Title of Invention	A PROCESS FOR THE PREPARATION OF A NOVEL BIFUNCTIONAL ION EXCHANGE RESIN CATALYST USEFUL FOR THE ETHERIFICATION OF FCC LIGHT GASOLINE
Abstract	A process for the preparation of a novel bifunctional ion exchange resin catalyst useful for the etherification of fluid catalytic cracking light gasoline The present invention relates to a process for the preparation of a novel bifunctional ion exchange resin catalyst useful for the etherification of fluid catalytic cracking light gasoline. The process is for the design of a bifunctional catalyst prepared by incorporation of palladium in acidic ion exchange resin for etherification of FCC (Fluid catalyzed caracked) light gasoline. The incorporation of Palladium is in the range of 0.46 to 1.83 wt%.

Title of Invention

A PROCESS FOR THE PREPARATION OF A NOVEL BIFUNCTIONAL ION EXCHANGE RESIN CATALYST USEFUL FOR THE ETHERIFICATION OF FCC LIGHT GASOLINE

Abstract

A process for the preparation of a novel bifunctional ion exchange resin catalyst useful for the etherification of fluid catalytic cracking light gasoline The present invention relates to a process for the preparation of a novel bifunctional ion exchange resin catalyst useful for the etherification of fluid catalytic cracking light gasoline. The process is for the design of a bifunctional catalyst prepared by incorporation of palladium in acidic ion exchange resin for etherification of FCC (Fluid catalyzed caracked) light gasoline. The incorporation of Palladium is in the range of 0.46 to 1.83 wt%.

