Continuous production of methyl pentenone using cation exchange resin in a fixed bed reactor

Abstract

Provided herein is a method for producing methyl pentenone (MPO) in high yield in a continuous mode in a fixed bed reactor having a plurality of sidewall injecting ports by reacting excess methyl ethyl ketone (MEK) with acetaldehyde in presence of a cation exchange resin catalyst, wherein the acetaldehyde is injected from the plurality of sidewall injecting ports of the reactor. The method is also effective in reducing the complete consumption of the catalyst during the course of the reaction.

Claims

1. A method for producing methyl pentenone (MPO) in a continuous mode in high yield, the method comprising a reaction between methyl ethyl ketone (MEK) and acetaldehyde in presence of a heterogeneous catalyst in a fixed bed reactor having a plurality of sidewall injecting ports, wherein MEK is fed in a bed of the heterogeneous catalyst in the reactor and acetaldehyde is injected from the plurality of sidewall injecting ports and wherein the concentration of acetaldehyde to methyl ethyl ketone is from 1:3 to 1:18 (feed molar ratio).

2. The method as claimed in claim 1, wherein the heterogeneous catalyst is a cation exchange resin catalyst.

3. The method as claimed in claim 2, wherein the cation exchange resin catalyst is selected from the group consisting of polystyrene sulphonated cation resin, a polymeric resin, a solid catalyst supported on clay, a solid acid catalyst supported on polymeric resin, solid aluminophosphate, zinc acetate, zinc acetate dehydrate, and aluminium phosphate.

4. The method as claimed in claim 1, wherein the reaction takes place at a temperature of 343-363 K.

5. The method as claimed in claim 1, wherein the reaction takes place at a residence time of 295-345 min.

6. The method as claimed in claim 1, wherein injection of acetaldehyde from the plurality of sidewall injecting ports reduces the production of oligomers in the reactor.

7. The method as claimed in claim 6, wherein the reduced oligomer concentration inhibits the deactivation of catalyst.

8. A continuous method for preparing methyl pentenone in a fixed bed reactor, wherein the method comprises steps of i) feeding methyl ethyl ketone into the reactor containing a bed of heterogenous catalyst; ii) injecting acetaldehyde from a plurality of sidewall injecting ports present in the reactor, wherein the reaction takes place at a temperature of 343-363 K with residence time of 295-345 min, wherein the concentration of acetaldehyde to methyl ethyl ketone is from 1:3 to 1:18, and wherein the heterogeneous catalyst is a cation exchange resin catalyst.

9. The method as claimed in claim 1, wherein the yield of methyl pentenone is in the range of 65% to 85% with respect to the amount of acetaldehyde.

10. The method as claimed in claim 8, wherein the yield of methyl pentenone is in the range of 65% to 85% with respect to the amount of acetaldehyde.

Description

BRIEF DESCRIPTION OF ACCOMPANYING DRAWINGS

(1) The above and other aspects, features and advantages of the embodiments of the present disclosure will be more apparent in the following description taken in conjunction with the accompanying drawings, in which:

(2) FIG. 1 illustrates HR-LCMS analysis of the oligomers formed in acetaldehyde oligomerization reaction over Amberlyst-15

(3) FIG. 2 illustrates process flow diagram in the case of side injection of acetaldehyde in the fixed bed reactor (FBR) in accordance with the present invention

(4) FIG. 3 illustrates process flow diagram for the method without side injection walls in the reactor

DETAILED DESCRIPTION OF THE INVENTION

(5) The present invention is directed to a continuous production method of methyl pentenone (MPO) by using a heterogenous catalyst.

(6) The following description with reference to the accompanying drawings is provided to assist in a comprehensive understanding of various embodiments of the present disclosure as defined by the claims and their equivalents. It includes various specific details to assist in that understanding but these are to be regarded as merely exemplary. Accordingly, those of ordinary skill in the art will recognize that various changes and modifications of the various embodiments described herein can be made without departing from the scope and spirit of the present disclosure. In addition, descriptions of well-known functions and constructions may be omitted for clarity and conciseness.

(7) The terms and words used in the following description and claims are not limited to the bibliographical meanings, but, are merely used by the inventor to enable a clear and consistent understanding of the present disclosure. Accordingly, it should be apparent to those skilled in the art that the following description of various embodiments of the present disclosure is provided for illustration purpose only and not for the purpose of limiting the present disclosure as defined by the appended claims and their equivalents.

