the acid/amine complex in the water immiscible solvent. The reaction phase is continuously dried. The method further includes forming a product of the acid and the water immiscible solvent.
The step of introducing a tertiary amine and CO2 to the dilute salt solution is typically conducted at near neutral pH while the solution is mixed with the tertiary amine with the CO2 being bubbled through the mixture. In this manner, the organic acid salt reacts with water, CO2 and the tertiary amine to form an acid/amine complex and the insoluble carbonate salt. The carbonate salt will fall out of the solution, thereby driving the reaction in the direction of forming the acid/amine complex, essentially to completion. A significant advantage of the present invention is that this reaction can be conducted under ambient conditions of temperature and pressure and at near neutral pH, such as the pH of a fermentation broth.
In addition, the step of forming the product can further include addition of a catalyst to the solvent. For example, the catalyst can be a strong acid catalyst, such as a catalyst having a pKa less than the organic acid and solid acid catalysts, including both Br�nsted and Lewis acids. In specific embodiments, the catalyst can be sulfuric acid, hydrochloric acid, and methane sulfonic acid.
Alternatively, when the acid/solvent product is an ester, the method for recovery of the organic acid can included hydrogenating the ester to form an alcohol of the acid and regenerate the solvent alcohol. Again, the regenerated solvent alcohol can be recycled for use as the water immiscible solvent. In this embodiment, the organic acid is recovered as an alcohol. The conditions for such a hydrogenation reaction are known to those of skill in the art. In a further embodiment, the alcohol of the acid can be dehydrated to form an olefin. The dehydration of alcohols to olefins has been described (Tsao et al. 1978), and the process has been practiced at the commercial scale. The process can be carried out in a fluidized bed with a phosphoric acid catalyst on an inert support. Similarly, the production of propionic acid by fermentation, conversion to propanol by hydrogenation of a suitable ester and dehydration to propylene is known. (Playne, Comprehensive Biotech, Chapter 37).
Concentrations of acid/amine complex in both aqueous and organic solutions were determined by potentiometric titration of 10-20 ml samples diluted with 30 ml of methanol and titrated with standardized KOH in methanol following the method of Ricker, et. al., �Solvent Properties of Organic Bases for Extraction of Acetic Acid from Water�, Journal of Separation Process Technology, Vol. 1, No. 1, 1979.
Example 1 500 ml of an aqueous calcium acetate solution (0.6 molar as acetate) was added to a 1 liter graduated cylinder and the pH was adjusted to 6.9-7.0 using acetic acid. A 5% molar excess of TBA was added, which formed a separate layer, then the solution was sparged with CO2 for 30 minutes at ambient pressure. The liquid mixture became homogeneous with a single layer. A copious white precipitate of CaCO3 was formed. The solution was filtered, the CaCO3 cake was washed once with water, washed again with acetone, dried and then weighed. The acidification experiments were conducted four times with CaCO3 yields ranging from 91.0-96.1% of theoretical. The resulting CaCO3 precipitates were easy to filter and wash. A fine white powder was generated in all cases.
Example 2 The experiment of Example 1 was scaled down to about 50 mls. Side by side experiments were conducted using the acetate solution from Example 1, 0.6 molar calcium lactate, 0.6 molar calcium propionate. After gassing with CO2 for 30 minutes each reaction produced the same volume of CaCO3 precipitate.
Example 3 Example 2 was reproduced except that instead of gassing with CO2, the reaction mixture was gassed with a mixture of nitrogen and CO2 in a ratio of N:CO2 of 10:1. The results were identical to those of Example 2.
Example 4 An experiment similar to Example 2 was run using only the acetate solution, but substituting trioctyl amine for the TBA. After gassing with CO2 for 30 minutes there was no obvious reaction at all. There was no CaCO3 precipitate and there were still two liquid layers. It is believed that trioctyl amine failed to react due to the acid/amine complex not being soluble in the calcium acetate solution.
Example 5 An experiment similar to Example 1 was run, except that a sodium acetate solution was used. No reaction appeared to have taken place. It is believed that since NaCO3 is soluble and does not precipitate, that a reaction forming an acid/amine complex was not driven forward.
Example 6 This example illustrates the use of a variety of water immiscible solvents for extraction of an acetic acid/TBA complex from water.