Full Text	The present invention relates to a process for the preparation of a novel bifuncitonal ion exchange resin catalyst useful for the etherification of fluid catalytic cracking light gasoline. In particular the invention relates to a process for the design of a bifuctional catalyst by incorporation of palladium in acidic ion exchange resin for etherification of FCC (Fluid catalyzed caracked) light gasoline. The invention more specifically relates to a process for the design of a novel bifuctional catalyst by incorporation FCC light gasoline is a major contributor of olefins in gasoline stream. Due to negative impact of these olefins on environment, the conversions to corresponding ethers are gaining more importance because of stringent environmental regulations on gasoline quality specifications. Due to MTBE (Methyl tertiary butyl ether) controversy, TAME (Tertiary amyl methyl ether) and TAEE (Tertiary amyl ethyl ether) seem to be most important alternatives because of very low water solubility and less volatility. Presence of diolefins in light gasoline is undesirable for etherification reaction, as it rapidly deactivates the catalyst due to formation of polymers over acid sides by polymerization of diolefins and produces undesirable coloured products. Macro porous acidic ion exchange resins are known catalysts for etherification of light olefins such as isobutylene and isoamylenes. In the prior art (G. Partchard, B. Schlepping off, Erdol und Khole -Erdgas-Petrochemie vol. 41, no. 4, 1988 pp 157-160) the inventors have attempted to prepare metal incorporated ion exchange resins for etherification of FCC light olefins and also to hydrogenate diolefins so that to avoid deactivation of catalyst. It is not explicit whether the hydrogenation function introduced to the catalyst also promotes the hydrogenation of some of the reactive olefins, which is an undesirable reaction during etherification. The novelty of the present invention is in modifying the ion exchange resin by incorporating palladium in balanced amount so that diolefins are saturated as evidenced by the formation of clear colorless products and mono olefins both reactive and unreactive remains intact towards hydrogenation reaction. Additionally, the catalyst designed by the present invention also promoteisomerizaiton reaction and convert some. Of olefins especially non reactive to reactive one, which is more required for etherification reaction. The main object of the present invention is to provide a process for the design of a novel bifunctional catalyst for etherification of light FCC gasoline, which obviates the drawbacks as detailed above. Accordingly the present invention provides a process for the preparation of a novel bifunctional ion exchange resin catalyst useful for the etherification of fluid catalytic cracking light gasoline which comprises, i) treating the acidic ion exchange resin with an alcohol such as herein described to remove the moisture, ii) treating the above said moisture free ion exchange resin with an alcohol diluted solution of palladium chloride in concentrated hydrochloric acid with a palladium chloride to dry ion exchange resin ratio in the range of 1:40 wt% to 1:135wt%, iii) stirring the above reaction mixture for a period ranging from for 2-3 hrs and keeping the resultant mass in the reaction mixture for 14-18hrs, iv) refluxing 5the above said reaction mixture at a temperature in the range of 65-75°C for a period 5-6 hrs followed by removal of solvent from reaction mixture by evaporation at a temperature in the range of 60-80°C to obtain the catalyst, v) drying the above resultant catalyst in vacuum oven at 60-65°C for 2-3 hrs and washing with a mixture of FCC light gasoline and alcohol 4-5 times to remove the remaining slats over the catalyst to obtain the desired catalyst. In an embodiment of the present invention the ion exchange resin used is having an acid value in the range of 5-6 meq/g, surface area in the range of 30-40 m2/g and porosity in the range of 0.25-0.35 ml/g. In another embodiment of the present invention acidic solution of palladium chloride diluted with methanol of strength ranging from 0.15 to 0.61 wt%. In yet another embodiment of the present invention palladium incorporated is in the range of 0.46 to 1.83 wt%. In still another embodiment of the present invention alcohol used is methanol and ethanol. In still another embodiment of the present invention palladium incorporated ion exchange resin catalyst is useful for etherification reaction of FCC gasoline with ethanol or methanol to produce TAEE and TAME a valuable gasoline blending components with clean burning characteristics. In carrying out the present invention, as a result of extensive research, four catalysts were prepared each having the same acidic ion exchange resin as a support, of the characteristics given in table-1. The metal palladium was loaded over the support in varying amount from 0.46 to 1.83 wt%. Tablel: Characteristics of Resin (Table Removed) The acidic resin was pretreated with methanol to remove moisture. Required quantities of Palladium Chloride were weighed for different calculated weight percentages of Pd and were dissolved in concentrated hydrochloric acid and diluted by methanol AR. The PdCl2 solutions added to pretreated resins followed by stirring initially for 2-3 hrs at ambient temperature and kept the stirred mass for overnight (14-18 hrs). The