Abstract:
A method for aging alcoholic liquids is disclosed, which utilizes an esterification catalyst to esterify alcoholic liquids in supercritical carbon dioxide, so as to significantly reduce the time required for aging of alcoholic liquids. The present invention also provides an apparatus for supercritical aging.

Description:
FIELD OF THE INVENTION 
       [0001]    The present invention relates to an apparatus and a method for aging alcoholic liquids, and more particularly to an apparatus and a method for aging alcoholic liquids using the supercritical technology. 
       DESCRIPTION OF PRIOR ART 
       [0002]    Traditionally, the aging of alcoholic liquids is most commonly achieved by the method of storage, in which alcoholic liquids may be stored in microporous casks or oak barrels and allowed to age naturally, thereby enhancing the aroma and the taste of the alcoholic liquids. In addition, the components in the alcoholic liquids that contribute to hangover and headaches, such as alcoholic impurities, ketone impurities, aldehyde impurities, and furan aldehydes; can be removed as a result. Though the method of aging alcoholic liquids by storage is natural, it has a major drawback of requiring long periods of time to allow the alcoholic liquids to age. 
         [0003]    Therefore, a number of other methods are commonly used to accelerate the aging of alcoholic liquids, which includes:
   (1) Via increasing the rate of oxygen infusion, which had been disclosed in the U.S. Pat. No. 6,966,250, and accelerates the aging of alcoholic liquids in the means of increasing the rate of oxygen infusion by approximately 50%. However, the acceleration in the aging of alcoholic liquids is limited (from multifold to more than tenfold), or the alcoholic liquids may become acidified.   (2) Via accelerating the esterification process by heating, as had been disclosed in the U.S. Pat. No. 6,869,630 and U.S. Pat. No. 6,703,060, which increased the temperature to approximately 200° C., so as to accelerate the esterification process by 30-40 times.   (3) Accelerating the esterification process by using oak barrels of various sizes and shapes that have continuous internal air passages, as had been disclosed in the U.S. Pat. No. 3,942,423, U.S. Pat. No. 5,537,913, and U.S. Pat. No. 6,378,419.   (4) Accelerating the aging of alcoholic liquids by using low frequency (20-400 Hz) and strong magnetic fields (10-120 Gauss), which had been described in the U.S. Pat. No. 5,860,353.   (5) Accelerating the aging of alcoholic liquids by using low frequency (20-400 Hz) and strong magnetic fields (10-120 Gauss), which had been disclosed in the U.S. Pat. No. 4,210,676 and Taiwan Utility Model Patent No. M241431.   (6) Via using catalysts like nano-size gold, silver, and platinum particles to accelerate the aging of alcoholic liquids, soy sauce, or vinegar, as had been described in the patent Taiwan Utility Model Patent No. M269964.   
 