All extraction experiments were conducted at room temperature (25� C.). For solvent screening, typically 100 g of an aqueous mixture containing 4.08 g of acetic acid (HAc) and 12.56 g of TBA, a 1:1 molar ratio, were mixed in a separatory funnel with 100 g of organic solvent. The mixture was shaken by hand and then allowed to separate. Each phase was recovered and weighed. Samples were taken and analyzed for acid/amine by the method of Ricker (Ricker et al., 1979) described above, and water by Karl Fischer.
Distribution Coefficient�KD 2-octanone
Example 7 This example illustrates the use of a series of higher alcohols (n-butanol, n-pentanol, n-hexanol, and n-octanol) for extraction of an acetic acid/TBA complex from water.
Example 8 This example shows the steps for recovery of propionic acid from a dilute salt solution using a process of the present invention.
A TBA/Pr amine/acid complex was prepared by mixing 199.92 gms of H2O, 10.46 gms propionic acid, and 21.66 gms of TBA. 50 gms of the H2O/TBA/HPr solution was mixed with 50 gms of each of n-butanol, n-pentanol and n-hexanol in three flasks, and separated in a separatory funnel. TBA/HPr in the organic phase was sampled and measured by the method of Ricker et al., 1979. The distribution coefficients for each of the three solvents were determined to be: n-butanol�1.39; n-pentanol�1.46; and n-hexanol�1.38.
Example 9 This example shows liquid-liquid phase equilibrium diagrams constructed for n-pentanol and n-hexanol. FIGS. 2 and 3 are the experimentally measured phase diagrams. The tie lines are created by varying the starting concentration of the TBA:HAc concentration in a series of extractions as described above. The two phase regions are fairly broad and the tie-lines have a favorable slope. Distribution coefficients become more favorable at higher TBA:HAc concentrations. Only a few stages are needed to produce a concentrated TBA:HAc extract from a dilute aqueous solution.
Example 10 This example shows the production of an acid/solvent product between acetic acid and the four alcohol solvents of Example 7. The n-hexanol solvent was run with and without a sulfuric acid catalyst.
A simple distillation of alcohol solvent and the acid/amine complex was conducted at atmospheric pressure (�630 mm Hg) in a glass still consisting of a electric heating mantle, a 1 liter round bottom flask, a vacuum jacketed 30 cm distillation column packed with 4 mm�4 mm glass rings, and an overhead condenser and product splitter allowing the removal of a variable amount of distillate and return of reflux to the column. A two-step process was observed. Initially, the water dissolved in the extract was removed by azeotropic distillation using the alcohol itself as the drying solvent for the extract producing a dry solution of the amine complex in the alcohol solvent. The overhead splitter was configured so that the water was removed continuously as it was produced and the solvent was returned to the still as reflux. All of the alcohols tested form heterogeneous azeotropes with water and forming two liquid phases overhead.
The esterification reactions were conducted in the setup described above, at atmospheric pressure (�630 mm Hg) for each of the solvents tested. 450 g of a room temperature solution containing a 3:1 molar ratio of alcohol to TBA:HAc complex were added to the still. The catalyzed run with n-hexanol included H2SO4 in the starting solution at a 0.1:1 mole ratio with respect to the TBA:HAc complex. The heating mantle was turned on and approximately thirty minutes later the solution began to boil. Water formed a second phase in the overheads as the reaction progressed. The water was collected and the volume recorded over time. Conversion was calculated as the percent of the maximum theoretical water if all of the acetic acid were converted to ester and confirmed by titration of residual TBA:HAc in the still pot samples. Ester formation was verified by gas chromatography using known ester samples as standards. The results of this experiment in terms of esterification yield are shown in Table 3.
Both esterification rate and yield increased with increasing molecular weight of the alcohol. Rather than being related to the chain length of the alcohol, this improvement in performance was probably caused by the higher boiling point and thus higher reaction temperature for the higher molecular weight alcohols. Adequate esterification rate and yield could be achieved with the lower molecular weight alcohols if the reaction was conducted at elevated pressure. The pressures required are not extreme; for example, n-butanol will boil at 170� C. and 482.6 kPa, well within the range of industrial importance.
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