Pd incorporated ion exchange resin catalysts containing salt solution was refluxed in silicon oil bath at 65-75°c for 5-6 hrs. The Pd incorporated catalysts containing salt solutions were evaporated to remove solvents completely by slow heating in silicon oil bath for 10-12 hrs at 60-80°c with occasional stirring. Finally dried resins were kept in the vacuum oven for 2-3 hours at 60-65°C. The prepared catalyst washed with FCC light gasoline and methanol/ethanol mixture, 4-5 times to remove the salt remaining over the catalysts. Finally the prepared Pd incorporated catalysts were used for etherification of FCC light gasoline (IBP-105°C & IBP-60°C, pretreated with the aqueous solutions of sodium hydroxide, gl. acetic acid and deionized water to remove soluble impurities and known catalyst poisons) with ethanol and methanol in a tubular reactor. The following examples are given by way of illustration and therefore should not be construed to limit the scope of the present invention. Example-1: The acidic ion exchange resin (15.24g wet=10.0g dry) was pretreated with methanol to remove moisture. For making 0.46 wt% Pd incorporated resin 0.076g of palladium chloride was dissolved in 5.0-5.5 ml of concentrate HC1 (warm) and after cooling of above prepared solution, diluted with 45 ml of methanol. The above prepared solution added to pretreated resin followed by stirring initially for 2-3 hrs at ambient temperature and kept the stirred mass for overnight (14-18 hrs). Pd incorporated ion exchange resin catalyst containing salt solution was evaporated to remove solvents completely by slow heating in silicon oil bath for 10-12 hrs at 60-80°c with occasional stirring. The dried Pd incorporated resin catalyst was kept in the vacuum oven for 2-3 hrs at 60-65°c. The prepared catalyst washed with FCC light gasoline and methanol/ethanol mixture, 4-5 times to remove the salt remaining over the catalyst. Example-2: The acidic ion exchange resin (15.24g wet=10.0g dry) was pretreated with methanol to remove moisture. For making 0.91wt%Pd incorporated resin 0.152g of palladium chloride was dissolved in 5.0-5.5 ml of concentrate HC1 (warm) and after cooling of above prepared solution, diluted with 45 ml of methanol. The above prepared solution added to pretreated resin followed by stirring initially for 2-3 hrs at ambient temperature and kept the stirred mass for overnight (14-18 hrs). Pd incorporated ion exchange resin catalyst containing salt solution was evaporated to remove solvents completely by slow heating in silicon oil bath for 10-12 hrs at 60-80°c with occasional stirring. The dried Pd incorporated resin catalyst was kept in the vacuum oven for 2-3 hrs at 60-65°c. The prepared catalyst washed with FCC light gasoline and methanol/ethanol mixture, 4-5 times to remove the salt remaining over the catalyst. Example-3: The acidic ion exchange resin (15.24g wet=10.0g dry) was pretreated with methanol to remove moisture. For making 1.37wt% Pd incorporated resin 0.228g of palladium chloride was dissolved in 5.0-5.5 ml of concentrate HC1 (warm) and after cooling of above prepared solution, diluted with 45 ml of methanol. The above prepared solution added to pretreated resin followed by stirring initially for 2-3 hrs at ambient temperature and kept the stirred mass for overnight (14-18 hrs). Pd incorporated ion exchange resin catalyst containing salt solution was evaporated to remove solvents completely by slow heating in silicon oil bath for 10-12 hrs at 60-80°c with occasional stirring. The dried Pd incorporated resin catalyst was kept in the vacuum oven for 2-3 hrs at 60-65°c. The prepared catalyst washed with FCC light gasoline and methanol/ethanol mixture, 4-5 times to remove the salt remaining over the catalyst." Example-4: The acidic ion exchange resin (15.24g wet=10.0g dry) was pretreated with methanol to remove moisture. For making 1.83wt% Pd incorporated resin 0.304g of palladium chloride was dissolved in 5.0-5.5 ml of concentrate HC1 (warm) and after cooling of above prepared solution, diluted with 45 ml of methanol. The above prepared solution added to pretreated resin followed by stirring initially for 2-3 hrs at ambient temperature and kept the stirred mass for overnight (14-18 hrs). Pd incorporated ion exchange resin catalyst containing salt solution was evaporated to remove solvents completely by slow heating in silicon oil bath for 10-12 hrs at 60-80°c with occasional stirring. The dried Pd incorporated resin catalyst was kept in the vacuum oven for 2-3 hrs at 60-65°c. The prepared catalyst washed with FCC light gasoline and methanol/ethanol mixture, 4-5 times to remove the salt remaining over the catalyst. Example-5: The acidic ion exchange resin (15.24g wet=10.0g dry) was pretreated with methanol to remove moisture. For making 0.46 wt% Pd incorporated resin 0.076g of palladium chloride was dissolved in 5.0-5.5 ml of concentrate HC1 (warm) and after cooling of above prepared solution, diluted with 45 ml of methanol. The above prepared solution added to pretreated resin followed by stirring initially for 2-3 hrs at ambient temperature and kept the stirred mass for overnight (14-18 hrs). The Pd incorporated ion exchange resin catalyst containing salt solution was refluxed in silicon oil bath at 65-75°c for 5-6 hrs. Pd incorporated ion exchange resin catalyst containing salt solution was evaporated to remove solvents completely by slow heating in silicon oil