(8) It is to be understood that the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a component surface” includes reference to one or more of such surfaces.

(9) The terminology used herein is for the purpose of describing particular various embodiments only and is not intended to be limiting of various embodiments. As used herein, the singular forms “a,” “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising” used herein specify the presence of stated features, integers, steps, operations, members, components, and/or groups thereof, but do not preclude the presence or addition of one or more other features, integers, steps, operations, members, components, and/or groups thereof. Also, expressions such as “at least one of,” when preceding a list of elements, modify the entire list of elements and do not modify the individual elements of the list.

(10) Described herein is a method for preparation of methyl pentenone (MPO) by using a heterogeneous catalyst.

(11) In an embodiment of the present invention, there is provided a method for improving the yield of methyl pentenone (MPO).

(12) The present invention provides a method comprising a reaction between methyl ethyl ketone and acetaldehyde in the presence of a heterogenous catalyst in a fixed bed reactor for producing MPO in high yield.

(13) Yield is defined as follows:

(14) $\mathrm{Yield}=\frac{\begin{array}{c}\mathrm{Actual}\mathrm{moles}\mathrm{of}\mathrm{MPO}\mathrm{formed}\mathrm{per}\\ \mathrm{mole}\mathrm{of}\mathrm{acetaldehyde}\mathrm{consumed}\end{array}}{\begin{array}{c}\mathrm{Ideal}\mathrm{moles}\mathrm{of}\mathrm{MPO}\mathrm{formed}\mathrm{per}\\ \mathrm{mole}\mathrm{of}\mathrm{acetaldehyde}\mathrm{consumed}\end{array}}$

(15) In an embodiment there is provided a method for producing methyl pentenone (MPO) in a continuous mode in high yield comprising a reaction between methyl ethyl ketone and acetaldehyde in presence of a heterogeneous catalyst, wherein the reaction takes place in a fixed bed reactor having plurality of sidewall injecting ports.

(16) The method of the present invention results in a high yield of 80% steady state MPO in the pilot scale for nearly 600 hours, wherein the production is based on the concentration of acetaldehyde to methyl ethyl ketone, which is in the range of from 1:3 to 1:18 (AcH:MEK).

(17) The present invention relates to a method for producing methyl pentenone (MPO) in a continuous mode in high yield, the method comprising a reaction between methyl ethyl ketone (MEK) and acetaldehyde in presence of a heterogeneous catalyst in a fixed bed reactor having a plurality of sidewall injecting ports,

(18) wherein MEK is fed in a bed of the heterogeneous catalyst in the reactor and acetaldehyde is injected from the plurality of sidewall injecting ports and wherein the concentration of acetaldehyde to methyl ethyl ketone is from 1:3 to 1:18 (feed molar ratio).

(19) In an embodiment of the present invention, the reaction conditions or parameters like temperature, flow rate, and residence time play an important role in controlling the yield of MPO.

(20) In an embodiment of the present invention there is provided various reaction conditions which governs the yield of MPO in a reaction between acetaldehyde and methyl ethyl ketone in a fixed bed reactor.

(21) The present invention provides that, relative improvement in MPO selectivity is insignificant beyond 363 K. Accordingly, in an implementation the present method is carried out in the temperature range of 343-363 K. This range is critical because the MPO yield increases with temperature.

(22) The present invention thus provides a method for production MPO in high yield, wherein the reaction is performed at a temperature of 343-363 K.

(23) In a further embodiment of the present invention, feed molar ratio shows prominent effect over MPO selectivity.

(24) It was found by the inventors that the steady state MPO yield for 1:3 feed ratio is only 67% (based on acetaldehyde) which increases up to 81% (based on acetaldehyde) for 1:10 and 84% (based on acetaldehyde) for 1:18 feed ratio in a fixed bed reactor with no sidewall injection.

(25) In an embodiment, where the reactions were performed using side injection of acetaldehyde from multiple side ports of the reactor the local feed concentration varies in the range of 1:11 to 1:18 when overall feed concentration was fixed at 1:3 (AcH:MEK). It was surprisingly found that in a fixed bed reactor where the acetaldehyde is injected through the sidewalls, the yield is 79% at 1:3 feed ratio and increased to 83% at 1:3.5 feed ratio.

(26) The method thus employing side wall injection of acetaldehyde attains the same yield of MPO at 1:3 feed ratio as compared to 1:10 feed ratio where there is no side wall injection of acetaldehyde.