         [0010]    According to the U.S. Pat. No. 6,869,630, the traditional method of aging alcoholic liquids requires 36-48 months for the esterification process to run its course, but it would take only 30-40 days by using the method disclosed in the patent (which accelerates the esterification process by approximately 36 times; please refer to the 56th to the 67th lines of the first column in the patent). On the other hand, using the method disclosed in the U.S. Pat. No. 5,860,353 to age alcoholic liquids for several days to several weeks would produce the same quality of alcoholic liquids aged for one year with regard to taste, color, and aroma thereof (which accelerates the esterification process by more than tenfold; please refer to the 28th to the 30th lines of the fifth column in the patent). Overall, the aforesaid methods generally accelerate aging of alcoholic liquids by several times to more than tenfold. 
       SUMMARY OF THE INVENTION 
       [0011]    The present invention utilizes the technique of esterification under supercritical conditions, which significantly accelerates aging of alcoholic liquids, and this means 36-48 months of esterification process could be achieved within minutes by using the method of the present invention, which would require at least 30-40 days to complete by using the method of U.S. Pat. No. 6,869,630 (please refer to the 56th to the 67th lines of the first column in the patent). 
         [0012]    The present invention provides a method for allowing esterification process to run its course under supercritical conditions, which not only enhances the taste of alcoholic liquids due to accumulation of esters therein, but also reduces or removes alcoholic impurities, ketone impurities, aldehyde impurities, and furan aldehydes that contribute to hangover and headaches. As a result, the disclosure effectively enhances the quality of alcoholic liquids and reduces the time for aging alcoholic liquids. 
         [0013]    An objective of the invention is to provide an apparatus for facilitating catalytic aging reactions under supercritical conditions. 
         [0014]    Another objective of the invention is to provide an apparatus for aging alcoholic liquids in the presence of esterification catalysts under supercritical conditions. 
         [0015]    Another objective of the invention is to provide an apparatus for accelerating aging of alcoholic liquids by using esterification catalysts under supercritical conditions. 
         [0016]    Another objective of the invention is to provide a method for facilitating catalytic aging reactions under supercritical conditions. 
         [0017]    A further objective of the invention is to provide a method for aging alcoholic liquids in the presence of esterification catalysts under supercritical conditions. 
         [0018]    A further objective of the invention is to provide a method for accelerating aging of alcoholic liquids by using esterification catalysts under supercritical conditions. 
         [0019]    An apparatus for supercritical aging constructed according to the present invention comprise: 
         [0020]    a supercritical trough including a trough body, a material supply device, and a supercritical fluid supply device; wherein said material supply device supplies a material to said trough body, and said supercritical fluid supply device supplies a supercritical fluid to said trough body, while said trough body holds the material and the supercritical fluid that have been supplied thereto, and allows the material and the supercritical fluid to form an evenly-distributed solution; and 
         [0021]    a catalyst trough including a trough body and a product drain device; wherein said trough body holds a catalyst therein, and said product drain device is for draining a product away from said trough body of said catalyst through; said catalyst trough and said supercritical trough are connected so as to allow said evenly-distributed solution to come into contact with said catalyst and undergo catalytic reactions. 
         [0022]    The aforesaid apparatus for supercritical aging may be a batch type production apparatus or a continuous type production apparatus, and is preferably a continuous type production apparatus. When said apparatus for supercritical aging is a continuous type production apparatus, said material supply device may be of any previously known continuous type material supply devices, such as a pump, for example. When said apparatus for supercritical aging is a batch type production apparatus, said material supply device may be of any previously known continuous type material supply devices, like a pump, for instance, or of simple openings and seal-off devices (openings are firstly opened, the material is poured in, and then seal-off devices are sealed). Said supercritical fluid supply device may be of any previously known supercritical fluid supply device, like a pump, for instance, and is preferably further comprised of control valves for controlling pressure and flow rate thereof. 
         [0023]    Said supercritical fluid is preferably supercritical carbon dioxide. 
         [0024]    Said supercritical trough is preferably filled with packing, and said packing may be any packing that increases the number of theoretical plates, such as distillation packing, one example of which is Pro-Pak® (a distillation packing produced by CANNON Instrument Company, an American company having a company website of www.cannoninstrument.com), which effectively speeds up reaction rates and allows a supercritical trough required for reactions to be smaller in size relatively. 
         [0025]    Said supercritical trough is not limited in size in any ways, and a larger supercritical trough allows for greater productivity, whereas a smaller supercritical trough allows for less productivity. The flow rate of supercritical carbon dioxide to the supercritical trough is decided by the size of the supercritical trough. 