bath for 10-12 hrs at 60-80°c with occasional stirring. The dried Pd incorporated resin catalyst was kept in the vacuum oven for 2-3 hrs at 60-65°c. The prepared catalyst washed with FCC light gasoline and methanol/ethanol mixture, 4-5 times to remove the salt remaining over the catalyst. Since 0.46wt% Pd incorporated catalyst was find with optimum level of metal and was used for etherification of FCC light gasoline (IBP-60°C, pretreated with the aqueous solutions of sodium hydroxide, gl. acetic acid and deionized water to remove soluble impurities and known catalyst poisons) with methanol in a tubular reactor at temp: 65-70°C, press H2: 6.0 kg/cm2 and LHSV: 2.0 h'1 to yield TAME. Example 6 Process of etherification using above Pd incorporated catalyst Finally the prepared Pd incorporated catalyst was used for etherification of FCC light gasoline (IBP-105°C, pretreated with the aqueous solutions of sodium hydroxide, gl. acetic acid and deionized water to remove soluble impurities and known catalyst poisons) with ethanol and methanol in a tubular reactor at temp: 70°C, press H2: 6.0 kg/cm2 and LHSV: 7-20h"' to yield TAEE and TAME. The reactants and products were analysed by conventional bromine number method and GC analysis. The results presented in table-2 clearly indicate that diolefins are saturated as it results a colourless product, at lowest Pd loading (0.46wt%) both isoamylenes conversion and selectivity to tertiary amyl ethyl ether (TAEE) is highest and mono olefins both reactive and unreactive remains intact towards hydrogenation reaction. Similar trend is also observed with the results presented in table-3 for etherification of FCC light gasoline (IBP-105°C) with methanol. The GC results also indicate that these catalysts promote isomerization of some of olefins especially unreactive like 3-Me-l-butene to reactive olefins 2-me-2-butene, desirable for etherification reaction. GC analysis of reactants and products provide clear indication that at higher amount of Pd loading (above 0.46 wt%) some of reactive/unreactive mono olefins are also saturated during the etherification reaction and hence catalyst with 0.46wt% is ranked as the best catalyst designed in the present investigation. So this catalyst with lowest Pd loading was also chosen for further experiments of etherification of FCC light gasoline (IBP-60°c) with methanol and results are presented in table-4. Table 2: Etherification of isoamylenes with ethanol in presence of bifunctional Catalysts (Table Removed) Table 3: Etherification of isoamylenes with methanol in presence of bifunctional Catalysts (Table Removed) Table 4: Effect of temperature on etheriflcation of isoamylenes with methanol in presence of bifunctional catalyst (Pd-H-Resin 0.46 wt %) (Table Removed) Advantages of the present invention 1) A palladium incorporated ion exchange resin catalyst is reported which is useful for the etheriflcation of olefins. 2) The reported catalyst also isomerise undesired diolefins into saturates. 3) The present catalyst converts non reactive olefins into reactive olefins which are more useful for the etheriflcation process. We Claim: 1. A process for the preparation of a novel bifunctional ion exchange resin catalyst useful for the etherification of fluid catalytic cracking light gasoline which comprises, i) treating the acidic ion exchange resin with an alcohol such as herein described to remove the moisture, ii) treating the above said moisture free ion exchange resin with an alcohol diluted solution of palladium chloride in concentrated hydrochloric acid with a palladium chloride to dry ion exchange resin ratio in the range of 1:40 wt% to 1:135wt%, iii) stirring the above reaction mixture for a period ranging from for 2-3 hrs and keeping the resultant mass in the reaction mixture for 14-18hrs, iv) refluxing ,' the above said reaction mixture at a temperature in the range of 65-75°C for a period 5-6 hrs followed by removal of solvent from reaction mixture by evaporation at a temperature in the range of 60-80°C to obtain the catalyst, v) drying the above resultant catalyst in vacuum oven at 60-65°C for 2-3 hrs and washing with a mixture of FCC light gasoline and alcohol 4-5 times to remove the remaining slats over the catalyst to obtain the desired catalyst. 2. A process as claimed in claim 1 wherein the ion exchange resin used is having an acid value ranging from 5-6 meq/g, surface area are ranging from 30-40 m2/g and porosity ranging from 0.25-0.35 ml/g. 3. A process as claimed in claims 1-2 wherein the acidic solution of palladium chloride diluted with methanol used is having a strength ranging from 0.15 to 0.61wt%. 4. A process as claimed in claims 1-3 wherein the ion exchange resin catalyst contains palladium in the range of 0.46 to 1.83wt%. 5. A process as claimed in claims 1 to 4 wherein al cohol used is selected from methanol and ethanol. 6. A process as claimed in claims 1 to 5 wherein palladium incorporated ion exchange resin catalyst is used for the etherification reaction of FCC light gasoline with ethanol or methanol to produce Tetra amyl ethyl ether and tetra amyl methyl ether, a valuable gasoline blending components with clean burning characteristics. 7. A process for the preparation of a novel bi-functional ion exchange resin catalyst useful for the etherification of fluid catalytic cracking light gasoline substantially as herein described with reference to the examples.