(27) Therefore, the present invention provides a method for preparing MPO in high yield, wherein the feed molar ratio of acetaldehyde to MEK varies from 1:3 to 1:18 (AcH:MEK).

(28) The inventors of the present invention have observed that the MPO yield increases from 55% to 85% by minimizing the acetaldehyde concentration with respect to MEK or in other words by increasing the concentration of MEK with respect to acetaldehyde.

(29) In another embodiment there is provided that residence time play an important role in the overall process development.

(30) As used herein “Residence time” is defined as volume of catalyst fed in the fixed bed reactor divided by the feed volumetric flow rate.

(31) It was further found by the present inventors that due to the low boiling point of acetaldehyde (291 K), it is difficult to recover the unconsumed acetaldehyde. Therefore, the overall residence time for fixed bed reactor is fixed at 295-345 min to ensure the complete conversion of acetaldehyde which has significant effect over MPO yield.

(32) Therefore, the present invention provides a method for preparation of MPO, wherein the overall residence time for fixed bed reactor is fixed at 295-345 min.

(33) In another embodiment of the present invention there is provided a method for preparation of MPO in high yield by controlling the concentration of acetaldehyde and MEK in the reactor.

(34) In an embodiment of the present invention there is provided a method for preparation of MPO by using a heterogeneous catalyst.

(35) The present invention aims to mitigate the problem of corrosion caused by a mineral acid such as sulfuric acid when used as a catalyst in the preparation of MPO.

(36) The existing process for the production of MPO is associated with the use of homogeneous catalysts, giving limited yields and imparting excessive load on the effluent treatment thereby making the process environment unfriendly.

(37) The present invention provides a process for preparation of MPO comprising heterogeneous catalysts selected from the group of: Polystyrene sulphonated cation resin, Polymeric resin, Solid catalyst supported on clay, Solid acid catalyst supported on polymeric resin, solid aluminophosphate, Amberlyst-15, Amberlyst-35, Langson dry Lewatit K2620 catalyst, Dry NKC, Dry purolite, Zinc acetate, zinc acetate dehydrate, aluminium phosphate.

(38) In a most preferred embodiment, there is provided a method for production of MPO in high yield, wherein the reaction takes place in between an excess of MEK and acetaldehyde in presence of cation exchange resin, Amberlyst-15.

(39) The heterogeneous catalysts are often associated with problems such as catalyst deactivation during the course of the reaction.

(40) The inventors of the present invention have observed that heterogeneous catalysts improve the yield of MPO for a limited time and after a certain time period the catalysts starts deactivating and further suppressing the yield of MPO.

(41) In an embodiment of the present invention there is provided a method for preparation of MPO in presence of heterogeneous catalyst with a controlled deactivation of heterogeneous catalysts.

(42) The inventors of the present invention propose that most of the metals (in ppm) travelling along with the feed are trapped in the guard column, which significantly control the deactivation of subsequent columns.

(43) The present invention provides a solution to minimize the blockage of column in the method for preparation of MPO, wherein the method comprises injection of acetaldehyde from the sidewall of the reactor.

(44) In an embodiment of the present invention when acetaldehyde is injected from the multiple sidewalls of the reactor containing excess of MEK, less amount of oligomers are generated and additionally, the overall oligomers concentration is low due to abundance of MEK. Due to this reason, blockage of the catalyst active sites will be less and hence catalysts deactivation is also less.

(45) As used herein “Oligomers” are formed by the repeated aldol condensation reaction of acetaldehyde with itself by repeating the acetaldehyde molecule for ‘n’ times, where n varies from 6 to 13. Molecular weight distribution of the oligomers formed during the reaction varies in the range of 300-500 a.m.u. HR-LCMS result showing molecular weight distribution of the oligomers usually formed are shown in FIG. 1. All possible oligomers produced are shown in Table 1.