         [0026]    Moreover, pressure in the supercritical trough is an essential factor in allowing carbon dioxide to remain as a supercritical fluid, and the intensity of pressure varies for different types of aging reactions. Using the aging of alcoholic liquids as an example, the pressure within the supercritical trough is preferably maintained at 1000-5000 psi; more preferably at 2000-4000 psi, and most preferably at 2500-3000 psi. 
         [0027]    In addition, temperature in the supercritical trough is another vital factor in allowing carbon dioxide to remain as a supercritical fluid, and the level of temperature varies for different types of aging reactions. Using the aging of alcoholic liquids as an example, the temperature is preferably 30-100° C.; is more preferably 40-90° C., and is most preferably 45-65° C. When the supercritical trough is larger in size, a temperature control device is preferably further included for maintaining temperature of said supercritical trough. Said temperature control device may be any previously known temperature control devices, such as controllable heating coils, or hot-water circulation devices, for instance. 
         [0028]    Said supercritical trough is not limited in size in any ways, and a larger supercritical trough allows for greater productivity, whereas a smaller supercritical trough allows for less productivity. 
         [0029]    The catalyst in the catalyst trough also varies according to different types of aging reactions. In the case of esterification process, said catalysts may be any previously known esterification catalysts, such as lipase, for example Novozym 435 (purchased from the Danish Novozymes company; the company website is: www.novozymes.com). Said catalyst is not limited in amount of usage in any ways; the more the catalyst is used, the more efficient the aging reaction is, whereas the less the catalysts is used, the less efficient the aging reaction is. 
         [0030]    The usage of said apparatus for supercritical aging is determined by the types of aging reaction. In the case of aging of alcoholic liquids, the reaction conditions are described in the following method for aging alcoholic liquids. 
         [0031]    The aforesaid apparatus for supercritical aging can be used to accelerate aging of alcoholic liquids, but anyone skilled in the manufacturing of foods and drugs could also use apparatuses identical or similar thereof to carry out aging of any foods or drugs; the aging of edible vinegar is one of the examples. 
         [0032]    A method for aging alcoholic liquids has also been included in this disclosure, in which an esterification catalyst is utilized to esterify the alcoholic liquids, characterized in that: said esterification reaction of alcoholic liquids is carried out in supercritical carbon dioxide, so as to significantly reduce the time required for aging alcoholic liquids. 
         [0033]    In order to allow said supercritical carbon dioxide to be effective for said esterification reaction, carbon dioxide is firstly allowed to form a supercritical fluid in the supercritical trough under 1000-5000 psi and at 30-100° C., and then the supercritical carbon dioxide brings alcoholic liquids into said catalyst trough to undergo esterification. 
         [0034]    Said supercritical trough is preferably filled with packing, and said packing may be any packing that increases the number of theoretical plates, such as distillation packing. For instance, the distillation packing Pro-Pak®, which effectively speeds up the reaction rate and allows a supercritical trough required for reaction to be smaller in size relatively. 
         [0035]    Said supercritical trough is not limited in size in any ways, and a larger supercritical trough allows for greater productivity, whereas a smaller supercritical trough allows for less productivity. The flow rate of carbon dioxide in the supercritical trough is determined by the size of the supercritical trough, but the pressure in the supercritical trough is preferably maintained at 1000-5000 psi; more preferably at 2000-4000 psi, and most preferably at 2500-3000 psi. 
         [0036]    The temperature in said supercritical trough is preferably 30-100° C.; is more preferably 40-90° C., and is most preferably 45-65° C. 
         [0037]    Said esterification process may be a batch type reaction or a continuous type reaction, and is preferably a continuous type reaction. In a continuous type reaction, the flow rate of alcoholic liquids to the supercritical trough is not limited in any ways; the greater the flow rate, the less effective the aging process is, while the less the flow rate, the more effective the aging process is. 
         [0038]    The pressure in said catalyst trough is preferably maintained at 1000-5000 psi; more preferably at 2000-4000 psi, and most preferably at 2500-3000 psi. It is generally more preferable to have the pressure in the catalyst trough identical to or slightly smaller than the pressure in the supercritical trough. 
         [0039]    The catalyst in said catalyst trough may be any previously known esterification catalysts, such as lipase. Said catalysts are not limited in amount of usage in any ways; the more the catalyst is used, the more efficient the aging reaction is, whereas the less the catalyst is used, the less efficient the aging reaction is. 
         [0040]    The temperature in said catalyst trough is preferably 30-100° C.; more preferably 40-90° C., and most preferably 45-65° C. It is generally more preferable to have the temperature in the catalyst trough identical to the temperature in the supercritical trough. 
         [0041]    Generally, the productivity is higher when using larger supercritical troughs and catalyst troughs, and smaller when using smaller supercritical troughs and catalyst troughs. Supercritical esterification is more effective by using smaller flow rate of alcoholic liquids and larger volume of catalysts, and vice versa. 
     