Full Text

The present invention relates to a process for the preparation of a novel bifuncitonal ion exchange resin catalyst useful for the etherification of fluid catalytic cracking light gasoline.
In particular the invention relates to a process for the design of a bifuctional catalyst by incorporation of palladium in acidic ion exchange resin for etherification of FCC (Fluid catalyzed caracked) light gasoline. The invention more specifically relates to a process for the design of a novel bifuctional catalyst by incorporation
FCC light gasoline is a major contributor of olefins in gasoline stream. Due to negative impact of these olefins on environment, the conversions to corresponding ethers are gaining more importance because of stringent environmental regulations on gasoline quality specifications. Due to MTBE (Methyl tertiary butyl ether) controversy, TAME (Tertiary amyl methyl ether) and TAEE (Tertiary amyl ethyl ether) seem to be most important alternatives because of very low water solubility and less volatility. Presence of diolefins in light gasoline is undesirable for etherification reaction, as it rapidly deactivates the catalyst due to formation of polymers over acid sides by polymerization of diolefins and produces undesirable coloured products. Macro porous acidic ion exchange resins are known catalysts for etherification of light olefins such as isobutylene and isoamylenes.
In the prior art (G. Partchard, B. Schlepping off, Erdol und Khole -Erdgas-Petrochemie vol. 41, no. 4, 1988 pp 157-160) the inventors have attempted to prepare metal incorporated ion exchange resins for etherification of FCC light olefins and also to hydrogenate diolefins so that to avoid deactivation of catalyst. It is not explicit whether the hydrogenation function introduced to the catalyst also promotes the hydrogenation of some of the reactive olefins, which is an undesirable reaction during etherification.
The novelty of the present invention is in modifying the ion exchange resin by incorporating palladium in balanced amount so that diolefins are saturated as evidenced by the formation of clear colorless products and mono olefins both reactive and unreactive remains intact towards hydrogenation reaction. Additionally, the catalyst designed by the present invention also promoteisomerizaiton reaction and convert some.
Of olefins especially non reactive to reactive one, which is more required for etherification reaction.
The main object of the present invention is to provide a process for the design of a novel bifunctional catalyst for etherification of light FCC gasoline, which obviates the drawbacks as detailed above.
Accordingly the present invention provides a process for the preparation of a novel bifunctional ion exchange resin catalyst useful for the etherification of fluid catalytic cracking light gasoline which comprises, i) treating the acidic ion exchange resin with an alcohol such as herein described to remove the moisture, ii) treating the above said moisture free ion exchange resin with an alcohol diluted solution of palladium chloride in concentrated hydrochloric acid with a palladium chloride to dry ion exchange resin ratio in the range of 1:40 wt% to 1:135wt%, iii) stirring the above reaction mixture for a period ranging from for 2-3 hrs and keeping the resultant mass in the reaction mixture for 14-18hrs, iv) refluxing 5the above said reaction mixture at a temperature in the range of 65-75°C for a period 5-6 hrs followed by removal of solvent from reaction mixture by evaporation at a temperature in the range of 60-80°C to obtain the catalyst, v) drying the above resultant catalyst in vacuum oven at 60-65°C for 2-3 hrs and washing with a mixture of FCC light gasoline and alcohol 4-5 times to remove the remaining slats over the catalyst to obtain the desired catalyst.
In an embodiment of the present invention the ion exchange resin used is having an acid value in the range of 5-6 meq/g, surface area in the range of 30-40 m2/g and porosity in the range of 0.25-0.35 ml/g.
In another embodiment of the present invention acidic solution of palladium chloride diluted with methanol of strength ranging from 0.15 to 0.61 wt%.
In yet another embodiment of the present invention palladium incorporated is in the range of 0.46 to 1.83 wt%.
In still another embodiment of the present invention alcohol used is methanol and
ethanol.
In still another embodiment of the present invention palladium incorporated ion
exchange resin catalyst is useful for etherification reaction of FCC gasoline with ethanol
or methanol to produce TAEE and TAME a valuable gasoline blending components with
clean burning characteristics.
In carrying out the present invention, as a result of extensive research, four catalysts were prepared each having the same acidic ion exchange resin as a support, of the characteristics given in table-1. The metal palladium was loaded over the support in varying amount from 0.46 to 1.83 wt%.
Tablel: Characteristics of Resin (Table Removed)
The acidic resin was pretreated with methanol to remove moisture. Required quantities of Palladium Chloride were weighed for different calculated weight percentages of Pd and were dissolved in concentrated hydrochloric acid and diluted by methanol AR. The PdCl2 solutions added to pretreated resins followed by stirring initially for 2-3 hrs at ambient temperature and kept the stirred mass for overnight (14-18 hrs). The Pd incorporated ion exchange resin catalysts containing salt solution was refluxed in silicon oil bath at 65-75°c for 5-6 hrs. The Pd incorporated catalysts containing salt solutions were evaporated
to remove solvents completely by slow heating in silicon oil bath for 10-12 hrs at 60-80°c with occasional stirring. Finally dried resins were kept in the vacuum oven for 2-3 hours at 60-65°C. The prepared catalyst washed with FCC light gasoline and methanol/ethanol mixture, 4-5 times to remove the salt remaining over the catalysts. Finally the prepared Pd incorporated catalysts were used for etherification of FCC light gasoline (IBP-105°C & IBP-60°C, pretreated with the aqueous solutions of sodium hydroxide, gl. acetic acid and deionized water to remove soluble impurities and known catalyst poisons) with ethanol and methanol in a tubular reactor.
The following examples are given by way of illustration and therefore should not be construed to limit the scope of the present invention.
Example-1:
The acidic ion exchange resin (15.24g wet=10.0g dry) was pretreated with methanol to remove moisture. For making 0.46 wt% Pd incorporated resin 0.076g of palladium chloride was dissolved in 5.0-5.5 ml of concentrate HC1 (warm) and after cooling of above prepared solution, diluted with 45 ml of methanol. The above prepared solution added to pretreated resin followed by stirring initially for 2-3 hrs at ambient temperature and kept the stirred mass for overnight (14-18 hrs). Pd incorporated ion exchange resin catalyst containing salt solution was evaporated to remove solvents completely by slow heating in silicon oil bath for 10-12 hrs at 60-80°c with occasional stirring. The dried Pd incorporated resin catalyst was kept in the vacuum oven for 2-3 hrs at 60-65°c. The prepared catalyst washed with FCC light gasoline and methanol/ethanol mixture, 4-5 times to remove the salt remaining over the catalyst.