(46) TABLE-US-00001 TABLE 1 Acetaldehyde condensation products identified in HR-LCMS S.No. Chemical name Structure Observed m/z 1 5,7,9,11-tetrahydroxydodec-2-enal 246 2 3,5,7,9,11-pentahydroxydodecanal 264 3 5,7,9,11,12-pentahydroxytetradec-2-enal 290 4 7,9,11,12,13- pentahydroxyhexadec-2,4-dienal 316 5 5,7,9,11,13,15- hexahydroxyhexadec-2-enal 334 6 7,9,11,13,15,17- hexahydroxyoctadeca-2,4-dienal 360 7 9,11,13,15,17,19- hexahydroxyicosa-2,4,6-trienal 386 8 11,13,15,17,19,21- hexahydroxydocasa-2,4,6,8- tetraenal 412 9 9,11,13,15,17,19,21- heptahydroxydocasa-2,4,6-trienal 430 10 11,13,15,17,19,21,23- heptahydroxytetracosa-2,4,6,8- tetraenal 0 456 11 13,15,17,19,21,23,25- heptahydroxyhexacosa-2,4,6,8,10- pentaenal 482 12 11,13,15,17,19,21,23,25- octahydroxyhexacosa-2,4,6,8-tetraenal 500 13 7,9,11,13,15,17,19,21,23,25- decahydroxyhexacosa-2,4-dienal 536

(47) The present invention thus provides a method for production of MPO which prevents formation of excess oligomers by providing abundance of methyl ethyl ketone and small amount of acetaldehyde in the reactor and thereby preventing the complete deactivation of catalyst.

(48) Therefore, in an embodiment of the present invention there is provided a method for minimizing the deactivation of a heterogeneous catalyst in a reaction between acetaldehyde and MEK for preparing MPO, wherein the concentration of acetaldehyde to methyl ethyl ketone is from 1:3 to 1:18, and wherein the acetaldehyde is introduced from the side walls of the fixed bed reactor.

(49) Therefore, in an embodiment of the present invention, there is provided a continuous method for preparation of MPO with an increased yield and minimum wastes.

(50) In an embodiment of the present invention there is provided a method for preparation of MPO in a continuous mode in a fixed bed reactor having plurality of sidewall injecting ports.

(51) It was found by the inventors that a plurality of sidewall injection of acetaldehyde and an excess of MEK in the reactor results in improving the yield of MPO by reducing the deactivation of catalyst.

(52) The method as described herein results in a yield of methyl pentenone in the range of 65% to 85% with respect to the amount of acetaldehyde.

(53) In a preferred embodiment, there is provided a continuous method for preparing methyl pentenone in a fixed bed reactor, wherein the method comprises steps of

(54) i) feeding methyl ethyl ketone into the reactor containing a bed of heterogenous catalyst;

(55) ii) injecting acetaldehyde from a plurality of sidewall injecting ports present in the reactor, wherein the reaction takes place at a temperature of 343-363 K with residence time of 295-345 min,

(56) wherein the concentration of acetaldehyde to methyl ethyl ketone is from 1:3 to 1:18, and

(57) wherein the heterogeneous catalyst is a cation exchange resin catalyst.

(58) In an embodiment, the present invention provides a continuous method for preparation of MPO, wherein the reaction takes place in a fixed bed reactor and wherein the reactor has plurality of side wall injecting ports as shown in FIG. 2. In a non-limiting embodiment, the fixed bed reactor with side wall injecting ports has at least the following units:

(59) TABLE-US-00002 S. No. Reference number Unit 1 201 MEK feed tank 2 202 MEK feed diaphragm pump, P1 3 203 Main inlet line 4 204 AcH feed tank 5 205 AcH feed diaphragm pump, P2 6 206 Side injection port, S1 7 207 Side injection port, S2 8 208 Side injection port, S3 9 209 Side injection port, S4 10 210 Side injection port, S5 11 211 Side injection port, S6 12 212 Temperature sensor 13 213 Amberlyst-15 bed 14 214 Outlet line 15 215 Pressure gauge 16 216 Back Pressure Regulator

(60) In a comparative embodiment, there is also provided a method for preparation of MPO comprising a reaction between methyl ethyl ketone and acetaldehyde in presence of a catalyst, wherein the reaction is performed at a temperature of 343-363 K with residence time of 8-50 min and wherein the concentration of acetaldehyde to the methyl ethyl ketone ranges from 1:3 to 1:18 (AcH:MEK). This method takes place in a fixed bed reactor as illustrated in FIG. 1 without side injection ports. The fixed bed reactor without side wall injecting ports as shown in FIG. 3 has at least the following units:

(61) TABLE-US-00003 S. No. Reference number Unit 1 101 Feed tank 2 102 Feed diaphragm pump 3 103 Feed inlet line 4 104 Amberlyst-15 bed 5 105 Temperature sensor 6 106 High temperature oil bath 7 107 Hot oil inlet line 8 108 Hot oil outlet line 9 109 Reaction Mixture outlet Line 10 110 Pressure gauge 11 111 Back Pressure Regulator (BPR)

(62) In an exemplary embodiment of the present invention, the present method as described herein is carried out in a fixed bed reactor with side wall injection ports as illustrated in FIG. 2 and described above. However, any modifications to the fixed bed reactor is also within the scope of a person skilled in the art.