    
     
       BRIEF DESCRIPTION OF DRAWINGS 
         [0042]      FIG. 1   a  is a GC/MS spectrum for the commercial Kinman Sorghum Wine. 
           [0043]      FIG. 1   b  is a GC/MS spectrum for the Kinman Sorghum Wine from Control Example 3. 
           [0044]      FIG. 1   c  is a GC/MS spectrum for the Kinman Sorghum Wine that had been stored for twenty years. 
           [0045]      FIG. 1   d  is a GC/MS spectrum for the Kinman Sorghum Wine that had been stored for fifty years. 
           [0046]      FIG. 1   e  is a GC/MS spectrum for the Kinman Sorghum Wine produced in Example 1. 
           [0047]      FIG. 2   a  is a GC/MS spectrum for the commercial Wuliangye Wine. 
           [0048]      FIGS. 2   b  and  2   c  are GC/MS spectra for the Wuliangye Wine produced in Examples 2 and 3, respectively. 
           [0049]      FIGS. 3   a ,  3   b ,  3   c ,  3   d , and  3   e  are GC/MS spectra for the Suntory Whisky produced in Examples 4, 5, 6, 7, and 8, respectively. 
           [0050]      FIG. 4  is a schematic block diagram that shows an apparatus for supercritical aging according to the present invention. 
           [0051]      FIG. 5  is a schematic view that shows an apparatus for supercritical aging according to a preferred embodiment of the present invention. 
       
    
    
     DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS 
       [0052]    The apparatus and method of the present invention can be best understood by referring to the following preferred embodiments and Examples (with Control Examples) of the invention. 
       A Preferred Embodiment 
       [0053]      FIG. 4  is a schematic block diagram that shows an apparatus for supercritical aging according to one of the preferred embodiments of the present invention, including a material supply device  100 , a supercritical fluid supply device  200 , a supercritical trough  300 , a catalyst trough  400 , and a product trough  500 . Moreover, a connector (indicated as a line linking between components in the diagram) is provide to connect the material supply device  100  and the supercritical trough  300 ; another connector (indicated as a line linking between components in the diagram) is provided to connect the supercritical fluid supply device  200  and the supercritical trough  300 , and yet another connector (indicated as a line linking between components in the diagram) is provided to connect the supercritical trough  300  and the catalyst trough  400 , while still another connector (indicated as a line linking between components in the diagram) is provided to connect the catalyst trough  400  and the product trough  500 . 
         [0054]      FIG. 5  is a schematic view that shows an apparatus for supercritical aging constructed according to the preferred embodiment of the present invention. The material supply device  100  in  FIG. 4  comprises a pump  110  in  FIG. 5 , which serves as a device for introducing a material into the supercritical trough  300  via a pipeline  613 . On the other hand, the supercritical fluid supply device  200  in  FIG. 4  comprises a pump  210  in  FIG. 5 , which serves as a device for introducing a supercritical fluid into the supercritical trough  300  via a pipeline  623 . In addition, a pipeline  634  is also connected between the supercritical trough  300  and the catalyst trough  400 , so as to allow the supercritical fluid to bring the material from the supercritical trough  300  into the catalyst trough  400  to undergo esterification. The catalyst trough  400  also has another pipeline  640  for draining a product out of the catalyst trough  400  into the product trough  500  (shown in  FIG. 4 ); the supercritical trough  300  is filled with packing  700 , and the catalyst trough  400  also includes lipase that has not been given any component number. The pipeline  623  is further connected with an emitting pipeline  630  for emitting a part or all of the supercritical fluid when necessary. The pipelines  613 ,  623 ,  630 ,  634 , and  640  are also provided with valves (indicated in the diagram but not given component numbers) for controlling flows of fluids. Furthermore, the pipeline  634  is also provided with pressure gauges (indicated in the diagram but not given component numbers) for displaying and controlling pressure levels at the supercritical trough  300  and the catalyst trough  400 . The supercritical trough  300  and the catalyst trough  400  also include a temperature control device, respectively (not indicated in the diagram), so as to control temperature at the supercritical trough  300  and the catalyst trough  400 . 
       Control Examples 1-3 
       [0055]    Respectively, 500 ml of 58° Kinman Sorghum Wine sold commercially in Taiwan was poured into different 1000 ml wine bottles, and then added 3 g, 5 g, and 10 g of an enzyme into each bottle. The bottles were sealed for 6 months, and were then opened for testing. The enzyme was Novozym 435. 
         [0056]    Wine samples that had been subjected to esterification were compared to those that had not in regard to taste, color, and aroma thereof. It was found that there were no significant differences between the two. 
       Example 1 
       [0057]    The apparatus shown in  FIG. 5  was used in this example, in which portions of the 58° Kinman Sorghum Wine sold commercially in Taiwan were aged. The supercritical trough had a volume of 37 liters and was filled with 18 kg of Pro-Pak®; 1 kg of a catalyst was used in the catalyst trough, and the catalyst used was Novozym 435. As for the reaction conditions, supercritical carbon dioxide in the troughs was maintained at 2500 psi and 50° C., and a flow rate of the Sorghum Wine was set at 50 L/hr. 
         [0058]    Subsequently, comparisons were made between the esterified wine, the non-esterified 58° Kinman Sorghum Wine, the Kinman Sorghum Wine that had been stored for 20 years, and the Kinman Sorghum Wine that had been stored for 50 years sold in Taiwan in regard to taste, color, and aroma thereof. The results are shown in Table 1, which indicates that wine samples produced in Example 1 are significantly better than the 20-year and the 50-year Kinman Sorghum Wine with regard to their taste, color, and aroma. 
         [0000]    
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Comparison of taste, color, and aroma between Kinman 
               