Example-2:
The acidic ion exchange resin (15.24g wet=10.0g dry) was pretreated with methanol to remove moisture. For making 0.91wt%Pd incorporated resin 0.152g of palladium chloride was dissolved in 5.0-5.5 ml of concentrate HC1 (warm) and after cooling of above prepared solution, diluted with 45 ml of methanol. The above prepared solution
added to pretreated resin followed by stirring initially for 2-3 hrs at ambient temperature and kept the stirred mass for overnight (14-18 hrs). Pd incorporated ion exchange resin catalyst containing salt solution was evaporated to remove solvents completely by slow heating in silicon oil bath for 10-12 hrs at 60-80°c with occasional stirring. The dried Pd incorporated resin catalyst was kept in the vacuum oven for 2-3 hrs at 60-65°c. The prepared catalyst washed with FCC light gasoline and methanol/ethanol mixture, 4-5 times to remove the salt remaining over the catalyst.
Example-3:
The acidic ion exchange resin (15.24g wet=10.0g dry) was pretreated with methanol to remove moisture. For making 1.37wt% Pd incorporated resin 0.228g of palladium chloride was dissolved in 5.0-5.5 ml of concentrate HC1 (warm) and after cooling of above prepared solution, diluted with 45 ml of methanol. The above prepared solution added to pretreated resin followed by stirring initially for 2-3 hrs at ambient temperature and kept the stirred mass for overnight (14-18 hrs). Pd incorporated ion exchange resin catalyst containing salt solution was evaporated to remove solvents completely by slow heating in silicon oil bath for 10-12 hrs at 60-80°c with occasional stirring. The dried Pd incorporated resin catalyst was kept in the vacuum oven for 2-3 hrs at 60-65°c. The prepared catalyst washed with FCC light gasoline and methanol/ethanol mixture, 4-5 times to remove the salt remaining over the catalyst."
Example-4:
The acidic ion exchange resin (15.24g wet=10.0g dry) was pretreated with methanol to remove moisture. For making 1.83wt% Pd incorporated resin 0.304g of palladium chloride was dissolved in 5.0-5.5 ml of concentrate HC1 (warm) and after cooling of above prepared solution, diluted with 45 ml of methanol. The above prepared solution added to pretreated resin followed by stirring initially for 2-3 hrs at ambient temperature and kept the stirred mass for overnight (14-18 hrs). Pd incorporated ion exchange resin catalyst containing salt solution was evaporated to remove solvents completely by slow heating in silicon oil bath for 10-12 hrs at 60-80°c with occasional stirring. The dried Pd incorporated resin catalyst was kept in the vacuum oven for 2-3 hrs at 60-65°c. The
prepared catalyst washed with FCC light gasoline and methanol/ethanol mixture, 4-5 times to remove the salt remaining over the catalyst.
Example-5:
The acidic ion exchange resin (15.24g wet=10.0g dry) was pretreated with methanol to remove moisture. For making 0.46 wt% Pd incorporated resin 0.076g of palladium chloride was dissolved in 5.0-5.5 ml of concentrate HC1 (warm) and after cooling of above prepared solution, diluted with 45 ml of methanol. The above prepared solution added to pretreated resin followed by stirring initially for 2-3 hrs at ambient temperature and kept the stirred mass for overnight (14-18 hrs). The Pd incorporated ion exchange resin catalyst containing salt solution was refluxed in silicon oil bath at 65-75°c for 5-6 hrs. Pd incorporated ion exchange resin catalyst containing salt solution was evaporated to remove solvents completely by slow heating in silicon oil bath for 10-12 hrs at 60-80°c with occasional stirring. The dried Pd incorporated resin catalyst was kept in the vacuum oven for 2-3 hrs at 60-65°c. The prepared catalyst washed with FCC light gasoline and methanol/ethanol mixture, 4-5 times to remove the salt remaining over the catalyst. Since 0.46wt% Pd incorporated catalyst was find with optimum level of metal and was used for etherification of FCC light gasoline (IBP-60°C, pretreated with the aqueous solutions of sodium hydroxide, gl. acetic acid and deionized water to remove soluble impurities and known catalyst poisons) with methanol in a tubular reactor at temp: 65-70°C, press H2: 6.0 kg/cm2 and LHSV: 2.0 h'1 to yield TAME.
Example 6 Process of etherification using above Pd incorporated catalyst
Finally the prepared Pd incorporated catalyst was used for etherification of FCC light gasoline (IBP-105°C, pretreated with the aqueous solutions of sodium hydroxide, gl. acetic acid and deionized water to remove soluble impurities and known catalyst poisons) with ethanol and methanol in a tubular reactor at temp: 70°C, press H2: 6.0 kg/cm2 and LHSV: 7-20h"' to yield TAEE and TAME.
The reactants and products were analysed by conventional bromine number method and GC analysis. The results presented in table-2 clearly indicate that diolefins are saturated
as it results a colourless product, at lowest Pd loading (0.46wt%) both isoamylenes conversion and selectivity to tertiary amyl ethyl ether (TAEE) is highest and mono olefins both reactive and unreactive remains intact towards hydrogenation reaction. Similar trend is also observed with the results presented in table-3 for etherification of FCC light gasoline (IBP-105°C) with methanol. The GC results also indicate that these catalysts promote isomerization of some of olefins especially unreactive like 3-Me-l-butene to reactive olefins 2-me-2-butene, desirable for etherification reaction. GC analysis of reactants and products provide clear indication that at higher amount of Pd loading (above 0.46 wt%) some of reactive/unreactive mono olefins are also saturated during the etherification reaction and hence catalyst with 0.46wt% is ranked as the best catalyst designed in the present investigation.
So this catalyst with lowest Pd loading was also chosen for further experiments of etherification of FCC light gasoline (IBP-60°c) with methanol and results are presented in table-4.
Table 2: Etherification of isoamylenes with ethanol in presence of bifunctional Catalysts
(Table Removed)
Table 3: Etherification of isoamylenes with methanol in presence of bifunctional Catalysts
(Table Removed)
Table 4: Effect of temperature on etheriflcation of isoamylenes with methanol in
presence of bifunctional catalyst (Pd-H-Resin 0.46 wt %)
(Table Removed)
Advantages of the present invention
1) A palladium incorporated ion exchange resin catalyst is reported which is useful
for the etheriflcation of olefins.
2) The reported catalyst also isomerise undesired diolefins into saturates.
3) The present catalyst converts non reactive olefins into reactive olefins which are
more useful for the etheriflcation process.