(63) In an embodiment, the method of the present invention is performed on the pilot scale FBR with 5-6 side injecting ports. Weight hourly space velocity (WHSV) is the basis for scale up in the absence of heat and mass transfer resistance. Pilot level experiments are performed at the scale up volume ratio of 1:120.

Advantage of the Invention

(64) The current invention has a potential to eliminate several expensive operations of conventional MPO processing. In addition, the method is effective in saving on the expensive, corrosion resistant glass lined equipment and additional investments needed for neutralization and Multi Effect Evaporation. The current process also has a potential to improve yields which will add to its economic potential.

(65) Henceforth, embodiments of the present disclosure are explained with one or more examples. However, such examples are provided for the illustration purpose for better understanding of the present disclosure and should not be construed as limitation on scope of the present disclosure.

EXAMPLES

Main Example 1

(66) A fixed bed reactor of stainless steel, SS-316 (length 470 cm, inner diameter 5.08 cm) is used for the reaction. Reactor is filled with the catalyst Amberlyst-15 (3.15 kg). MEK is fed to the reactor at 8.67 gm/min in the main line using pump. Acetaldehyde is sent to the column through 6 side injection ports at 0.9 gm/min (MEK 55.56% (w/w)) as shown in the FIG. 2. Experiment was performed at overall feed ratio of 1:3 (AcH:MEK) at an overall feed flow rate of 18-18.5 kg per day (295 min of residence time) at 363-368 K and 5 bar (gauge). Reactor was heated using electric coil wrapped over the reactor column. Experiments was performed for 300 hours continuously. It was found that for the 300 hours when average feed molar ratio is nearly 1:3 (AcH:MEK), MPO yield varied in the range of 75-80% (based on acetaldehyde). MPO yield was verified by the distillation. This result was very important because it demonstrates the extended use of Amberlyst-15 for production of methyl pentenone at industrial scale because of catalyst thermal, chemical and mechanical stability.

(67) (Amount of reactant/catalyst: Catalyst=3.15 kg, Total Feed=228.75 kg (AcH=38.71 kg and MEK=190.04 kg), MPO produced=68.97 kg)

Main Example 2

(68) A fixed bed reactor of stainless steel, SS-316 (length 470 cm, inner diameter 5.08 cm) is used for the reaction. Reactor is filled with the catalyst Amberlyst-15 (3.15 kg). MEK is fed to the reactor at 8.67 gm/min in the main line using pump. Acetaldehyde is sent to the column through 6 side injection ports at 0.71 gm/min (MEK 55.56% (w/w)) as shown in the FIG. 2. Experiment was performed at overall feed ratio of 1:3.5 (AcH:MEK) at an overall feed flow rate of 18-18.5 kg per day (345 min of residence time) at 363-368 K and 5 bar (gauge). Reactor was heated using electric coil wrapped over the reactor column. Experiments was performed for 300 hours on a continuously. It was found that MPO yield varied in the range of 80-85% (based on acetaldehyde). MPO yield was verified by the actual distillation. This result was very important because it demonstrate the extended use of Amberlyst-15 for production of methyl pentenone at industrial scale because of catalyst thermal, chemical and mechanical stability.

(69) (Amount of reactant/catalyst: Catalyst=3.15 kg, Total Feed=228.75 kg (AcH=34 kg and MEK=194.75 kg), MPO produced=62.85 kg)

Comparative Example 1

(70) An experiment is performed at 1:3 (AcH:MEK) feed molar ratio at 363 K, 5 bar (gauge) and 1 ml/min of flow rate (50 min of residence time) for 180 hours in a simple fixed bed reactor (height: 35 cm and internal diameter 1.5 cm, FIG. 1) having no sidewall injecting ports. It was found from the experiment that MPO yield is constant only up to first 30 hours, after that it has decreased from 65% to nearly 40% (based on acetaldehyde) at the end of 180 hours. This justifies the decrement in MPO selectivity because of catalyst deactivation.