               
                 Sorghum Wine and wine produced in Example 1. 
               
             
          
           
               
                   
                 Taste 
                 Color 
                 Aroma 
               
               
                   
                   
               
             
          
           
               
                 58° Kinman Sorghum Wine 
                 Sharp 
                 Transparent 
                 Pungent 
               
               
                   
                   
                 and colorless 
               
               
                 20-year Kinman Sorghum Wine 
                 Slightly 
                 Slightly 
                 Slightly 
               
               
                   
                 sharp 
                 golden 
                 pungent 
               
               
                 50-year Kinman Sorghum Wine 
                 Mildly 
                 Lightly golden 
                 Mildly 
               
               
                   
                 sharp 
                   
                 pungent 
               
               
                 Wine produced in Example 1 
                 Smooth 
                 Golden 
                 Aromatic 
               
               
                   
               
             
          
         
       
     
         [0059]    In the next step, GC/MS (Gas Chromatograph/Mass Spectroscopy) analyses were carried out for the commercial 58° Kinman Sorghum Wine, wine produced in Control Example 3, 20-year and 50-year Kinman Sorghum Wines, and wine produced in Example 1; with the flowing rate of the GC/MS analyzer set at 1 ml/min, initial temperature of 40° C., temperature rising rate of 5° C./min, and the temperature was fixed once 260° C. was reached. The resultant spectra are shown in  FIGS. 1   a ,  1   b ,  1   c ,  1   d , and  1   e ; wherein the peaks shown at the left hand side in the circles indicate the presence of ethyl hexadecanoate, which has an abundance of approximately 700K (equivalent to 700000), 100K, 900K, 1050K, and greater than 5500K, respectively in  FIGS. 1   a  to  1   e , whereas the peaks shown at the right hand side in the circles of the spectra indicate the presence of ethyl linoleate, which has an abundance of approximately 400K, 50K, 500K, 500K, and 4500K, respectively in  FIGS. 1   a  to  1   e . The results indicated that esterification under supercritical conditions of the present invention increases ester concentration in the wine, which makes the wine more aromatic. 
       Examples 2-3 
       [0060]    The apparatus shown in  FIG. 5  was used in this example, in which portions of the Wuliangye Wine produced in China were aged. The supercritical trough had a volume of 10 liters and was filled with 5 kg of Pro-Pak®; 200 g of a catalyst was used in the catalyst trough, and the catalyst used was Novozym 435. As for the reaction conditions, supercritical carbon dioxide in the troughs was maintained at 2500 psi and 50° C., and flow rates of the Wuliangye Wine were set at 3 L/hr and 1.5 L/hr for Examples 2 and 3, respectively. 
         [0061]    Table 2 shows the comparisons of taste, color, and aroma between wine samples that had undergone esterification and that had not. It was discovered that the taste, color, and aroma of the wine produced in Examples 2 and 3 were clearly better than that of the unesterified wine. 
         [0000]    
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Comparison of taste, color, and aroma between Wuliangye 
               