We Claim:
1. A process for the preparation of a novel bifunctional ion exchange resin
catalyst useful for the etherification of fluid catalytic cracking light gasoline
which comprises, i) treating the acidic ion exchange resin with an alcohol such
as herein described to remove the moisture, ii) treating the above said
moisture free ion exchange resin with an alcohol diluted solution of palladium
chloride in concentrated hydrochloric acid with a palladium chloride to dry
ion exchange resin ratio in the range of 1:40 wt% to 1:135wt%, iii) stirring the
above reaction mixture for a period ranging from for 2-3 hrs and keeping the
resultant mass in the reaction mixture for 14-18hrs, iv) refluxing ,' the above
said reaction mixture at a temperature in the range of 65-75°C for a period 5-6
hrs followed by removal of solvent from reaction mixture by evaporation at a
temperature in the range of 60-80°C to obtain the catalyst, v) drying the above
resultant catalyst in vacuum oven at 60-65°C for 2-3 hrs and washing with a
mixture of FCC light gasoline and alcohol 4-5 times to remove the remaining
slats over the catalyst to obtain the desired catalyst.
2. A process as claimed in claim 1 wherein the ion exchange resin used is having
an acid value ranging from 5-6 meq/g, surface area are ranging from 30-40
m2/g and porosity ranging from 0.25-0.35 ml/g.
3. A process as claimed in claims 1-2 wherein the acidic solution of palladium
chloride diluted with methanol used is having a strength ranging from 0.15 to
0.61wt%.
4. A process as claimed in claims 1-3 wherein the ion exchange resin catalyst
contains palladium in the range of 0.46 to 1.83wt%.
5. A process as claimed in claims 1 to 4 wherein al cohol used is selected from
methanol and ethanol.
6. A process as claimed in claims 1 to 5 wherein palladium incorporated ion
exchange resin catalyst is used for the etherification reaction of FCC light
gasoline with ethanol or methanol to produce Tetra amyl ethyl ether and tetra
amyl methyl ether, a valuable gasoline blending components with clean
burning characteristics.
7. A process for the preparation of a novel bi-functional ion exchange resin
catalyst useful for the etherification of fluid catalytic cracking light gasoline
substantially as herein described with reference to the examples.