(71) (Amount of reactant/catalyst: Catalyst=30 g, Total Feed=8640 g (AcH=1462.15 g and MEK=7177.85 g), MPO produced=1750 g)

Comparative Example 2

(72) Another experiment was performed at 1:10 (AcH:MEK) feed molar ratio at 363 K, 5 bar (gauge) and 1 ml/min of flow rate (50 min of residence time) for 180 hours in a fixed bed reactor (height: 35 cm and internal diameter 1.5 cm, FIG. 1) having no sidewall injecting ports. It was found from the experiment that, MPO yield was constant at 81% (based on acetaldehyde) till the end of 180.sup.th hours. This justifies that MPO yield is stable with time at lower concentration of acetaldehyde compared with MEK.

(73) (Amount of reactant/catalyst: Catalyst=30 g, Total Feed=8640 g (AcH=497.6 g and MEK=8142.4 g), MPO produced=900 g)

Comparative Example 3

(74) Another experiment was performed at 1:18 (AcH:MEK) feed molar ratio at 363 K, 5 bar (gauge) and 1 ml/min of flow rate (50 min of residence time) for 12 hours in a fixed bed reactor (height: 35 cm and internal diameter 1.5 cm, FIG. 1). It was found from the experiment that, MPO yield was constant at 84% (based on acetaldehyde) till the end of 12.sup.th hours.

(75) (Amount of reactant/catalyst: Catalyst=30 g, Total Feed=576 g (AcH=18.91 g and MEK=557.09 g), MPO produced=35.37 g)

Comparative Example 4

(76) Comparative Example Reaction with Amberlyst-15 vs. Sulfuric Acid for the Self-Aldol Reaction of MEK

(77) Example 4A: An experiment was performed in an SS-316 batch reactor using 100 g pure methyl ethyl ketone (MEK) at 343 K and 10 g Amberlyst-15 for 6 hours. MEK loss due to self-aldol reactions was barely 4-5% by the formation of 4-5 gm 5-methyl-4-hepten-3-one as evident from GC-FID. The volume of the batch reactor used in the reaction was 250 ml in which 125 ml MEK was taken.

(78) Example 4B: An experiment was performed in a glass reactor using 100 g pure methyl ethyl ketone (MEK) at 343 K and 10 g sulfuric acid for 6 hours. MEK loss due to self-aldol reactions was nearly 14-15% by the formation of 7-8 gm 5-methyl-4-hepten-3-one as evident from GC-FID and other 7-8 gm by the oligomers which was obtained by mass balance. The volume of the glass reactor was 250 ml in which 125 ml MEK was taken.

(79) MEK loss in the side products in Amberlyst-15 is very low (4-5%), which is likely to give an edge to cation exchange resin over homogeneous sulfuric acid catalyst. In the presence of sulfuric acid, 14-15% (w/w) MEK undergoes a self-aldol reaction.

Comparative Example 5

(80) Comparative Example Reaction with Amberlyst-15 vs. Sulfuric Acid for the Self-Aldol Reaction of MPO

(81) Example 5A: An experiment was performed in an SS-316 batch reactor using 100 g pure methyl pentenone (MPO) at 343 K and 10 g Amberlyst-15 for 6 hours. MPO loss due to self-aldol reactions was negligible due to no reaction. Volume of the batch reactor was 250 ml in which 115 ml MPO was taken.

(82) Example 5B: An experiment was performed in a glass reactor using 100 g pure methyl pentenone (MPO) at 343 K and 10 g sulfuric acid for 6 hours. MPO loss due to self-aldol reactions was nearly 14-15% by the formation of 14-15 gm oligomers which was obtained by mass balance. Volume of the glass reactor was 250 ml in which 125 ml MPO was taken.

(83) MPO loss in the side products in Amberlyst-15 is negligible, which is likely to give an edge to cation exchange resin over homogeneous sulfuric acid catalyst. In the presence of sulfuric acid, 14-15% (w/w) MPO undergoes a self-aldol reaction.

(84) The present invention is not to be limited in scope by the specific embodiments described herein. Indeed, various modifications of the invention, in addition to those described herein, will become apparent to those skilled in the art from the foregoing description and accompanying figures. Such modifications are intended to fall within the scope of the appended claims. The invention is, therefore, to be limited only by the terms of the appended claims along with the full scope of equivalents to which the claims are entitled.