               
                 Wine and the wine produced in Examples 2 and 3. 
               
             
          
           
               
                   
                 Taste 
                 Color 
                 Aroma 
               
               
                   
                   
               
             
          
           
               
                 Commercial Wuliangye Wine 
                 Sharp 
                 Transparent 
                 Pungent 
               
               
                   
                   
                 and colorless 
               
               
                 Wine produced in Example 2 
                 Smooth 
                 Golden 
                 Aromatic 
               
               
                 Wine produced in Example 3 
                 Smooth 
                 Golden 
                 Aromatic 
               
               
                   
               
             
          
         
       
     
         [0062]    Subsequently, GC/MS analyses were also carried out for the unesterified wine and the wine produced in Examples 2 and 3; with the flow rate of the GC/MS analyzer set at 1 ml/min, initial temperature of 40° C., temperature rising rate of 5° C./min, and the temperature was fixed once 260° C. was reached. The resultant spectra are displayed in  FIGS. 2   a ,  2   b , and  2   c ; wherein the abundance of ethyl hexadecanoate is approximately 100K, 300K, and 550K, respectively; whereas the abundance of ethyl linoleate is approximately 50K, 200K, and 400K, respectively. The results demonstrate that esterification under supercritical conditions raises ester concentration in alcohols, which in turn makes the alcohols more aromatic. 
       Examples 4-8 
       [0063]    Portions of commercial Suntory Whisky were put into the supercritical trough shown in  FIG. 5  to undergo reactions, wherein the supercritical trough had a volume of 10 liters and was filled with 5 kg of Pro-Pak®; 200 g of catalysts were used in the catalyst trough, and the catalysts used was Novozym 435. As for the reaction conditions, supercritical carbon dioxide in the troughs was maintained at 2500 psi and 50° C., and flow rates of the Suntory Whisky in Examples 4, 5, 6, 7 and 8 were set at 3.0 L/hr, 2.5 L/hr, 2.0 L/hr, 1.5 L/hr, and 1.0 L/hr. 
         [0064]    Table 3 shows the comparison of taste, color, and aroma between wine samples that had undergone esterification and that had not. It was found that the taste, color, and aroma of the wine produced in Examples 4-8 were clearly better than that of the unesterified wine. 
         [0000]    
       
         
               
             
               
               
               
               
             
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Comparison of taste, color, and aroma between Suntory 
               
               
                 Whisky and wine produced in Examples 4-8. 
               
             
          
           
               
                   
                 Taste 
                 Color 
                 Aroma 
               
               
                   
                   
               
             
          
           
               
                 Suntory Whisky 
                 Sharp 
                 Brownish yellow 
                 Pungent and dense 
               
               
                 Wine produced in Example 4 
                 Smooth 
                 Light brown 
                 Light fruity aroma 
               
               
                 Wine produced in Example 5 
                 Smooth 
                 Light brown 
                 Light fruity aroma 
               
               
                 Wine produced in Example 6 
                 Smooth 
                 Light brown 
                 Light fruity aroma 
               
               
                 Wine produced in Example 7 
                 Smooth 
                 Light brown 
                 Light fruity aroma 
               
               
                 Wine produced in Example 8 
                 Smooth 
                 Light brown 
                 Light fruity aroma 
               
               
                   
               
             
          
         
       
     