Documents:

421-del-2001-abstract.pdf

421-del-2001-claims.pdf

421-del-2001-correspondence-others.pdf

421-del-2001-correspondence-po.pdf

421-del-2001-description (complete).pdf

421-del-2001-form-1.pdf

421-del-2001-form-18.pdf

421-del-2001-form-2.pdf

421-del-2001-form-3.pdf

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Patent Number

230560

Indian Patent Application Number

421/DEL/2001

PG Journal Number

11/2009

Publication Date

13-Mar-2009

Grant Date

27-Feb-2009

Date of Filing

30-Mar-2001

Name of Patentee

COUNCIL OF SCIENTIFIC AND INDUSTRIAL RESEARCH

Applicant Address

RAFI MARG, NEW DELHI-110 001, INDIA.

Inventors:

#	Inventor's Name	Inventor's Address
1	ASHOK KUMAR PUNETHA	INDIAN INSTITUTE OF PRTROLEUM.
2	UMA SHANKER	INDIAN INSTITUTE OF PRTROLEUM.
3	KANDADI NARSIMHA	INDIAN INSTITUTE OF PRTROLEUM.
4	TURAGA SUNDARA RAM PRASADA RAO	INDIAN INSTITUTE OF PRTROLEUM.
5	NIRMALA RAY	INDIAN INSTITUTE OF PRTROLEUM.

PCT International Classification Number

B01J0 23/44

PCT International Application Number

N/A

PCT International Filing date

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1			NA