         [0065]    Again, GC/MS analyses were carried out for the wine produced in Examples 4-8; with the flow rate of the GC/MS analyzer set at 1 ml/min, initial temperature of 40° C., temperature rising rate of 5° C./min, and the temperature was fixed once 260° C. was reached. The resultant spectra are shown in  FIGS. 3   a ,  3   b ,  3   c ,  3   d , and  3   e . In each of the spectra, a peak representing acetic acid (Peak 2) and a peak representing impurities mainly of 3-methyl 1-butanol (Peak 1) have been enlarged and displayed at the center of each spectrum. The results indicate that esterification under supercritical conditions effectively reduces the concentration of impurities in alcohols, thus reducing the sharp taste and pungent smell of the alcohols. 
       Examples 9-24 
       [0066]    Kinman Sorghum Wine sold in Taiwan was subjected to esterification under supercritical conditions by using the equipment described in Example 2 (please refer to Table 4 for the amount of catalyst used) and the reaction conditions listed in Table 4, and the taste, color, and aroma of the esterified wines were compared and shown in Table 4. 
         [0000]    
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 The reaction conditions and results of Examples 9-24. 
               
             
          
           
               
                   
                   
                   
                 Catalyst 
                 Flow 
                   
                   
                   
               
               
                   
                 Pressure 
                 Temp. 
                 amount 
                 rate 
               
               
                 Ex. 
                 (psi) 
                 (° C.) 
                 (g) 
                 (L/hr) 
                 Taste 
                 Color 
                 Aroma 
               
               
                   
               
             
          
           
               
                 9 
                 2000 
                 65 
                 200 
                 1.5 
                 Smooth 
                 Golden 
                 Aromatic 
               
               
                 10 
                 2500 
                 65 
                 200 
                 1.5 
                 Smooth 
                 Golden 
                 Aromatic 
               
               
                 11 
                 3000 
                 65 
                 200 
                 1.5 
                 Smooth 
                 Golden 
                 Aromatic 
               
               
                 12 
                 3500 
                 65 
                 200 
                 1.5 
                 Smooth 
                 Golden 
                 Aromatic 
               
               
                 13 
                 4000 
                 65 
                 200 
                 1.5 
                 Smooth 
                 Golden 
                 Aromatic 
               
               
                 14 
                 3000 
                 40 
                 200 
                 2.5 
                 Smooth 
                 Light gold 
                 Aromatic 
               
               
                 15 
                 3000 
                 50 
                 200 
                 2.5 
                 Smooth 
                 Light gold 
                 Aromatic 
               
               
                 16 
                 3000 
                 60 
                 200 
                 2.5 
                 Smooth 
                 Light gold 
                 Aromatic 
               
               
                 17 
                 3000 
                 70 
                 200 
                 2.5 
                 Smooth 
                 Golden 
                 Aromatic 
               
               
                 18 
                 3000 
                 80 
                 200 
                 2.5 
                 Smooth 
                 Golden 
                 Aromatic 
               
               
                 19 
                 3000 
                 90 
                 200 
                 2.5 
                 Smooth 
                 Golden 
                 Aromatic 
               
               
                 20 
                 2800 
                 45 
                 100 
                 1.0 
                 Smooth 
                 Golden 
                 Aromatic 
               
               
                 21 
                 2800 
                 45 
                 150 
                 1.5 
                 Smooth 
                 Golden 
                 Aromatic 
               
               
                 22 
                 2800 
                 45 
                 200 
                 2.0 
                 Smooth 
                 Light gold 
                 Aromatic 
               
               
                 23 
                 2800 
                 45 
                 250 
                 2.5 
                 Smooth 
                 Light gold 
                 Aromatic 
               
               
                 24 
                 2800 
                 45 
                 300 
                 3.0 
                 Smooth 
                 Slightly 
                 Aromatic 
               
               
                   
                   
                   
                   
                   
                   
                 golden 
               
               
                   
               
             
          
         
       
     
         [0067]    The present invention has been described with a preferred embodiment thereof and it is understood that many changes and modifications to the described embodiment can be carried out without departing from the scope and the spirit of the invention that is intended to be limited only by the appended claims.